ENVIRONMENTAL CHEMISTRY

Table of contents

Units Name Page no Remarks

1. Fundamentals 1
2. Aquatic chemistry 45
3. Atmospheric chemistry 102
4. Soil chemistry 140
5. Emerging pollutants 174

PRIYANKA
PSY college of Eng. YR 2021-23
1

ENVIRONMENTAL CHEMISTRY
UNIT-1 FUNDAMENTALS
STOICHIOMETRY AND MASS BALANCE:

1|Page
2

2|Page
3

3|Page
4

4|Page
5

5|Page
6

6|Page
7

7|Page
8

Mass balance / MATERIAL BALANCE:

 Mass balance, also called a material balance, is an application of conservation of
mass to the analysis of physical systems. By accounting for material entering and
leaving a system, mass flows can be identified which might have been unknown, or
difficult to measure without this technique.

 The exact conservation law used in the analysis of the system depends on the
context of the problem, but all revolve around mass conservation, i.e.,
that matter cannot disappear or be created spontaneously.[1]: 59–62
 Therefore, mass balances are used widely in engineering and environmental
analyses.
 For example, mass balance theory is used to design chemical reactors, to analyse
alternative processes to produce chemicals, as well as to model pollution dispersion
and other processes of physical systems.
 Closely related and complementary analysis techniques include the population
balance, energy balance and the somewhat more complex entropy balance.
 These techniques are required for thorough design and analysis of systems such as
the refrigeration cycle.
 In environmental monitoring the term budget calculations is used to describe mass
balance equations where they are used to evaluate the monitoring data (comparing
input and output, etc.).
 In biology the dynamic energy budget theory for metabolic organisation makes
explicit use of mass and energy balance

8|Page
9

Introduction
 The general form quoted for a mass balance is The mass that enters a system must,
by conservation of mass, either leave the system or accumulate within the system.
 Mathematically the mass balance for a system without a chemical reaction is as
follows:
 INPUT = OUTPUT + ACCUMULATION

 Strictly speaking the above equation holds also for systems with chemical reactions if
the terms in the balance equation are taken to refer to total mass, i.e. the sum of all
the chemical species of the system. In the absence of a chemical reaction the
amount of any chemical species flowing in and out will be the same; this gives rise to
an equation for each species present in the system.
 However, if this is not the case then the mass balance equation must be amended to
allow for the generation or depletion (consumption) of each chemical species.
 Some use one term in this equation to account for chemical reactions, which will be
negative for depletion and positive for generation.
 However, the conventional form of this equation is written to account for both a
positive generation term (i.e. product of reaction) and a negative consumption term
(the reactants used to produce the products).
 Although overall one term will account for the total balance on the system, if this
balance equation is to be applied to an individual species and then the entire
process, both terms are necessary.
 This modified equation can be used not only for reactive systems, but for population
balances such as arise in particle mechanics problems.
 The equation is given below; note that it simplifies to the earlier equation in the case
that the generation term is zero
INPUT + GENERATION = OUTPUT + ACCUMULATION
+ CONSUMPTION

 In the absence of a nuclear reaction the number of atoms flowing in and out must
remain the same, even in the presence of a chemical reaction.
 For a balance to be formed, the boundaries of the system must be clearly defined.
 Mass balances can be taken over physical systems at multiple scales.
 Mass balances can be simplified with the assumption of steady state, in which the
accumulation term is zero.

Differential mass balances

 A mass balance can also be taken differentially.
 The concept is the same as for a large mass balance, but it is performed in the
context of a limiting system (for example, one can consider the limiting case in time
or, more commonly, volume).

9|Page
10

 A differential mass balance is used to generate differential equations that can

provide an effective tool for modelling and understanding the target system.
 The differential mass balance is usually solved in two steps: first, a set of governing
differential equations must be obtained, and then these equations must be solved,
either analytically or, for less tractable problems, numerically.
The following systems are good examples of the applications of the differential mass
balance:

1. Ideal (stirred) batch reactor

2. Ideal tank reactor, also named Continuous Stirred Tank Reactor (CSTR)
3. Ideal Plug Flow Reactor (PFR)

Ideal batch reactor

 The ideal completely mixed batch reactor is a closed system. Isothermal
conditions are assumed, and mixing prevents concentration gradients as reactant
concentrations decrease and product concentrations increase over time.
 Many chemistry textbooks implicitly assume that the studied system can be
described as a batch reactor when they write about reaction kinetics and chemical
equilibrium.
The mass balance for a substance A becomes

where rA denotes the rate at which substance A is produced, V is the volume (which may be
constant or not), nA the number of moles (n) of substance A.
In a fed-batch reactor some reactants/ingredients are added continuously or in pulses
(compare making porridge by either first blending all ingredients and then letting it boil,
which can be described as a batch reactor, or by first mixing only water and salt and making
that boil before the other ingredients are added, which can be described as a fed-batch
reactor).
Mass balances for fed-batch reactors become a bit more complicated.
Reactive example
In the first example, we will show how to use a mass balance to derive a relationship
between the percent excess air for the combustion of a hydrocarbon-base fuel oil and the
percent oxygen in the combustion product gas.
First, normal dry air contains 0.2095 mol of oxygen per mole of air, so there is one mole
of O2 in 4.773 mol of dry air.

10 | P a g e
11

For stoichiometric combustion, the relationships between the mass of air and the mass of
each combustible element in a fuel oil are:

Considering the accuracy of typical analytical procedures, an equation for the mass of air
per mass of fuel at stoichiometric combustion is:

where wC, wH, wS,

and wO refer to the mass fraction of each element in the fuel oil, sulfur burning to SO2, and
AFRmass refers to the air-fuel ratio in mass units.
For 1 kg of fuel oil containing 86.1% C, 13.6% H, 0.2% O, and 0.1% S the stoichiometric mass
of air is 14.56 kg, so AFR = 14.56.
The combustion product mass is then 15.56 kg.
At exact stoichiometry, O2 should be absent. At 15 percent excess air, the AFR = 16.75, and
the mass of the combustion product gas is 17.75 kg, which contains 0.505 kg of excess
oxygen.
The combustion gas thus contains 2.84 percent O2 by mass.
The relationships between percent excess air and %O2 in the combustion gas are accurately
expressed by quadratic equations, valid over the range 0–30 percent excess air:

In the second example, we will use the law of mass action to derive the expression for
a chemical equilibrium constant.
Assume we have a closed reactor in which the following liquid phase reversible reaction
occurs:

11 | P a g e
12

In many textbooks this is given as the definition of reaction rate without specifying the
implicit assumption that we are talking about reaction rate in a closed system with only one
reaction.
This is an unfortunate mistake that has confused many students over the years.

According to the law of mass action the forward reaction rate can be written as

Ideal tank reactor/continuously stirred tank reactor

The continuously mixed tank reactor is an open system with an influent stream of reactants
and an effluent stream of products.
A lake can be regarded as a tank reactor, and lakes with long turnover times (e.g. with low
flux-to-volume ratios) can for many purposes be regarded as continuously stirred (e.g.
homogeneous in all respects).
The mass balance then becomes

where Q0 and Q denote the volumetric flow in and out of the system respectively
and CA,0 and CA the concentration of A in the inflow and outflow respective. In an open

12 | P a g e
13

system we can never reach a chemical equilibrium. We can, however, reach a steady
state where all state variables (temperature, concentrations, etc.) remain constant (ACC=0).
Example
Consider a bathtub in which there is some bathing salt dissolved. We now fill in more water,
keeping the bottom plug in. What happens?
Since there is no reaction, PROD=0 and since there is no outflow Q=0. The mass balance
becomes

Ideal plug flow reactor (PFR)

The idealized plug flow reactor is an open system resembling a tube with no mixing in the
direction of flow but perfect mixing perpendicular to the direction of flow, often used for
systems like rivers and water pipes if the flow is turbulent.
When a mass balance is made for a tube, one first considers an infinitesimal part of the tube
and make a mass balance over that using the ideal tank reactor model.
That mass balance is then integrated over the entire reactor volume to obtain:

In numeric solutions, e.g. when using computers, the ideal tube is often translated to a
series of tank reactors, as it can be shown that a PFR is equivalent to an infinite number of
stirred tanks in series, but the latter is often easier to analyze, especially at steady state.

13 | P a g e
14

CHEMICAL EQULIBRIA:

 Describe the nature of equilibrium systems

 Explain the dynamic nature of a chemical equilibrium
 A chemical reaction is usually written in a way that suggests it proceeds in one
direction, the direction in which we read, but all chemical reactions are reversible,
and both the forward and reverse reaction occur to one degree or another
depending on conditions.
 In a chemical equilibrium, the forward and reverse reactions occur at equal
rates, and the concentrations of products and reactants remain constant.
 If we run a reaction in a closed system so that the products cannot escape,
we often find the reaction does not give a 100% yield of products.
 Instead, some reactants remain after the concentrations stop changing.
 At this point, when there is no further change in concentrations of reactants
and products, we say the reaction is at equilibrium. A mixture of reactants
and products is found at equilibrium.
 For example, when we place a sample of dinitrogen tetroxide (N2O4, a colorless gas)
in a glass tube, it forms nitrogen dioxide (NO2, a brown gas) by the reaction

N2O4(g)⇌2NO2(g) (13.1.1)

 The color becomes darker as N2O4 is converted to NO2.

When the system reaches equilibrium, both N2O4N2O4 and NO2NO2 are present
(Figure 13.1.1).

Figure 13.1.1: A mixture of NO2 and N2O4 moves toward equilibrium. Colorless N2O4 reacts
to form brown NO2. As the reaction proceeds toward equilibrium, the color of the mixture
darkens due to the increasing concentration of NO2.

14 | P a g e
15

 The formation of NO2 from N2O4 is a reversible reaction, which is identified by the
equilibrium arrow (⇌⇌).

 All reactions are reversible, but many reactions, for all practical purposes, proceed in
one direction until the reactants are exhausted and will reverse only under certain
conditions. Such reactions are often depicted with a one-way arrow from reactants
to products.

 Many other reactions, such as the formation of NO2 from N2O4, are reversible
under more easily obtainable conditions and, therefore, are named as such.

 In a reversible reaction, the reactants can combine to form products and the
products can react to form the reactants.

 Thus, not only can N2O4 decompose to form NO2, but the NO2 produced can react
to form N2O4.

 As soon as the forward reaction produces any NO2, the reverse reaction begins
and NO2 starts to react to form N2O4.

 At equilibrium, the concentrations of N2O4 and NO2 no longer change because the
rate of formation of NO2 is exactly equal to the rate of consumption of NO2, and the
rate of formation of N2O4 is exactly equal to the rate of consumption of N2O4.

Chemical equilibrium is a dynamic process: As with the swimmers and the sunbathers, the
numbers of each remain constant, yet there is a flux back and forth between them

 In a chemical equilibrium, the forward and reverse reactions do not stop, rather they
continue to occur at the same rate, leading to constant concentrations of the
reactants and the products.

 Plots showing how the reaction rates and concentrations change with respect to
time are shown in Figure 13.1.1.

 We can detect a state of equilibrium because the concentrations of reactants and

products do not appear to change.

 However, it is important that we verify that the absence of change is due to

equilibrium and not to a reaction rate that is so slow that changes in concentration
are difficult to detect.

We use a double arrow when writing an equation for a reversible reaction. Such a reaction
may or may not be at equilibrium. For example, Figure 13.1.1 shows the reaction:

15 | P a g e
16

N2O4(g)⇌2NO2(g) (13.1.2)

When we wish to speak about one particular component of a reversible reaction, we use a
single arrow. For example, in the equilibrium shown in Figure 13.1.113.1.1, the rate of the
forward reaction

2NO2(g)→N2O4(g) (13.1.3)

is equal to the rate of the backward reaction

N2O4(g)→2NO2(g) (13.1.4)
Summary

A reaction is at equilibrium when the amounts of reactants or products no longer change.

Chemical equilibrium is a dynamic process, meaning the rate of formation of products by
the forward reaction is equal to the rate at which the products re-form reactants by the
reverse reaction.

ACID BASE:

Definitions of Acidity and Basicity

For more than two-hundred years, chemists have struggled to come up with a way to
describe acid-base reactions that is at the same time physically relevant, specific enough to
be accurate, and general enough to include everything that should be considered an acid-
base relationship.

Svante Arrhenius first defined acids to be proton (H+) donors and bases to be hydroxide ion
(OH-) donors in aqueous solution.
The Arrhenius model of acids and bases is summarized by the following two reactions:

Figure %: The Arrhenius model of acids and bases, where A = acid and B = base

At the time that Arrhenius proposed these definitions, water was virtually the only solvent
used in chemistry, and nearly all known acids and bases contained protons (H+) and hydroxyl
groups (OH), respectively.

His definition was sufficient for the chemistry that was understood then.

16 | P a g e
17

But progress in chemistry necessitated new definitions: it was discovered that ammonia
behaves like a base, and HCl donates protons in non-aqueous solvents.

The Bronsted-Lowry model of acids and bases serves that need by describing acids as
proton donors and bases as proton acceptors.

These definitions remove the role of solvent and allow bases like ammonia and fluoride ion
to be classified as bases, so long as they bond to protons.

The Bronsted-Lowry model implies that there is a relationship between acids and bases
(acids transfer protons to bases) and allows us to define conjugate acids and conjugate
bases, as seen in .

Figure %: The Bronsted model of acids and bases

You should note in the figure above that the conjugate acid of the base, BH +, acts as an acid
in the reverse reaction by donating a proton to the conjugate base, A-, of the acid HA.

Despite the usefulness of the Bronsted-Lowry definition, there is an even more general
definition of acids and bases provided by G. N. Lewis.

The Lewis model of acids and bases proposes that an acid is an electron pair acceptor while
a base is an electron pair donor.

This model of acidity and basicity broadens the characterization of acid-base reactions to
include reactions like the following which do not involve any hydrogen transfers. The
nitrogen atom in ammonia donates an electron pair to complete the valence octet of boron.

Figure %: Example of a Lewis acid-base reaction

Because we are more interested now in describing terms and processes that involve proton
transfers (pH, titration), we will focus on the Bronsted-Lowry definitions of acids and bases.

We will leave consideration of the Lewis model of acids and bases for studying reactions in
organic chemistry.

Reactions of Acids and Bases with Water

17 | P a g e
18

As you may have noted already in the acid-base reactions above, we use arrows in both
reaction directions to indicate that these are equilibrium processes.

Proportions of reagents and products at equilibrium can be described by an equilibrium

constant.

The equilibrium constant given in is for the reaction of an acid, HA, with water as shown.

Although water is a reactant in the above reaction and belongs in the equilibrium constant,
its value of 55.6 M in aqueous solution is so large in comparison with the change in water
concentration at equilibrium that we will assume that the value of [H2O] is constant.

Using that assumption, we will define the acid dissociation constant, Ka, in to be the
following:

Figure %: Definition of the acid dissociation constant

From the form of the above equation we can see that stronger acids, those that dissociate
to a greater extent, will have larger values of Ka whereas weaker acids will have smaller
values of Ka.

A practical range for Ka values runs from 10-12 for very weak acids to 1013 for the strongest
acids.

Knowing this practical range of acidity constants will aid in judging how reasonable your
answers are when you calculate values for Ka in problems.

In an analogous way, we define Kb, the base constant in to be the following:

Figure %: Definition of the base dissociation constant

18 | P a g e
19

Stronger bases have larger values of Kb while weaker bases have smaller values of Kb.

Kb's of typical bases in inorganic chemistry tend to have a range of values between 10 -11 and
103.

As you may have discovered in our above discussion, water can act as both an acid and as a
base.

For this reason water is said to be amphiprotic. Water is often incorrectly termed
amphoteric.

An amphiprotic species like water can either donate or accept a proton. Amphoteric species
can both donate and accept hydroxide ions, as water cannot.

The following reaction in , called the autoionization of water, has the equilibrium
constant Kw defined in the manner of Ka and Kb.

The dissociation constant Kw for water is 1 x 10-14 at room temperature (298 K), and tends to
rise with higher temperatures.

Figure %: The autoionization of water

Knowing that Kw = 1 x 10-14 is useful because the relationship between Ka and Kb for a
conjugate acid-base pair is Ka * Kb = Kw.

Therefore, you can calculate the Ka of the conjugate acid of a base when given its Kb.

This point is proved in below.

19 | P a g e
20

Figure %: The autoionization constant of water equals the product of the acid and base
dissociation constants of a conjugate acid-base pair.

From the proven expression, we see that strong acids (large Ka's) form weak conjugate bases
and weak acids form strong conjugate bases.

In the following section, we will discuss acid and base strength in more depth.

SOLUBILITY PRODUCT(ksp):

Solubility Product (Ksp)

What is Solubility Product, Ksp?

The solubility product constant is the equilibrium constant for the dissolution of a solid
substance into an aqueous solution. It is denoted by the symbol Ksp.
The solubility product is a kind of equilibrium constant and its value depends on
temperature.

Ksp usually increases with an increase in temperature due to increased solubility.

Solubility is defined as a property of a substance called solute to get dissolved in a solvent in

order to form a solution.
The solubility of ionic compounds (which disassociate to form cations and anions) in water
varies to a great deal.
Some compounds are highly soluble and may even absorb moisture from the atmosphere
whereas others are highly insoluble.

20 | P a g e
21

Significance of Solubility Product

Solubility depends on a number of parameters amongst which lattice enthalpy of salt and
solvation enthalpy of ions in the solution are of most importance.

 When a salt is dissolved in a solvent the strong forces of attraction of solute (lattice
enthalpy of its ions) must be overcome by the interactions between ions and the
solvent.
 The solvation enthalpy of ions is always negative which means that energy is released
during this process.
 The nature of the solvent determines the amount of energy released during solvation
that is solvation enthalpy.
 Non-polar solvents have a small value of solvation enthalpy, meaning that this energy
is not sufficient to overcome the lattice enthalpy.
 So the salts are not dissolved in non-polar solvents. Hence, for salt to be dissolved in
a solvent, its solvation enthalpy should be greater than its lattice enthalpy.
 Solubility depends on temperature and it is different for every salt.

Salts are classified on the basis of their solubility in the following table.

Category I Soluble Solubility > 0.1M

Category II Slightly soluble 0.01M< Solubility<0.1M

Category III Sparingly soluble Solubility < 0.1M

Solubility Product Constant

Suppose barium sulphate along with its saturated aqueous solution is taken. The following
equation represents the equilibrium set up between the undissolved solids and ions:

21 | P a g e
22

HEAVY METAL PRECIPITATION:

 The principle technology to remove metals pollutants from wastewater is by

chemical precipitation.

 Chemical precipitation includes two secondary removal

mechanisms, coprecipitation and adsorption .

 Precipitation processes are characterized by the solubility of the metal to be

removed.

 They are generally designed to precipitate trace metals to their solubility limits and
obtain additional removal by coprecipitation and adsorption during the precipitation
reaction.

 There are many different treatment variables that affect these processes.

 They include the optimum pH , the type of chemical treatments used, and the
number of treatment stages, as well as the temperature and volume of wastewater,
and the chemical specifications of the pollutants to be removed.

 Each of these variables directly influences treatment objectives and costs.

 Treatability studies must be performed to optimize the relevant variables, so that

goals are met and costs minimized.

22 | P a g e
23

 In theory, the precipitation process has two steps, nucleation followed by particle
growth.

 Nucleation is represented by the appearance of very small particle seeds which are
generally composed of 10–100 molecules.

 Particle growth involves the addition of more atoms or molecules into this particle
structure.

 The rate and extent of this process is dependent upon the temperature and chemical
characteristics of the wastewater, such as the concentration of metal initially present
and other ionic species present, which can compete with or form soluble complexes
with the target metal species.

 Heavy metals are present in many industrial wastewaters.

 Examples of such metals are cadmium , copper , lead , mercury , nickel , and zinc. In
general, these metals can be complexed to insoluble species by adding sulfide,
hydroxide, and carbonate ions to a solution.

 For example, the precipitation of copper (Cu) hydroxide is accomplished by adjusting

the pH of the water to above 8, using precipitant chemicals such as lime (Ca(OH)2)
or sodium hydroxide (NaOH).

 Precipitation of metallic carbonate and sulfide species can be accomplished by the

addition of calcium carbonate or sodium sulfide.

 The removal of coprecipitive metals during precipitation of the soluble metals is

aided by the presence of solid ferric oxide, which acts as an adsorbent during the
precipitation reaction.

 For example, hydroxide precipitation of ferric chloride can be used as the source of
ferric oxide for coprecipitation and adsorption reactions.

 Precipitation, coprecipitation, and adsorption reactions generate suspended solids

which must be separated from the wastewater.

 Flocculation and clarification are again employed to assist in solids separation.

 The treatment is an important variable which must be optimized to effect the

maximum metal removal possible.

 Determining the optimal pH range to facilitate the maximum precipitation of metal is

a difficult task.

 It is typically accomplished by laboratory studies, such as by-jar tests rather than

theoretical calculations.

23 | P a g e
24

 Often the actual wastestream behaves differently, and the theoretical metal
solubilities and corresponding optimal pH ranges can vary considerably from
theoretical values.

AMPHOTERIC HYDROXIDES:

Amphoterism Definition

 Amphoteric meaning, in the simplest term, can be stated as any compound that can
be mixed with other compounds both as a base and an acid.
 For example, water is amphoteric.
 It can be transformed into a compound that can be used as an alkali or an acid.
 Most amphoteric compounds are metal oxides or hydroxides.

 Amphoterism is a popular term in the field of chemistry explaining the reactivity of a

compound that shows alkaline nature when mixed with an acid and demonstrates
acidic characteristics in an alkaline environment.

 As water is amphoteric, it is used widely for such reactions. When acid reacts with
water, it gives off H3O+ ion adding an H+ ion from the acid.

 On the other hand, when water is combined with a base, it donates an H+ ion to the
base and releases OH- ion.

 Besides water, many oxides and hydroxides are vastly utilized in amphoterism.

 Now that amphoteric meaning is clear enough, let us see how you can identify an
amphoteric substance.

How to Identify an Amphoteric Substance?

While experimenting in the laboratory, how would you recognize an amphoteric compound?
How to match the properties to the amphoteric definition that you have just read? Here is
how you can define the amphoteric characteristics in a compound.

 When an amphoteric substance is mixed with an acid, it would take up hydrogen from
the acid creating an H3O+ ion.

 When the amphoteric compound reacts to a base, it supplies hydrogen to the alkaline
compound and releases an OH- ion.

The Bronsted Lowry theory states that 'acids are proton donors and bases are proton
acceptors.'. The substances that have both these characteristics are identified as amphoteric
substances.

Amphoteric Hydroxides

 Hydroxides are famous for using amphoterism. Not all metals can be used as
amphoteric hydroxides.

24 | P a g e
25

 Hydroxides that are made of highly charged metal cations are used for amphoterism.

 They can react in two conditions.

 They can either function as a Bronsted lowry base by receiving protons or work as
Lewis acid by receiving a pair of electrons.

 In acidic conditions, a simple neutralization reaction occurs.

 As mentioned before, here the hydroxide would react as a base and would either give
off protons or accept electrons.

 In an alkaline condition, the hydroxide will behave just like an acid by accepting
protons from the other reactant.

Amphoteric Hydroxide Examples or Simply, Amphoteric Examples List is Given Below.

 Aluminium hydroxide

 Zinc hydroxide

 Copper hydroxide

 Chromium hydroxide

 Beryllium hydroxide

 Tin hydroxide

Amphoteric Amino Acid

 The carboxyl group in amino acids is responsible for their amphoteric properties. They
are widely used for amphoterism.

 An amphoteric amino acid contains both acidic and alkaline elements like COOH and
NH2.

 When present in an acidic condition, an amino acid would act as a base.

 It will carry away the positively charged ions and get attracted to the negative ions.

 It gives off the protons or accepts electrons.

 On the other hand, while reacting with a base, it possesses acidic characteristics by
carrying negative ions and accepting protons.

 Amino acids are excellent for amphoterism.

 One example of amphoteric amino acids is glycine.

Amphoteric Oxides

 Just like the hydroxides, some oxides are also amphoteric.

25 | P a g e
26

 The amphoteric characteristics depend on the oxidation state of the compound.

 When a metal oxide reacts with an acid, you can witness a neutralization reaction just
like an amphoteric hydroxide.

 It will accept protons from the acid and produce salt.

 In contrast to this reaction, a metal oxide would produce salt and water when it reacts
with an alkali.

 It would give off protons to the other reactant.

 Amphoteric oxides are pretty similar to amphoteric hydroxides.

Some Common Oxide Amphoteric Examples are Given Below.

 Aluminum oxide

 Lead oxide

 Zinc oxide

 Tin oxide

 Beryllium oxide

 Chromium oxide

 Copper oxide

Aluminum Amphoteric

 Aluminum is well-known for its amphoteric properties. All compounds made with
aluminum are amphoteric compounds.

 All of these compounds can be used as both acids or bases.

 Aluminum amphoteric can be used in many forms to let them react as acids or bases.
It reacts similarly to other amphoteric compounds.

 It accepts protons when mixed with an acid and releases protons when it reacts to an
alkali.

 Aluminum chloride, aluminum oxide, aluminum hydroxide are some examples of

aluminum amphoteric.

 As you can see in the amphoteric list above, you can imagine how important it is in
the field of chemistry.

 Amphoteric reactions are used to study the properties of elements and analyze the
periodic table.

26 | P a g e
27

 The amphoteric examples given above have many compounds that can be applied
both as an acid and an alkali.
 These compounds help in laboratory work as well. As one compound acts both as an
acid and a base, you can observe various reactions with the same compound.

Learning Objective

 Identify the conditions under which amphoteric hydroxides act as acids.

Key Points

o Amphoteric molecules can act as either acids or bases.

o Hydroxides with highly-charged metal cations are often amphoteric.
o Amphoteric hydroxides act as either Bronsted-Lowry bases (accepting protons)
or Lewis acids (accepting an electron pair), depending on reaction conditions.

Terms

 basea proton acceptor or an electron pair donor

 Lewis acidan electron pair acceptor

In our discussion of acids and bases so far, hydroxides have always been synonymous with
bases.

Now we will examine amphoteric hydroxides—that is, hydroxide salts that can act as either
an acid or a base, depending on reaction conditions.

We will begin with the familiar case of a hydroxide acting as a base.

Reaction of Amphoteric Hydroxides in Acidic Solution

One of the most common and familiar examples of an amphoteric hydroxide is aluminum
hydroxide, Al(OH)3.

From our solubility rules, we know that Al(OH)3 is largely insoluble in neutral water;
however, in a strongly acidic solution, the situation changes.

For example, consider the reaction of Al(OH)3 with HCl:

HCl(aq)+Al(OH)3(aq) → AlCl3(aq)+3H2O(l)

This is a classic acid-base neutralization reaction: the HCl completely protonates all three
hydroxides per mole of Al(OH)3, yielding pure water and the salt AlCl3.

27 | P a g e
28

From what we know about the basic properties of hydroxides so far, this is exactly as we
would expect—so how can a hydroxide act as an acid?

Reaction of Amphoteric Hydroxides in Basic Solution

We will now consider aluminum hydroxide’s reaction in a strongly basic solution:

Al(OH)3(aq)+OH−(aq)→Al(OH)−4(aq)

Here, aluminum hydroxide picks up an hydroxide ion out of solution, thereby acting as a
Lewis acid. How is this possible? Consider the Lewis structure for Al(OH)3.

Aluminum hydroxideAluminum hydroxide can act as either a Bronsted-Lowry base, by

accepting protons from an acidic solution, or as a Lewis acid, by accepting an electron pair
from hydroxide ions in a basic solution.

The central aluminum atom is electron deficient—it forms only three bonds, and the octet
rule is not fulfilled; thus, Al3+ is quite happy to accept a pair of electrons and form another
bond, given the right conditions.

In a basic solution, it forms a bond with an OH– ion, pulling it out of solution and lowering
the solution’s pH.

Conclusion

Metal hydroxides with a highly-charged central metal atom can be amphoteric. In addition
to aluminum, metals such as zinc, tin, lead, and beryllium can also form amphoteric oxides
or hydroxides.

Whether such hydroxides behave as acids or bases depends on the surrounding solution’s
pH.

OCEAN ACIDIFICATION:

What is Ocean Acidification?

The Chemistry

 When carbon dioxide (CO2) is absorbed by seawater, chemical reactions occur that
reduce seawater pH, carbonate ion concentration, and saturation states of
biologically important calcium carbonate minerals.

28 | P a g e
29

 These chemical reactions are termed "ocean acidification" or "OA" for short. Calcium
carbonate minerals are the building blocks for the skeletons and shells of many
marine organisms.

 In areas where most life now congregates in the ocean, the seawater is
supersaturated with respect to calcium carbonate minerals.

 This means there are abundant building blocks for calcifying organisms to build their
skeletons and shells.

 However, continued ocean acidification is causing many parts of the ocean to

become undersaturated with these minerals, which is likely to affect the ability of
some organisms to produce and maintain their shells.

 Since the beginning of the Industrial Revolution, the pH of surface ocean waters has
fallen by 0.1 pH units. Since the pH scale, like the Richter scale, is logarithmic, this
change represents approximately a 30 percent increase in acidity (see our pH
primer web page for more information).

 Future predictions indicate that the oceans will continue to absorb carbon dioxide,
further increasing ocean acidity.

 Estimates of future carbon dioxide levels, based on business as usual emission

scenarios, indicate that by the end of this century the surface waters of the ocean
could have acidity levels nearly 150 percent higher, resulting in a pH that the oceans
haven’t experienced for more than 20 million years.

The Biological Impacts

 Ocean acidification is expected to impact ocean species to varying degrees.

 Photosynthetic algae and seagrasses may benefit from higher CO2 conditions in the
ocean, as they require CO2 to live just like plants on land.

 On the other hand, studies have shown that lower environmental calcium carbonate
saturation states can have a dramatic effect on some calcifying species, including
oysters, clams, sea urchins, shallow water corals, deep sea corals, and calcareous
plankton.

 Today, more than a billion people worldwide rely on food from the ocean as their
primary source of protein.

 Thus, both jobs and food security in the U.S. and around the world depend on the
fish and shellfish in our oceans.

29 | P a g e
30

Pteropods

 The pteropod, or “sea butterfly”, is a tiny sea creature about the size of a small pea.

 Pteropods are eaten by organisms ranging in size from tiny krill to whales and are a
food source for North Pacific juvenile salmon.

 The photos below show that a pteropod’s shell dissolves over 45 day when placed in
sea water with pH and carbonate levels projected for the year 2100.

ShellfisH

 In recent years, there have been near total failures of developing oysters in both
aquaculture facilities and natural ecosystems on the West Coast.

 These larval oyster failures appear to be correlated with naturally occurring

upwelling events that bring low pH waters undersaturated in aragonite as well as
other water quality changes to nearshore environments.

 Lower pH values occur naturally on the West Coast during upwelling events, but a
recent observations indicate that anthropogenic CO2 is contributing to seasonal
undersaturation.

 Low pH may be a factor in the current oyster reproductive failure; however, more
research is needed to disentangle potential acidification effects from other risk
factors, such as episodic freshwater inflow, pathogen increases, or low dissolved
oxygen.

 It is premature to conclude that acidification is responsible for the recent oyster

failures, but acidification is a potential factor in the current crisis to this $100 million
a year industry, prompting new collaborations and accelerated research on ocean
acidification and potential biological impacts.

Coral

 Many marine organisms that produce calcium carbonate shells or skeletons are
negatively impacted by increasing CO2 levels and decreasing pH in seawater.

 For example, increasing ocean acidification has been shown to significantly reduce
the ability of reef-building corals to produce their skeletons.

30 | P a g e
31

 In a recent paper, coral biologists reported that ocean acidification could

compromise the successful fertilization, larval settlement and survivorship of Elkhorn
coral, an endangered species.

 These research results suggest that ocean acidification could severely impact the
ability of coral reefs to recover from disturbance.

 Other research indicates that, by the end of this century, coral reefs may erode
faster than they can be rebuilt.

 This could compromise the long-term viability of these ecosystems and perhaps
impact the estimated one million species that depend on coral reef habitat.

Ocean Acidification: An Emerging Global Problem

 Ocean acidification is an emerging global problem.

 Over the last decade, there has been much focus in the ocean science community on
studying the potential impacts of ocean acidification.

 Since sustained efforts to monitor ocean acidification worldwide are only beginning,
it is currently impossible to predict exactly how ocean acidification impacts will
cascade throughout the marine food chain and affect the overall structure of marine
ecosystems.

 With the pace of ocean acidification accelerating, scientists, resource managers, and
policymakers recognize the urgent need to strengthen the science as a basis for
sound decision making and action.

What causes ocean acidification?

 Ocean acidification is mainly caused by carbon dioxide gas in the atmosphere
dissolving into the ocean. This leads to a lowering of the water's pH, making the
ocean more acidic.

 Many factors contribute to rising carbon dioxide levels. Currently, the burning of
fossil fuels such as coal, oil and gas for human industry is one of the major causes.

 Deforestation results in fewer trees to absorb the gas. Also, when plants are cut
down and burnt or left to rot, the carbon that makes up their organic tissue is
released as carbon dioxide.

 Some parts of the ocean are naturally acidic, such as at hydrothermal vent sites -
underwater 'hot springs'.

 In the past, ocean acidification occurred naturally but over much longer periods of
time. It is occurring faster now than in the last 20 million years.

31 | P a g e
32

CHEMICAL KINETICS:

 Chemical kinetics, also known as reaction kinetics, is the branch of physical

chemistry that is concerned with understanding the rates of chemical reactions.
 It is to be contrasted with thermodynamics, which deals with the direction in which a
process occurs but in itself tells nothing about its rate.
 Chemical kinetics includes investigations of how experimental conditions influence
the speed of a chemical reaction and yield information about the reaction's
mechanism and transition states, as well as the construction of mathematical
models that also can describe the characteristics of a chemical reaction.

Factors affecting reaction rate

Nature of the reactants
 The reaction rate varies depending upon what substances are reacting. Acid/base
reactions, the formation of salts, and ion exchange are usually fast reactions.
 When covalent bond formation takes place between the molecules and when large
molecules are formed, the reactions tend to be slower.
 The nature and strength of bonds in reactant molecules greatly influence the rate of
their transformation into products.
Physical state
 The physical state (solid, liquid, or gas) of a reactant is also an important factor of
the rate of change.
 When reactants are in the same phase, as in aqueous solution, thermal motion
brings them into contact.
 However, when they are in separate phases, the reaction is limited to the interface
between the reactants.
 Reaction can occur only at their area of contact; in the case of a liquid and a gas, at
the surface of the liquid.
 Vigorous shaking and stirring may be needed to bring the reaction to completion.
 This means that the more finely divided a solid or liquid reactant the greater
its surface area per unit volume and the more contact it with the other reactant,
thus the faster the reaction.
 To make an analogy, for example, when one starts a fire, one uses wood chips and
small branches — one does not start with large logs right away.
 In organic chemistry, on water reactions are the exception to the rule that
homogeneous reactions take place faster than heterogeneous reactions ( are those
reactions in which solute and solvent not mix properly)

32 | P a g e
33

Surface area of solid state

 In a solid, only those particles that are at the surface can be involved in a reaction.
 Crushing a solid into smaller parts means that more particles are present at the
surface, and the frequency of collisions between these and reactant particles
increases, and so reaction occurs more rapidly.
 For example, Sherbet (powder) is a mixture of very fine powder of malic acid (a weak
organic acid) and sodium hydrogen carbonate.
 On contact with the saliva in the mouth, these chemicals quickly dissolve and react,
releasing carbon dioxide and providing for the fizzy sensation.
 Also, fireworks manufacturers modify the surface area of solid reactants to control
the rate at which the fuels in fireworks are oxidised, using this to create diverse
effects.
 For example, finely divided aluminium confined in a shell explodes violently. If larger
pieces of aluminium are used, the reaction is slower and sparks are seen as pieces of
burning metal are ejected.
Concentration
 The reactions are due to collisions of reactant species. The frequency with which the
molecules or ions collide depends upon their concentrations.
 The more crowded the molecules are, the more likely they are to collide and react
with one another.
 Thus, an increase in the concentrations of the reactants will usually result in the
corresponding increase in the reaction rate, while a decrease in the concentrations
will usually have a reverse effect.
 For example, combustion will occur more rapidly in pure oxygen than in air (21%
oxygen).
 The rate equation shows the detailed dependence of the reaction rate on the
concentrations of reactants and other species present.
 The mathematical forms depend on the reaction mechanism.
 The actual rate equation for a given reaction is determined experimentally and
provides information about the reaction mechanism. The mathematical expression
of the rate equation is often given by

 Here K is the reaction rate constant, Ci is the molar concentration of

reactant i and Mi is the partial order of reaction for this reactant.

33 | P a g e
34

 The partial order for a reactant can only be determined experimentally and is often
not indicated by its stoichiometric coefficient.
Temperature
 Temperature usually has a major effect on the rate of a chemical reaction.
 Molecules at a higher temperature have more thermal energy.
 Although collision frequency is greater at higher temperatures, this alone
contributes only a very small proportion to the increase in rate of reaction.
 Much more important is the fact that the proportion of reactant molecules with
sufficient energy to react (energy greater than activation energy: E > Ea) is
significantly higher and is explained in detail by the Maxwell–Boltzmann
distribution of molecular energies.
 The effect of temperature on the reaction rate constant usually obeys the Arrhenius
equation k=Ae^-Ea/(RT), where A is the pre-exponential factor or A-factor, Ea is the
activation energy, R is the molar gas constant and T is the absolute temperature.[7]
 At a given temperature, the chemical rate of a reaction depends on the value of the
A-factor, the magnitude of the activation energy, and the concentrations of the
reactants.
 Usually, rapid reactions require relatively small activation energies.
 The 'rule of thumb' that the rate of chemical reactions doubles for every 10 °C
temperature rise is a common misconception.
 This may have been generalized from the special case of biological systems, where
the α (temperature coefficient) is often between 1.5 and 2.5.
 The kinetics of rapid reactions can be studied with the temperature jump method.
 This involves using a sharp rise in temperature and observing the relaxation time of
the return to equilibrium.
 A particularly useful form of temperature jump apparatus is a shock tube, which can
rapidly increase a gas's temperature by more than 1000 degrees.
Catalysts

34 | P a g e
35

Generic potential energy diagram showing the effect of a catalyst in a hypothetical

endothermic chemical reaction. The presence of the catalyst opens a new reaction
pathway (shown in red) with a lower activation energy. The final result and the overall
thermodynamics are the same.
 A catalyst is a substance that alters the rate of a chemical reaction but it
remains chemically unchanged afterwards.
 The catalyst increases the rate of the reaction by providing a new reaction
mechanism to occur with in a lower activation energy. In autocatalysis a reaction
product is itself a catalyst for that reaction leading to positive feedback.
 Proteins that act as catalysts in biochemical reactions are called enzymes. Michaelis–
Menten kinetics describe the rate of enzyme mediated reactions.
 A catalyst does not affect the position of the equilibrium, as the catalyst speeds up
the backward and forward reactions equally.
 In certain organic molecules, specific substituents can have an influence on reaction
rate in neighbouring group participation.
Pressure
 Increasing the pressure in a gaseous reaction will increase the number of collisions
between reactants, increasing the rate of reaction.
 This is because the activity of a gas is directly proportional to the partial pressure of
the gas.
 This is similar to the effect of increasing the concentration of a solution.
 In addition to this straightforward mass-action effect, the rate coefficients
themselves can change due to pressure.
 The rate coefficients and products of many high-temperature gas-phase reactions
change if an inert gas is added to the mixture; variations on this effect are called fall-
off and chemical activation.
 These phenomena are due to exothermic or endothermic reactions occurring faster
than heat transfer, causing the reacting molecules to have non-thermal energy
distributions (non-Boltzmann distribution).
 Increasing the pressure increases the heat transfer rate between the reacting
molecules and the rest of the system, reducing this effect.
 Condensed-phase rate coefficients can also be affected by pressure, although rather
high pressures are required for a measurable effect because ions and molecules are
not very compressible.
 This effect is often studied using diamond anvils.
A reaction's kinetics can also be studied with a pressure jump approach. This involves
making fast changes in pressure and observing the relaxation time of the return to
equilibrium.

35 | P a g e
36

Absorption of light
 The activation energy for a chemical reaction can be provided when one reactant
molecule absorbs light of suitable wavelength and is promoted to an excited state.
 The study of reactions initiated by light is photochemistry, one prominent example
being photosynthesis.
 The experimental determination of reaction rates involves measuring how the
concentrations of reactants or products change over time.
 For example, the concentration of a reactant can be measured
by spectrophotometry at a wavelength where no other reactant or product in the
system absorbs light.
 For reactions which take at least several minutes, it is possible to start the
observations after the reactants have been mixed at the temperature of interest.
Fast reactions
For faster reactions, the time required to mix the reactants and bring them to a
specified temperature may be comparable or longer than the half-life of the reaction.
Special methods to start fast reactions without slow mixing step include

 Stopped flow methods, which can reduce the mixing time to the order of a
millisecond[8][9][10] The stopped flow methods have limitation, for example, we need
to consider the time it takes to mix gases or solutions and are not suitable if the
half-life is less than about a hundredth of a second.
 Chemical relaxation methods such as temperature jump and pressure jump, in which
a pre-mixed system initially at equilibrium is perturbed by rapid heating or
depressurization so that it is no longer at equilibrium, and the relaxation back to
equilibrium is observed.[8][11][12][13] For example, this method has been used to study
the neutralization H3O+ + OH− with a half-life of 1 μs or less under ordinary
conditions.[8][13]
 Flash photolysis, in which a laser pulse produces highly excited species such as free
radicals, whose reactions are then studied.[10][14][15][16]

Equilibrium
 While chemical kinetics is concerned with the rate of a chemical
reaction, thermodynamics determines the extent to which reactions occur.
 In a reversible reaction, chemical equilibrium is reached when the rates of the
forward and reverse reactions are equal (the principle of dynamic equilibrium) and
the concentrations of the reactants and products no longer change.
 This is demonstrated by, for example, the Haber–Bosch process for combining
nitrogen and hydrogen to produce ammonia. Chemical clock reactions such as
the Belousov–Zhabotinsky reaction demonstrate that component concentrations can
oscillate for a long time before finally attaining the equilibrium.

36 | P a g e
37

Free energy
 In general terms, the free energy change (ΔG) of a reaction determines whether a
chemical change will take place, but kinetics describes how fast the reaction is.
 A reaction can be very exothermic and have a very positive entropy change but will
not happen in practice if the reaction is too slow.
 If a reactant can produce two products, the thermodynamically most stable one will
form in general, except in special circumstances when the reaction is said to be
under kinetic reaction control. The Curtin–Hammett principle applies when
determining the product ratio for two reactants interconverting rapidly, each going
to a distinct product. It is possible to make predictions about reaction rate constants
for a reaction from free-energy relationships.
 The kinetic isotope effect is the difference in the rate of a chemical reaction when an
atom in one of the reactants is replaced by one of its isotopes.
 Chemical kinetics provides information on residence time and heat transfer in
a chemical reactor in chemical engineering and the molar mass
distribution in polymer chemistry. It is also provides information in corrosion
engineering.

Applications and models

 The mathematical models that describe chemical reaction kinetics provide chemists
and chemical engineers with tools to better understand and describe chemical
processes such as food decomposition, microorganism growth, stratospheric ozone
decomposition, and the chemistry of biological systems.
 These models can also be used in the design or modification of chemical reactors to
optimize product yield, more efficiently separate products, and eliminate
environmentally harmful by-products.
 When performing catalytic cracking of heavy hydrocarbons into gasoline and light
gas, for example, kinetic models can be used to find the temperature and pressure at
which the highest yield of heavy hydrocarbons into gasoline will occur.
 Chemical Kinetics is frequently validated and explored through modeling in
specialized packages as a function of ordinary differential equation-solving (ODE-
solving) and curve-fitting.[17]
Numerical methods
 In some cases, equations are unsolvable analytically, but can be solved using
numerical methods if data values are given.
 There are two different ways to do this, by either using software programmes or
mathematical methods such as the Euler method.
 Examples of software for chemical kinetics are i) Tenua, a Java app which simulates
chemical reactions numerically and allows comparison of the simulation to real data,
ii) Python coding for calculations and estimates and iii) the Kintecus software
compiler to model, regress, fit and optimize reactions.

37 | P a g e
38

 Stochastic methods → probabilities of the differential rate laws and

the kinetic constants.
In an equilibrioum reaction with directed and inverse rate constants, it's
easier to transform from A to B rather than B to A.
As for probability computations, at each time it choose a random
number to be compared with a threshold to know if the reaction runs
from A to B or the other way around.

38 | P a g e
39

12 PRINCIPLES OF GREEN CHEMISTRY:

39 | P a g e
40

1: Waste Prevention

 This tenet simply states that chemical processes should be optimised to produce the
minimum amount of waste possible.
 A metric, known as the environmental factor (or E factor for short), was developed
to gauge the amount of waste a process created, and is calculated by simply dividing
the mass of waste the production process produces by the mass of product
obtained, with a lower E factor being better.
 Drug production processes historically had notoriously high E factors, but the
application of some of the other green chemistry principles can help to reduce this.
 Other methods of assessing amounts of waste, such as comparing the mass of the
raw materials to that of the product, are also used.

2: Atom Economy

 Atom economy is a measure of the amount of atoms from the starting material that
are present in the useful products at the end of a chemical process.
 Side products from reactions that aren’t useful can lead to a lower atom economy,
and more waste.
 In many ways, atom economy is a better measure of reaction efficiency than the
yield of the reaction; the yield compares the amount of useful product obtained
compared to the amount you’d theoretically expect from calculations.
 Therefore, processes that maximise atom economy are preferred.

3: Less Hazardous Chemical Synthesis

 Ideally, we want chemicals we create for whatever purpose to not pose a health
hazard to humans.
 We also want to make the synthesis of chemicals as safe as possible, so the aim is to
avoid using hazardous chemicals as starting points if safer alternatives are available.
 Additionally, having hazardous waste from chemical processes is something we want
to avoid, as this can cause problems with disposal.

4: Designing Safer Chemicals

 This principle links closely to the previous one.

 Chemists must aim to produce chemical products that fulfil their role, be that
medical, industrial, or otherwise, but which also have minimal toxicity to humans.
 The design of safer chemical targets requires a knowledge of how chemicals act in
our bodies and in the environment.
 In some cases, a degree of toxicity to animals or humans may be unavoidable, but
alternatives should be sought.
 5: Safer Solvents & Auxiliaries
 Many chemical reactions require the use of solvents or other agents in order to
facilitate the reaction.

40 | P a g e
41

 They can also have a number of hazards associated with them, such as flammability
and volatility.
 Solvents might be unavoidable in most processes, but they should be chosen to
reduce the energy needed for the reaction, should have minimal toxicity, and should
be recycled if possible.

6: Design for Energy Efficiency

 Energy-intensive processes are frowned upon in green chemistry.

 Where it is possible, it is better to minimise the energy used to create a chemical
product, by carrying out reactions at room temperature and pressure.
 Considerations of reaction design also have to be made; removal of solvents, or
processes to remove impurities, can increase the energy required, and by association
increase the process’s environmental impacts.

7: Use of Renewable Feedstocks

 The perspective of this principle is largely towards petrochemicals: chemical

products derived from crude oil.
 These are used as starting materials in a range of chemical processes, but are non-
renewable, and can be depleted.
 Processes can be made more sustainable by the use of renewable feedstocks, such
as chemicals derived from biological sources.

8: Reduce Derivatives

 Protecting groups are often used in chemical synthesis, as they can prevent
alteration of certain parts of a molecule’s structure during a chemical reaction, whilst
allowing transformations to be carried out on other parts of the structure.
 However, these steps require extra reagents, and also increase the amount of waste
a process produces.
 An alternative that has been explored in some processes is the use of enzymes.
 As enzymes are highly specific, they can be used to target particular parts of a
molecule’s structure without the need for the use of protecting groups or other
derivatives.

9: Catalysis

 The use of catalysts can enable reactions with higher atom economies.
 Catalysts themselves aren’t used up by chemical processes, and as such can be
recycled many times over, and don’t contribute to waste.
 They can allow for the utilisation of reactions which would not proceed under
normal conditions, but which also produce less waste.

41 | P a g e
42

10: Design for Degradation

 Ideally, chemical products should be designed so that, once they have fulfilled their
purpose, they break down into harmless products and don’t have negative impacts
on the environment.
 Persistent organic pollutants are products which don’t break down and can
accumulate and persist in the environment; they are typically halogenated
compounds, with DDT being the most famous example.
 Where possible, these chemicals should be replaced in their uses with chemicals that
are more easily broken down by water, UV light, or biodegradation

11: Real Time Pollution Prevention

 Monitoring a chemical reaction as it is occurring can help prevent release of

hazardous and polluting substances due to accidents or unexpected reactions.
 With real time monitoring, warning signs can be spotted, and the reaction can be
stopped or managed before such an event occurs.

12: Safer Chemistry for Accident Prevention

 Working with chemicals always carries a degree of risk. However, if hazards are
managed well, the risk can be minimised.
 This principle clearly links with a number of the other principles that discuss
hazardous products or reagents.
 Where possible, exposure to hazards should be eliminated from processes, and
should be designed to minimise the risks where elimination is not possible.

The Future of Green Chemistry

 Though the tenets of green chemistry might seem simple to

implement, improvements can still be made in a large number of chemical
processes.
 A lot of the chemical products we all utilise come from processes that still fail to
meet a number of these principles; plenty of these products are still derived from
chemicals from crude oil, and many still produce large amounts of waste.
 There are, of course, challenges involved in meeting some of the principles in a large
number of processes, but it can also drive new research and the discovery of new
chemistry.
 It is to be hoped that, in the coming years, many more processes will be
adapted with these principles in mind.

42 | P a g e
43

FIRST ORDER REACTION:

Learning Objective

Design initial rate experiments to determine order of reaction with respect to individual
reactants
Key Points
 k is the first-order rate constant, which has units of 1/s.
 The method of determining the order of a reaction is known as the method
of initial rates.
 The overall order of a reaction is the sum of all the exponents of the
concentration terms in the rate equation.
Term
 first-order reactionA reaction that depends on the concentration of only one reactant
(a unimolecular reaction). Other reactants can be present, but each will be zero-order.

A first-order reaction depends on the concentration of only one reactant.

As such, a first-order reaction is sometimes referred to as a unimolecular reaction. While

other reactants can be present, each will be zero-order, since the concentrations of these
reactants do not affect the rate.

Thus, the rate law for an elementary reaction that is first order with respect to a reactant A
is given by:

r=−d[A]dt=k[A]

As usual, k is the rate constant, and must have units of concentration/time; in this case it
has units of 1/s.

Hydrogen peroxide
The decomposition of hydrogen peroxide to form oxygen and hydrogen is a first-order
reaction.

Using the Method of Initial Rates to Determine Reaction Order Experimentally

2N2O5(g)→4NO2(g)+O2(g)

43 | P a g e
44

The balanced chemical equation for the decomposition of dinitrogen pentoxide is given
above. Since there is only one reactant, the rate law for this reaction has the general form:

Rate = k[N2O5]m

In order to determine the overall order of the reaction, we need to determine the value of
the exponent m.

To do this, we can measure an initial concentration of N 2O5 in a flask, and record the rate at
which the N2O5 decomposes.

We can then run the reaction a second time, but with a different initial concentration of
N2O5.

We then measure the new rate at which the N2O5 decomposes. By comparing these rates, it
is possible for us to find the order of the decomposition reaction.

Example

Let’s say that at 25 °C, we observe that the rate of decomposition of N 2O5 is 1.4×10-3 M/s
when the initial concentration of N2O5 is 0.020 M.

Then, let’s say that we run the experiment again at the same temperature, but this time we
begin with a different concentration of N2O5 , which is 0.010 M. On this second trial, we
observe that the rate of decomposition of N2O5 is 7.0×10-4 M/s. We can now set up a ratio of
the first rate to the second rate:

Rate1Rate2 = k[N2O5]i1mk[N2O5]i2m

1.4×10−37.0×10−4=k(0.020)mk(0.010)m

Notice that the left side of the equation is simply equal to 2, and that the rate constants
cancel on the right side of the equation. Everything simplifies to:

2.0=2.0m

Clearly, then, m=1, and the decomposition is a first-order reaction.

Determining the Rate Constant kOnce we have determined the order of the reaction,
we can go back and plug in one set of our initial values and solve for k. We find
that:rate=k[N2O5]1=k[N2O5]

Substituting in our first set of values, we have

1.4×10−3=k(0.020)

k=0.070s−1

44 | P a g e
45

UNIT – 2 AQUATIC CHEMISTRY

WATER AND WASTEWATER QUALITY PARAMETERS:

Water Quality Parameters

 Water quality parameters include chemical, physical, and biological properties and
can be tested or monitored based on the desired water parameters of concern.

 Parameters that are frequently sampled or monitored for water quality include
temperature, dissolved oxygen, pH, conductivity, ORP, and turbidity.

 However water monitoring may also include measuring total algae, ISEs (ammonia,
nitrate, chloride), or laboratory parameters such as BOD, titration, or TOC.

1. Introduction

Water is the second most important need for life to exist after air. As a result, water quality
has been described extensively in the scientific literature.

The most popular definition of water quality is “it is the physical, chemical, and biological
characteristics of water” .

Water quality is a measure of the condition of water relative to the requirements of one or
more biotic species and/or to any human need or purpose.n 2019?

Fewer th2. Classification of water

Based on its source, water can be divided into ground water and surface water .

Both types of water can be exposed to contamination risks from agricultural, industrial, and
domestic activities, which may include many types of pollutants such as heavy metals,
pesticides, fertilizers, hazardous chemicals, and oils.

Water quality can be classified into four types—potable water, palatable water,
contaminated (polluted) water, and infected water .

The most common scientific definitions of these types of water quality are as follows:

1. Potable water: It is safe to drink, pleasant to taste, and usable for domestic purposes [1, 7].
2. Palatable water: It is esthetically pleasing; it considers the presence of chemicals that do
not cause a threat to human health [7].
3. Contaminated (polluted) water: It is that water containing unwanted physical, chemical,
biological, or radiological substances, and it is unfit for drinking or domestic use [7].
4. Infected water: It is contaminated with pathogenic organism [7].

45 | P a g e
46

3. Parameters of water quality

There are three types of water quality parameters physical, chemical, and biological. They
are

3.1 Physical parameters of water quality

3.1.1 Turbidity

 Turbidity is the cloudiness of water.

 It is a measure of the ability of light to pass through water.
 It is caused by suspended material such as clay, silt, organic material, plankton, and
other particulate materials in water .

Turbidity in drinking water is esthetically unacceptable, which makes the water look
unappetizing. The impact of turbidity can be summarized in the following points:

1. It can increase the cost of water treatment for various uses [11].
2. The particulates can provide hiding places for harmful microorganisms and thereby shield
them from the disinfection process [12].
3. Suspended materials can clog or damage fish gills, decreasing its resistance to diseases,
reducing its growth rates, affecting egg and larval maturing, and affecting the efficiency of
fish catching method [13, 14].
4. Suspended particles provide adsorption media for heavy metals such as mercury, chromium,
lead, cadmium, and many hazardous organic pollutants such as polychlorinated biphenyls
(PCBs), polycyclic aromatic hydrocarbons (PAHs), and many pesticides [15].
5. The amount of available food is reduced [15] because higher turbidity raises water
temperatures in light of the fact that suspended particles absorb more sun heat.
Consequently, the concentration of the dissolved oxygen (DO) can be decreased since warm
water carries less dissolved oxygen than cold water.

Turbidity is measured by an instrument called nephelometric turbidimeter, which expresses

turbidity in terms of NTU or TU. A TU is equivalent to 1 mg/L of silica in suspension [10].

Turbidity more than 5 NTU can be visible to the average person while turbidity in muddy
water, it exceeds 100 NTU [10]. Groundwater normally has very low turbidity because of the
natural filtration that occurs as the water penetrates through the soil [9, 16].

3.1.2 Temperature

 Palatability, viscosity, solubility, odors, and chemical reactions are influenced by

temperature
 Thereby, the sedimentation and chlorination processes and biological oxygen
demand (BOD) are temperature dependent .
 It also affects the biosorption process of the dissolved heavy metals in water . Most
people find water at temperatures of 10–15°C most palatable .

46 | P a g e
47

3.1.3 Color

 Materials decayed from organic matter, namely, vegetation and inorganic matter
such as soil, stones, and rocks impart color to water, which is objectionable for
esthetic reasons, not for health reasons .
 Color is measured by comparing the water sample with standard color solutions or
colored glass disks .
 One color unit is equivalent to the color produced by a 1 mg/L solution of platinum
(potassium chloroplatinate (K2PtCl6)) .

The color of a water sample can be reported as follows:

 Apparent color is the entire water sample color and consists of both dissolved and
suspended components color [10].
 True color is measured after filtering the water sample to remove all suspended
material [19].

Color is graded on scale of 0 (clear) to 70 color units. Pure water is colorless, which is
equivalent to 0 color units.

3.1.4 Taste and odor

Taste and odor in water can be caused by foreign matter such as organic materials,
inorganic compounds, or dissolved gasses .

These materials may come from natural, domestic, or agricultural sources .

The numerical value of odor or taste is determined quantitatively by measuring a volume of

sample A and diluting it with a volume of sample B of an odor-free distilled water so that the
odor of the resulting mixture is just detectable at a total mixture volume of 200 ml .

The unit of odor or taste is expressed in terms of a threshold number as follows:

TON or TTN=(A+B)/A

where TON is the threshold odor number and TTN is the threshold taste number.

3.1.5 Solids

Solids occur in water either in solution or in suspension .

These two types of solids can be identified by using a glass fiber filter that the water sample
passes through .

By definition, the suspended solids are retained on the top of the filter and the dissolved
solids pass through the filter with the water .

47 | P a g e
48

If the filtered portion of the water sample is placed in a small dish and then evaporated, the
solids as a residue.

This material is usually called total dissolved solids or TDS .

Total solid (TS)=Total dissolved solid (TDS)+Total suspended solid (TSS)

Water can be classified by the amount of TDS per liter as follows:

 freshwater: <1500 mg/L TDS;

 brackish water: 1500–5000 mg/L TDS;
 saline water: >5000 mg/L TDS.

The residue of TSS and TDS after heating to dryness for a defined period of time and at a
specific temperature is defined as fixed solids. Volatile solids are those solids lost on ignition
(heating to 550°C) .

These measures are helpful to the operators of the wastewater treatment plant because
they roughly approximate the amount of organic matter existing in the total solids of
wastewater, activated sludge, and industrial wastes .

Figure 1 describes the interrelationship of solids found in water . They are calculated as
follows:

 Total solids:

48 | P a g e
49

Figure 1.

Interrelationship of solids found in water .

Total solids (mg/L) = [(TSA–TSB)]×1000/sample (mL)

where TSA = weight of dried residue + dish in milligrams and TSB = weight of dish in
milligrams.

 Total dissolved solids:

Total dissolved solids (mg/L) = [(TDSA–TDSB)]×1000/sample (mL)

where TDSA = weight of dried residue + dish in milligrams and TDSB = weight of dish in
milligrams.

 Total suspended solids:

Total suspended solids(mg/L) = [(TSSA–TSSB)]×1000/sample(mL)

49 | P a g e
50

where TSSA = weight of dish and filter paper + dried residue and TSSB = weight of dish and
filter paper in milligram.

 Fixed and volatile suspended solids:

Volatile suspended solids(mg/L) = [(VSSA–VSSB)]×1000/sample (mL)

where VSSA = weight of residue + dish and filter before ignition, mg and VSSB = weight of
residue + dish and filter after ignition, mg.

3.1.6 Electrical conductivity (EC)

The electrical conductivity (EC) of water is a measure of the ability of a solution to carry or
conduct an electrical current .

Since the electrical current is carried by ions in solution, the conductivity increases as the
concentration [10] of ions increases.

Therefore, it is one of the main parameters used to determine the suitability of water for
irrigation and firefighting.

Units of its measurement are as follows:

 U.S. units = micromhos/cm

 S.I. units = milliSiemens/m (mS/m) or dS/m (deciSiemens/m)

where (mS/m) = 10 umho/cm (1000 μS/cm = 1 dS/m).

Pure water is not a good conductor of electricity [2, 10]. Typical conductivity of water is as
follows:

 Ultra-pure water: 5.5 × 10−6 S/m;

 Drinking water: 0.005–0.05 S/m;
 Seawater: 5 S/m.

The electrical conductivity can be used to estimate the TDS value of water as follows
[10, 22]:

TDS(mg/L) ≅ EC (dS/m or umho /cm)×(0.55–0.7)

TDS can be used to estimate the ionic strength of water in the applications of groundwater
recharging by treated wastewater . The normal method of measurement is electrometric
method .

50 | P a g e
51

3.2 Chemical parameters of water quality

3.2.1 pH

 pH is one of the most important parameters of water quality. It is defined as the

negative logarithm of the hydrogen ion concentration .
 It is a dimensionless number indicating the strength of an acidic or a basic solution .
 Actually, pH of water is a measure of how acidic/basic water is .
 Acidic water contains extra hydrogen ions (H+) and basic water contains extra
hydroxyl (OH−) ions .
 As shown in Figure 2, pH ranges from 0 to 14, with 7 being neutral. pH of less than 7
indicates acidity, whereas a pH of greater than 7 indicates a base solution .
 Pure water is neutral, with a pH close to 7.0 at 25°C. Normal rainfall has a pH of
approximately 5.6 (slightly acidic) owing to atmospheric carbon dioxide gas .
 Safe ranges of pH for drinking water are from 6.5 to 8.5 for domestic use and living
organisms need .

Figure 2.

pH of water.

A change of 1 unit on a pH scale represents a 10-fold change in the pH [10], so that water
with pH of 7 is 10 times more acidic than water with a pH of 8, and water with a pH of 5 is
100 times more acidic than water with a pH of 7.

There are two methods available for the determination of pH: electrometric and
colorimetric methods .

Excessively high and low pHs can be detrimental for the use of water.

A high pH makes the taste bitter and decreases the effectiveness of the chlorine
disinfection, thereby causing the need for additional chlorine .

The amount of oxygen in water increases as pH rises. Low-pH water will corrode or dissolve
metals and other substances .

Pollution can modify the pH of water, which can damage animals and plants that live in the
water .

The effects of pH on animals and plants can be summarized as follows:

 Most aquatic animals and plants have adapted to life in water with a specific pH and
may suffer from even a slight change [15].
 Even moderately acidic water (low pH) can decrease the number of hatched fish
eggs, irritate fish and aquatic insect gills, and damage membranes [14].
 Water with very low or high pH is fatal. A pH below 4 or above 10 will kill most fish,
and very few animals can endure water with a pH below 3 or above 11 [15].

51 | P a g e
52

 Amphibians are extremely endangered by low pH because their skin is very sensitive
to contaminants [15]. Some scientists believe that the current decrease in amphibian
population throughout the globe may be due to low pH levels induced by acid rain.

The effects of pH on other chemicals in water can be summarized as follows:

 Heavy metals such as cadmium, lead, and chromium dissolve more easily in highly
acidic water (lower pH). This is important because many heavy metals become much
more toxic when dissolved in water [21].
 A change in the pH can change the forms of some chemicals in the water. Therefore,
it may affect aquatic plants and animals [21]. For instance, ammonia is relatively
harmless to fish in neutral or acidic water. However, as the water becomes more
alkaline (the pH increases), ammonia becomes progressively more poisonous to
these same organisms.

3.2.2 Acidity

Acidity is the measure of acids in a solution. The acidity of water is its quantitative capacity
to neutralize a strong base to a selected pH level .

Acidity in water is usually due to carbon dioxide, mineral acids, and hydrolyzed salts such as
ferric and aluminum sulfates .

Acids can influence many processes such as corrosion, chemical reactions and biological
activities .

Carbon dioxide from the atmosphere or from the respiration of aquatic organisms causes
acidity when dissolved in water by forming carbonic acid (H2CO3).

The level of acidity is determined by titration with standard sodium hydroxide (0.02 N) using
phenolphthalein as an indicator [10, 20].

3.2.3 Alkalinity

The alkalinity of water is its acid-neutralizing capacity comprised of the total of all titratable
bases .

The measurement of alkalinity of water is necessary to determine the amount of lime and
soda needed for water softening (e.g., for corrosion control in conditioning the boiler feed
water) .

Alkalinity of water is mainly caused by the presence of hydroxide ions (OH−), bicarbonate
ions (HCO3−), and carbonate ions (CO32−), or a mixture of two of these ions in water.

As stated in the following equation, the possibility of OH− and HCO3− ions together are not
possible because they react together to produce CO32− ions:

OH−+HCO3−→CO32−+H2O

52 | P a g e
53

Alkalinity is determined by titration with a standard acid solution (H2SO4 of 0.02 N) using
selective indicators (methyl orange or phenolphthalein).

The high levels of either acidity or alkalinity in water may be an indication of industrial or
chemical pollution.

Alkalinity or acidity can also occur from natural sources such as volcanoes.

The acidity and alkalinity in natural waters provide a buffering action that protects fish and
other aquatic organisms from sudden changes in pH.

For instance, if an acidic chemical has somehow contaminated a lake that had natural
alkalinity, a neutralization reaction occurs between the acid and alkaline substances; the pH
of the lake water remains unchanged.

For the protection of aquatic life, the buffering capacity should be at least 20 mg/L as
calcium carbonate.

3.2.4 Chloride

Chloride occurs naturally in groundwater, streams, and lakes, but the presence of relatively
high chloride concentration in freshwater (about 250 mg/L or more) may indicate
wastewater pollution .

Chlorides may enter surface water from several sources including chloride-containing rock,
agricultural runoff, and wastewater.

Chloride ions Cl− in drinking water do not cause any harmful effects on public health, but
high concentrations can cause an unpleasant salty taste for most people.

Chlorides are not usually harmful to people; however, the sodium part of table salt has been
connected to kidney and heart diseases .

Small amounts of chlorides are essential for ordinary cell functions in animal and plant life.

Sodium chloride may impart a salty taste at 250 mg/L; however, magnesium or calcium
chloride are generally not detected by taste until reaching levels of 1000 mg/L .

Standards for public drinking water require chloride levels that do not exceed 250 mg/L.

There are many methods to measure the chloride concentration in water, but the normal
one is the titration method by silver nitrate .

3.2.5 Chlorine residual

Chlorine (Cl2) does not occur naturally in water but is added to water and wastewater for
disinfection .

53 | P a g e
54

While chlorine itself is a toxic gas, in dilute aqueous solution, it is not harmful to human
health.

In drinking water, a residual of about 0.2 mg/L is optimal. The residual concentration which
is maintained in the water distribution system ensures good sanitary quality of water .

Chlorine can react with organics in water forming toxic compounds called trihalomethanes
or THMs, which are carcinogens such as chloroform CHCl3 .

Chlorine residual is normally measured by a color comparator test kit or spectrophotometer

.

3.2.6 Sulfate

Sulfate ions (SO42−) occur in natural water and in wastewater.

The high concentration of sulfate in natural water is usually caused by leaching of natural
deposits of sodium sulfate (Glauber’s salt) or magnesium sulfate (Epson salt)

If high concentrations are consumed in drinking water, there may be objectionable tastes
or unwanted laxative effects, but there is no significant danger to public health.

3.2.7 Nitrogen

There are four forms of nitrogen in water and wastewater: organic nitrogen, ammonia
nitrogen, nitrite nitrogen, and nitrate nitrogen .

If water is contaminated with sewage, most of the nitrogen is in the forms of organic and
ammonia, which are transformed by microbes to form nitrites and nitrates .

Nitrogen in the nitrate form is a basic nutrient to the growth of plants and can be a growth-
limiting nutrient factor .

A high concentration of nitrate in surface water can stimulate the rapid growth of the algae
which degrades the water quality .

Nitrates can enter the groundwater from chemical fertilizers used in the agricultural areas .

Excessive nitrate concentration (more than 10 mg/L) in drinking water causes an immediate
and severe health threat to infants .

The nitrate ions react with blood hemoglobin, thereby reducing the blood’s ability to hold
oxygen which leads to a disease called blue baby or methemoglobinemia .

3.2.8 Fluoride

A moderate amount of fluoride ions (F−) in drinking water contributes to good dental health
.

54 | P a g e
55

About 1.0 mg/L is effective in preventing tooth decay, particularly in children .

Excessive amounts of fluoride cause discolored teeth, a condition known as dental fluorosis

The maximum allowable levels of fluoride in public water supplies depend on local climate.

In the warmer regions of the country, the maximum allowable concentration of fluoride for
potable water is 1.4 mg/L; in colder climates, up to 2.4 mg/L is allowed.

There are four methods to determine ion fluoride in water; the selection of the used
method depends on the type of water sample .

3.2.9 Iron and manganese

Although iron (Fe) and manganese (Mn) do not cause health problems, they impart a
noticeable bitter taste to drinking water even at very low concentration.

These metals usually occur in groundwater in solution as ferrous (Fe2+) and manganous
(Mn2+) ions.

When these ions are exposed to air, they form the insoluble ferric (Fe3+) and manganic
(Mn3+) forms making the water turbid and unacceptable to most people.

These ions can also cause black or brown stains on laundry and plumbing fixtures.

They are measured by many instrumental methods such as atomic absorption spectrometry,
flame atomic absorption spectrometry, cold vapor atomic absorption spectrometry,
electrothermal atomic absorption spectrometry, and inductively coupled plasma (ICP).

3.2.10 Copper and zinc

Copper (Cu) and zinc (Zn) are nontoxic if found in small concentrations .

Actually, they are both essential and beneficial for human health and growth of plants and
animals .

They can cause undesirable tastes in drinking water.

At high concentrations, zinc imparts a milky appearance to the water .

They are measured by the same methods used for iron and manganese measurements .

3.2.11 Hardness

Hardness is a term used to express the properties of highly mineralized waters.

The dissolved minerals in water cause problems such as scale deposits in hot water pipes
and difficulty in producing lather with soap .

55 | P a g e
56

Calcium (Ca2+) and magnesium (Mg2+) ions cause the greatest portion of hardness in
naturally occurring waters .

They enter water mainly from contact with soil and rock, particularly limestone deposits.

These ions are present as bicarbonates, sulfates, and sometimes as chlorides and nitrates .

Generally, groundwater is harder than surface water. There are two types of hardness:

 Temporary hardness which is due to carbonates and bicarbonates can be removed

by boiling, and
 Permanent hardness which is remaining after boiling is caused mainly by sulfates and
chlorides

Water with more than 300 mg/L of hardness is generally considered to be hard, and more
than 150 mg/L of hardness is noticed by most people, and water with less than 75 mg/L is
considered to be soft.

From health viewpoint, hardness up to 500 mg/L is safe, but more than that may cause a
laxative effect .

Hardness is normally determined by titration with ethylene diamine tetra acidic acid or
(EDTA) and Eriochrome Black and Blue indicators.

It is usually expressed in terms of mg/L of CaCO3 .

Total hardness mg/L as CaCO3 = calcium hardness mg/L as CaCO3 + magnesium hardness
mg/L as CaCO3

An accepted water classification according to its hardness is as in Table 2 .

DISSOLVED OXYGEN:

Dissolved oxygen (DO) is considered to be one of the most important parameters of water
quality in streams, rivers, and lakes.

It is a key test of water pollution.

The higher the concentration of dissolved oxygen, the better the water quality.

Oxygen is slightly soluble in water and very sensitive to temperature. For example, the
saturation concentration at 20°C is about 9 mg/L and at 0°C is 14.6 mg/L .

The actual amount of dissolved oxygen varies depending on pressure, temperature, and
salinity of the water.

Dissolved oxygen has no direct effect on public health, but drinking water with very little or
no oxygen tastes unpalatable to some people.

56 | P a g e
57

There are three main methods used for measuring dissolved oxygen concentrations: the
colorimetric method—quick and inexpensive, the Winkler titration method—traditional
method, and the electrometric method .

3.2.13 Biochemical oxygen demand (BOD)

Bacteria and other microorganisms use organic substances for food. As they metabolize
organic material, they consume oxygen .

The organics are broken down into simpler compounds, such as CO2 and H2O, and the
microbes use the energy released for growth and reproduction.

When this process occurs in water, the oxygen consumed is the DO in the water.

If oxygen is not continuously replaced by natural or artificial means in the water, the DO
concentration will reduce as the microbes decompose the organic materials.

This need for oxygen is called the biochemical oxygen demand (BOD). The more organic
material there is in the water, the higher the BOD used by the microbes will be.

BOD is used as a measure of the power of sewage; strong sewage has a high BOD and weak
sewage has low BOD .

The complete decomposition of organic material by microorganisms takes time, usually 20 d

or more under ordinary circumstances .

The quantity of oxygen used in a specified volume of water to fully decompose or stabilize
all biodegradable organic substances is called the ultimate BOD or BOD L.

BOD is a function of time. At time = 0, no oxygen will have been consumed and the BOD = 0.
As each day goes by, oxygen is used by the microbes and the BOD increases. Ultimately, the
BODL is reached and the organic materials are completely decomposed.

A graph of the BOD versus time is illustrated as in Figure 3. This is called the BOD curve,
which can be expressed mathematically by the following equation:

57 | P a g e
58

Figure 3.

BOD curve [22].

BODt=BODL×(1−10−kt)BODt=BODL×1−10−ktE10

where BODt = BOD at any time t, mg/L; BODL = ultimate BOD, mg/L; k = a constant
representing the rate of the BOD reaction; t = time, d.

The value of the constant rate k depends on the temperature, the type of organic materials,
and the type of microbes exerting the BOD.

3.2.14 Chemical oxygen demand (COD)

The chemical oxygen demand (COD) is a parameter that measures all organics: the
biodegradable and the non-biodegradable substances .

It is a chemical test using strong oxidizing chemicals (potassium dichromate), sulfuric acid,
and heat, and the result can be available in just 2 h .

COD values are always higher than BOD values for the same sample .

3.2.15 Toxic inorganic substances

A wide variety of inorganic toxic substances may be found in water in very small or trace
amounts. Even in trace amounts, they can be a danger to public health .

Some toxic substances occur from natural sources but many others occur due to industrial
activities and/or improper management of hazardous waste .

They can be divided into two groups:

 Metallic compounds: This group includes some heavy metals that are toxic, namely,
cadmium (Cd), chromium (Cr), lead (Pb), mercury (Hg), silver (Ag), arsenic (As),
barium (Ba), thallium (Tl), and selenium (Se) .
 They have a wide range of dangerous effects that differ from one metal to another.
They may be acute fatal poisons such as (As) and (Cr6+) or may produce chronic
diseases such as (Cd, Hg, Pb, and Tl)

 The heavy metals concentration can be determined by atomic absorption

photometers, spectrophotometer, or inductively coupled plasma (ICP) for very low
concentration .

58 | P a g e
59

 Nonmetallic compounds: This group includes nitrates (NO3−) and cyanides (CN−),
nitrate has been discussed with the nitrogen in the previous section.

 Regarding cyanide, as Mackenzie stated [11] it causes oxygen deprivation by binding

the hemoglobin sites and prevents the red blood cell from carrying the oxygen [11].

 This causes a blue skin color syndrome, which is called cyanosis . It also causes
chronic effects on the central nervous system and thyroid . Cyanide is normally
measured by colorimetric, titrimetric, or electrometric methods .

3.2.16 Toxic organic substances

There are more than 100 compounds in water that have been listed in the literature as toxic
organic compounds .

They will not be found naturally in water; they are usually man-made pollutants.

These compounds include insecticides, pesticides, solvents, detergents, and disinfectants .

They are measured by highly sophisticated instrumental methods, namely, gas

chromatographic (GC), high-performance liquid chromatographic (HPLC), and mass
spectrophotometric .

3.2.17 Radioactive substances

Potential sources of radioactive substances in water include wastes from nuclear power
plants, industries, or medical research using radioactive chemicals and mining of uranium
ores or other radioactive materials .

When radioactive substances decay, they release beta, alpha, and gamma radiation .

Exposure of humans and other living things to radiation can cause genetic and somatic
damage to the living tissues .

Radon gas is of a great health concern because it occurs naturally in groundwater and is a
highly volatile gas, which can be inhaled during the showering process .

For drinking water, there are established standards commonly used for alpha particles, beta
particles, photons emitters, radium-226 and -228, and uranium .

The unit of radioactivity used in water quality applications is the picocurie per liter (pCi/L);
1 pCi is equivalent to about two atoms disintegrating per minute. There are many
sophisticated instrumental methods to measure it .

59 | P a g e
60

3.3 Biological parameters of water quality

One of the most helpful indicators of water quality may be the presence or lack of living
organisms .

Biologists can survey fish and insect life of natural waters and assess the water quality on
the basis of a computed species diversity index (SDI) ;

hence, a water body with a large number of well-balanced species is regarded as a healthy
system .

Some organisms can be used as an indication for the existence of pollutants based on their
known tolerance for a specified pollutant .

Microorganisms exist everywhere in nature .

Human bodies maintain a normal population of microbes in the intestinal tract; a big portion
of which is made up of coliform bacteria .

Although there are millions of microbes per milliliter in wastewater, most of them are
harmless .

It is only harmful when wastewater contains wastes from people infected with diseases that
the presence of harmful microorganisms in wastewater is likely to occur .

3.3.1 Bacteria

Bacteria are considered to be single-celled plants because of their cell structure and the way
they ingest food .

Bacteria occur in three basic cell shapes: rod-shaped or bacillus, sphere-shaped or coccus,
and spiral-shaped or spirellus .

In less than 30 min, a single bacterial cell can mature and divide into two new cells .

Under favorable conditions of food supply, temperature, and pH, bacteria can reproduce so
rapidly that a bacterial culture may contain 20 million cells per milliliter after just 1 day .

This rapid growth of visible colonies of bacteria on a suitable nutrient medium makes it
possible to detect and count the number of bacteria in water .

There are several distinctions among the various species of bacteria. One distinction
depends on how they metabolize their food .

Bacteria that require oxygen for their metabolism are called aerobic bacteria, while those
live only in an oxygen-free environment are called anaerobic bacteria.

60 | P a g e
61

Some species called facultative bacteria can live in either the absence or the presence of
oxygen .

At low temperatures, bacteria grow and reproduce slowly.

As the temperature increases, the rate of growth and reproduction doubles in every
additional 10°C (up to the optimum temperature for the species) .

The majority of the species of bacteria having an optimal temperature of about 35°C .

A lot of dangerous waterborne diseases are caused by bacteria, namely, typhoid and
paratyphoid fever, leptospirosis, tularemia, shigellosis, and cholera .

Sometimes, the absence of good sanitary practices results in gastroenteritis outbreaks of

one or more of those diseases .

3.3.2 Algae

Algae are microscopic plants, which contain photosynthetic pigments, such as chlorophyll .

They are autotrophic organisms and support themselves by converting inorganic materials
into organic matter by using energy from the sun, during this process they take in carbon
dioxide and give off oxygen .

They are also important for wastewater treatment in stabilization ponds .

Algae are primarily nuisance organisms in the water supply because of the taste and odor
problems they create .

Certain species of algae cause serious environmental and public health problems; for
example, blue-green algae can kill cattle and other domestic animals if the animals drink
water containing those species .

3.3.3 Viruses

Viruses are the smallest biological structures known to contain all genetic information
necessary for their own reproduction .

They can only be seen by a powerful electronic microscope .

Viruses are parasites that need a host to live .

They can pass through filters that do not permit the passage of bacteria .

Waterborne viral pathogens are known to cause infectious hepatitis and poliomyelitis .

Most of the waterborne viruses can be deactivated by the disinfection process conducted in
the water treatment plant .

61 | P a g e
62

3.3.4 Protozoa

Protozoa are single-celled microscopic animal , consume solid organic particles, bacteria,
and algae for food, and they are in turn ingested as food by higher level multicellular
animals .

Aquatic protozoa are floating freely in water and sometimes called zooplankton [37]. They
form cysts that are difficult to inactivate by disinfection

3.3.5 Indicator organisms

A very important biological indicator of water and pollution is the group of bacteria called
coliforms.

Pathogenic coliforms always exist in the intestinal system of humans, and millions are
excreted with body wastes.

Consequently, water that has been recently contaminated with sewage will always contain
coliforms.

A particular species of coliforms found in domestic sewage is Escherichia coli or E. coli .

Even if the water is only slightly polluted, they are very likely to be found. There are roughly
3 million of E. coli bacteria in 100 mL volume of untreated sewage .

Coliform bacteria are aggressive organisms and survive in the water longer than most
pathogens.

There are normally two methods to test the coliform bacteria—the membrane filter method
and multiple-tube fermentation method .

Since the test of coliform bacteria is very important for public health, the first method will
be described in details in the coming section.

3.3.5.1 Testing for coliforms: membrane filter method

A measured volume of sample is filtered through a special membrane filter by applying a

partial vacuum .

The filter, a flat paper-like disk, has uniform microscopic pores small enough to retain the
bacteria on its surface while allowing the water to pass through.

The filter paper is then placed in a sterile container called a petri dish, which contains a
special culture medium that the bacteria use as a food source .

Then, the petri dish is usually placed in an incubator, which keeps the temperature at 35°C,
for 24 h.

62 | P a g e
63

After incubation, colonies of coliform bacteria each containing millions of organisms will be
visible .

The coliform concentration is obtained by counting the number of colonies on the filter;
each colony counted represents only one coliform in the original sample .

Coliform concentrations are expressed in terms of the number of organisms per 100 mL of
water as follows:

coliformsper100mL=number of colonies×100/mLof sample

4. Water quality requirements

 Water quality requirements differ depending on the proposed used of water [19]. As
reported by Tchobanoglous et al. ,
 “water unsuitable for one use may be quite satisfactory for another and water may
be considered acceptable for a particular use if water of better quality is not
available.”
 Water quality requirements should be agreed with the water quality standards,
which are put down by the governmental agency and represent the legislation
requirements.
 In general, there are three types of standards: in-stream, potable water, and
wastewater effluent, each type has its own criteria by using the same methods of
measurement.
 The World Health Organization (WHO) has established minimum standards for
drinking water that all countries are recommended to meet .

5. Conclusion

The physical, chemical, and biological parameters of water quality are reviewed in terms of
definition, sources, impacts, effects, and measuring methods.

The classification of water according to its quality is also covered with a specific definition
for each type.

WASTEWATER QUALITY PARAMETERS:

Wastewater is characterized according to its physical, chemical and biological composition.

Depending on the level of pollutants and local regulations, physical, chemical and/or
biological treatment will be used.

Most of the time, the three treatments are combined to obtain the best water quality.
Wastewater characteristics vary considerably from industry to industry. Therefore, the
specific characteristics will determine the treatment techniques to be used to satisfy the
compliance discharge requirements.

63 | P a g e
64

Due to the large number of pollutants, characteristics are generally not considered for each
substance. Materials with similar pollution effects are grouped into pollutant or
characteristic classes.

Wastewater physical parameters

 Color: Fresh wastewater is normally brown and yellowish, but over time it turns
black.
 Suspended solids: these are insoluble solids suspended in a liquid and visible to the
naked eye
 Temperature: For wastewater, it is correlated to the outside temperature while
being warmer because almost nobody takes a cold shower
 Turbidity: Due to suspended solids, wastewater will have higher turbidity.

Chemical characteristics of wastewater

Wastewater contains different chemicals in various forms, as shown below.

 Chemical oxygen demand (COD): This is a measure of the amount of organic

matter in wastewater based on the oxygen required to oxidize it.
 Nitrogen: It is measured in its different forms: nitrite, nitrate, ammonia, and
organic nitrogen (which is the amount of nitrogen present in organic compounds)
 Phosphorus: It is generally measured in its mineral and organic form, total
phosphorus
 Chlorine (Cl-)
 Sulfates (SO4-2)
 Heavy metals

Biological parameters of wastewater

 Biochemical Oxygen Demand (BOD) – BOD is the amount of oxygen required to
stabilize organic matter using micro-organisms.
 Oil and Grease – Oil and grease are generated from food waste and petroleum
products.
 Microbial life in wastewater: Wastewater contains the following microbes:
 Bacteria
 Protozoa
 Mushrooms
 Virus
 Seaweed
 Rotifers
 Nematodes
The most commonly used parameters in wastewater treatment plants are BOD, COD and
TSS. When degrading environments, it is common to analyze nitrogen (NGL, NH4,
NO3) and phosphorus parameters.
In order to control the environmental risks caused by wastewater, an analysis is required. It
is indeed a question of determining and quantifying the substances and micro-organisms
contained in these waters. These in order to :
 find ways to remove them

64 | P a g e
65

 reduce them to an acceptable level for release to the environment.

Micro-organism analyses are performed when the discharge area is located near a bathing
area. The parameters to be analyzed are defined in the regulations of each country and can
be adjusted by the local authorities.

WASTEWATER QUALITY PARAMETER:

Depending on the country and the receiving environment, government agencies define
wastewater quality parameters. Indeed, they allow to follow and measure the impact of
human activities on a river.

In some special cases or for large municipal wastewater treatment plants, special
parameters complete them, such as :

 hard nitrogen: which can be found in mineral (ammonia, nitrate) or organic form. Its
organic or ammoniacal presence results in a consumption of oxygen in the natural
environment and alters the living conditions.
 ratio such as COD / BOD5: this ratio gives an indication of the source and origin of
the organic pollution. The BOD5 of unpolluted surface water varies between 2 and
20 mg/l. Measures that go beyond that indicate water pollution.

Often, they are supplemented with various ratios and evaluated with respect to the entire
stream flow. Wastewater quality parameters generally include BOD5, COD and TSS.
These parameters are often associated with the :
 NGL : the global nitrogen
 NH4 : ammoniacal nitrogen
 NO3 : nitrates
 Pt
In this section, we have described:
 The relationship between BOD and COD
 The nitrogen cycle in wastewater treatment
 Phosphate components in wastewater

RELATION BETWEEN BOD & COD:

Particle and colloidal COD

According to an IRSTEA study on wastewater in activated mud prolonged aeration, 1 mg of
SS at the outlet of a municipal plant brings an average of 1.2 mg of COD and 0.5 mg of
BOD5.

Knowing that this TSS is about 20 mg/L, the corresponding particulate COD is 24mg COD/L
(20 x 1.2).

The particle or colloidal COD is determined by the difference between the raw COD and the
COD after filtrationof the sample.

65 | P a g e
66

It is mainly constituted of TSS.

Biodegradable soluble COD

At the outlet of the treatment plant, the soluble biodegradable COD represents only a small
part of the total COD.

This leakage of soluble COD normally degraded by bacteria can be related to either:
 an overdose of reagent (use of methanol for denitrification for example)
 insufficient residence time in the ponds to allow full biodegradation.

This leak may also indicate:

 a bypass of a treatment step
 hydraulic drilling at some biological filters
 poor ventilation.

To determine the soluble biodegradable COD at the municipal plant outlet, the :
 Total BOD5 (about 12 mg/L O2)
 TSS concentration (20 mg/L) multiplied by a factor of 2.4:

Total soluble COD = (Total BOD5 – SS BOD5) x 2.4 = (12 – 20 x 0.5) x 2.4 = 4.8 mg/L O2

Refractory COD known as "hard COD"

Hard COD is the residual COD of a sample after an ultimate BOD5 analysis.
On average in domestic wastewater, hard COD represents 3 to 5% of the total COD.

Hard COD = Total COD – Particle COD – Soluble COD

Still according to IRSTEA, with a total COD concentration at the outlet of 70 mg/L, we can
estimate that :
Hard COD = 70 – 24 – 4.8 = 41.2 mg/L O2.

Knowing that a domestic wastewater contains about 900 mg/L O2 at the inlet, the 3 to 5%
ratio is confirmed.
This content in the inlet water can increase in case of non-domestic wastewater additions.
These contain organic matter that is resistant to biological treatment (certain industrial
effluents, landfill leachate, etc.).

Thus, the nature of the non-domestic water must be analyzed before approving inputs to
the collection system.

Furthermore, it is necessary to regularly ensure that these concentrations follow the

thresholds defined by the local authorities.

When setting discharge standards for a plant, authorities should consider:

 the proportion of refractory stubs for domestic wastewater

66 | P a g e
67

 non-domestic wastewater.

A high COD standard for wastewater containing high hard COD means the installation of
extensive treatment equipment and higher operating costs.

COD/BOD5 ratio

The BOD5 of unpolluted surface water varies between 2 and 20 mg/l. Measurements
beyond that level indicate that the water is polluted.

The COD / BOD5 ratio gives an indication of the source and origin of the organic pollution.

The measurements close to 1 of the ratio COD / BOD5 a very good biodegradability (milk,
yogurt).

 From 1 to 2: wastewater from food processing industries, which contain elements

that bacteria love, resulting in a high COD5.
 Between 2 and 3: urban wastewater.
 From 3 to 4: Wastewater is not easily biodegradable.
 >4: Hardly biodegradable effluent

NITROGEN CYCLE IN WASTEWATER TREATMENT PLANT:NITRIFICATION &

DENITRIFICATION:

Nitrogen removal is one of the essential steps in wastewater treatment.

In fact, there are regulatory standards for nitrogen concentrations at the plant outlet in
many countries.

Therefore, to meet these concentrations, nitrification and denitrification must be optimally

controlled.
Nitrogen in water can be found in mineral (ammonia, nitrate) or organic form. Its organic or
ammoniacal presence results in a consumption of oxygen in the natural environment and
alters the living conditions.

In sanitation, the nitrogen cycle follows the different stages of biogeochemical evolution of
the component.

It leads to the formation of nitrogen gas (nitrogen N2) starting with organic nitrogen, and
passing by: ammonia, nitrite, nitrate.

In wastewater treatment plants, several forms of nitrogen are present:

 Nitrites and nitrates: oxidized nitrogen
 the non-oxidized states: Kjeldhal nitrogen including organic nitrogen and
ammoniacal nitrogen (NH4+)
 Ammonifiable organic nitrogen

67 | P a g e
68

 Refractory organic nitrogen

The measurement of all forms represents the total nitrogen.

The wastewater is mainly composed of :

 ammonifiable or refractory organic nitrogen (in soluble and particulate form)
 ammoniacal nitrogen

Ammonifiable organic nitrogen

It is the most common form and ammoniacal nitrogen (NH4-H). Indeed, it is the one present
in the urine.

The wastewater coming into a wastewater treatment plant contains a large part of organic
nitrogen (albumin, carbamide, etc.).

In addition, the nitrogen released from a home is originally slightly more concentrated in
ammonifiable organic nitrogen.

Organic nitrogen is said to be ammonifiable when it can be transformed by enzymatic

hydrolysis into ammoniacal nitrogen.

In other words, the ratio of ammonium to ammonia may depend on factors such as
temperature and incubation time (depending on the length of the network) because this is
where the transformation of organic nitrogen to NH4-H begins.

During the treatment in a wastewater treatment plant, ammonification continues until the
majority of the nitrogen is transformed into NH4-N.

Soluble and particulate refractory nitrogen known as "hard nitrogen

Soluble refractory nitrogen is the non-biodegradable element in nitrogen. Moreover, this

part is already detected when it enters the station.

On the other hand, the orders of magnitude of this nitrogen for a standard urban water are
between 1.5 to 2.5 mg/liter.

The hard or refractory particulate nitrogen has the same concentrations but it will be
trapped in the mud.

In some cases, the order of hard soluble nitrogen may be more important.

This is usually because of the sludge returns or a network with a long residence time.

Among the technologies that impact the hard organic nitrogen rate, there are the backflows
from thermal drying.

68 | P a g e
69

Biological nitrification
This is the biological cycle of transformation of reduced nitrogen into the oxidized form
nitrate (NO3-). And micro-organisms play a major role in this process.

Nitrification occurs in two stages:

 the transformation of ammonia into nitrite by oxidation
 then the evolution of nitrite (NO2-) into nitrate (NO3-). This is called nitritation and
then nitration.

Micro-organisms responsible for nitrification are Nitrosomonas and Nitrobacter. They are
very fragile and require a constant temperature (above or equal to 12°).

However, an adequate oxygen supply and a favorable C/P/N supply are also essential.
Maximum growth rate of nitrifying bacteria is significantly lower than that of heterotrophic
bacteria (those feeding on carbonaceous substrate).

In a treatment plant, the mass of nitrifying bacteria is directly related to the amount of
substrate it receives and the temperature of the water.

Nitrifying populations grow at a rate that is more or less adapted to the mass of nitrogen to
be treated.

Biological nitrification of 1 kg of ammoniacal nitrogen :

 requires nominally 4.2 kg of oxygen, 80% of which is included in the nitrates formed,
 is associated with a reduction in alkalinity (compensated by 3.9 kg of quicklime CaO),
 produces 170 g of nitrifying bacteria which is very low compared to the production
of sludge generated during the degradation of the carbonaceous organic load.
To summarize, to ensure proper nitrification without additional chemical additions, one
must:
 Ammonia
 A minimum temperature of 12°C
 Sufficient natural alkalinity in the raw water
 A lot of oxygen
 Sufficient nitrifying bacteria
 pH between 7.2 and 8.5

Biological denitrification

The purpose of biological denitrification is to completely remove nitrogen from wastewater.

During this treatment process, the nitrogen evaporates into the atmosphere in its molecular
form N2.

Denitrification is an anaerobic mechanism that enables a large number of heterotrophic

bacteria to cover their energy needs from nitrates when dissolved oxygen is lacking.

69 | P a g e
70

To put it simply, since they lack O2, these bacteria must use the oxygen contained in the
nitrates to breathe.

Indeed, they breathe nitrates. And to ensure a good denitrification, it is necessary to avoid
having O2 in the water to be treated.

Bacteria involved in the denitrification cycle are also involved in carbon alteration. Since
they eat a ” healthy ” diet, they need a source of carbon to complete their nitrogenous
menu.

In wastewater treatment plants, it is common to add methanol or vinegar to compensate

for carbon deficiencies.

Another advantage of denitrification is the recovery of alkalinity (part of that lost in the
nitrification stage).

Indeed, denitrification ensures a restitution of alkalinity equal to half the consumption

necessary for nitrification. i.e. 1 kg of denitrified nitrate nitrogen is equivalent to the
addition of 1.95 kg of quicklime CaO.

In addition, it is interesting to implement a recirculation system in the water treatment

process to reuse this alkalinity.

In conclusion, to ensure proper denitrification, one must:

 Nitrates
 No oxygen
 Enough denitrifying bacteria
 A supplementary carbon source that can be easily assimilated (aim for a minimum
BOD5 / NO3- pollution ratio greater than 2).

COD/NTK ratio

As explained earlier, bacteria have a healthy diet. The COD/NTK ratio is used to measure this
balance.

However, a low COD/NTK ratio has a negative impact on the biotransformation of nitrogen
into oxidized and gaseous nitrogen.

In other words, this type of effluent cannot promote good denitrification.

By contrast, a high ratio will lead to a total assimilation of nitrogen but there will be a
carbonaceous pollution residue.

For a municipal wastewater, the COD/NTK ratio is therefore between 7 and 20.

70 | P a g e
71

That is to say, the lower the ratio, the more it will be necessary to add a complementary
carbon source during the denitrification step.

PHOSPHOROUS COMPOUND IN WASTEWATER:PHOSPHOROUS ,ORTHOPHOSPHATES

Phosphorus is naturally present in very small quantities in the soil and in water.

A high concentration of phosphates can cause seaweed blooms which is a nutrient for
plants.

However, seaweed is responsible for the eutrophication of stagnant waters.

This eutrophication phenomenon is then more or less important according to the phosphate
content in the wastewater. However, phosphorus is a major constraint to reduce
eutrophication.

Based on a study, 1g of phosphate-phosphorus (PO4-P) can cause an seaweed expansion of

100g.
When these seaweeds die, they require about 150 g of oxygen to decompose. This
phenomenon starts at very low P-PO4 concentrations:

 0.1-0.2 mg/l in tap water

 of 0.005-0.01 mg/l in stagnant water.

The chemical forms of phosphorus in wastewater are very diverse. They can be soluble or
particulate, mineral and organic.

Total Phosphorus = Particulate Phosphorus + Dissolved Phosphorus = Mineral Phosphorus

+ Organic Phosphorus

In order to meet the recommended limits, a targeted phosphorus removal process is then
required in wastewater treatment plants.

We implement a process that could be chemical or biological, and often both cases.

Orthophosphates and total phosphorus

Orthophosphates (PO4 ions) are the most common and basic form of phosphates in water.

Phosphates (called orthophosphates) are an oxidized mineral form of phosphorus.

Phosphates are present in dissolved, colloidal or solid form.

These different forms of phosphates, from the orthophosphoric acid salt (H3 PO4), are
present in water because they ionize:

71 | P a g e
72

 in H2 PO4-,
 HPO4- -,
 PO4- – –

Orthophosphate is the most common component of the total phosphate load.

In general, orthophosphates have limited toxicity to fish. Furthermore, they are used in fish
farming to increase the planktonic biomass. However, they can promote eutrophication
when present in excessive quantities.

The amount of phosphates in water is measured in mg/l. of P-PO4.

But the most commonly used parameter is total phosphorus, which is the sum of organic
and inorganic phosphorus. It is expressed in mg/l Pt.

The difference between total phosphorus and orthophosphates is a measure of the organic
fraction of phosphorus in the water.

The treatment process must allow the removal of phosphorus components until they reach
the legal limits allowed at the outlet of the treatment plant. Two methods are available to
do this:

 biological removal
 Chemical precipitation of phosphates or chemical removal

Biological removal of phosphorus compounds

Biological dephosphatization consists in the overaccumulation of phosphorus in a biomass.

If phosphorus contents of 2-3% are reached in the mud under normal conditions of
degradation of an organic substrate, the overaccumulation mechanism requires stressing
the biomass, alternatively in anaerobic (without oxygen) and aerobic phase.

However, the denitrification zone, characterized by the presence of oxygen via nitrates, is
therefore assimilated to an aerobic zone, and does not allow biological dephosphatation.

Under stress conditions (phase alternation), the micro-organisms accumulate phosphorus,

up to 10% of their dry weight, in the form of polyphosphate granules.

The reactions occurring in each area can be summarized as follows:

 anaerobic zone: the micro-organisms use their reserves and release intracellular
phosphorus;
 aerobic area: overaccumulation of phosphorus in the form of polyphosphate
granules.

72 | P a g e
73

These phenomena, which are essential to the biological dephosphatisation process, will
condition the design of treatment plants. The basic layout shall include at least:

 an anaerobic zone where the release of phosphorus will take place

 an aerated area where over-assimilation reactions will take place.

To achieve good biological phosphorus removal, the essential element is the presence of a
sufficient quantity of easily assimilable organic matter in the water to be treated.

From a conventional urban wastewater, an average ratio of 3.5% of phosphorus removed

per BOD5 consumed is obtained. This leads to a biological elimination of only 50 to 65% of
the phosphorus.

This performance is often not sufficient to meet discharge standards. It is necessary to add a
chemical precipitation step where the remaining phosphorus will be precipitated by the
addition of reagent.

Biological disposal is only effective when sufficient quantities of readily biodegradable

organic matter (BOD5) are present.

Chemical precipitation of phosphates

This process includes the precipitation of soluble phosphorus with a metal salt compound. It
could be iron or aluminum salt.

Iron or aluminum salts are also capable of combining with phosphate ions to form an iron or
aluminum phosphate precipitate (Fe PO4 or AIPO4).
We talk about coagulation.

Due to the competitiveness of the hydroxide or phosphate precipitate formation reactions,

the molar ratio to be used between Fe/P or Al/P varies from 1 to 3.

Chemical precipitation is usually carried out in structures dedicated to settling.

The metal phosphate precipitates flow and are extracted in the wastewater mud.

The addition of coagulants can be done during primary settling, or once in the biological
tank, or in an additional treatment structure located after the biological tank.

However, it must be remembered that the level of mud increases considerably due to the
precipitation of phosphate salts.

To limit the costs of mud treatment and coagulants, most wastewater treatment plants
combine biological and chemical processes for phosphorus removal.

73 | P a g e
74

COD/Pt ratio: Prediction of phosphorus removal efficiency

For wastewater, variations in phosphorus removal efficiency by assimilation alone are

primarily correlated:
 COD/P (or BOD5/P) ratio
 in the mud age

The removal efficiency increases in a quasi-linear way when COD/P increases: as the mud
production is proportional to the applied COD load, an increase in the COD flow for a
constant P flow causes an increase in the assimilated P flow and thus a better overall
removal.

In addition, low mud ages improve phosphorus efficiency, while very long mud ages
decrease phosphorus efficiency.

For a median COD/P ratio of 70 g COD/g P, the removal efficiency can be :

 38% with a mud age of 20 days
 38% with a mud age of 20 days

TSS concentration has only a small effect on phosphorus removal efficiency. The lower the
concentration, the better the efficiency.

In wastewater, the normal COD/Pt ratio is between 25 and 100.

74 | P a g e
75

FATE OF CHEMICALS IN AQUATIC ENVIRONMENT:

75 | P a g e
76

76 | P a g e
77

VOLATILIZATION:

Volatilization is the process whereby a dissolved sample is vaporised. In atomic

spectroscopy this is usually a two-step process.

The analyte is turned into small droplets in a nebuliser which are entrained in a gas flow which
is in turn volatilised in a high temperature flame in the case of AAS or volatilised in a gas
plasma torch in the case of ICP spectroscopy.

The process of converting a chemical substance from a liquid or solid state to a gaseous or
vapor state.
Other terms used to describe the same process are vaporization, distillation, and sublimation.
A substance can often be separated from another by volatilization and can then be recovered
by condensation of the vapor.

The substance can be made to volatilize more rapidly either by heating to increase its vapor
pressure or by removal of the vapor using a stream of inert gas or a vacuum pump.

Heating procedures include the volatilization of water, of mercury, or of arsenic trichloride to

separate these substances from interfering elements.

Chemical reactions are sometimes utilized to produce volatile products as in the release of
carbon dioxide from carbonates, of ammonia in the Kjeldahl method for the determination of
nitrogen, and of sulfur dioxide in the determination of sulfur in steel.

Volatilization methods are generally characterized by great simplicity and ease of operation,
except when high temperatures or highly corrosion-resistant materials are needed.

PARTITIONING:

The partition of marine environment

The marine environment can be classified into two macro domains: the benthic domain,
composed of the seabed and benthic organisms, and the pelagic domain composed of the
overlying water column.

The coast is the boundary between the sea and the land, and is partially submerged by the
water. It can be high and rocky or low and sandy but it is always formed by different areas

77 | P a g e
78

Fig1_SES2.1 Costal components. Fondazione Cetacea

– littoral zone: the area emerges wet by the waves only when the sea is rough;
– intertidal zone: the area affected by the tide (VIDEO 1_SES2.1). It’s compose by:
a. high tide zone, relatively dry
b. middle tide zone, covered by high tide and exposed by low tide
c. low tide zone, usually wet
– infralitoral: submerged area from the low tide limit to the depth where the light cannot
reach.
– circalittoral: submerged area where darkness starts from a deep of 200 meters.

 In each zone it is possible to find a characteristic marine organisms adapted to the

particular environmentalconditions.
For example, in the rocky littoral zone, it’s easy find as animal life sea snails that feed
on algae and move according to the movements of the sea or barnacles (FIG.2_SES2.1)
that attacked to the rock, conserve sea water to survive during the tide dry period.

 Partition or distribution coefficients (and increasingly referred to as partition ratios)

are widely used in environmental science to relate the concentration of a chemical
solute in one phase to that in a second phase between which equilibrium applies or is
approached.

 The solutes include organic and inorganic substances; the focus of this paper being on
the former. The phases of interest include air, water, soils, sediments, aerosols, and
biotic phases, such as lipids, blood, and various tissues.

 Availability of reliable partition coefficients for contaminants is essential for regulatory

and scientific purposes, the general aim being to understand and predict the
distribution of the substances in multimedia environmental and biological systems.

 The history of partition coefficients is reviewed, followed by a brief outline of their

theoretical basis and a discussion of methods for determining partition coefficients
both empirically and using a variety of predictive methods.

78 | P a g e
79

 It is suggested that ultimately a combination of empirical measurements, quantitative

structure–property relationships, and computationally intensive quantum chemical
molecular modeling techniques is required to provide accurate data for the large and
increasing number of chemicals of commerce that may enter the environment.

Photochemical Transformations

• Photochemical transformations are important fate processes for organics in the

near-surface aquatic environment as well as in the upper atmosphere.

Enhanced photochemical processes are also being used for the treatment of some
hazardous wastes.

Inorganic pollutants can also be transformed by photochemical reactions; the best

known such case is the production of photochemical smog.

There are four major photochemical reactions of environmental significance: direct

photolysis, indirect photolysis, oxidation, and free-radical oxidation.

• In direct photolysis, the organic absorbs light energy (photons) and is converted into
an excited state which then releases this energy in conjunction with conversion into
a product (different) compound.

In indirect photolysis, a nontarget compound (for example, dissolved organic

material such as humic substances) absorbs the photons and becomes excited.

This energized molecule then transmits its energy to the pollutant (target organic)
causing it to be transformed.

• In oxidation and free-radical oxidation, light energy is typically absorbed by an

intermediate compound such as dissolved organic matter, nitrate, or Fe(III), with the
resultant production of oxidants such as H2O2 and O3, free radicals such as hydroxyl
(-OH) and peroxy (-OOR), and/or other reactive species such as singlet oxygen O2.

These oxidants are then available to oxidize a wide variety of organics.

• Chlorinated compounds are particularly susceptible to oxidation by these species.

Mixtures of ultraviolet light and ozone or hydrogen peroxide are used in engineered
systems for treatment of trace levels of organics in gases and water, and rely on
production of these activated chemical species.

HYDROLYSIS:

79 | P a g e
80

In its simplest definition, hydrolysis is a chemical reaction in which water is used to break
down the bonds of a particular substance.

In biotechnology and as far as living organisms are concerned, these substances are often
polymers (simply put, many similar molecules can that join together).

The word hydrolysis comes from the word hydro, which is Greek for water, and lysis, which
means "to unbind.

Hydrolysis can also be thought of as the exact opposite reaction to condensation, which is
the process whereby two molecules combine to form one larger molecule.

3 Common Types of Hydrolysis

 Salts: Hydrolysis occurs when salt from a weak base or acid dissolves in liquid. When
this occurs, water spontaneously ionizes into hydroxide anions and hydronium
cations. This is the most common type of hydrolysis.
 Acid: Water can act as an acid or a base, according to the Bronsted-Lowry acid
theory. In this case, the water molecule would give away a proton. Perhaps the
oldest commercially-practiced example of this type of hydrolysis is saponification,
the formation of soap.
 Base: This reaction is very similar to the hydrolysis for base dissociation. Again, on a
practical note, a base that often dissociates in water is ammonia.

What Is a Hydrolysis Reaction?

In a hydrolysis reaction involving an ester link, such as that found between two amino acids
in a protein, the molecule is split.

The resulting product is a split of the water molecule (H2O) into an OH and an H+ that form a
hydroxyl (OH) group, and another that becomes a carboxylic acid with the addition of the
remaining hydrogen proton (H+).

Reactions in Living Organisms

Hydrolysis reactions in living organisms are performed with the help of catalysis by a class
of enzymes known as hydrolases.

The biochemical reactions that break down polymers, such as proteins (which are peptide
bonds between amino acids), nucleotides, complex sugars or starch, and fats are catalyzed
by this class of enzymes.

Within this class are lipases, amylases, proteinases, hydrolyzed fats, sugars, and proteins,
respectively.

Cellulose-degrading bacteria and fungi play a special role in paper production and other
everyday biotechnology applications because they have enzymes (such as cellulases and

80 | P a g e
81

esterases) that can break cellulose into polysaccharides (ii.e., polymers of sugar molecules)
or glucose, and break down stickies.

For example, proteinase could be added to a cell extract, to hydrolyze the peptides and
produce a mixture of free amino acids.

DEGRADATION OF SYNTHETIC CHEMICALS:

Microorganisms are crucial participants in the detoxification of water and soil.

Key Points
 Bacteria decompose organic matter by producing a number of different enzymes for
more general reactions such as hydrolysis, acetogenesis and methanogenesis, and
highly specific enzymes such as deoxygenases that can break aromatic compounds.
 Bacterial species are assisted in the process of degradation by fungi (e.g., Aspergillus
sp.), protozoa, and representatives of Archaea.
 The recent advances in genomics, proteomics, and bioinformatics fields allow new
insights into the tremendous metabolic potential of microorganisms.
Key Terms
 bioremediation: The use of biological organisms, usually microorganisms, to remove
contaminants, especially from polluted water.
 bioavailability: The amount of matter that is physicochemically accesible for
degradation by microorganisms.

Our planet is contaminated with many chemicals that are toxic to living organisms. These
chemicals are products or byproducts from different industries.

Examples of such contaminants are polychlorinated biphenyls (PCBs), polyaromatic

hydrocarbons (PAHs), chloroethenes, and pharmaceutical substances.

These pollutants can cause dangerous contamination of the air, soil, and water.
Microorganisms play a major role in eliminating such pollutants from the environment.

Bioremediation of Soil

Soil is a major reservoir of microorganisms with each gram containing about one billion
microbes. Microbes are used for bioremediation in situ of contaminated soil.

Microorganisms that can remove contaminants from the environment are called
bioremediators.

Contaminations are most often caused by a mixture of pollutants and the best strategy for
cleanup is to use a cocktail of different species since each one of them will be optimized for
the degradation of a specific toxic compound.

81 | P a g e
82

The microbe activity is usually monitored on such sites to ensure optimal conditions for
bacterial growth and hence degradation.

Decomposition of the toxic substances can be performed both in the presence (aerobically)
and absence (anaerobically) of oxygen. The limiting factor for bioremediaton in soils is the
bioavailability of the contaminant agents.

Bioremediation of Water

The treatment of sewage water is a critical process to assure the purification of wastewater
that will prevent chemical and microbiological pollution of the environment, especially for
the drinking water supplies.

An important part of this process is the biological step which involves the activity of living
organisms to clean the water from organic matter.

This happens in the secondary step of sewage purification. Microorganisms substantially

lessen the concentration of nutrients which if released in the environment can lead to
undesirable overgrowth of microorganisms and algae.

They also have the potential to clean the water from toxic components.

The degradation is performed in the anaerobic, aerobic, and composting steps. Anaerobic
digestion by bacteria is allowed to procede for almost two weeks to guarantee enough time
to complete the process.

During this time, the organic matter undergoes four different enzymatic
transformations: hydrolysis, acidogenesis, acetogenesis and methanogenesis.

The final products are water, carbon dioxide, and methane.

In the aerobic step, oxygen is added into the system and the organic matter is converted to
carbon dioxide.

In the composting step, additional carbon sources are added to aid the final steps of
degradation.

In recent years, advances in genomics, proteomics, and bioinformatics studies of

environmental microorganisms have revealed a tremendous potential in metabolic
pathways.

Such studies showed that Burkholderia xenovorans LB400 and Rhodococcus sp. strain RHA1,
have evolved pathways to degrade aromatic compounds, which are some of the toughest
contaminants to eliminate.

The bacteria have genes coding for deoxygenases to open the aromatic ring structures of
these chemicals.

82 | P a g e
83

Hydrocarbons and their derivatives were long believed to be degraded only in the presence
of oxygen.

This would often lead to oxygen depletion in environments heavily polluted with oil.

Studies in recent years have proven that there are numerous anaerobic bacterial species
capable of decomposing this group of pollutants.

A common feature among these bacteria is that they possess reductive dehalogenases.

Bacterial species are assisted in the process of degradation by fungi (e.g., Aspergillus sp.),
protozoa, and representatives of Archaea.

The primary role of fungi is in secreting numerous extracellular enzymes that break down
complex molecules into their components and make them readily available to the bacterial
community.

OXIDATION AND REDUCTION:

DEFINITION:

What is Oxidation?
According to Classical or earlier concept oxidation is a process which involves the addition of
oxygen or any electronegative element or the removal of hydrogen or any electropositive
element.
According to electronic concept oxidation is defined as the process in which an atom or ion
loses one or more electrons.

What is Reduction?
According to Classical or earlier concept reduction is a process which involves the addition
of hydrogen or any electropositive element or the removal of oxygen or any electronegative
element.
According to electronic concept reduction is defined as the process in which an atom or ion
gains one or more electrons.

Classical Idea of Oxidation and Reduction reactions:

Oxidation reactions involve:
1. Addition of oxygen:
C + O2 → CO2 (oxidation of carbon)
2. Addition of electronegative element:
Fe + S → FeS (oxidation of Iron)
3. Removal of hydrogen:

83 | P a g e
84

H2S + Br2 → 2 HBr + S (oxidation of sulphide)

4. Removal of electropositive elements:
2 KI + H2O2 → I2 + 2 KOH (oxidation of iodide)
Oxidising agent is a substance which brings about oxidation. In the above examples O2, S,
Cl2, Br2, and H2O2 are oxidising agents.
Reduction reactions involve:
1. Addition of hydrogen:
N2 + 3 H2 → 2NH3 ( reduction of nitrogen)
2. Addition of electropositive element:
SnCl2 + 2HgCl2 → SnCl4 + Hg2Cl2 ( reduction of mercuric chloride)
3. Removal of oxygen
ZnO + C → Zn + CO (reduction of zinc oxide)
4. Removal of electronegative element
2FeCl3 + H2 → 2FeCl2 + 2HCl (reduction of ferric chloride)
Reducing agent is a substance which brings about reduction. In the above examples H2,
HgCl2 and C are Reducing agents.
Note: A substance, which undergoes oxidation, acts as a reducing agent while a substance,
which undergoes reduction, acts as an oxidising agent.

Oxidation and Reduction in terms of Electron Transfer

 This is the most commonly used definition of oxidation and reduction and most widely
applicable.
 In this case, Oxidation is the loss of electrons and Reduction is the gain of electrons.
 A very clever mnemonic to remember this concept is oil rig.
OIL RIG
Oxidation is loss Reduction is gain
Oxidation and Reduction reactions are always interlinked. Because electrons are neither
created nor destroyed in a chemical reaction, oxidation and reduction always occur in pairs,
it is impossible to have one without the other. In the below reaction Magnesium gets oxidized
by losing two electrons to oxygen which gets reduced by accepting two electrons from
magnesium.

84 | P a g e
85

Since oxidation and reduction cannot occur individually, they as a whole are called ‘Redox
Reactions’. The reactant that oxidizes the other reactants is called as the Oxidizing agent and
reactant that reduces is called Reducing agent. There is quite some confusion about the
aspect of whether oxidizing agents accept or give away electrons.
The following steps can help you figure it out.

 An oxidizing agent oxidizes the other reactants

 This must mean that the oxidizing agent is getting reduced
 Oxidation is the loss of electrons (OIL RIG)
 So an oxidizing agent must gain electrons

Common Redox Reactions

The three common redox reactions are discussed below:
1. Combustion reaction – It is a type of redox reaction which occurs between molecular
oxygen and compound to form oxygen-containing products.
2C8H18+25O2 → 16CO2(g)+18H2O
2. Disproportionation reaction – It is a type of redox reaction where a single reactant is
reduced and oxidized. It is also known as an auto-oxidation reaction.
3ClO−(aq) → ClO3−(aq)+2Cl−(aq)
3. Single replacement reaction – It is a type of redox reaction that involves two elements
switching places within a compound. It is also known as a single displacement reaction.
Zn(s)+2HCl(aq) → ZnCl2(aq)+H2(g)

How to Balance Redox Reaction?

Every chemical reaction must be balanced according to the “Law of conservation of mass”.
The chemical equations which involve oxidation and reduction can also be balanced with
the help of the following methods

 Oxidation number method.

 Ion electron method ( or half reaction method)

Oxidation number method:

The various steps involved in balancing a redox equation by oxidation method are discussed
here through an example.
Example: Balance the chemical equation by the oxidation number method
CuO + NH3 → Cu + N2 + H2O

85 | P a g e
86

Solution:
Step-1 : Write the oxidation number of each atom in the skeleton equation

Step-2 : Identify the atoms which undergo change in oxidation number.

Step-3 : Calculate the increase and decrease in oxidation number w.r.t reactant atoms.

Step-4 : Equate the increase and decrease in oxidation number on the reactant side.

Step-5 : Balance the number of Cu and N atoms on both sides of the equation.

Step-6 : Now balance H and O atoms by hit and trial method.

Note:(i) In the reactions taking place in acidic medium, balance the O atom by adding the
required number of H2O molecules to the side deficient in O atoms. Then balance the H
atoms by adding H+ to the side deficient in H atoms.
(ii) In the basic medium, first balance the number of negative charges by adding the
required number of OH– ions to the side deficient in the magnitude of the charges. Then add
H2O molecules on the other side in order to balance the OH– ions added.

Ion electron method ( or half reaction method):

It is based on the Principle that the electrons lost during oxidation half reaction in a
particular redox reactions is equal to the electrons gained in the reduction half reaction. The
method is called half reaction method. The balancing is completed in the following steps:
Example: Balance the chemical equation by ion-electron method:
Cr2O72- + Fe2+ + H+ → Cr3+ + Fe3+ + H2O

86 | P a g e
87

Step-1 : Write the oxidation number of each atom in the skeleton

equation: Step-2 : Find out the

species involved in the oxidation and reduction half reactions:

Step-3 : Balancing oxidation half reaction:

As oxidation number increases 1, add one e– on the product side to balance change in O.N.

Step-4 : Balancing reduction half reaction:

The decrease in oxidation number per Cr atom is 3 and the total decrease in O.N for two Cr
atoms is 6. Therefore, add 6e– on the reactant side. In order to balance O atoms add 7 H2O
molecules on the product side then balance H atoms by adding 14 H+ on reactant side.

Step-5 : Adding the two half reactions:

Oxidation vs Reduction
When a reactant loses electrons during a reaction, it is called oxidation. When a reactant
accumulates electrons during a reaction, it is called reduction. When metals react with acid,
this is a common occurrence. When a reactant loses electrons during a reaction, it is called
oxidation. When a reactant accumulates electrons during a reaction, it is called reduction.
When metals react with acid, this is a common occurrence.
A reduction-oxidation or redox reaction is a type of chemical reaction in which reduction
and oxidation occur at the same time. The reduced species receives electrons whereas the
oxidised species loses them. An oxidation process does not need the presence of oxygen,
despite its name.

Summary
Originally, the term oxidation was used to describe reactions where an element combines
with oxygen. For example, the oxidation of magnesium involves the chemical reaction

87 | P a g e
88

between magnesium metal and oxygen to form magnesium oxide.

The word reduction comes from the “to lead back” sense of the Latin stem. Thus, everything
that leads back to magnesium metal in the previously mentioned chemical reaction implies
reduction. An example of the reduction of magnesium oxide to magnesium metal is a
reaction between magnesium oxide and carbon at 2000 degrees Celsius to form magnesium
metal and carbon monoxide.
Due to the changes in oxidation states that occur without the independent transfer of
electrons, many reactions in organic chemistry can be classified as redox reactions. For
instance, the oxidation state of carbon atoms in the wood increases during the combustion
of wood with molecular oxygen, and that of oxygen atoms decreases as carbon dioxide and
water are produced. The oxygen atoms are reduced, formally receiving electrons, while the
carbon atoms are oxidised, losing electrons. Therefore, oxygen is the oxidising agent and the
reducing agent in this reaction is carbon.

Frequently Asked Questions – FAQs

What is the difference between oxidation and reduction?

It loses electrons in a reaction in chemistry if a substance is oxidized. It gains electrons in a
reaction if a substance is reduced. A reaction within which there is both oxidation and
reduction is called a REDOX reaction.

Why are oxidation and reduction Important?

Oxidation-reduction (redox) reactions are significant because they are the main natural or
biological and artificial energy sources on this planet. Oxidation of molecules usually
releases large amounts of energy by removing hydrogen and replacing it with oxygen.

What is the oxidation-reduction process?

It oxidizes the material that gives electrons. It forms a chemical called rust when iron reacts
with oxygen because it has been oxidized (the iron has lost some electrons) and the oxygen
has been reduced (the oxygen has gained some electrons). The cause of reduction is
oxidation.

What is called the oxidation state?

The oxidation state, also referred to as the amount of oxidation, defines a chemical
compound’s degree of oxidation (loss of electrons) of an atom. Antoine Lavoisier first used
the term oxidation to describe a substance’s reaction with oxygen.

What is an example of slow oxidation?

Iron rusting and wood-rotting are good examples of gradual oxidation.

What is meant by the oxidation-reduction reaction?

A chemical reaction where the oxidation number of an atom, ion, or molecule changes by
losing or gaining an electron is called an oxidation-reduction reaction.

88 | P a g e
89

What is the major difference between oxidation and reduction?

Reduction is the gain of electrons whereas oxidation is the loss of electrons.
To learn more about oxidation and reduction, register with BYJU’S and download our app.
Read more:

 Types of chemical reactions

 Oxidation state

This page discusses the various definitions of oxidation and reduction (redox) in terms of the
transfer of oxygen, hydrogen, and electrons.

It also explains the terms oxidizing agent and reducing agent.

Oxidation and reduction in terms of oxygen transfer

The terms oxidation and reduction can be defined in terms of the adding or removing
oxygen to a compound. while this is not the most robust definition, as discussed below, it is
the easiest to remember.

Oxidation and Reduction with respect to Oxygen Transfer

 Oxidation is the gain of oxygen.
 Reduction is the loss of oxygen.

For example, in the extraction of iron from its ore:

Because both reduction and oxidation are occurring simultaneously, this is known as a redox
reaction.

An oxidizing agent is substance which oxidizes something else. In the above example, the
iron(III) oxide is the oxidizing agent. A reducing agent reduces something else. In the
equation, the carbon monoxide is the reducing agent.

 Oxidizing agents give oxygen to another substance.

 Reducing agents remove oxygen from another substance.

Oxidation and reduction in terms of hydrogen transfer

These are old definitions which are no longer used, except occasionally in organic chemistry.

Oxidation and Reduction with respect to Hydrogen Transfer

89 | P a g e
90

 Oxidation is the loss of hydrogen.

 Reduction is the gain of hydrogen.

Notice that these are exactly the opposite of the oxygen definitions (#1).

For example, ethanol can be oxidized to ethanal:

An oxidizing agent is required to remove the hydrogen from the ethanol. A commonly used
oxidizing agent is potassium dichromate(VI) solution acidified with dilute sulfuric acid.
Ethanal can also be reduced back to ethanol by adding hydrogen. A possible reducing agent
is sodium tetrahydridoborate, NaBH4. Again the equation is too complicated to consider at
this point.

More precise definitionsof oxidizing and reducing agents are

 Oxidizing agents add oxygen to another substance or remove hydrogen from it.
 Reducing agents remove oxygen from another substance or add hydrogen to it.

Oxidation and reduction in terms of electron transfer

Oxidation and Reduction with respect to Electron Transfer

 Oxidation is loss of electrons
 Reduction is gain of electrons

Remembering these definitions is essential, and easily done using this convenient acronym:

Example 1

The equation below shows an obvious example of oxygen transfer in a simple redox
reaction:

CuO+Mg→Cu+MgOCuO+Mg→Cu+MgO

Copper(II) oxide and magnesium oxide are both ionic compounds. If the above is written as
an ionic equation, it becomes apparent that the oxide ions are spectator ions. Omitting
them gives:

90 | P a g e
91

In the above reaction, magnesium reduces the copper(II) ion by transferring electrons to the
ion and neutralizing its charge. Therefore, magnesium is a reducing agent. Another way of
putting this is that the copper(II) ion is removing electrons from the magnesium to create a
magnesium ion. The copper(II) ion is acting as an oxidizing agent.

Summary

Confusion can result from trying to learn both the definitions of oxidation and reduction in
terms of electron transfer and the definitions of oxidizing and reducing agents in the same
terms. The following thought pattern can be helpful:

 An oxidizing agent oxidizes something else.

 Oxidation is loss of electrons (OIL RIG).
 Therefore, an oxidizing agent takes electrons from that other substance.
 Therefore, an oxidizing agent must gain electrons.

Here is another mental exercise:

 An oxidizing agent oxidizes something else.

 Therefore, the oxidizing agent must be reduced.
 Reduction is gain of electrons (OIL RIG).
 Therefore, an oxidizing agent must gain electrons.

pE – Ph DIAGRAM:

Eh–pH diagram, any of a class of diagrams that illustrate the fields of stability of mineral or
chemical species in terms of the activity of hydrogen ions (pH) and the activity of electrons
(Eh).

Consequently, the reactions illustrated on Eh–pH diagrams involve either proton transfer
(e.g., hydrolysis) or electron transfer (oxidation or reduction) or both.

In natural environments, pH values extend from 1 to 9.5, and Eh values from -500 to +800
millivolts.

Rarely are temperatures and pressures other than those normally encountered on the
Earth’s surface considered.

The area on an Eh–pH diagram that represents the range of these variables within which a
particular mineral is stable is called the stability field of that mineral.

91 | P a g e
92

Such a representation enables a geochemist to determine whether a mineral is

in equilibrium with its surroundings or subject to chemical transformation.

REDOX ZONE:

What is redox Zone?

Definition. Redox zonation is the subdivision of natural environments (geochemical,
ecological, or sedimentary) based on the availability of O2 to be consumed to completion
by biological respiration and inorganic chemical reactions.

SORPTION:

Sorption Process

Sorption is a physical and chemical process by which a substance (typically a gas or liquid)
accumulates within another phase or on the phase boundary of two phases.

Depending on the place of accumulation, a differentiation is made between absorption

(accumulation in a phase) and adsorption (accumulation at the phase boundary).

The reverse process is called desorption.

Sorption processes can be investigated by Thermogravimetric Analysis (TGA), Differential

Scanning Calorimetry (DSC) and Evolved Gas Analysis (EGA).

The figure below shows two sorption-desorption cycles on a zeolite sample.

The zeolite sample was treated with atmospheric cycles between wet and dry nitrogen gas
flows.

During the injection of a wet gas flow, the sample exhibits a distinct mass increase which is a
result of the water absorption within the zeolite network, whereas during the dry gas flow,
desorption takes place.

The graph presented shows that the water absorption of a zeolite is a totally reversible
process.

Two sorption-desorption cycles on a zeolite sample

92 | P a g e
93

COLLOIDS:

What are Colloids?

A colloid is a heterogeneous mixture in which the minute particles of one substance are
dispersed in another substance, called the dispersion medium.

The minute particles here are 1 to 1000 nanometers in diameter, but they still remain
suspended and do not settle at the bottom of the mixture. Sol, aerosol, foam, emulsion,
etc., are some types of colloids. In this section, we will see how colloids are present in our
everyday items of use and their applications in different fields.

Examples of Colloid

 Most of the food products which we eat today are colloids, including the dairy
products. Cake, bread, milk, cream, butter, ice cream, margarine, fruit juices, whipped
cream, etc. are colloidal in nature.
 The natural phenomena which we observe such as fog, mist, clouds, and rain are
colloids in different forms. Even dust and smoke are colloidal.
 The blue colour of the sky can be credited to the suspended dust and water particles
in the air which scatter blue light more than any other wavelength. Similarly, seawater
is blue because of the colloidal impurities present in it, which also scatter blue light.
 A colloid is present in the fertile soil in the form of clay and humus material. It also
plays a vital role in the storage and exchange of minerals.

Commercial Applications of Colloid:

 A colloid is used as thickening agents in industrial products such as lubricants, lotions,

toothpaste, coatings, etc.
 In the manufacture of paints and inks, colloids are useful. In ball-point pens, the ink
used is a gel (liquid-solid colloid).
 The suspended impurities contained in the natural water are removed by adding
sulfates of aluminium (alum) and of iron which coagulates them.
 Most of the medicines are colloidal.

Colloidal gold and calcium are injected into the human body for the vitality of the
muscles. Argyrol (silver sol) is used as an eye lotion.

Albumin, Hetastarch, and Dextran are a few other colloids used in medicine.

What is a colloid solution?

A colloidal solution is a type of mixture which consists of particles whose size varies between
1 and 1000 nanometres.

93 | P a g e
94

In colloidal solution the particles are distributed evenly. During this process the particles do
not settle down. This is one of the best know thing about colloidal solutions.
Properties of colloids and their variation are a well-known area ever since the primitive age.
The best example to prove their familiarity with us is that we know from very early times
that coagulation of milk results in the formation of curd.

Physical properties of colloids

1. The nature of the colloidal solution is heterogeneous i.e. unlike. These solutions
dwell with two different phases:
 Dispersed medium
 Dispersed phase
2. Despite the fact that colloidal dispersions are unlike in description (nature), yet the
dispersed fragments are not detectable by the human eye. This is due to the
microscopic size of the particles in the solution.
3. The colour of the colloidal dispersion is determined by particles in the solution based
on their size. The wavelengths of light that is absorbed will be longer if the size of the
particle is large.
4. As a result of its size, the colloidal fragments can easily be passed through a
traditional filter paper. However, these particles can be filtered by using membranes
such as animal, cellophane, and ultrafilters.

Electrical properties of colloids

1. Electrical double layer theory: In this theory, charge is imparted to the particles by
placing ions which are adsorbed preferentially at immovable points which for the
first layer. The second layer consists of diffused mobile ions.

The charge present on both the layers is equal. This two-layer arrangement leads to
a development of potential called zeta or Electrokinetic potential.

As a result of this potential developed across the particles, under the influence of
electric field these particles move.

2. Electrophoresis: It is a process in which an electric field is been applied to a colloidal

solution which is responsible for the movement of colloidal particles.

Depending upon the accumulation near the electrodes the charge of the particles
can be predicted. The charge of the particles is positive if the particles get collected
near a negative electrode

94 | P a g e
95

and vice versa.

3. Electro-osmosis: It is a process in which the dispersing medium of the colloidal

solution is brought under the influence of electric field and the particles are arrested.

Optical properties of colloids

Tyndall’s effect is defined as the phenomenon in which light is scattered by the colloidal
particles. The light is been absorbed by the particles present in the solution.
Once the light is been absorbed a part of the light gets scattered in all the directions. The
result of scattering exhibits this effect.

Kinetic properties of colloids

During the observation of the colloidal dispersion under an ultra-microscope, it is clearly
seen that the particles are in a continuous movement in the solution. This random zigzag
movement of the particles in the colloidal solution is called Brownian effect.
This movement is mainly due to the unique bombardment of the molecules present in the
dispersed medium on the colloidal particles.
Stabilization
The stability of a colloidal system is defined by particles remaining suspended in solution
and depends on the interaction forces between the particles.
These include electrostatic interactions and van der Waals forces, because they both
contribute to the overall free energy of the system.[15]

95 | P a g e
96

A colloid is stable if the interaction energy due to attractive forces between the colloidal
particles is less than kT, where k is the Boltzmann constant and T is the absolute
temperature.
If this is the case, then the colloidal particles will repel or only weakly attract each other,
and the substance will remain a suspension.
If the interaction energy is greater than kT, the attractive forces will prevail, and the
colloidal particles will begin to clump together.
This process is referred to generally as aggregation, but is also referred to
as flocculation, coagulation or precipitation.[16] meanings.
For example, coagulation can be used to describe irreversible, permanent aggregation
where the forces holding the particles together are stronger than any external forces caused
by stirring or mixing.
Flocculation can be used to describe reversible aggregation involving weaker attractive
forces, and the aggregate is usually called a floc.
The term precipitation is normally reserved for describing a phase change from a colloid
dispersion to a solid (precipitate) when it is subjected to a perturbation.[13]
Aggregation causes sedimentation or creaming, therefore the colloid is unstable: if either of
these processes occur the colloid will no longer be a suspension.

Examples of a stable and of an unstable colloidal dispersion.

Electrostatic stabilization and steric stabilization are the two main mechanisms for
stabilization against aggregation.

 Electrostatic stabilization is based on the mutual repulsion of like electrical charges. The
charge of colloidal particles is structured in an electrical double layer, where the
particles are charged on the surface, but then attract counterions (ions of opposite
charge) which surround the particle.

The electrostatic repulsion between suspended colloidal particles is most readily

quantified in terms of the zeta potential.

The combined effect of van der Waals attraction and electrostatic repulsion on
aggregation is described quantitatively by the DLVO theory.[17]

A common method of stabilising a colloid (converting it from a precipitate)

is peptization, a process where it is shaken with an electrolyte.

96 | P a g e
97

 Steric stabilization consists absorbing a layer of a polymer or surfactant on the particles

to prevent them from getting close in the range of attractive forces.[13]

The polymer consists of chains that are attached to the particle surface, and the part of
the chain that extends out is soluble in the suspension medium.[18] This technique is
used to stabilize colloidal particles in all types of solvents, including organic solvents.[19]
A combination of the two mechanisms is also possible (electrosteric stabilization).

Steric and gel network stabilization.

A method called gel network stabilization represents the principal way to produce colloids
stable to both aggregation and sedimentation.
The method consists in adding to the colloidal suspension a polymer able to form a gel
network. Particle settling is hindered by the stiffness of the polymeric matrix where particles
are trapped,[20] and the long polymeric chains can provide a steric or electrosteric
stabilization to dispersed particles.
Examples of such substances are xanthan and guar gum.
Destabilization
Destabilization can be accomplished by different methods:

 Removal of the electrostatic barrier that prevents aggregation of the particles. This can
be accomplished by the addition of salt to a suspension to reduce the Debye screening
length (the width of the electrical double layer) of the particles.

It is also accomplished by changing the pH of a suspension to effectively neutralise the

surface charge of the particles in suspension.[1]

This removes the repulsive forces that keep colloidal particles separate and allows for
aggregation due to van der Waals forces.

Minor changes in pH can manifest in significant alteration to the zeta potential. When
the magnitude of the zeta potential lies below a certain threshold, typically around ±
5mV, rapid coagulation or aggregation tends to occur.[21]

 Addition of a charged polymer flocculant. Polymer flocculants can bridge individual

colloidal particles by attractive electrostatic interactions. For example, negatively
charged colloidal silica or clay particles can be flocculated by the addition of a positively
charged polymer.
 Addition of non-adsorbed polymers called depletants that cause aggregation due to
entropic effects.

97 | P a g e
98

Unstable colloidal suspensions of low-volume fraction form clustered liquid suspensions,

wherein individual clusters of particles sediment if they are more dense than the suspension
medium, or cream if they are less dense. However, colloidal suspensions of higher-volume
fraction form colloidal gels with viscoelastic properties. Viscoelastic colloidal gels, such
as bentonite and toothpaste, flow like liquids under shear, but maintain their shape when
shear is removed. It is for this reason that toothpaste can be squeezed from a toothpaste
tube, but stays on the toothbrush after it is applied.
Monitoring stability
The most widely used technique to monitor the dispersion state of a product, and to
identify and quantify destabilization phenomena, is multiple light scattering coupled with
vertical scanning.[22][23][24][25]
This method, known as turbidimetry, is based on measuring the fraction of light that, after
being sent through the sample, it backscattered by the colloidal particles.
The backscattering intensity is directly proportional to the average particle size and volume
fraction of the dispersed phase.
Therefore, local changes in concentration caused by sedimentation or creaming, and
clumping together of particles caused by aggregation, are detected and monitored.[26] These
phenomena are associated with unstable colloids.
Dynamic light scattering can be used to detect the size of a colloidal particle by measuring
how fast they diffuse.
This method involves directing laser light towards a colloid. The scattered light will form an
interference pattern, and the fluctuation in light intensity in this pattern is caused by the
Brownian motion of the particles.
If the apparent size of the particles increases due to them clumping together via
aggregation, it will result in slower Brownian motion. This technique can confirm that
aggregation has occurred if the apparent particle size is determined to be beyond the typical
size range for colloidal particles.[15]

COAGULATION :
 Coagulation is a physicochemical process that is often used to remove turbidity and
color from materials that are typically colloidal in nature (1–200 μm).

 Both inorganic and organic coagulants have been used. The optimum time for rapid
mixing is often achieved in few minutes. Rapid mixing is frequently followed
by flocculation whereby agglomeration of settled turbid particles into larger flocs
takes place.

 The flocs then settle and remove the contaminants in the sludge. Coagulation is
often carried out using chemicals such as ferric chloride, ferrous sulfate, ferric
sulfate, alum, lime, polymers, or a combination of these chemicals.

98 | P a g e
99

 Sometimes a combination of coagulation and adsorption processes is used (Nowack

et al., 1999).
 pH plays an important role in chemical coagulation.

 The use of several chemical coagulants and disposal of sludge is a major problem in
this technique.

 Further, desirable limits for the pollutants are rarely achieved using coagulation
alone.

DOUBLE LAYER THEORY:

Electric Double Layer

 An electric double layer is a phenomenon that plays a fundamental role in the

mechanism of the electrostatic stabilization of colloids.

 Colloidal particles gain negative electric charge when negatively charged ions of the
dispersion medium are adsorbed on the particle surface.

 A negatively charged particle attracts the positive counterions surrounding the

particle. As shown in Fig. 1-17, an electric double layer is the layer surrounding a
particle of dispersed phase, including the ions adsorbed on the particle surface and a
film of the countercharged dispersion medium.

 The electric double layer is electrically neutral.

An electric double layer consists of three parts:

1. Surface charge: charged ions (commonly negative) adsorbed on the particle
surface.
2. Stern layer: counterions (charged opposite to the surface charge), attracted to
the particle surface and closely attached to it by the electrostatic force.
3. Diffuse layer: a film of the dispersion medium (solvent) adjacent to the particle.
Diffuse layer contains free ions with a higher concentration of the counterions. The
ions of the diffuse layer are affected by the electrostatic force of the charged
particle.
The electrical potential within the electric double layer has a maximum value on the particle
surface (Stern layer).
The potential drops with the increase of distance from the surface and reaches 0 at the
boundary of the electric double layer.
When a colloidal particle moves in the dispersion medium, a layer of the surrounding liquid
remains attached to the particle.

99 | P a g e
100

The boundary of this layer is called the slipping plane (shear plane).

Fig. 1-17. Diagram of electric double layer.

The boundary of this layer is called the slipping plane (shear plane).
The value of the electric potential at the slipping plane is called the zeta potential, which is a
very important parameter in the theory of interaction of colloidal particles.
Although many important assumptions of the DLVO theory were not satisfied in real
colloidal systems, in which small particles dispersed in a diffusive medium, the DLVO theory
was still found to be valid and was widely applied in practice, as long as the following
conditions are met:
1. Dispersion is very dilute, so that the charge density and distribution on each
particle surface and the electric potential in the proximity next to each particle
surface are not interfered with by other particles.
2. No other force is present besides the van der Waals force and the electrostatic
potential; i.e., gravity is negligible or the particle is significantly small, and there
exist no other forces, such as magnetic fields.
3. Geometry of particles is relatively simple, so that the surface properties are the
same over the entire particle surface, and, thus surface charge density and

100 | P a g e
101

distribution as well as the electric potential in the surrounding medium are the
same.
4. The double layer is purely diffusive, so that the distributions of counter-ions and
charge determining ions are determined by all the three forces: electrostatic force,
entropic dispersion, and Brownian motion.
However, it should be noted that electrostatic stabilization is limited by the following facts:
1. Electrostatic stabilization is a kinetic stabilization method.
2. It is only applicable to dilute systems.
3. It is not applicable to electrolyte sensitive systems.
4. It is almost impossible to re-disperse the agglomerated particles.
5. It is difficult to apply to multiple phase systems, since, in a given condition,
different solids develop different surface charges and electric potentials.
It is very clear that some of the assumptions are far from the real picture of two particles
dispersed in a suspension.
For example, the surface of particles is not infinitely flat, and the surface charge density is
likely to change when two charged particles get very close to each other.
However, in spite of the assumptions, the DLVO theory works very well in explaining the
interactions between two approaching particles that are electrically charged, and thus the
theory is widely accepted in the research community of colloidal science.

101 | P a g e
102

UNIT – 3 ATMOSPHERIC CHEMISTRY

ATMOSPHERIC STRUCTURE – CHEMICAL AND PHOTOCHEMICAL REACTIONS

ATMOSPHERIC STRUCTURE:

The gaseous area surrounding the planet is divided into several concentric strata or layers.
About 99% of the total atmospheric mass is concentrated in the first 20 miles (32 km) above
Earth's surface.
Historical outline on the discovery of atmospheric structure.
THERMAL STRUCTURE
Atmospheric layers are characterized by variations in temperature resulting primarily from
the absorption of solar radiation; visible light at the surface, near ultraviolet radiation in the
middle atmosphere, and far ultraviolet radiation in the upper atmosphere.

Troposphere
 The troposphere is the atmospheric layer closest to the planet and contains the
largest percentage (around 80%) of the mass of the total atmosphere. Temperature
and water vapor content in the troposphere decrease rapidly with altitude. Water
vapor plays a major role in regulating air temperature because it absorbs solar
energy and thermal radiation from the planet's surface.
 The troposphere contains 99 % of the water vapor in the atmosphere. Water vapor
concentrations vary with latitude.
 They are greatest above the tropics, where they may be as high as 3 %, and decrease
toward the polar regions.

 All weather phenomena occur within the troposphere, although turbulence may
extend into the lower portion of the stratosphere.
 Troposphere means "region of mixing" and is so named because of vigorous
convective air currents within the layer.
 The upper boundary of the layer, known as the tropopause, ranges in height from 5
miles (8 km) near the poles up to 11 miles (18 km) above the equator.
 Its height also varies with the seasons; highest in the summer and lowest in the
winter.

Stratosphere
 The stratosphere is the second major strata of air in the atmosphere. It extends
above the tropopause to an altitude of about 30 miles (50 km) above the planet's
surface.
 The air temperature in the stratosphere remains relatively constant up to an altitude
of 15 miles (25 km).
 Then it increases gradually to up to the stratopause. Because the air temperature in
the stratosphere increases with altitude, it does not cause convection and has a
stabilizing effect on atmospheric conditions in the region.

102 | P a g e
103

 Ozone plays the major role in regulating the thermal regime of the stratosphere, as
water vapor content within the layer is very low. Temperature increases with ozone
concentration.
 Solar energy is converted to kinetic energy when ozone molecules absorb ultraviolet
radiation, resulting in heating of the stratosphere.

The ozone layer is centered at an altitude between 10-15 miles (15-25 km).

Approximately 90 % of the ozone in the atmosphere resides in the stratosphere. Ozone

concentration in the this region is about 10 parts per million by volume (ppmv) as compared
to approximately 0.04 ppmv in the troposphere.

Ozone absorbs the bulk of solar ultraviolet radiation in wavelengths from 290 nm - 320 nm
(UV-B radiation).

These wavelengths are harmful to life because they can be absorbed by the nucleic acid in
cells.

Increased penetration of ultraviolet radiation to the planet's surface would damage plant
life and have harmful environmental consequences.

Appreciably large amounts of solar ultraviolet radiation would result in a host of biological
effects, such as a dramatic increase in cancers.

Mesosphere
 The mesosphere a layer extending from approximately 30 to 50 miles (50 to 85 km)
above the surface, is characterized by decreasing temperatures.
 The coldest temperatures in Earth's atmosphere occur at the top of this layer,
the mesopause, especially in the summer near the pole.
 The mesosphere has sometimes jocularly been referred to as the "ignorosphere"
because it had been probably the least studied of the atmospheric layers.
 The stratosphere and mesosphere together are sometimes referred to as the middle
atmosphere.
Thermosphere
 The thermosphere is located above the mesosphere. The temperature in the
thermosphere generally increases with altitude reaching 600 to 3000 F (600-2000 K)
depending on solar activity.
 This increase in temperature is due to the absorption of intense solar radiation by
the limited amount of remaining molecular oxygen.
 At this extreme altitude gas molecules are widely separated.
 Above 60 miles (100 km) from Earth's surface the chemical composition of air
becomes strongly dependent on altitude and the atmosphere becomes enriched
with lighter gases (atomic oxygen, helium and hydrogen).

103 | P a g e
104

 Also at 60 miles (100 km) altitude, Earth's atmosphere becomes too thin to support
aircraft and vehicles need to travel at orbital velocities to stay aloft.
 This demarcation between aeronautics and astronautics is known as the Karman
Line. Above about 100 miles (160 km) altitude the major atmospheric component
becomes atomic oxygen.
 At very high altitudes, the residual gases begin to stratify according to molecular
mass, because of gravitational separation.

Exosphere
 The exosphere is the most distant atmospheric region from Earth's surface. In the
exosphere, an upward travelling molecule can escape to space (if it is moving fast
enough) or be pulled back to Earth by gravity (if it isn't) with little probability of
colliding with another molecule.
 The altitude of its lower boundary, known as the thermopause or exobase, ranges
from about 150 to 300 miles (250-500 km) depending on solar activity.
 The upper boundary can be defined theoretically by the altitude (about 120,000
miles, half the distance to the Moon) at which the influence of solar radiation
pressure on atomic hydrogen velocities exceeds that of the Earth's gravitational pull.
 The exosphere observable from space as the geocorona is seen to extend to at least
60,000 miles from the surface of the Earth.
 The exosphere is a transitional zone between Earth's atmosphere and interplanetary
space.
MAGNETO-ELECTRONIC STRUCTURE
The upper atmosphere is also divided into regions based on the behavior and number of
free electrons and other charged particles.
Ionosphere
The ionosphere is defined by atmospheric effects on radiowave propagation as a result of
the presence and variation in concentration of free electrons in the atmosphere.

D-region is about 35 to 55 miles (60 - 90 km) in altitude but disappears at night.

E-region is about 55 to 90 miles (90 - 140 km) in altitude.
F-region is above 90 miles (140 km) in atitude.

During the day it has two regions known as the F1-region from about 90 to 115 miles (140 to
180 km) altitude and the F2-region in which the concentration of electrons peaks in the
altitude range of 150 to 300 miles (around 250 to 500 km).

Most recent map of the Height of Maximum (hmF2). The ionosphere above the peak
electron concentration is usually referred to as the Topside Ionosphere.

104 | P a g e
105

Plasmasphere

 The plasmasphere is not really spherical but a doughnut-shaped region (a torus) with
the hole aligned with Earth's magnetic axis. [In this case the use of the suffix -sphere
is more in the figurative sense of a "sphere of influence".]
 The Earth's plasmasphere is made of just that, a plasma, the fourth state of matter.
(Test your skills on sorting the states of matter with the Matter Sorter.)
 This plasma is composed mostly of hydrogen ions (protons) and electrons.
 It has a very sharp edge called the plasmapause. The outer edge of this doughnut
over the equator is usually some 4 to 6 Earth radii from the center of the Earth or
12,000-20,000 miles (19,000-32,000 km) above the surface.
 The plasmasphere is essentially an extension of the ionosphere. Inside of the
plasmapause, geomagnetic field lines rotate with the Earth.
 The inner edge of the plasmasphere is taken as the altitude at which protons replace
oxygen as the dominant species in the ionospheric plasma which usually occurs at
about 600 miles (1000 km) altitude.
 The plasmasphere can also be considered to be a structure within the
magnetosphere.

Magnetosphere

 Outside the plasmapause, magnetic field lines are unable to corotate because they
are influenced strongly by electric fields of solar wind origin.
 The magnetosphere is a cavity (also not spherical) in which the Earth's magnetic field
is constrained by the solar wind and interplanetary magnetic field (IMF).
 The outer boundary of the magnetosphere is called the magnetopause.
 The magnetosphere is shaped like an elongated teardrop (like a Christmas Tree
ornament) with the tail pointing away from the Sun.
 The magnetopause is typically located at about 10 Earth radii or some 35,000 miles
(about 56,000 km) above the Earth's surface on the day side and stretches into a
long tail, the magnetotail, a few million miles long (about 1000 Earth radii), well past
the orbit of the Moon (at around 60 Earth radii), on the night side of the Earth.
 However, the Moon itself is usually not within the magnetosphere except for a
couple of days around the Full Moon.
 Beyond the magnetopause are the magnetosheath and bow shock which are regions
in the solar wind disturbed by the presence of Earth and its magnetic field.

INTRODUCTION:

 The various chemical and photochemical reactions taking place in atmosphere,

mostly depend upon the temperature , composition, humidity and intensity of
sunlight. Photochemical reaction take place in atmosphere by the absorption of
solar radiation in the ultraviolet region.

105 | P a g e
106

 Absorption of photons by chemical species gives rise to electronically excited

molecules, which can bring about certain reactions.
 These reactions are not possible thermal condition except at higher temperatures
and in presence of catalysts.

The Chemical and Photochemical Reactions in the Atmosphere – Introduction, Examples, and

Theoretical Concepts
The Chemical and Photochemical Reactions in the Atmosphere:

 Photochemistry is a special branch of chemist ry that deals with the

reactions that occur on exposure to light radiations.

 The chemical reactions that occur due to light radiations are known as
photochemical reactions.

 They occur due to the excitation of an electron to the excited state on

gaining energy.

 Photochemical reactions are the basis of many important processes

which are responsible for sustainable life on the Earth.

 Photosynthesis in plants with the help of sunlight is a very good

example of a photochemical reaction in nature.

 In the atmosphere, there are numerous photochemical reactions taking

place all the time.

 Some of the famous examples include the formation of ozone in the

atmosphere, photochemical smog, etc.

 There are many gases present in the atmosphere like oxygen, carbon
dioxide, nitrogen, aerosols, etc.

 When they react with hydroxyl radicals present in the atmosphere, they
cause profound effects on the atmospheric composition.

What are Photochemical Reactions?

 Those chemical reactions which take place due to the absorpti on of light
energy are called photochemical reactions.

 Most photochemical reactions occur by the absorption of ultraviolet

radiations, visible light, or infrared radiation.

106 | P a g e
107

 Apart from thermal reactions in the presence of heat energy,

photochemical reactions are light-driven reactions.

 High energy intermediates are formed in paths of photochemical

reactions which cannot be formed thermally.

 In these reactions, large activation energy barriers are crossed in a

short time span. Some photochemical reactions are very destructive to
the atmosphere, such as the photodegradation of plastics.

Thermochemical and Photochemical Reaction in the Atmosphere with

Examples
Thermochemical Reactions
The chemical reactions that involve the absorption or evolution of heat are
known as thermochemical reactions.

They can occur in the absence of light. In this type of reaction, temperature
plays a significant role in the rate of the reaction.
Gibbs free energy change ΔGΔG and the enthalpy change ΔHΔH of a
thermochemical reaction vary for different chemical reactions.

For example, sulphur dioxide in the atmosphere reacts with oxygen to form
sulphur trioxide with an enthalpy change of –98.9kJ/mol–98.9kJ/mol.

2SO2(g)+O2(g)→2SO3(g)(ΔH=–98.9kJ/mol)

Another example of the thermochemical reaction is the reaction between

carbon and oxygen to form carbon dioxide gas.

C(S)+O2(g)→CO2(g)

Photochemical Reactions
Photosynthesis
Photosynthesis is the most common example of a phot ochemical reaction. In
photosynthesis plants, plants prepare their food using sunlight and water to
convert carbon dioxide into glucose and oxygen. The chemical reaction is given
below:

107 | P a g e
108

Photochemical Smog
Photochemical smog, or ‘summer smog,’ is formed w hen
ultraviolet (UV)(UV) rays coming from the sun react with nitrogen oxides and
volatile organic compounds (VOCs)(VOCs) present in the atmosphere.

It is noticed as a visible haze during the morning and in the afternoon.

Photochemical smogs are likely to occur more often on dry summer days when
a particular region experiences maximum sunlight.

It is commonly found in densely populated urban cities such as Los Angeles,

Sydney, New Delhi, Beijing, etc.

The chemical reactions involved in the formation of Ph otochemical smog are:

1. In the morning, nitrogen gas is oxidized when released from automobiles to

form nitric oxide. It is an oxidation step.
N2+O2→2NO
2. After some time, nitric oxide (NO) undergoes another oxidation reaction
and combines with more oxygen to form nitrogen dioxide.
2N2+O2→2NO2
3. This Nitrogen dioxide absorbs sunlight to break down and forms nitric oxide
(NO) and oxygen radical (O) as carried in a reduction reaction.
NO2+Sunlight→NO+O

 Photochemical smog, also known as summer smog, is a type of smog that is

produced when UV light originating from the sun interacts with the oxides of
nitrogen present in the atmosphere.
 This type of smog usually manifests as a brown haze and is most commonly seen in
highly populated cities that are placed in relatively warm climates.
 Furthermore, photochemical smog is most prominently visible during the mornings
and afternoons.

108 | P a g e
109

How is Photochemical Smog Formed?

Photochemical form is formed by a complex series of chemical reactions involving sunlight,
oxides of nitrogen, and volatile organic compounds that are present in the atmosphere as a
result of air pollution.
These reactions often result in the formation of ground level ozone and certain airborne
particles. The formation of photochemical smog is closely related to the concentration of
primary pollutants in the atmosphere. It is also related to the concentration of secondary
pollutants (in some cases).
Common examples of primary pollutants that contribute towards photochemical smog
include oxides of nitrogen such as nitric oxide, nitrogen dioxide, and nitrous oxide and most
VOCs (volatile organic compounds).
Common examples of secondary pollutants that contribute towards the formation of
photochemical smog include aldehydes, tropospheric ozone, and peroxylacyl nitrates (often
abbreviated to PAN).
During peak-traffic hours in the morning, large amounts of nitrogen oxides and volatile
hydrocarbons are released into the atmosphere.
These pollutants can be traced to automobile emissions and industrial discharge. Some of
these hydrocarbon pollutants rapidly undergo oxidation by the hydroxyl groups in the
atmosphere, resulting in the formation of peroxy radicals.
These peroxy radicals go on to convert nitric oxide into nitrogen dioxide.

What are the Effects of Photochemical Smog?

Photochemical smog has a number of negative effects on the environment and human
beings. The chemicals contained within it, when combined with hydrocarbons, form
molecules which cause eye irritation.
The atmospheric radicals interfere with the nitrogen cycle by stopping ground level ozone
from being eliminated. Ground level ozone can prove to be extremely toxic to human
beings.
Other negative symptoms associated with photochemical smog include decreased vision
and shortness of breath.
To learn more about photochemical smog and other important environmental concerns
such as eutrophication, register with BYJU’S and download the mobile application on your
smartphone.

Formation of Ozone
Ozone can be defined as a pale blue gas that forms a protective shield against
the harmful UV radiations coming from the sun.

It is also known as trioxygen because of the presence of three oxygen

molecules having chemical formulas as O3O3

109 | P a g e
110

Ozone in the Stratosphere

Ozone is formed naturally by the series of photochemical reactions bet ween

the oxygen molecules and ultraviolet light in the stratosphere layer of the
atmosphere.

The concentration of stratospheric ozone is 21%21% higher than the

tropospheric ozone.
Photolysis of Oxygen to form Ozone

1. The photochemical reaction to form oz one is a two-step mechanism. The

first step involves a short UVUV-light wavelength (240240 and 160nm160nm),
which splits molecular oxygen (O2)(O2) into two free atomic oxygen
molecules (O)(O).
2. The second step results in the combination of the highly reacti ve atomic
oxygen with molecular oxygen to generate ozone (O3)(O3)
3. At last, the ozone splits off again into a highly reactive oxygen atom and
one oxygen molecule due to solar UVUV radiation. This series of reactions is
continuous. This means that the ozone is continuously generated and
dissociated in the stratosphere layer of the atmosphere.

Good Ozone
The stratospheric ozone is a good zone as it shields the potent UVUV radiations
coming to the surface of the Earth.

Tropospheric Ozone or Bad Ozone

In the Troposphere layer (ground layer) of the atmosphere, the gases released
from the vehicles, factories, etc., contribute to the greenhouse gases
accumulation, which then reacts with the heat or solar UVUV- radiations and
turns out to be more toxic.

Compounds like VOCs, nitrogen oxides and CO behave as the precursors of

tropospheric ozone, which leads to the depletion of the ozone layer.

110 | P a g e
111

The oxides of nitrogen are predominantly formed via high -temperature

combustion in power plants, nuclear reactors etc., whi le CO or carbon
monoxide originates via fuel combustion.

Therefore, ground-level ozone is referred to as bad ozone as it can act as a

toxic air pollutant, which can affect plants and animals; harmful health effects
like respiratory disorders etc., occur d ue to this bad ozone.

The concentration of tropospheric ozone is about 10%10% of the total

atmospheric concentration.

Photochemical Reactions of Other Atmospheric Gases

1. Photochemical Reaction of Carbon Monoxide

Hydroxyl radicals in the atmosphere react with carbon monoxide to yield
carbon dioxide and hydrogen radicals.
CO+⋅OHlight→CO2+⋅H
2. Photochemical Reaction of Formaldehyde
Formaldehyde is found in trace quantities in the atmosphere as they are
formed due to various atmospheric reactions and is oxidized by hydroxyl
radical.
3. Photochemical Reaction with Methane
Methane is naturally emitted from the Earth’s surface. In the atmosphere,
methane is oxidized by hydroxyl radical yielding methyl radical and water.
Methane undergoes a series of photochemical chemical reactions in the
methane cycle to form acetic acid.

Summary
 The atmosphere is defined as the gaseous surrounding around a star or
planetary body held in place by gravity.

 It acts as a blanket that covers the Earth from the harmful radiations
coming from the sun.

 The Earth’s atmosphere is composed of

about 78%78% nitrogen, 21%21% oxygen, 0.9%0.9% argon, and other gases
also.

 In the inside atmosphere, there are continuous chemical and

photochemical reactions occurring.

 A photochemical reaction is a chemical reaction triggered when light

energy is absorbed by the molecules of a substance. We can take the
examples of ozone formation in the atmosphere, formation of
photochemical smog, etc.

111 | P a g e
112

 The other gases present in the atmosphere, including methane, oxides

of nitrogen, oxides of sulphur, etc.

 When reacted with hydroxyl radical or other radicals present in the

atmosphere, it causes intense effects on the atmospheric composition.
 Photosynthesis in plants is a very good example of a photochemical
reaction in nature.

 The major environmental issue that we are facing is due to ozone layer
depletion.

 The ozone layer is formed by a series of photochemical reactions, which

forms a layer of shield around the atmosphere as the high concentration
of ozone in the stratosphere safeguards against the harmful UVUV light.

 Conversely, the high concentration of ozone in the troposphere layer

contributes to greenhouse gases and causes various respiratory hazards.

 Thus, we can conclude that in normal chemical reactions, the source of

energy is mostly heating, but in photochemical reactions, the source of
energy is light.

Frequently Asked Questions (FAQs)

Q.1. What is the chemical and photochemical reaction?

Ans: A chemical reaction is a reaction where the source of energy is mostly
heating, but in a photochemical reaction, as th e word “photo” itself signifies,
the source of energy is light.

Q.2. What is a chemical reaction in the atmosphere?

Ans: Chemical reactions in the atmosphere lead to the oxidation of atoms over
time in the atmosphere. Atoms that enter the atmosphere as ga ses are in a
reduced state that is oxidized in a stepwise manner to form ionic substances
that are eventually washed out of the atmosphere along with the rainfall.

Q.3. What are examples of photochemical reactions?

Ans: Some examples of photochemical reac tions include photosynthesis in
plants, formation of photochemical smog in the air, ozone formation from
oxygen gas, the photochemical reaction of carbon monoxide, methane, and
formaldehyde, etc.

Q.4. Why are photochemical reactions so important in the at mosphere?

Ans: One of the most important photochemical reactions in the atmosphere is
ozone layer formation. It involves two -step mechanisms; the first step involves
a short UVUV light that splits molecular oxygen (O2)(O2) into two free atomic

112 | P a g e
113

oxygen molecules (O)(O), and the second step results in the combination of the
highly reactive atomic oxygen with molecular oxygen to generate
ozone (O3).(O3). This stratospheric ozone is good ozone as it shields the
potent UVUV radiations coming to the surface of the Earth and protects us
from various harmful diseases.

Q.5. Which is the most important thing in photochemical reactions?

Ans: The presence of free radicals and light energy are the two most im portant
in photochemical reaction

OZONE LAYER DEPLETION:

Ozone Layer Definition

“The ozone layer is a region in the earth’s stratosphere that contains high concentrations
of ozone and protects the earth from the harmful ultraviolet radiations of the sun.”

What is Ozone Layer?

 The ozone layer is found in the lower portion of the earth’s atmosphere.
 It has the potential to absorb around 97-99% of the harmful ultraviolet radiations
coming from the sun that can damage life on earth.
 If the ozone layer was absent, millions of people would develop skin diseases and
may have weakened immune systems.
 However, scientists have discovered a hole in the ozone layer over the Antarctica.
 This has focussed their concern on various environmental issues and steps to control
them.
 The main reasons for the ozone hole are chlorofluorocarbons, carbon tetrachloride,
methyl bromide and hydrochlorofluorocarbons.
 Let us have a detailed look at the various causes and effects of ozone layer
depletion.

Ozone Layer Depletion

“Ozone layer depletion is the gradual thinning of the earth’s ozone layer in the upper
atmosphere caused due to the release of chemical compounds containing gaseous
bromine or chlorine from industries or other human activities.”

What is Ozone Layer Depletion?

 Ozone layer depletion is the thinning of the ozone layer present in the upper
atmosphere. This happens when the chlorine and bromine atoms in the atmosphere
come in contact with ozone and destroy the ozone molecules.
 One chlorine can destroy 100,000 molecules of ozone.

113 | P a g e
114

 It is destroyed more quickly than it is created.

 Some compounds release chlorine and bromine on exposure to high ultraviolet light,
which then contributes to the ozone layer depletion.
 Such compounds are known as Ozone Depleting Substances (ODS).
 The ozone-depleting substances that contain chlorine include chlorofluorocarbon,
carbon tetrachloride, hydrochlorofluorocarbons, and methyl chloroform.
 Whereas, the ozone-depleting substances that contain bromine are halons, methyl
bromide, and hydro bromofluorocarbons.
 Chlorofluorocarbons are the most abundant ozone-depleting substance.
 It is only when the chlorine atom reacts with some other molecule, it does not react
with ozone.
 Montreal Protocol was proposed in 1987 to stop the use, production and import of
ozone-depleting substances and minimise their concentration in the atmosphere to
protect the ozone layer of the earth.

Causes of Ozone Layer Depletion

The ozone layer depletion is a major concern and is associated with a number of factors. The
main causes responsible for the depletion of the ozone layer are listed below:
Chlorofluorocarbons
Chlorofluorocarbons or CFCs are the main cause of ozone layer depletion.
These are released by solvents, spray aerosols, refrigerators, air-conditioners, etc.
The molecules of chlorofluorocarbons in the stratosphere are broken down by the
ultraviolet radiations and release chlorine atoms. These atoms react with ozone and destroy
it.
Unregulated Rocket Launches
Researches say that the unregulated launching of rockets result in much more depletion of
ozone layer than the CFCs do.
If not controlled, this might result in a huge loss of the ozone layer by the year 2050.
Nitrogenous Compounds
The nitrogenous compounds such as NO2, NO, N2O are highly responsible for the depletion
of the ozone layer.
Natural Causes
The ozone layer has been found to be depleted by certain natural processes such as Sun-
spots and stratospheric winds. But it does not cause more than 1-2% of the ozone layer
depletion.
The volcanic eruptions are also responsible for the depletion of the ozone layer.

114 | P a g e
115

Ozone Depleting Substances (ODS)

“Ozone depleting substances are the substances such as chlorofluorocarbons, halons,
carbon tetrachloride, hydrofluorocarbons, etc. that are responsible for the depletion of
ozone layer.”

Following is the list of some main ozone-depleting substances and the sources from where
they are released:

Ozone-Depleting Sources
Substances

Chlorofluorocarbons Refrigerators, air-conditioners, solvents, dry-cleaning

(CFCs) agents, etc.

Halons Fire-extinguishers

Carbon tetrachloride Fire extinguishers, solvents

Methyl chloroform Adhesives, aerosols

Hydrofluorocarbons fire extinguishers, air-conditioners, solvents

Effects Of Ozone Layer Depletion

The depletion of the ozone layer has harmful effects on the environment. Let us see the
major effects of ozone layer depletion on man and environment.
Effects on Human Health
The humans will be directly exposed to the harmful ultraviolet radiations of the sun due to
the depletion of the ozone layer.
This might result in serious health issues among humans, such as skin diseases, cancer,
sunburns, cataract, quick ageing and weak immune system.
Effects on Animals
Direct exposure to ultraviolet radiations leads to skin and eye cancer in animals.
Effects on the Environment
Strong ultraviolet rays may lead to minimal growth, flowering and photosynthesis in plants.
The forests also have to bear the harmful effects of the ultraviolet rays.
Effects on Marine Life
Planktons are greatly affected by the exposure to harmful ultraviolet rays. These are higher
in the aquatic food chain. If the planktons are destroyed, the organisms present in the food
chain are also affected.

115 | P a g e
116

Solutions to Ozone Layer Depletion

The depletion of the ozone layer is a serious issue and various programmes have been
launched by the government of various countries to prevent it. However, steps should be
taken at the individual level as well to prevent the depletion of the ozone layer.
Following are some points that would help in preventing this problem at a global level:
Avoid Using ODS
Reduce the use of ozone depleting substances. E.g. avoid the use of CFCs in refrigerators
and air conditioners, replacing the halon based fire extinguishers, etc.
Minimise the Use of Vehicles
The vehicles emit a large amount of greenhouse gases that lead to global warming as well as
ozone depletion. Therefore, the use of vehicles should be minimised as much as possible.
Use Eco-friendly Cleaning Products
Most of the cleaning products have chlorine and bromine releasing chemicals that find a
way into the atmosphere and affect the ozone layer. These should be substituted with
natural products to protect the environment.
Use of Nitrous Oxide should be Prohibited
The government should take actions and prohibit the use of harmful nitrous oxide that is
adversely affecting the ozone layer. People should be made aware of the harmful effects of
nitrous oxide and the products emitting the gas so that its use is minimised at the individual
level as well.

GREENHOUSE GAS:
What Are Greenhouse Gases?
Earth’s greenhouse gases trap heat in the atmosphere and warm the planet. The main gases
responsible for the greenhouse effect include carbon dioxide, methane, nitrous oxide, and
water vapor (which all occur naturally), and fluorinated gases (which are synthetic)
Greenhouse gases have different chemical properties and are removed from the
atmosphere, over time, by different processes.
Carbon dioxide, for example, is absorbed by so-called carbon sinks such as plants, soil, and
the ocean. Fluorinated gases are destroyed only by sunlight in the far upper atmosphere.
How much any one greenhouse gas influences global warming depends on three key
factors.
The first is how much of it exists in the atmosphere.

Concentrations are measured in parts per million (ppm), parts per billion (ppb), or parts per
trillion (ppt); 1 ppm for a given gas means, for example, that there is one molecule of that
gas in every 1 million molecules of air.

116 | P a g e
117

The second is its lifetime—how long it remains in the atmosphere. The third is how effective
it is at trapping heat. This is referred to as its global warming potential, or GWP, and is a
measure of the total energy that a gas absorbs over a given period of time (usually 100
years) relative to the emissions of 1 ton of carbon dioxide.

Radiative forcing (RF) is another way to measure greenhouse gases (and other climate
drivers, such as the sun’s brightness and large volcanic eruptions).

Also known as climate forcing, RF quantifies the difference between how much of the sun’s
energy gets absorbed by the earth and how much is released into space as a result of any
one climate driver.

A climate driver with a positive RF value indicates that it has a warming effect on the planet;
a negative value represents cooling.

What Are Greenhouse Gas Emissions?

Since the start of the Industrial Revolution and the advent of coal-powered steam engines,
human activities have vastly increased the volume of greenhouse gases emitted into the
atmosphere.
It is estimated that between 1750 and 2011, atmospheric concentrations of carbon dioxide
increased by 40 percent, methane by 150 percent, and nitrous oxide by 20 percent.
In the late 1920s, we started adding man-made fluorinated gases like chlorofluorocarbons,
or CFCs, to the mix.

In recent decades we’ve only picked up the pace. Of all the man-made emissions of carbon
dioxide—the most abundant greenhouse gas released by human activities, and one of the
longest-lasting—from 1750 to 2010, approximately half were generated in the last 40 years
alone, in large part due to fossil fuel combustion and industrial processes.
And while global greenhouse gas emissions have occasionally plateaued or dropped from
year to year (most recently between 2014 and 2016), they’re accelerating once again.
In 2017, carbon emissions rose by 1.6 percent; in 2018 they increased by an estimated 2.7
percent.

117 | P a g e
118

Five Major Greenhouse Gases

The most significant gases that cause global warming via the greenhouse effect are the
following:
Carbon Dioxide
Accounting for about 76 percent of global human-caused emissions, carbon dioxide (CO2)
sticks around for quite a while. Once it’s emitted into the atmosphere, 40 percent still
remains after 100 years, 20 percent after 1,000 years, and 10 percent as long as 10,000
years later.

Methane
Although methane (CH4) persists in the atmosphere for far less time than carbon dioxide
(about a decade), it is much more potent in terms of the greenhouse effect. In fact, pound
for pound, its global warming impact is 25 times greater than that of carbon dioxide over a
100-year period. Globally it accounts for approximately 16 percent of human-generated
greenhouse gas emissions.

Nitrous Oxide
Nitrous oxide (N2O) is a powerful greenhouse gas: It has a GWP 300 times that of carbon
dioxide on a 100-year time scale, and it remains in the atmosphere, on average, a little more
than a century. It accounts for about 6 percent of human-caused greenhouse gas emissions
worldwide.

118 | P a g e
119

 Fluorinated Gases
Emitted from a variety of manufacturing and industrial processes, fluorinated
gases are man-made.
 There are four main categories: hydrofluorocarbons (HFCs), perfluorocarbons (PFCs),
sulfur hexafluoride (SF6), and nitrogen trifluoride (NF3).
 Although fluorinated gases are emitted in smaller quantities than other greenhouse
gases (they account for just 2 percent of man-made global greenhouse gas
emissions), they trap substantially more heat. Indeed, the GWP for these gases can
be in the thousands to tens of thousands, and they have long atmospheric lifetimes,
in some cases lasting tens of thousands of years.
 HFCs are used as a replacement for ozone-depleting chlorofluorocarbons (CFCs) and
hydrochlorofluorocarbons (HCFCs), usually in air conditioners and refrigerators, but
some are being phased out because of their high GWP. Replacing these HFCs and
properly disposing of them is considered to be one of the most important climate
actions the world can take.
Water Vapor
The most abundant greenhouse gas overall, water vapor differs from other greenhouse
gases in that changes in its atmospheric concentrations are linked not to human activities
directly, but rather to the warming that results from the other greenhouse gases we emit.
Warmer air holds more water.
And since water vapor is a greenhouse gas, more water absorbs more heat, inducing even
greater warming and perpetuating a positive feedback loop. (It’s worth noting, however,
that the net impact of this feedback loop is still uncertain, as increased water vapor also
increases cloud cover that reflects the sun’s energy away from the earth.)
Where Do Greenhouse Gases Come From?
Population size, economic activity, lifestyle, energy use, land use patterns, technology, and
climate policy: According to the Intergovernmental Panel on Climate Change (IPCC), these
are the broad forcings that drive nearly all human-caused greenhouse gas emissions. Here’s
a closer look at greenhouse gas emissions by source.
Electricity and Heat Production
The burning of coal, oil, and natural gas to produce electricity and heat accounts for one-
quarter of worldwide human-driven emissions, making it the largest single source.

In the United States it’s the second-largest (behind transportation), responsible for
about 27.5 percent of U.S. emissions in 2017, with carbon dioxide the primary gas released
(along with small amounts of methane and nitrous oxide), mainly from coal combustion.

Agriculture and Land Use Changes

About another quarter of global greenhouse gas emissions stem from agriculture and other
land-use activities (such as deforestation).
In the United States, agricultural activities—primarily the raising of livestock and crops for
food—accounted for 8.4 percent of greenhouse gas emissions in 2017.
119 | P a g e
120

Of those, the vast majority were methane (which is produced as manure decomposes and as
beef and dairy cows belch and pass gas) and nitrous oxide (often released with the use of
nitrogen-heavy fertilizers).
Trees, plants, and soil absorb carbon dioxide from the air.
The plants and trees do it via photosynthesis (a process by which they turn carbon dioxide
into glucose); the soil houses microbes that carbon binds to.
So nonagricultural land-use changes such as deforestation, reforestation (replanting in
existing forested areas), and afforestation (creating new forested areas) can either increase
the amount of carbon in the atmosphere (as in the case of deforestation) or decrease it via
absorption, removing more carbon dioxide from the air than they emit.
(When trees or plants are cut down, they no longer absorb carbon dioxide, and when they
are burned or decompose, they release carbon dioxide back into the atmosphere.)
In the United States, land-use activities currently represent a net carbon sink, absorbing
more carbon dioxide from the air than they emit.
Industry
About one-fifth of global human-driven emissions come from the industrial sector, which
includes the manufacturing of goods and raw materials (like cement and steel), food
processing, and construction.

In 2017, industry accounted for 22.4 percent of U.S. man-made emissions, of which the
majority was carbon dioxide, though methane, nitrous oxide, and fluorinated gases were
also released.

Transportation
The burning of petroleum-based fuels, namely gasoline and diesel, to power the world’s
transportation systems accounts for 14 percent of global greenhouse gas emissions.

In the United States, with Americans buying larger cars and taking more flights and with low
gas prices encouraging drivers to use their cars more, transportation is the largest
contributor of greenhouse gases.
(It accounted for 28.7 percent of U.S. emissions in 2017.) Carbon dioxide is the primary gas
emitted, though fuel combustion also releases small amounts of methane and nitrous oxide,
and vehicle air conditioning and refrigerated transport release fluorinated gases too.
Nationwide, cars and trucks are responsible for more than 80 percent of transportation-
related carbon emissions.
Buildings
Operating buildings around the world generates 6.4 percent of global greenhouse gases. In
the United States, homes and businesses accounted for about 11 percent of warming
emissions.

120 | P a g e
121

These emissions, made up mostly of carbon dioxide and methane, stem primarily from
burning natural gas and oil for heating and cooking, though other sources include managing
waste and wastewater and leaking refrigerants from air-conditioning and refrigeration
systems.

Other Sources
This category includes emissions from energy-related activities other than fossil fuel
combustion, such as the extraction, refining, processing, and transportation of oil, gas, and
coal. Globally, this sector accounts for 9.6 percent of emissions.

Greenhouse Gas Emissions by Country

Since the start of the Industrial Revolution, more than 2,000 billion tons of carbon dioxide
have been released into the atmosphere by human activities, according to the Global
Carbon Project.

North America and Europe are responsible for approximately half of that total, while the
emerging economies of China and India have contributed another 14 percent. For the
remainder, 150-plus countries share responsibility.

An analysis of carbon dioxide emissions by country today shows that China now leads the
pack, responsible for 27 percent of all emissions.

Next comes the United States (15 percent), the European Union’s 28 member states
including the United Kingdom (10 percent), and India (7 percent) next. Together, these
global powers account for almost 60 percent of all emissions.

The Consequences of the Greenhouse Effect

Today’s human-caused greenhouse gas emissions are higher than ever, the concentration of
greenhouse gases in the atmosphere is rising rapidly, and according to the IPCC, the planet
is heating up.

Between preindustrial times and now, the earth’s average temperature has increased 1.8
degrees Fahrenheit (1.0 degrees Celsius), with approximately two-thirds of that warming
occurring in the last handful of decades alone.
According to the IPCC, 1983 to 2012 was likely the warmest 30-year period of the last 1,400
years (in the Northern Hemisphere, where assessment is possible).
And all five of the years from 2014 to 2018 were the hottest on record globally.
If warming trends continue at the current rate, it’s estimated global warming will reach 2.7
degrees Fahrenheit (1.5 degrees Celsius) above preindustrial levels between 2030 and 2052.
Fueled by man-made greenhouse gas emissions, global warming is altering the earth’s
climate systems in many ways. It is:

121 | P a g e
122

Causing more frequent and/or intense extreme weather events, including heat
waves, hurricanes, droughts, and floods.
Exacerbating precipitation extremes, making wet regions wetter and dry regions drier.

Raising sea levels due to melting glaciers and sea ice and an increase in ocean temperatures
(warmer water expands, which can contribute to sea level rise).

Altering ecosystems and natural habitat, shifting the geographic ranges, seasonal activities,
migration patterns, and abundance of land, freshwater, and marine species.

These changes pose threats not only to plants and wildlife, but directly to people. Warmer
temperatures mean insects that spread diseases like dengue fever and Zika can thrive—and
heat waves are getting hotter and more lethal to humans.

People could go hungry when our food supply is diminished thanks to droughts and floods—
a 2011 National Research Council study found that for every degree Celsius that the planet
heats up, crop yields will go down 5 to 15 percent.
Food insecurity can lead to mass human migration and political instability.
And in January 2019, the Department of Defense released a report that described the
threats to U.S. military installations and operations around the world due to flooding,
droughts, and other impacts of climate change.

The Greenhouse Effect Solution

The earth has always experienced warm and cool phases, with natural forces—from the
sun’s intensity, volcanic eruptions, and natural changes in greenhouse gas concentrations—
affecting how much energy from the sun our planet absorbs.

Scientists say that as recently as a couple of centuries ago, the planet underwent a “Little Ice
Age,” caused by a decrease in solar activity and an increase in volcanic activity. But today’s
climatic warming—particularly the increase in temperatures since the mid-20th century—is
occurring at a pace that can’t be explained by natural causes alone.
According to NASA, “natural causes are still in play today, but their influence is too small or
they occur too slowly to explain the rapid warming seen in recent decades.”
In other words, humans are the problem. But we may also be the solution. We have the
ability to rein in greenhouse gas emissions, though doing so certainly won’t be easy.

Overhauling our energy systems will require transformative, aggressive global action—and
now.

According to the IPCC, we must decrease greenhouse gas pollution by 45 percent from 2010
levels by 2030 and reach net zero emissions by 2050.
To allow global warming to exceed 1.5 degrees Celsius (which the IPCC has identified as the
threshold for avoiding climate change’s worst impacts) would mean more intense drought,

122 | P a g e
123

extreme heat, flooding, and poverty, the decline of species (including a mass die-off of the
world’s coral reefs), and the worsening of food shortages and wildfires.
Reducing our greenhouse gas emissions will require significant effort at the international,
national, and local levels.
First and foremost, we must slash fossil fuel production, consumption, and pollution by
ramping up our use of clean, renewable energy and energy-efficient technologies and by
investing in fuel-efficient and electric vehicles.
We must end fossil fuel subsidies and better leverage “cap and invest” programs, carbon
pricing, and carbon capture, storage, and utilization technologies (which catch the carbon
dioxide from emissions sources like power plants or directly from the air and permanently
bury it underground or convert it into other materials).

We must protect our carbon-storing forests and reduce food waste and the emissions that
go with it. And as individuals, we must commit to taking carbon-cutting actions in our daily
lives.

Currently the United States faces the additional hurdle of an administration doubling down
on fossil fuel use by rolling back standards aimed at reducing emissions from dirty power
plants and cars and trucks (in other words, from the electricity and transportation sectors,
the nation’s two largest sources of greenhouse gas emissions).
President Trump is also working to withdraw the nation from the landmark 2015 Paris
climate agreement even though nearly two-thirds of Americans believe we should do more
to tackle climate change, not less.
Still, decision makers, companies, leaders, and activists across the country and around the
world staunchly believe we must act on climate change.
For just as the emissions of man-made greenhouse gases long ago are inducing the climate
change we see now, the emissions we release today will impact us long into the future.

What Is the Greenhouse Effect?

Identified by scientists as far back as 1896, the greenhouse effect is the natural warming of
the earth that results when gases in the atmosphere trap heat from the sun that would
otherwise escape into space.
What Causes the Greenhouse Effect?

Sunlight makes the earth habitable. While 30 percent of the solar energy that reaches our
world is reflected back to space, approximately 70 percent passes through the atmosphere
to the earth’s surface, where it is absorbed by the land, oceans, and atmosphere, and heats
the planet.
This heat is then radiated back up in the form of invisible infrared light. While some of this
infrared light continues on into space, the vast majority—indeed, some 90 percent—gets

123 | P a g e
124

absorbed by atmospheric gases, known as greenhouse gases, and redirected back toward
the earth, causing further warming.
For most of the past 800,000 years—much longer than human civilization has existed—the
concentration of greenhouse gases in our atmosphere was between about 200 and 280
parts per million.
(In other words, there were 200 to 280 molecules of the gases per million molecules of air.)
But in the past century, that concentration has jumped to more than 400 parts per million,
driven up by human activities such as burning fossil fuels and deforestation.

The higher concentrations of greenhouse gases—and carbon dioxide in particular—is

causing extra heat to be trapped and global temperatures to rise.
GLOBAL WARMING:
Global Warming is a term almost everyone is familiar with. But, its meaning is still not clear
to most of us.

So, Global warming refers to the gradual rise in the overall temperature of the atmosphere
of the Earth.

There are various activities taking place which have been increasing the temperature
gradually.
Global warming is melting our ice glaciers rapidly.
This is extremely harmful to the earth as well as humans.
It is quite challenging to control global warming; however, it is not unmanageable.
The first step in solving any problem is identifying the cause of the problem.
Therefore, we need to first understand the causes of global warming that will help us
proceed further in solving it.
In this essay on Global Warming, we will see the causes and solutions of Global Warming.
Causes of Global Warming
Global warming has become a grave problem which needs undivided attention. It is not
happening because of a single cause but several causes.
These causes are both natural as well as manmade.
The natural causes include the release of greenhouses gases which are not able to escape
from earth, causing the temperature to increase.
Further, volcanic eruptions are also responsible for global warming.

That is to say, these eruptions release tons of carbon dioxide which contributes to global
warming.
Similarly, methane is also one big issue responsible for global warming.

124 | P a g e
125

After that, the excessive use of automobiles and fossil fuels results in increased levels
of carbon dioxide.
In addition, activities like mining and cattle rearing are very harmful to the environment.
One of the most common issues that are taking place rapidly is deforestation.

So, when one of the biggest sources of absorption of carbon dioxide will only disappear,
there will be nothing left to regulate the gas.

Thus, it will result in global warming. Steps must be taken immediately to stop global
warming and make the earth better again.
Global Warming Solutions
As stated earlier, it might be challenging but it is not entirely impossible.
Global warming can be stopped when combined efforts are put in.
For that, individuals and governments, both have to take steps towards achieving it.
We must begin with the reduction of greenhouse gas.
Furthermore, they need to monitor the consumption of gasoline.
Switch to a hybrid car and reduce the release of carbon dioxide.
Moreover, citizens can choose public transport or carpool together. Subsequently, recycling
must also be encouraged.
For instance, when you go shopping, carry your own cloth bag.

Another step you can take is to limit the use of electricity which will prevent the release of
carbon dioxide.

On the government’s part, they must regulate industrial waste and ban them from emitting
harmful gases in the air.
Deforestation must be stopped immediately and planting of trees must be encouraged.
In short, all of us must realize the fact that our earth is not well.
It needs to treatment and we can help it heal.
The present generation must take up the responsibility of stopping global warming in order
to prevent the suffering of future generations.
Therefore, every little step, no matter how small carries a lot of weight and is quite
significant in stopping global warming.

125 | P a g e
126

FAQs on Global Warming

Q.1 List the causes of Global Warming.

A.1 There are various causes of global warming both natural and manmade. The natural one
includes a greenhouse gas, volcanic eruption, methane gas and more. Next up, manmade
causes are deforestation, mining, cattle rearing, fossil fuel burning and more.
Q.2 How can one stop Global Warming?

A.2 Global warming can be stopped by a joint effort by the individuals and the government.
Deforestation must be banned and trees should be planted more. The use of automobiles
must be limited and recycling must be encouraged.

CO2 CAPTURE AND SEQUESTRATION:

What is carbon dioxide capture and sequestration?
Carbon dioxide (CO2) capture and sequestration (CCS) is a set of technologies that can
greatly reduce CO2 emissions from new and existing coal- and gas-fired power plants and
large industrial sources. CCS is a three-step process that includes:

 Capture of CO2 from power plants or industrial processes

 Transport of the captured and compressed CO2 (usually in pipelines).
 Underground injection and geologic sequestration (also referred to as storage) of the
CO2 into deep underground rock formations. These formations are often a mile or more
beneath the surface and consist of porous rock that holds the CO2. Overlying these
formations are impermeable, non-porous layers of rock that trap the CO2 and prevent it
from migrating upward.

What's the difference between carbon dioxide capture and sequestration (CCS) and
geologic sequestration?
 Geologic sequestration is one step in the CCS process.

 Unlike terrestrial, or biologic, sequestration, where carbon is stored via agricultural

and forestry practices, geologic sequestration involves injecting carbon dioxide deep
underground where it stays permanently.

 The figure below illustrates the general CCS process and shows a typical depth at
which CO2 would be injected.

Why is it important?

EPA's Greenhouse Gas Reporting Program (GHGRP) collects information from facilities in 41
industry types that directly emit large quantities of GHGs, suppliers of certain fossil fuels,
and facilities that inject CO2 underground.

126 | P a g e
127

 Carbon dioxide (CO2) capture and sequestration (CCS) could play an important role in
reducing greenhouse gas emissions, while enabling low-carbon electricity generation
from power plants.

 As estimated in the U.S. Inventory of Greenhouse Gas Emissions and Sinks, more than
40% of CO2 emissions in the United States are from electric power generation.

 CCS technologies are currently available and can dramatically reduce (by 80-90%)
CO2 emissions from power plants that burn fossil fuels.

 Applied to a 500 MW coal-fired power plant, which emits roughly 3 million tons of
CO2 per year,[1] the amount of GHG emissions avoided (with a 90% reduction
efficiency) would be equivalent to:

 Planting more than 62 million trees, and waiting at least 10 years for them to grow.
 Avoiding annual electricity-related emissions from more than 300,000 homes.

CCS could also viably be used to reduce emissions from industrial process such as cement
production and natural gas processing facilities.

What sources of carbon dioxide can it be applied to?

 Carbon dioxide (CO2) capture and sequestration (CCS) can significantly reduce
emissions from large stationary sources of CO2, which include coal- and natural-gas-
fired power plants, as well as certain industry types such as ethanol and natural gas
processing plants.

 EPA's Greenhouse Gas Reporting Program includes facilities that capture CO2 for the
purpose of supplying the CO2 to the economy or for injecting it underground
(Subpart PP).

 According to the Greenhouse Gas Reporting Program, CO2 capture is currently

occurring at over 120 facilities in the United States, mainly on industrial processes,
and the CO2 is used for a wide range of end uses.

 End uses of CO2 include enhanced oil recovery (EOR), food and beverage
manufacturing, pulp and paper manufacturing, and metal fabrication.

 The figure below shows the portion of CO2 that is currently being captured from
power plants and other industrial facilities and the portion that is extracted by
production wells from natural CO2 bearing formations in the United States.

 The second figure shows the various domestic end uses of captured and extracted
CO2. (Note that natural sources of CO2 are not considered in the Total CO2 Supply
End Uses figure).

127 | P a g e
128

 As CCS becomes more widespread, it is expected that the portion of CO2 captured in
the United States from power generation and industrial processes will increase.

Where can captured carbon dioxide be stored?

 After capture, carbon dioxide (CO2) is compressed and then transported to a site
where it is injected underground for permanent storage (also known as
"sequestration").

 CO2 is commonly transported by pipeline, but it can also be transported by train,

truck, or ship.

 Geologic formations suitable for sequestration include depleted oil and gas fields,
deep coal seams, and saline formations.

 The U.S. Department of Energy estimates that anywhere from 1,800 to 20,000 billion
metric tons of CO2 could be stored underground in the United States.[2]

 That is equivalent to 600 to 6,700 years of current level emissions from large
stationary sources in the United States.[3]

Overview of Geologic Storage Potential in the United States (Source: U.S. Department of
Energy, NATCARB)

 Potential sequestration sites must undergo appropriate site characterization to

ensure that the site can safely and securely store CO2.

128 | P a g e
129

 After being transported to the sequestration site, the compressed CO2 is injected
deep underground into solid, but porous rock, such as sandstone, shale, dolomite,
basalt, or deep coal seams.

 Suitable formations for CO2 sequestration are located under one or more layers of
cap rock, which trap the CO2 and prevent upward migration.

 These sites are then rigorously monitored to ensure that the CO2 remains
permanently underground.

 The safety and security of CO2 geologic sequestration is a priority for EPA.

ACID RAIN:

What is Acid Rain?

Acid rain, or acid deposition, is a broad term that includes any form of precipitation with
acidic components, such as sulfuric or nitric acid that fall to the ground from the
atmosphere in wet or dry forms. This can include rain, snow, fog, hail or even dust that is
acidic.

What Causes Acid Rain?

This image illustrates the pathway for acid rain in our environment:
(1) Emissions of SO2 and NOx are released into the air, where
(2) the pollutants are transformed into acid particles that may be transported long
distances.
(3) These acid particles then fall to the earth as wet and dry deposition (dust, rain, snow,
etc.) and (4) may cause harmful effects on soil, forests, streams, and lakes.
Acid rain results when sulfur dioxide (SO2) and nitrogen oxides (NOX) are emitted into the
atmosphere and transported by wind and air currents.

The SO2 and NOX react with water, oxygen and other chemicals to form sulfuric and nitric
acids.

These then mix with water and other materials before falling to the ground.

While a small portion of the SO2 and NOX that cause acid rain is from natural sources such as
volcanoes, most of it comes from the burning of fossil fuels.

The major sources of SO2 and NOX in the atmosphere are:

129 | P a g e
130

 Burning of fossil fuels to generate electricity. Two thirds of SO2 and one fourth of
NOX in the atmosphere come from electric power generators.
 Vehicles and heavy equipment.
 Manufacturing, oil refineries and other industries.
Winds can blow SO2 and NOX over long distances and across borders making acid rain a
problem for everyone and not just those who live close to these sources.

Forms of Acid Deposition

Wet Deposition
Wet deposition is what we most commonly think of as acid rain.

The sulfuric and nitric acids formed in the atmosphere fall to the ground mixed with rain,
snow, fog, or hail.

Dry Deposition
Acidic particles and gases can also deposit from the atmosphere in the absence of moisture
as dry deposition.

The acidic particles and gases may deposit to surfaces (water bodies, vegetation, buildings)
quickly or may react during atmospheric transport to form larger particles that can be
harmful to human health.

When the accumulated acids are washed off a surface by the next rain, this acidic water
flows over and through the ground, and can harm plants and wildlife, such as insects and
fish.

The amount of acidity in the atmosphere that deposits to earth through dry deposition
depends on the amount of rainfall an area receives.

For example, in desert areas the ratio of dry to wet deposition is higher than an area that
receives several inches of rain each year.

Measuring Acid Rain

 Acidity and alkalinity are measured using a pH scale for which 7.0 is neutral.
 The lower a substance's pH (less than 7), the more acidic it is; the higher a
substance's pH (greater than 7), the more alkaline it is.

130 | P a g e
131

 Normal rain has a pH of about 5.6; it is slightly acidic because carbon dioxide (CO2)
dissolves into it forming weak carbonic acid.
 Acid rain usually has a pH between 4.2 and 4.4.

 Policymakers, research scientists, ecologists, and modelers rely on the National

Atmospheric Deposition Program’s (NADP) National Trends Network (NTN) for
measurements of wet deposition.
 The NADP/NTN collects acid rain at more than 250 monitoring sites throughout the
US, Canada, Alaska, Hawaii and the US Virgin Islands.
 Unlike wet deposition, dry deposition is difficult and expensive to measure.
 Dry deposition estimates for nitrogen and sulfur pollutants are provided by the Clean
Air Status and Trends Network (CASTNET). Air concentrations are measured by
CASTNET at more than 90 locations.
 When acid deposition is washed into lakes and streams, it can cause some to turn
acidic.
 The Long-Term Monitoring (LTM) Network measures and monitors surface water
chemistry at over 280 sites to provide valuable information on aquatic ecosystem
health and how water bodies respond to changes in acid-causing emissions and acid
deposition.

The Effects of Acid Rain on Ecosystems

 This figure illustrates the pH level at which key organisms may be lost as their
environment becomes more acidic.
 Not all fish, shellfish, or the insects that they eat can tolerate the same amount of
acid.

 An ecosystem is a community of plants, animals and other organisms along with

their environment including the air, water and soil.
 Everything in an ecosystem is connected.
 If something harms one part of an ecosystem – one species of plant or animal, the
soil or the water – it can have an impact on everything else.

Effects of Acid Rain on Fish and Wildlife

 The ecological effects of acid rain are most clearly seen in aquatic environments,
such as streams, lakes, and marshes where it can be harmful to fish and other
wildlife.
 As it flows through the soil, acidic rain water can leach aluminum from soil clay
particles and then flow into streams and lakes.
 The more acid that is introduced to the ecosystem, the more aluminum is released.
 Some types of plants and animals are able to tolerate acidic waters and moderate
amounts of aluminum.
 Others, however, are acid-sensitive and will be lost as the pH declines. Generally, the
young of most species are more sensitive to environmental conditions than adults.

131 | P a g e
132

 At pH 5, most fish eggs cannot hatch. At lower pH levels, some adult fish die. Some
acidic lakes have no fish.
 Even if a species of fish or animal can tolerate moderately acidic water, the animals
or plants it eats might not.
 For example, frogs have a critical pH around 4, but the mayflies they eat are more
sensitive and may not survive pH below 5.5.

Effects of Acid Rain on Plants and Trees

 Dead or dying trees are a common sight in areas effected by acid rain. Acid rain
leaches aluminum from the soil.
 That aluminum may be harmful to plants as well as animals.
 Acid rain also removes minerals and nutrients from the soil that trees need to grow.
 At high elevations, acidic fog and clouds might strip nutrients from trees’ foliage,
leaving them with brown or dead leaves and needles.
 The trees are then less able to absorb sunlight, which makes them weak and less
able to withstand freezing temperatures.

Buffering Capacity

 Many forests, streams, and lakes that experience acid rain don’t suffer effects
because the soil in those areas can buffer the acid rain by neutralizing the acidity in
the rainwater flowing through it.
 This capacity depends on the thickness and composition of the soil and the type of
bedrock underneath it.
 In areas such as mountainous parts of the Northeast United States, the soil is thin
and lacks the ability to adequately neutralize the acid in the rain water.
 As a result, these areas are particularly vulnerable and the acid and aluminum can
accumulate in the soil, streams, or lakes.

Episodic Acidification

 Melting snow and heavy rain downpours can result in what is known as episodic
acidification.
 Lakes that do not normally have a high level of acidity may temporarily experience
effects of acid rain when the melting snow or downpour brings greater amounts of
acidic deposition and the soil can’t buffer it.
 This short duration of higher acidity (i.e., lower pH) can result in a short-term stress
on the ecosystem where a variety of organisms or species may be injured or killed.

132 | P a g e
133

Nitrogen Pollution

It’s not just the acidity of acid rain that can cause problems.

Acid rain also contains nitrogen, and this can have an impact on some ecosystems.

For example, nitrogen pollution in our coastal waters is partially responsible for declining
fish and shellfish populations in some areas.

In addition to agriculture and wastewater, much of the nitrogen produced by human

activity that reaches coastal waters comes from the atmosphere.

Effects of Acid Rain on Materials

 Not all acidic deposition is wet.

 Sometimes dust particles can become acidic as well, and this is called dry deposition.
 When acid rain and dry acidic particles fall to earth, the nitric and sulfuric acid that
make the particles acidic can land on statues, buildings, and other manmade
structures, and damage their surfaces.
 The acidic particles corrode metal and cause paint and stone to deteriorate more
quickly.
 They also dirty the surfaces of buildings and other structures such as monuments.

The consequences of this damage can be costly:

 damaged materials that need to be repaired or replaced,

 increased maintenance costs, and
 loss of detail on stone and metal statues, monuments and tombstones.

Other Effects of SO2 and NOX

Visibility
In the atmosphere, SO2 and NOX gases can be transformed into sulfate and nitrate particles,
while some NOX can also react with other pollutants to form ozone.

These particles and ozone make the air hazy and difficult to see through. This affects our
enjoyment of national parks that we visit for the scenic view such as Shenandoah and the
Great Smoky Mountains.

Human Health
 Walking in acid rain, or even swimming in a lake affected by acid rain, is no more
dangerous to humans than walking in normal rain or swimming in non-acidic lakes.

133 | P a g e
134

 However, when the pollutants that cause acid rain —SO2 and NOX, as well as sulfate
and nitrate particles— are in the air, they can be harmful to humans.
 SO2 and NOX react in the atmosphere to form fine sulfate and nitrate particles that
people can inhale into their lungs.
 Many scientific studies have shown a relationship between these particles and
effects on heart function, such as heart attacks resulting in death for people with
increased heart disease risk, and effects on lung function, such as breathing
difficulties for people with asthma.

BLACK CARBON:

WHAT IS BLACK CARBON?

 Black carbon, or soot, is part of fine particulate air pollution (PM2.5) and contributes
to climate change.

 Black carbon is formed by the incomplete combustion of fossil fuels, wood and other
fuels.

 Complete combustion would turn all carbon in the fuel into carbon dioxide (CO2), but
combustion is never complete and CO2, carbon monoxide, volatile organic
compounds, and organic carbon and black carbon particles are all formed in the
process.
 The complex mixture of particulate matter resulting from incomplete combustion is
often referred to as soot.

 Black carbon is a short-lived climate pollutant with a lifetime of only days to weeks
after release in the atmosphere.

 During this short period of time, black carbon can have significant direct and indirect
impacts on the climate, the cryosphere (snow and ice), agriculture and human
health.

 Several studies have demonstrated that measures to prevent black carbon emissions
can reduce near-term warming of the climate, increase crop yields and prevent
premature deaths.

134 | P a g e
135

K E Y F IG URE S

460-1,500x 4–12 days 6.6 million 51%

tonnes

Black carbon has a The average About 6.6 Household cooking

warming impact on atmospheric lifetime million tonnes of and heating account
climate 460-1,500 of black carbon black carbon for 51% of global
times stronger than particles is 4-12 days were emitted in black carbon
CO2 per unit of mass 2015 emissions

PRIMARY SOURCES OF BLACK CARBON EMISSIONS

 Black carbon emissions have been decreasing over the past decades in many
developed countries due to stricter air quality regulations.

 By contrast, emissions are increasing rapidly in many developing countries where air
quality is not regulated.

 As the result of open biomass burning and residential solid fuel combustion, Asia,
Africa and Latin America contribute approximately 88% of global black carbon
emissions.

 Black carbon is always co-emitted with other particles and gases, some of which
have a cooling effect on the climate.

 The type and quantity of co-pollutants differs according to the source.

 Sources that release a high ratio of warming to cooling pollutants represent the most
promising targets for mitigation and achieving climate and health benefits in the
near term.

BLACK CARBON IMPACTS

C LI MA T E I MPA CT S
 Black carbon is an important contributor to warming because it is very effective at
absorbing light and heating its surroundings.

 Per unit of mass, black carbon has a warming impact on climate that is 460-1,500
times stronger than CO2.

 When suspended in the atmosphere, black carbon contributes to warming by

converting incoming solar radiation to heat.

135 | P a g e
136

 It also influences cloud formation and impacts regional circulation and rainfall
patterns.

 When deposited on ice and snow, black carbon and co-emitted particles reduce
surface albedo (the ability to reflect sunlight) and heat the surface.

 The Arctic and glaciated regions such as the Himalayas are particularly vulnerable to
melting as a result.

HE A LT H I MPA CT S
Black carbon and its co-pollutants are key components of fine particulate matter (PM2.5) air
pollution, the leading environmental cause of poor health and premature deaths.
At 2.5 micrometres or smaller in diameter, these particles are, many times smaller than a
grain of table salt, which allows them to penetrate into the deepest regions of the lungs and
facilitate the transport of toxic compounds into the bloodstream.
PM2.5 has been linked to a number of health impacts including premature death in adults
with heart and lung disease, strokes, heart attacks, chronic respiratory disease such as
bronchitis, aggravated asthma and other cardio-respiratory symptoms.
It is also responsible for premature deaths of children from acute lower respiratory
infections such as pneumonia.
Each year, an estimated 7 million premature deaths are attributed to household and
ambient (outdoor) PM2.5 air pollution.

I MPA C T S O N VE G ETA T IO N A ND E CO SYST E MS

Black carbon can affect the health of ecosystems in several ways: by depositing on plant
leaves and increasing their temperature, dimming sunlight that reaches the earth, and
modifying rainfall patterns.

Changing rain patterns can have far-reaching consequences for both ecosystems and human
livelihoods, for example by disrupting monsoons, which are critical for agriculture in large
parts of Asia and Africa.

SOLUTIONS
Black carbon’s short atmospheric lifetime, combined with its strong warming potential,
means that targeted strategies to reduce emissions can provide climate and health benefits
within a relatively short period of time.

The Coalition supports implementation of control measures that, if globally implemented by

2030, could reduce global black carbon emissions by as much as 80% (UNEP & WMO 2011).

136 | P a g e
137

Several of these emission reductions could be achieved with net cost savings. Adopting
these measures would have major positive co-benefits for public health, especially in the
developing world.

BLACK CARBON - 70% emissions reduction potential globally by 2030

HOUSEHOLD  Replace traditional cooking to clean burning modern fuel cookstoves
ENERGY  Replace traditional cooking and heating with clean-burning biomass
stoves
 Eliminate kerosene lamps
 Replace lump coal with coal briquettes for cooking and heating
 Replace wood stove and burners with pellet stoves and boilers
INDUSTRIAL  Modernize traditional brick kilns to vertical shaft brick kilns
PRODUCTION  Modernize coke ovens to recovery ovens

TRANSPORT  Use diesel particular filters for road and off-road vehicles
 Fast transition to Euro VI/6 vehicles and soot-free buses and trucks
 Eliminate high-emitting diesel vehicles
AGRICULTURE  Ban open-field burning of agricultural waste
FOSSIL FUELS  Capture and improve oil flaring and gas production
WASTE  Ban open burning of municipal waste
MANAGEMENT

AIR QUALITY PARAMETERS DETERMINATION:

What Is Air Quality Index, How Is It Measured And Its

Health Impact:

Eight pollutants namely particulate matter (PM) 10, PM2.5, Ozone (O3), Sulphur dioxide
(SO2), nitrogen dioxide (NO2), carbon monoxide (CO), lead (Pb) and ammonia (NH3) act as
major parameters in deriving the AQI of an area

What is Air Quality Index?

AQI is the air quality index; it gives you the index value that what is
the current pollution status in the city, how polluted the air currently
is. Different levels of AQI symbolises different things like on
prolonged exposure to ‘poor’ AQI, individuals might witness
breathing problem, says Shambhavi Shukla, Senior Research
Associate at Centre for Science and Environment.

137 | P a g e
138

How Is AQI Measured?

Eight pollutants namely particulate matter (PM) 10, PM2.5, Ozone (O3), Sulphur dioxide
(SO2), nitrogen dioxide (NO2), carbon monoxide (CO), lead (Pb) and ammonia (NH3) act as
major parameters in deriving the AQI of an area.

Short-term (upto 24-hours and 8-hours for CO and O3) National Ambient Air Quality
Standards are prescribed for these pollutants.

There are eight pollutants whose concentration is measured and then

based on the ambient concentrations, corresponding standards and
likely health impact, a sub-index is calculated for each of these
pollutants.

The worst sub-index determines the overall AQI for the city and the
pollutant whose sub-index is the worst becomes the prominent
pollutant, explains Ms Shukla.

As per CPCB’s (Central Pollution Control Board) air quality standards, AQI is categorised into
six parts. AQI between 0-50 is considered ‘good’, 51-100 ‘satisfactory’, 101-200 ‘moderate’,
201-300 ‘poor’, 301-400 ‘very poor’, and between 401-500 ‘severe’.

138 | P a g e
139

Different levels of air quality index and what they mean

All the eight pollutants may not be monitored at all the locations.
Overall AQI is calculated only if data is available for a minimum three
pollutants out of which one should necessarily be either PM2.5 or
PM10.

Similarly, a minimum of 16 hours of data is considered necessary for

calculating sub-index, says Anumita Roy Chowdhury, CSE.

As the AQI value increases, health impacts become serious. For instance, while under
satisfactory AQI, sensitive people might witness minor breathing discomfort, severe AQI
may cause respiratory impact even on healthy people, and serious health issue in people
with existing respiratory issues.

How Do Different Pollutants Affect The Human Body?

PM10 gets filtered at the top of your respiratory system that is nose.
PM2.5 is the hazardous of the lot.

70-80 per cent of the health issues are caused by PM2.5 only as it
crosses body’s natural barriers, and enter the lungs.

Ozone is the second most dangerous parameter as it aggravate lung

diseases such as asthma, emphysema, and chronic bronchitis, IIT
Kanpur Scientist and Professor, Sachchida Nand Tripathi.

Other gases too lead to cardiovascular diseases like heart attack and pulmonary diseases
such as asthma.

139 | P a g e
140

The problem is, air pollution masks and purifiers currently we have, do not protect you from
gases. The only way to evade from these gases is to control their sources.

What are the three main factors that determine air quality?
When studying air quality, it is important to measure the following factors as they can help
us understand the chemical reactions that occur in the atmosphere:
 wind speed and direction.
 temperature.
 humidity.
 rainfall.
 solar radiation

UNIT – 4 SOIL CHEMISTRY

NATURE AND COMPOSITION OF SOIL

140 | P a g e
141

141 | P a g e
142

142 | P a g e
143

RELATIVE AVAILABILITIES OF PLANT NUTRIENTS IN SOIL AS AFFECTED BY Ph:

Soil pH and Nutrient Availability

 The desirable soil pH range for optimum plant growth varies among crops.

 Generally, soil pH 6.0-7.5 is acceptable for most plants as most nutrients become
available in this pH range.

 Soil pH can be determined by mixing soil sample with water and then measuring the
resulting aqueous solution.

143 | P a g e
144

Introduction
 Soil pH is a measure of the acidity or alkalinity in soils. In the pH scale, pH 7.0 is
neutral.

 Below 7.0 is acidic and above 7.0 is basic or alkaline.

 Soil pH affects nutrients available for plant growth. In highly acidic soil, aluminum
and manganese can become more available and more toxic to plant while calcium,
phosphorus, and magnesium are less available to the plant.

In highly alkaline soil, phosphorus and most micronutrients become less available.

When designing or planting new garden or landscape, it is helpful to check the soil pH as
different plants thrive in different soil pH ranges.

pH determination can give indication whether soil is suitable for the plants to be grown or it
needs to be adjusted to produce optimum plant growth.

Soil pH can be measured easily and inexpensively at home or on-site using LAQUAtwin pH
meters.

There are three (3) LAQUAtwin pH meter models available, namely pH 11, 22, and 33. These
pocket-sized compact meters allow two to five calibration points using either NIST or USA
pH buffers.

Among the above-mentioned models, the pH 33 meter has built-in temperature sensor that
measures and displays temperature reading and automatic temperature compensation
feature (ATC) that performs automatic calibration to the exact pH of the buffer at the
measured temperature.

Refer to the specifications of each meter model for more information.

144 | P a g e
145

Method
Calibrate the LAQUAtwin pH meter according to manufacturer’s instructions using at least
two pH buffers that bracket the expected sample pH.

Sample Preparation And Measurement


The method described below is based on US EPA Method 9045D. This is also
applicable for measuring pH of waste samples, which may be solids, sludges, or non-
aqueous liquids. If water is present, it must constitute less than 20% of the total
volume of the sample.
 Add 20ml of pure water to 20g sample in a beaker or container. Stir for 5 minutes
then cover.
Let the soil suspension stand for about 1 hour. Alternatively, filter or centrifuge off
the water phase.
Measure the pH of water phase. Record the pH value and the temperature.
 To obtain accurate results, standard buffer solutions and samples should be
measured at the same temperature. If the electrode is coated with oily material from
a sample, clean it with detergent and warm water.

Results and Benefits

 The desirable soil pH range for optimum plant growth varies among crops.

 Generally, soil pH 6.0-7.5 is acceptable for most plants as most nutrients become
available in this pH range.

 Soil pH is important because it affects the availability of nutrients to plants.

 Nitrogen, phosphorus, and potassium are the primary nutrients needed in fairly large
quantities. Calcium, magnesium, and sulfur are secondary nutrients required by the
plant in lesser quantities.

 Zinc and manganese are micronutrients required by the plant in very small amounts.
Most secondary and micronutrient deficiencies are easily corrected by keeping the
soil at the optimum pH value.

Soil pH also affects activity of soil microorganisms.

The population of bacteria that decompose organic matter declines and their activity is
hindered in highly acidic soil, which results in accumulation of organic matter and the bound
nutrients, particularly nitrogen.

145 | P a g e
146

Increasing Soil pH

Applying a material that contains some form of lime (calcium carbonate) like the ground
agricultural limestone and wood ashes can increase the soil pH.

The finer the limestone, the more rapid it becomes effective.

Different soils will require a different amount of lime to adjust the soil pH. Wood ashes
contain high amounts of potassium and calcium, and small amounts of phosphate, boron
and other nutrients.

Although not as effective as limestone, these can drastically increase the soil pH with
repeated use.

Decreasing Soil pH
Aside from ammonium-based fertilizers and organic matter, aluminum sulfate and sulfur
are common materials used for decreasing soil pH.

Aluminum sulfate is preferred as it changes the soil pH as soon as it dissolves in the soil
because of the aluminum. However, too much of this is toxic to plant.

Sulfur takes some time to produce effect as it needs to be converted to sulfuric acid by soil
bacteria.

ORGANIC AND INORGANIC COMPONENTS OF SOIL:

Soil is a mixture of organic and inorganic constituents.

The inorganic components come from the weathering of various rock types.

Organic particles are the result of both plants and animals inhabiting the area.

While some soil has only one particle type, the most fertile soil is a mixture of several
organic and inorganic components.

Inorganic Sand

Sand is a medium to coarse-grained sediment that is visible to the naked eye.

Sand particles range in size from 0.05 millimeters to 2.0 millimeters and consist of pieces
of weathered rock, such as quartz, magnetite or other mineral or shell fragments.

Sand in your garden soil will help promote good drainage and aeration of the area.

However, sand alone will not retain significant amounts of moisture to support plant
growth. In addition, sand does not contain nutrients that promote healthy plants.

146 | P a g e
147

Inorganic Silt

Silt is a fine-grained sediment that you cannot see with the naked eye.

Silt is larger than clay and smaller than sand and may feel gritty between your fingers.

Silt particles range from 0.002 millimeters to 0.05 millimeters. Like sand, silt results from
the weathering of rocks and consists of grains of quartz, feldspar and other minerals.

Silt-rich soil will retain moisture for plant growth, but at times, it can limit drainage and
make the soil difficult to till.

Silt itself does not contain plant nutrients; however, existing nutrients in the area may
adhere to the surface of the silt particles in the garden soil.

Inorganic Clay

Clay is another fine-grained sediment that is smaller than silt.

Clay particles are smaller than 0.002 millimeters and result from significant weathering of
rocks. Minerals, such as feldspars, degrade over time to form clay.

Like silt, clay-rich soil will retain moisture for plant growth and may limit drainage in the
area.

You can amend fine-grained soils with sand and organic matter to improve the drainage
quality of the area. Unlike sand and silt, the aluminum-silicate minerals that degrade to
clay will provide important plant nutrients such as iron, calcium, magnesium and
potassium.

Existing nutrients will cling to the clay soil particles and help to feed plant growth in the
root area.

Organic Matter

Organics in soil are due to the presence and decomposition of plant and animal matter in
the area.

Humus, a partially decomposed organic matter, is a common form of organics in garden

soil that will continue to decompose over time.

While the percent of organic matter in most topsoil is only 2 to 4 percent, it plays an
important role in the garden.

Organic matter is good for promoting aeration, drainage and soil moisture retention in the
soil.

147 | P a g e
148

The organic matter also reduces erosion and supplies plant nutrients such as sulfur,
phosphorous and nitrogen to the plant’s root zone.

The organics will also help to reduce the threat of plant disease in the garden by
promoting a healthy growing environment.

CATION EXCHANGE CAPACITY:

Cation exchange capacity

Cation exchange capacity (CEC) is a useful indicator of soil fertility because it shows the soil's
ability to supply three important plant nutrients: calcium, magnesium and potassium.

Cations
What CEC actually measures is the soil's ability to hold cations by electrical attraction.
Cations are positively charged elements, the positive charge indicated by a + sign after the
element symbol.

The number of + signs indicates the amount of charge the element possesses.
The five most abundant exchangeable cations in the soil are calcium (Ca++ ), magnesium (Mg++),
potassium (K+), sodium (Na+) and aluminium (Al+++).

Cations are held by negatively charged particles of clay and humus called colloids.
Colloids consist of thin, flat plates, and for their size have a comparatively large surface area.
For this reason they are capable of holding enormous quantities of cations. They act as a
storehouse of nutrients for plant roots.

As plant roots take up cations, other cations in the soil water replace them on the colloid.

If there is a concentration of one particular cation in the soil water, those cations will force
other cations off the colloid and take their place.

The stronger the colloid's negative charge, the greater its capacity to hold and exchange
cations, hence the term cation exchange capacity (CEC).

CEC measurement
Concentrations of cations are expressed in centimoles of positive charge per kilogram of soil
(cmol(+)/kg).
This measurement is equivalent to the previously used unit me/100 g.

Adding the concentrations of each cation gives you an estimate of the CEC figure.
A figure above 10 cmol(+)/kg is preferred for plant production.

Soils with high levels of swelling clay and organic matter can have a CEC of 30 cmol(+)/kg or
more.

The five exchangeable cations are also shown in soil test results as percentages of CEC.

148 | P a g e
149

The desirable ranges for them are: calcium 65–80% of CEC, magnesium 10–15%, potassium 1–
5%, sodium 0–1% and aluminium 0%.

pH and CEC
Soil pH is important for CEC because as pH increases (becomes less acid), the number of
negative charges on the colloids increase, thereby increasing CEC.

CEC levels
Humus
CEC varies according to the type of soil. Humus, the end product of decomposed organic
matter, has the highest CEC value because organic matter colloids have large quantities of
negative charges.

Humus has a CEC two to five times greater than montmorillonite clay and up to 30 times
greater than kaolinite clay, so is very important in improving soil fertility.

Clay
Clay has a great capacity to attract and hold cations because of its chemical structure.

However, CEC varies according to the type of clay.

It is highest in montmorillonite clay, found in chocolate soils and black puggy alluvials.

It is lowest in heavily weathered kaolinite clay, found in krasnozem soils, and slightly higher in
the less weathered illite clay.

Low CEC values can be improved by adding organic matter.

Sand
Sand has no capacity to exchange cations because it has no electrical charge.

This means sandy soils such as podzolic topsoils have very low CEC, but this can be improved by
adding organic matter.

Aluminium and sodium

Aluminium (Al+++) and sodium (Na++) cations are not plant nutrients, so are not wanted by the
plant.

Aluminium is not present as a cation when soil pH (CaCl2) is over 5 because it is precipitated out
of the soil solution

. It is only at pH (CaCl2) levels below 5 that it may become available as a cation, and under 4.5
may become available in toxic levels, displacing other cations from the clay or humus colloids.

149 | P a g e
150

This is one reason why it is important to maintain pH levels at 5.0 or more.

When exchangeable sodium is present in quantities greater than about 5% of the CEC, it makes
the clay particles unstable in rainwater.

This shows up as dispersion or cloudiness in water.

Dispersive soils have poor water entry and drainage and set hard on drying.

Leaching
If a soil has a low CEC and high sodium levels, up to half the cations in the soil may be in the
water around the soil particles, and not actually held by the particles.

These cations are very susceptible to being leached or drained away in the soil water.

Soils with a high CEC have a much lower percentage of cations in the soil water, so are far less
susceptible to nutrient loss by leaching.

Improving CEC
You can improve CEC in weathered soils by adding lime and raising the pH.

Otherwise, adding organic matter is the most effective way of improving the CEC of your soil.

This can be done with permanent pasture, regular slashing, green manure crops, leaving crop
stubbles to rot, rotating crops or pasture, and the addition of mulch and manure.

Calculating Cation Exchange Capacity, Base Saturation, and Calcium Saturation

The purpose of this fact sheet is to define soil cation exchange capacity, base
saturation and calcium saturation, and demonstrate how these values are calculated in
soil test reports.

Cation Exchange Capacity (CEC)

Cation exchange capacity (CEC) is a fundamental soil property used to predict plant
nutrient availability and retention in the soil.

It is the potential of available nutrient supply, not a direct measurement of available

nutrients.
Soil CEC typically increases as clay content and organic matter incre ase because cation
exchange occurs on surfaces of clay minerals, organic matter, and roots.

Soils in Ohio can encompass a wide CEC range, but typically fall somewhere between 5
to 25 meq/100 g soil (Table 1).

Values over 25 meq/100 g soil are found with heavy clay soils, organic, or muck soils.

150 | P a g e
151

Table 1. The relationship between soil

texture and CEC

Typical
Soil Texture CEC (meq/100 g
soil)

Sands 3-5

Loams 10-15

Silt loams 15-25

Clay and clay loams 20-50

Organic soils 50-100

Cation exchange capacity is defined as a soil’s total quantity of negative surface

charges.
It is measured commonly in commercial soil testing labs by summing cations (positively
charged ions that are attracted to the negative surface charges in soil).
Exchangeable cations include base cations, calcium (Ca 2+), magnesium (Mg 2+),
potassium (K +) and sodium (Na +), as well as acid cations such as hydrogen (H +),
aluminum (Al 3+) and ammonium (NH 4+).

CEC = Base cations + Acid cations

(Ca 2+ + Mg2+ + K+ + Na+) + (H+ + Al 3+ + NH4 +)

Figure 1 illustrates a low CEC soil, with a small number of negative charges and
associated cations (left) and a high CEC soil with a larger amount of negative charges,
occupied by a greater number of total cations (right).

Base Saturation

Base saturation is calculated as the percentage of CEC occupied by base cations.

Figure 2 shows two soils with the same CEC, but the soil on the right has more base
cations (in blue).

Therefore, it has a higher base saturation. Base saturation is closely related to pH; as
base saturation increases, pH increases.

Base Saturation (%) = (Base cations/CEC) x 100x 100

151 | P a g e
152

Similarly, we can calculate the base saturation for each individual base cation.
Calcium base saturation is calculated as the percentage of CEC occupied by calcium
cations. In Figure 2, the soil on the right has twice as many calcium cations (Ca2+), thus
a higher calcium saturation.

Calcium Saturation (%) = (Calcium cations/CEC) x 100x 100

Calculating CEC from a Soil Test

CEC is reported as milliequivalents per 100 grams of soil (meq/100g), or charge per
weight of soil.

Milliequivalents are used instead of weight because charge is more useful when talking
about ion exchange.

So, how do we take the concentration of nutrients in a soil test (ppm) and convert to
charges (meq/100g soil)?
Soil testing laboratories often provide these values already on the soil test report, or
will provide them upon request. However, to gain a better understanding of the
relationships, the steps to perform these calculations are outlined below.

Step 1: Determine the gram equivalent weight of each base cation. Each base cation
has an atomic weight and valence number (charge) in the periodic table of elements.
Figure 3 shows the base cations. For calcium, the atomic weight is ~40 grams per mole
and the charge is 2. We divide each atomic weight (40) by the charge (2) to calculate
the gram equivalent weight (20). The value for each base cation is outlined in Table 2.

Figure 3. Basic cations from the periodic

table.
Step 2. Convert gram equivalent weight into charge per weight of soil (meq/100g
soil).
equivalent×1000 milliequivalent1 equivalent×1100 g soil=10 meq g soilequivalent×1000 milli
equivalent1 equivalent×1100 g soil=10 meq g soil
Step 3. Multiply the gram equivalent weight by 10 to convert to meq/100g of soil.
Again, for calcium, the gram equivalent weight of 20 grams multiplied by 10 gives us
200 meq/100 g soil.

This meq/100g soil value is used as a conversion factor for the nutrient concentration
values (ppm) received in a soil test.

152 | P a g e
153

The bolded values in the last column in Table 2 can be used as a conversion factor each
time and will not change.
Table 2. The meq/100g soil constants for the base cations Ca, Mg, K, and Na.

Atomic Charge Gram Equivalent Milliequivalent/ 100 g

Base Cation
Weight (Valence) Weight (g) soil

Calcium (Ca) 40 2 20 200

Magnesium
24 2 12 120
(Mg)

Potassium (K) 39 1 39 390

Sodium (Na) 23 1 23 230

Step 4. Convert soil test nutrient concentration to charge.

Table 3 provides an example of typical soil test levels in Ohio (in ppm).

We can calculate the collective charge each cation occupies on the exchange sites by
taking the values calculated in Table 2 (last column) and dividing them by the soil test
levels.

For calcium, a soil test level of 2000 ppm, divided by 200 equals 10.0 meq/100 g soil.
This is done for each cation individually.

Step 5. Calculate collective charge from base cations.

Next, we add up the charges of each base cation. For this example, the sum of base
cations equals 12.4 meq/100g soil (Table 3).

Step 6. Calculate exchangeable acidity, using the buffer pH with the empirically
derived conversion equation (Table 3).

If the soil has a pH greater than 7.0, you essentially have no exchangeable acidity and
CEC is just the sum of base cations.
A soil with a buffer pH of 6.6 indicates that acidic cations occupy 4.8 meq per 100
grams of soil.

153 | P a g e
154

Table 3. Conversion of soil test values (ppm) to meq/100 g soil for base and acid cations
to determine CEC.

Soil test level

Base Cation Milliequivalent/ 100 g soil meq/100 g soil
(ppm)

Calcium (Ca2+) 2000 200 10.0

Magnesium (Mg2+) 240 120 2.0

Potassium (K+) 100 390 0.26

Sodium (Na+) 20 230 0.09

Subtotal 12.4

meq/ 100 g
Acid Cation Buffer pH Conversion Equation
soil

Exchangeable acidity (H+, Al3+,

6.6 12 x (7.0 – 6.6) 4.8
NH4+)

*If soil test values are in pound per acre, then first convert pound per acre to ppm by
dividing soil test values by 2.

**If buffer pH is 7 or above, then you have no exchangeable acidity (CEC = sum of base
cations).

Step 7. Calculate CEC by adding the base cations and acid cations:
Cation exchange capacity (CEC) = Base cations + Acid cations
=12.4 + 4.8=12.4 + 4.8

= 17.2 meq/100 g
With CEC, we can calculate the following (multiplying by 100 to get a percentage):

Base Saturation (%) = (Base cations/CEC) x 100x 100

= (12.4/17.2) x 100x 100
= 72%
Calcium Saturation (%) = (Calcium cations/CEC) x 100x 100
= (10/17.2) x 100x 100
= 58%
Magnesium Saturation (%) = (Magnesium cations/CEC) x 100x 100
= (2.0/17.2) x 100x 100
= 12%

154 | P a g e
155

Summary

Cation exchange capacity and base saturation are important soil measurements that
help determine how a soil is managed and fertilized.

While standard soil testing laboratories commonly calculate and report these values in
soil test reports, it is helpful to have a solid understanding of CEC and base saturation
calculations.

ION EXCHANGE REACTION IN SOIL:

9.1 INTRODUCTION

Soil colloids are the seat of reaction. Ion exchange (cation and anions) takes place in colloids.
The phenomenon of ion exchange is of great importance in agriculture.
It has considerable influence on the liberation of plant nutrients such as Ca, K, P etc. It controls
soil structure and crumb formation.
It is also responsible for imparting a stable structure. It controls the processes plays an
important role in the reclamation of acid and alkali soils.
It also influences the effect of fertilizers and fertilizer practices.
Ion exchange is two types:

(1) cation exchange or base exchange and

(2) anion exchange or acid exchange.

Ion exchange is a reversible process in which cation and anion exchanged between solid and
liquid phase.

9.2 CATION EXCHANGE OR BASE EXCHANGE

In a near neutral soil, Ca is remaining adsorbed on colloidal particle H ion generated as organic
and mineral acid formed due to decomposition of organic matter.

In colloid, H ion is adsorbed more strongly than is the Ca and H is chemically equivalent.

The reaction is as follow:

This phenomenon of the exchange of cations between soil and salt solution is known as calion
exchange or Base Exchange and the cations that take part in this reaction are
called exchangeable cations.

155 | P a g e
156

It is the interchange between a cation in solution and another cation on the surface of clay or
organic matter (colloids).

Thompson and Way (1892) first recognised cation exchange phenomenon.

They passed a solution of (NH4)2SO4 through a soil column and found that effluent contained
no NH4- salt but CaSO4.

This phenomenon is always in equivalent quantities of ions.

A. Types of silicate clay mineral

In case of kaolinite, monovalent cations are more strongly held than divalent, while in case of
montmorillonite, divalent cations are strongly held than monovalent cations.

The normal order of adsorbed cations on clay particles is:

H+ > Al+3 > Ca +2 = Mg+2 > K+ = NH4+> Na+.

B. Significance of cation exchange

Cation exchange is an important reation in soil fertility, in causing and correcting soil acidity
and basicity.

In changes altering soil physical properties, and as a mechanism in purifying or altering

percolating Waters.

The plant nutrients like calcium, magnesium and potassium are supplied to plants in large
measure from exchangeable forms.

Cation exchange is very important in soils because of the following relationships:

(l) The exchangeable K is a major source of plant K.

(2) The exchangeable Mg is often, a major source of plant Mg.

(3) The amount of lime required to raise the pH of an acidic soil is greater as the CEC is greater.

(4) Cation exchange sites hold Ca+2, Mg+2, K+, Na+ and NH4+ ions and slow down their losses by
leaching.

156 | P a g e
157

(5) Cation exchange sites hold- fertilizer K+ and NH4+ and greatly reduces their mobility in
soils.

(6) Cation exchange sites adsorb many metals (Cd+2, Zn+2, Ni+2 and Pb+2) that might be present
in wastewater. Adsorption removes them from the percolating water, thereby cleansing the
water that drains into groundwater.

9.3 Anion exchange

The process of anion exchange is similar to that of cation exchange.

Under certain conditions hydrous oxides of iron and aluminium shows evidence of having
positive charges on their crystal surfaces.

The positive charges of colloids are due to addition of hydrogen (H+) in hydroxyl group (OH-)
resulted in net positive charge (OH2+).

This positive charge will attract anions. The capacity for holding anions increases with increase
in acidity.

The lower the pH the greater is the adsorption. All anions are not adsorbed equally readily.

Some anions such as H2PO4 are adsorbed very quickly at all pH values in the acid as well as
alkaline range, Cl- and SO4-- ions are adsorbed slightly at low pH but none at neutral soil, while
NO3- ions are not adsorbed at all.

Hence, at the pH commonly prevailing in cultivated soils- nitrate (NO3), chloride (Cl) and
sulphate (SO4) ions are easily lost by leaching. In general, the relative order of anion exchange
is:

OH- > H2PO4-> SO4- > NO3-

This adsorbed negatively changed anion is replaceable as under:

In this way there is fixation of phosphate ion, in which OH ion of silicate clay mineral is
substitute by H2PO4 ion by isomorphrous substitution.

The H2PO4 ion becomes a part of the silicate clay minerals and the phosphate fixed by this
way is known as colloid bound phosphate.

157 | P a g e
158

This phosphate is not exchangeable and available to the plant. The anions like NO3 and OH
are not bound at pH above 7. The adsorbing power of anions is in the order of:

Importance of anion exchange in nutrient availability

The phenomenon of anion exchange assumes in relation to phosphate ions and their fixation.

The exchange is brought mainly by the replacement of OH ions of the clay minerals.

The adsorption of phosphate ions by clay particles from soil solution reduces its availability to
plants.

This is also known as colloid bound phosphate fixation.

The phosphate ion again becomes available when lime is applied to increase the pH of acidic
soil.

The OH ion originated not only from silicate clay minerals but also from hydrous oxides of iron
and aluminum present in the soil.

The phosphates ions react with the hydrous oxides also get fixed forming insoluble hydroxyl
phosphate of ion and aluminum. Which is called saloid bound phosphate.

If the reaction takes place at a low pH under strongly acid conditions, the phosphate ions are
irreversibly fixed and are totally unavailable for the use of plants.

AGRICULTURAL CHEMICALS IN SOIL:

GOAL - to provide the reader with a framework for:

1. examining the problem of agricultural chemicals in soil

2. designing ecologically sound management strategies for dealing with non-productive
soils, pests and diseases.

158 | P a g e
159

BEHAVIOURAL OBJECTIVES

- after having read this paper you will be able to understand and accept that:

 the long-term disbenefits associated with the production and use of agricultural
chemicals, particularly pesticides (resource depletion, environmental damage and
health consequences), are such that alternative, ecologically sound strategies must
be developed and used;
 in order to make a soil productive and keep it so, it is necessary to cater to the needs
of its beneficial biota;
 outbreaks of pests and diseases are symptoms of poor management and
consequently can and should be prevented and controlled by developing and
employing ecologically sound management strategies;
 the replacement of chemical by management solutions will require cooperation
between the general public, industry and commerce (including the producers),
researchers, communicators and governments.
 develop ecologically sound strategies that can be used in the readers' farm or garden
to:
o establish and maintain productive soils;
o prevent the development of pests and diseases and control them in the event
of outbreaks;
 play an active role (e.g., as producer, consumer, voter, etc.) in the process of
implementing the changes proposed in this paper.

INTRODUCTION

In a summary of a symposium on pesticides in soil, Professor Audus (1970), pleaded that

"we must realize the fantastic complexity of the physical and biological structure of the soil
and the dynamic nature of its biological equilibria".

He went on to say that "a central characteristic of these equilibria is the intimate
interdependence of the various soil organisms".

There have been hundreds of papers and dozens of reviews concerning the relationships
between chemicals used in agriculture and forestry and the soil (e.g., Guenzi et al., 1974).

However, after reading many of these papers I cannot help but agree with Howard Evans'
(1970) comment in his book "Life on a Little Known Planet" that "we have learned a great
deal....but seem unable to conclude very much from all of it".

Joseph Needham's (1932) criticism of biologists as scientists "so busily engaged in

accumulating new facts as to be left with no time at all to devote any thought to those
[they] already have" seems to apply to many scientists engaged in this aspect of soil
research.

As Sir Peter Medawar (1969) has noted, there are plenty of analysts among modern
scientists but few synthesists.

159 | P a g e
160

I believe that our poor understanding of soil is closely related to lack of synthesis.

This became particularly evident to me some years ago when, with a number of colleagues, I
attempted to review the effects of pesticides and fertilizers on soil and its inhabitants (Hill
1972, Weetman et al. 1972, Weetman & Hill 1973, Hill et al. 1975).

It was extremely difficult to compare the results of different workers, partly because none
of them had measured sufficient variables to draw meaningful conclusions, but more
particularly because there is really no established framework for viewing the relationships in
soil.

In this paper I will

(1) critically review representative examples of studies on the effects of agricultural

chemicals on soil organisms,

(2) present a case for replacing chemicals with ecologically sound alternatives, and

(3) comment on how this might be implemented.

The framework for considering these topics will emphasize a normative, rather than
extrapolative, approach (cf. Lovins 1976) and collaboration with nature to reach optimal
levels of productivity.

1. EFFECTS OF AGRICULTURAL CHEMICALS IN SOIL

As Dr. Clive Edwards is one of the most prolific reviewers of studies on the effects of
agricultural chemicals on soil organisms, it is fitting that I repeat one of his conclusions;

he states "The most usual effect of agricultural practice is to decrease the number of species
of soil organisms and the few species that remain are often able to multiply rapidly until the
total numbers are greater than they were originally.

The main difference from cultivation is that the effects of chemicals lasts longer. Whereas
ploughing or rotation may only change the balance of the soil fauna or flora for a matter of
weeks or at most months, persistent chemicals can alter them for months or years".

(Edwards 1965; see also Edwards & Thompson 1973, Thompson & Edwards 1974).

However, behind such broad generalizations are the kinds of results summarized in Table 1.

It is difficult; if not impossible, to interpret results such as these as soil is very variable and
all agricultural practices influence the effects of all others; none of the authors of these
studies adequately described or measured the properties of the soil or the agricultural
practices that were being employed.

Those variables that were largely ignored are listed in Table 2.

160 | P a g e
161

Another problem that I encountered was that many authors wrote as if they believed that a)
insecticides and fertilizers are the only agricultural chemicals, b) that they only affect soil
organisms directly and c) that they are either lethal or without effect.

In fact, there are a vast array of agricultural chemicals (Figure 1), most effects and are
sublethal rather than lethal (Table 3).

Another common misconception is that increases in population density are good whereas
decreases are bad.

Thus, Harris (1969), after noting that the density of Collembola, a largely beneficial group of
soil arthropods, increased after the application of DDT stated, "it is apparent that DDT in this
instance changes in species composition, population density be viewed with respect to their
long-term influence the balance between mobilization and immobilization has a beneficial
influence".

Changes in species composition , population density and activity should rather on such
relationships as of plant nutrients and their availability to plants.

Unfortunately the role of most organisms in soil is too poorly defined to permit such
analysis at the present time.

From the above discussion the reader might conclude that I am advocating that a vast army
of soil physicists, chemists and biologists be assembled to study all the variables and
relationships that I indicated were largely ignored in previous studies.

This would certainly be the logical thing to do if there were no alternatives but to continue
to use agricultural chemicals.

On the other hand, if there are viable alternatives-it would make more sense to direct the
army of scientists to work on them.

In the following section I will indicate why I consider that "ecological" alternatives must be
developed.

2. ECOLOGICAL ALTERNATIVES TO AGRICULTURAL CHEMICALS

In my opinion the scientific evidence available indicates that in most instances Developing
and maintaining fertile soils

the use of agricultural chemicals is inappropriate.

Developing and maintaining fertile soils

With respect to soil fertility it is relevant to review how soil is formed (Figure 4).

The process requires two material inputs, rock (the earth's crust) and dead organic matter,
these being converted to soil largely through the process of decomposition.

161 | P a g e
162

There is certainly no shortage of rock and in temperate countries there should be no

shortage of dead organic matter, as the optimum temperature for its production is nearer
the annual mean temperature than is the optimum temperature for its decomposition
(Figure 5).

This, in fact, is the main reason why we find a deep litter layer in most of our forests
whereas there is usually no litter layer in lowland tropical forests.

The biological decomposition process is carried out largely by bacteria and fungi. However,
at least six factors limit their activity (Figure 6).

This is where the soil fauna play such an important role because through their feeding and
movement they are continually removing the limiting factors for the microflora, particularly
through their ability to distribute the spores of the latter.

Thus, if certain members of the fauna are killed or reduced by agricultural chemicals, the
activity of the bacteria and fungi species will decline (Figure 7).

Increases in the population density of certain groups of soil organisms can also lead to
problems through imbalance.

While our detailed knowledge of these processes is poor, it is sufficient to know that by
taking into account the organisms in the soil, and catering to their needs, soil fertility can be
built-up and maintained.

The primary requirement is that organic materials taken from the land be returned.

This follows from the law of ecology concerning cycles given in Table 4.

Rather than forcing the resident "decomposer industry" out of business by applying
synthetic chemical fertilizers, or killing some of them by applying biocides, we should be
investigating their productive potential within each soil type and developing management
strategies whereby it can be realized.

Such strategies are likely to save money, energy, and avoid damage to the support
environment and to human and livestock health (figure 8).

This contrasts with our current approach, which involves the removal of several dozen
minerals at harvest time followed by the replacement of only a few of them as chemical
fertilizers (Figure 9).

Preventing outbreaks of pests and diseases

Pests and diseases are symptoms of poor management (Figure 10). Pesticides, antibiotics
and drugs have generally been regarded as "magical bullets" that can eliminate problems
(Figure 11).

162 | P a g e
163

The real situation is that we do not suffer from pests because of a deficiency of pesticide in
the environment just as we do not get a headache because of a deficiency of aspirin in the
blood.

The use of pesticides and antibiotics to control pests and pathogens leads to the
development of a long list of serious secondary problems (Figure 12, Table 5,6).As most
pesticides are synthetic organic compounds that have no counterpart in nature they are
likely to accumulate in the environment (Table 4, Figure 13, 14).

Moore (1967) has pointed out that we really only have three alternatives with respect to
controlling pests (Figure 15).

The pesticide approach predominates largely because most of the costs (e.g.,
environmental, human health) are not taken into account in our cost:benefit analysis (Figure
16) As a member of the British labour party once explained, "we encourage private, short-
term gain at public long-term expense".

In order to treat pest problems at the causal level, it is necessary to examine more closely
the relationships between agricultural practices and pest damage (Figure 17).

Th is approach has been used to generate the strategies outlined in Table 7.

These must be designed for each unique situation; consequently the particular strategies
employed should ideally be selected by the farmer himself, or someone else who is familiar
with the area and the operation of the particular farm.

While these approaches could be considerably refined if the money and effort currently
directed towards pesticides were used to develop such ecological strategies, I believe that
most pests could be brought below the economic threshold with the knowledge that we
posses right now: we just need to use it!

The history of pest control (Figure 15) indicates that this ecological approach comprises the
only means to achieve long-term control of pests and diseases.

It is significant to note that the use of pesticides has not decreased the percentage loss of
crops to pests, it remains at about 33% (May 1977).

3. IMPLEMENTING CHANGE

Changing from chemical to management strategies will not be easy. Modern agriculture has
become dependent on chemicals just as heroin addicts have become dependent on their
drug (neither pesticides nor stimulatory drugs treat problems at the causal level).

The irrational outbursts experienced on withdrawal of these two "drugs" share certain
features in common; such outbursts are a measure of a loss of true freedom, the kind that is
unfortunately not protected by any Bill of Rights'.

163 | P a g e
164

Because of the addictive nature of the problem, the implementation of alternative

ecological strategies will require an enormous cooperative effort involving the general
public (consumers), industry and commerce (including producers), researchers (in federal
and provincial governments, universities and industry), communicators (media people,
educators, and extension agents) and governments (federal, provincial and local) (Figure
18).

The alternative to cooperation is to respond to the crises that will undoubtedly occur with
increasing frequency if we continue with the kinds of solutions to problems that are
exemplified by the use of agricultural chemicals (Whiteside 1977).

Some of the strategies available to governments are listed in figure 19.

CONCLUSIONS
1) the long-term disbenefits associated with the production and use of agricultural
chemicals, particularly pesticides (resource depletion, environmental damage and health
consequences), are such that alternative ecologically sound strategies must be developed
and used;
2) in order to make a soil productive and keep it so, it is necessary to cater to the needs of
its beneficial biota;
3) outbreaks of pests and diseases are symptoms of poor management and consequently
can and should be prevented and controlled by developing and employing ecologically
sound management strategies;
4) the replacement of chemical by management solutions will require cooperation between
the general public, industry and commerce (including the producers), researchers,
communicators and governments).
WHAT IS LEECHING:
 leaching, in geology, loss of soluble substances and colloids from the top layer
of soil by percolating precipitation.
 The materials lost are carried downward (eluviated) and are generally redeposited
(illuviated) in a lower layer.
 This transport results in a porous and open top layer and a dense, compact lower
layer.
 The rate of leaching increases with the amount of rainfall, high temperatures, and
the removal of protective vegetation.
 In areas of extensive leaching, many plant nutrients are lost, leaving quartz and
hydroxides of iron, manganese, and aluminum.
 This remainder forms a distinctive type of soil, called laterite, or latosol, and may
result in deposits of bauxite.

164 | P a g e
165

 In such areas rapid bacterial action results in the absence of humus in the soil,
because fallen plant material is completely oxidized and the products
are leached away.
 Accumulations of residual minerals and of those redeposited in lower layers may
coalesce to form continuous, tough, impermeable layers called duricrusts.

HEAVY METALS BY ELECTROKINETIC REMEDIATION:

Electrokinetic remediation of heavy metal-contaminated soils: performance comparison
between one- and two-dimensional electrode configurations

Abstract
Purpose
Electrokinetic (EK) soil remediation is significantly affected by the electrode configurations.

Therefore, this study was conducted to compare the performance of one-dimensional (1D)
and two-dimensional (2D) arrays with respect to the remediation of heavy metal-
contaminated soils.

Materials and methods

A series of laboratory-scale experiments were carried out using two types of soils: kaolinite
soil (KS) artificially spiked with heavy metals (Cd, Cu, Pb, Ni, and Zn) and smelter soil (SS)
contaminated with Cu and Pb, obtained near a closed smelting factory.

First, stepwise experiments on the KS were conducted to compare the EK performance

between the 1D and 2D electrode arrays.

More specifically, the effect of the number of anode–cathode pairs was investigated in the
experiments on the 1D electrode configuration, and trigonal and hexagonal arrangements
were compared in the 2D EK experiments.

Additionally, the performance of the trigonal array was evaluated according to changes in
the anode positions, to switch the areas of effective and ineffective electric field.

Results and discussion

The removal efficiencies of the 1D electrode configuration with four anode–cathode pairs
(eight electrodes in total) were 69.1% for Cd, 69.2% for Cu, 74.7% for Ni, 28.3% for Pb, and
71.3% for Zn.

The removal efficiencies of the 2D hexagonal electrode array, with a similar number of
electrodes (six anodes and one cathode for seven electrodes in total), were 79.8% (Cd),
82.6% (Cu), 83.7% (Ni), 34.3% (Pb), and 81.1% (Zn).

165 | P a g e
166

The total electric power consumptions for the two types of electrode configurations were
investigated to be 15.6 and 22.0 kWh/ton, respectively.

Despite the increase in electric power consumption in the 2D electrode configuration, it was
more efficient than the 1D configuration due to the increased area of effective (active)
electric field and subsequently higher removal efficiency.

As a result of changing the positions of anodes in the trigonal 2D arrangement, the removal
efficiencies of Cu and Pb were increased to a level similar to that obtained with the
hexagonal configuration.

Conclusions
This study demonstrated that a 2D electrode configuration increased the EK removal
efficiency of contaminants compared with a 1D array.

However, cost-effectiveness should be taken into account when optimizing electrode

design.
Furthermore, the performance of the trigonal 2D EK process was improved by changing the
positions of anodes, as a result of the increase in the removal efficiency and decrease in the
electrode cost and energy consumption.

ELECTROKINETIC REMOVAL OF HEAVY METAL FROM SOIL:

166 | P a g e
167

167 | P a g e
168

168 | P a g e
169

169 | P a g e
170

170 | P a g e
171

171 | P a g e
172

172 | P a g e
173

173 | P a g e
174

UNIT – 5 EMERGING POLLUTANTS

HEAVY METALS:

EFFECTS OF MERCURY ON THE ENVIRONMENT

174 | P a g e
175

175 | P a g e
176

176 | P a g e
177

177 | P a g e
178

178 | P a g e
179

ENDOCRINE DISTURBING CHEMICALS:

The endocrine system is a network of glands and organs that produce, store, and
secrete hormones.

When functioning normally, the endocrine system works with other systems to regulate
your body's healthy development and function throughout life.

Endocrine-disrupting chemicals (EDCs) are substances in the environment (air, soil, or water
supply), food sources, personal care products, and manufactured products that interfere
with the normal function of your body’s endocrine system.

Since EDCs come from many different sources, people are exposed in several ways,
including the air we breathe, the food we eat, and the water we drink. EDCs also can enter
the body through the skin.

Endocrine Connection

EDCs are chemicals or mixtures of chemicals that interfere with the way the body’s
hormones work.

Some EDCs act like "hormone mimics" and trick our body into thinking that they are
hormones, while other EDCs block natural hormones from doing their job.

Other EDCs can increase or decrease the levels of hormones in our blood by affecting how
they are made, broken down, or stored in our body.

Finally, other EDCs can change how sensitive our bodies are to different hormones.

EDCs can disrupt many different hormones, which is why they have been linked to
numerous adverse human health outcomes including alterations in sperm quality and

179 | P a g e
180

fertility, abnormalities in sex organs, endometriosis, early puberty, altered nervous system
function, immune function, certain cancers, respiratory problems, metabolic
issues, diabetes, obesity, cardiovascular problems, growth, neurological and learning
disabilities, and more.

Taking Precautions
Even if some health effects are not fully proven, taking precautions is wise. Become familiar
with EDCs to which you and your family may be exposed.

Try to avoid unnecessary, preventable exposure to EDC-containing consumer products.

The following is a list of precautionary steps that one can take to minimize EDC exposures.

These precautions are especially important if you are pregnant or planning a family.

180 | P a g e
181

Food and Water

 Consult local guides regarding which sport fish are safe to consume.
 Trim fat from meat and the skin from fish and cook using a rack to allow fat to drain.
 Thoroughly wash fruits and vegetables before consuming them.
 Don’t microwave plastic food containers or use them for storing hot liquids.
 Avoid plastic containers designated #3, #6, and #7.
 Reduce consumption of canned and processed foods.
 Use glass, porcelain, or stainless-steel containers, when possible, especially for hot
food and drinks.
 Prepare more meals at home and emphasize fresh ingredients.
 Consider using a water filter.
 If possible, purchase organic produce, meat, and dairy products.
 Replace older non-stick pans with newer ceramic-coated pans.
 Eat a diversified diet with plenty of variety.

Exercise and Activity

 Check air quality in your area [https://airnow.gov].

 Avoid outdoor exercise when pollution levels are high.
 Avoid exercise near high traffic areas. Choose routes away from busy roads and
vehicles
Personal Care

 Read labels and avoid products containing phthalates.

 Choose products labeled “Phthalate-Free”, “BPA-Free”, and "Paraben-Free".
 Avoid fragrances and opt for cosmetics labeled “no synthetic fragrance”, “scented
only with essential oils”.
 Wash your hands often, especially before preparing and eating food.
 Minimize handling of receipts and thermal paper.
Around the Home

 For those with a submersible pump in their well who notice an oily film or fuel odor
in their well water, check to see if the pump has failed and, if so, replace it. Contact
your local Department of Public Health for information on how to clean the well.
 Replace and discard safely old fluorescent bulbs and deteriorating construction
materials from older buildings.
 Minimize burning wood or trash.
 Use hand-powered or electric lawn care equipment instead of gas-powered
alternatives.
 Forbid smoking indoors and advocate for measures to make public spaces tobacco-
free.
 Clean your floors regularly and remove dust from your home.
 Plant trees, which filter out airborne gases and particulate matter.

181 | P a g e
182

For Children

 Avoid hand-me-down plastic toys.

 Use infant formula bottles and toys that are labeled “BPA-Free”.
Transportation

 Choose transportation options and transit routes that limit time sitting in traffic.
 Encourage your child’s school to reduce school bus emissions, including reducing
idling.
Sources of Common EDCs
Example of Common EDC Sources:

 Industrial chemicals and pesticides can leach into soil and groundwater, and make
their way into the food chain by building up in fish, animals, and people.
 Non-organic produce can have pesticide residues
 Some consumer products contain EDCs or are packaged in containers which can
leach EDCs, such as household chemicals, fabrics treated with flame retardants,
cosmetics, lotions, products with fragrance, and anti-bacterial soaps
 Processed foods can accumulate traces of EDCs that leach out of materials used in
manufacturing, processing, transportation, and storage
 Soy-based products contain phytoestrogens, which are chemicals produced by plants
that mimic estrogen
 Household dust can contain EDCs such as lead, flame retardants, and PCBs from
weathering construction material or furniture
Common EDCs Used In

DDT, Chlorpyrifos, Atrazine, 2, 4- Pesticides

D, Glyphosate
Lead, Phthalates, Cadmium Children's Products
Polychlorinated biphenyls (PCBs) Industrial Solvents or Lubricants and their Byproducts
and Dioxins
Bisphenol A (BPA), Phthalates, Plastics and Food Storage Materials
Phenol
Brominated Flame Retardants, Electronics and Building Materials
PCBs
Phthalates, Parabens, UV Filters Personal Care Products, Medical Tubing, Sunscreen

Triclosan Anti-Bacterial Soaps, Colgate Total

Perfluorochemicals Textiles, Clothing, Non-Stick Food
Wrappers, Microwave Popcorn Bags, Old Teflon Cookware

Symptoms and Risk Factors

More research is needed, but we know EDCs affect:

182 | P a g e
183

Response to psychological stress

 Neurological and behavioral changes

 Reduced ability to handle stress
Metabolism

 Some EDCs have been linked to obesity and type 2 diabetes

 Some industrial chemicals and flame retardants can interfere with thyroid function
Reproduction

 Some classes of EDCs (DDT, BPA, phthalates, PCBs, others) can affect reproductive
health by mimicking or blocking the effects of male and female sex hormones
Growth and development

 High exposures to EDCs during gestation can lead to low-birth weight

 Altered development

 Disrupted sexual development

 Weakened immune system

Cancer

 Exposure to estrogen or androgen mimicking EDCs can promote breast and prostate
cancer growth and/or interfere with hormonal cancer therapy
 Prenatal exposure to some EDCs may after mammary gland development and
increase breast cancer risk later-in-life

DIOXINS:
What to know about dioxins
Dioxins are a group of highly toxic chemical compounds that are harmful to health.
They can cause problems with reproduction, development, and the immune system. They
can also disrupt hormones and lead to cancer.
Dioxins, which are known as persistent environmental pollutants (POPs), can remain in the
environment for many years. They are everywhere around us.
Some countries are trying to reduce the production of dioxins in industry.

In the United States, people do not produce or use dioxins commercially, but they may be a
byproduct of other processes.
The Environmental Protection Agency (EPA) and other bodies have reduced the production
of dioxin levels in the U.S. by 90%Trusted Source since 1987.

183 | P a g e
184

However, it is not easy to eliminate dioxins.

They can come from natural sources such as volcanoes and forest fires, they can cross
borders, and they do not break down quickly, so they stay in the environment for a long
time.
Where do dioxins come from?

Dioxins in microscopic particles are toxic chemicals that are present almost everywhere in
the world.

Pure dioxin looks like white, crystalline needles. In the environment, however, it is present
that people cannot see.
Sources:

 burning processes, such as backyard burning and commercial or municipal waste

incineration
 the use of fuels, such as wood, coal, or oil
 natural phenomena, such as volcanic activity and forest fires
 industrial processes, such as chlorine bleaching of paper pulp and smelting
 the production of some herbicides and pesticides
 the dismantlingTrusted Source and recycling of electronic products
 cigarette smoking
Dioxins can travel long distances in the air or water.

When they settle in soil and sediment, they can stay there for a long time because they
break down slowly.
Fish and other organisms can swallow or absorb dioxins so that they enter the food chain.
Animals tend to have higher concentrations than plants, water, soil, or sediments. In
animals, dioxins tend to accumulate in fat.
Exposure to dioxins can come through:

 consuming food, especially animal fats, where dioxins have accumulated

 drinking water where dioxins have settled or where there is contamination from
industries
 breathing in vapor or air that contains trace amounts
 accidentally ingesting soil that contains dioxins
 absorbing dioxins through skin contact with air, soil, or water
Dioxins can stay in the body for a long time. It may take 7–11 yearsTrusted Source for a
dioxin’s toxicity to reduce to half its original level.

184 | P a g e
185

Major contamination
According to the World Health Organization (WHO)Trusted Source, most reports of dioxin
contamination occur in industrialized nations where there is a system of monitoring and
reporting. In other places, high dioxin levels may go unreported.
There have been some cases of major contamination. Here are some examples:

In 2008, contaminated animal feed led to pork products from Ireland containing more than
200 times the permitted levels of dioxins.

In 1999, the illegal disposal of industrial oil led to the contamination of animal feed and
animal-based food products from Belgium and some other countries.
In 1976, an industrial accident produced a cloud of toxic chemicals, including dioxins, which
affected thousands of people in Italy.
In 2004, Viktor Yushchenko, the President of Ukraine, was intentionally poisoned with
dioxins.
Dioxins in food

When dioxins enter an animal in the food chain, they accumulate in fat. More
than 90%Trusted Source of human exposure to dioxins comes through food — primarily
animal products, such as dairy, meat, fish, and shellfish.
Older research reported traces of dioxins in the following foods:

 freshwater fish
 butter
 cheese
 hot dogs and bologna
 human milk (from breastfeeding)
 ice cream
 eggs
 ocean fish
 beef, chicken, and pork
Of these, freshwater fish contained by far the highest amounts.
To reduce the risk of exposure from food, the WHOTrusted Source recommends:

 choosing lean meats and fish

 cutting off fat when preparing meat
 varying the diet to reduce the risk of exposure to a high concentration in a specific
food
 favoring fruits, vegetables, and whole grains over meat and fish where possible

185 | P a g e
186

When fishing for food, the National Institute of Environmental Health Sciences
(NIEHS)Trusted Source advises people to check first on current dioxin levels with the local
authority.
Dioxins in tampons
Some people have raised concerns about dioxins in menstrual and sanitary products,
especially tampons.
Before the late 1990s, manufacturers used chlorine for bleaching in tampon production, and
dioxin levels were higher. They no longer use chlorine bleaching, and, as a result, dioxin
levels in these products have fallen.
However, an articleTrusted Source that the NIEHS published in 2014 notes that there is not
enough research to show how the chemicals in tampons can affect a person’s health.
Dioxins in water bottles

In the past, some people have also claimed that plastic water bottles contain dioxins, but
experts say that this is not true.
They warn, however, that water bottles contain bisphenol A (BPA) phthalates, which can
lead to hormonal and endocrine problems and possibly reproductive issues, as well.
Types of dioxins
There are several hundred dioxins, which belong to threeTrusted Source closely related
families.
These are:

 chlorinated dibenzo-p-dioxins (CDDs)

 polychlorinated dibenzofurans (PCDFs)
 some polychlorinated biphenyls (PCBs)
People do not create CDDs and PCDFs intentionally. These occur as byproducts of human
activities or because of natural processes.
PCBs are manufactured products, but manufacturers no longer produce them in the U.S.
Sometimes, people also use the term dioxin to refer to 2,3,7,8-tetrachlorodibenzo-p-dioxin
(TCDD), one of the most toxic dioxins. Experts have linked TCDD to the herbicide Agent
Orange, which people used during the Vietnam War to strip the leaves from trees.
Health risks
Scientists have linked exposure to dioxins to various adverse effects, including:

 cancer
 congenital disabilities
 pregnancy loss
 decreased fertility

186 | P a g e
187

 reduced sperm counts and low testosterone levels

 endometriosis
 diabetes
 learning disabilities
 immune system suppression
 lung problems
 skin disorders
Dioxins can pass from a person to a fetus during pregnancy and to a baby through
breastfeeding. If this occurs, it could lead to neurodevelopmental problems.
The risks depend on a variety of factors, including:

 the level of exposure

 when the exposure occurred
 the length and frequency of exposure
According to the WHOTrusted Source, however, the background exposure that most people
experience in daily life is unlikely to be hazardous.
Top of Form
Bottom of Form
Symptoms of dioxin poisoning

Although it rarely occurs, high levels of exposure over a short time can sometimes lead
toTrusted Source chloracne. This severe skin disease produces acne-like lesions, mainly on
the face and upper body. Chloracne can happen if there is an accident or a significant
contamination event.
Other possible effects of exposure include:
skin rashes
skin discoloration
mild liver damage
Reducing exposure
Dioxin testing for humans is not routinely available, but some measures can help reduce the
risk of exposure. They include:

 avoiding fatty meats or cutting the fat off meat before using
 checking dioxin levels in local waters before fishing for food
 following best practices when carrying out backyard burning
The EPA notes that burning waste materials in the backyard can create levels of dioxins
higher than those from industrial incinerators. Backyard burning releases pollutants at
ground level, where they are more likely to affect people and enter the food chain.

187 | P a g e
188

Summary
Dioxins are poisonous substances resulting from human and natural processes, including
manufacturing, volcanic activity, and backyard burning.

Manufacturers can no longer produce dioxins in the U.S., but these substances are present
in the environment and possibly in the food chain.

Exposure to dioxins increases the risk of cancer and some developmental and reproductive
problems.

Ways of avoiding dioxin exposure include trimming any fat from meats, consuming a varied
diet, and avoiding backyard burning.
Sources to the Atmosphere

Dioxins and furans are emitted into the atmosphere through combustion and chemical
processes.
Governmental entities have compiled thorough reviews of the many sources of
PCDD/PCDFs,
for example, in UNEP [200] and US EPA4 [201]. These sources are categorized by US
EPA [202] as follows:

 waste incineration (e.g., municipal waste, boilers, medical waste, tires),

 power/energy generation (e.g., vehicle fuel combustion, wood, coal, and oil
combustion for residential heating and industrial/municipal power
generation),
 other high temperature sources (e.g., asphalt mixing plants, cigarette
smoking),
 minimally controlled or uncontrolled combustion (e.g., backyard barrel
burning, combustion of landfill gas, landfill fires, accidental building or car
fires, forest, brush or straw fires, burning of candles),
 metal smelting and refining (sintering plants, coke production, arc furnaces,
foundries, nonferrous smelting/refining) and metal recovery (scrap electric
wire recovery, drum and barrel reclamation),
 chemical manufacturing (e.g., pentachlorophenol, chlorobenzenes, vinyl
chloride, dioxazine dyes and pigments, and 2,4-dichlorophenoxy acetic acid
[2,4-D]),
 reservoir sources (land, air, water, and sediments impacted by above and
pentachlorophenol-treated wood in structures).
In source evaluation studies, it is important to identify current and, more importantly,
historic atmospheric sources upwind from potentially impacted properties.

Large industrial facilities are typically the focus of the investigations; however, smaller
facilities like medical

188 | P a g e
189

waste incinerators can be an important local source to downwind communities. As these

were often located beside hospitals, they constitute important PCDD/PCDF sources well
away from heavy industrial areas and often are located within residential communities.

Combustion engines emit PCDD/PCDFs and the effect of traffic needs to be accounted for in
evaluating the relative impact of point sources compared to local neighborhood sources of
PCDD/PCDFs.

The concentration and composition vary with engine type and fuel type (diesel, leaded, and
unleaded gasoline) [202,203].

The concentration of dioxins and furans in soils from vehicle emissions depends on traffic
frequency, frequency and duration of idling, and proximity.

Soil samples near busy roads can have TEQDF98 values as high as 140 pg/g [204].

In more rural areas, open burning of yard debris, and especially household waste containing
plastic, can be an important local source of PCDD/PCDFs.

Indeed, uncontrolled outdoor burning is the most significant source of dioxins/furans in the
United States [196].

Dioxin/furan emission concentrations and congener composition vary with waste

characteristics (e.g., household trash, garden waste, clean wood, construction debris),
moisture content, fire temperature, frequency and duration of burning, and wind speed and
direction during burning [205–207].

Polychlorinated Biphenyls (PCBs):

What are polychlorinated biphenyls?

Polychlorinated biphenyls (PCBs) are a group of manmade chemicals. They are oily liquids or
solids, clear to yellow in color, with no smell or taste.

PCBs are very stable mixtures that are resistant to extreme temperature and pressure.

PCBs were used widely in electrical equipment like capacitors and transformers.

They also were used in hydraulic fluids, heat transfer fluids, lubricants, and plasticizers. The
primary company that made PCBs in the United States was Monsanto Inc., mainly using the
name Aroclor.

Commercial production of PCBs ended in 1977 because of health effects associated with
exposure. In 1979, the U.S.

Environmental Protection Agency (USEPA) banned the use of PCBs; however, PCBs are still
present in many pre-1979 products.

189 | P a g e
190

How do PCBs get into the environment?

PCBs have been released into the environment through spills, leaks from electrical and
other equipment, and improper disposal and storage.

It is estimated that more than half of the PCBs produced have been released into the
environment.

Once in the environment, PCBs can be transported long distances and they bind strongly to
soil and sediment so they tend to be persistent in the environment.

They have been found in air, water, soil, and sediments throughout the world. Because
PCBs have not been made since 1977, the levels in the environment and in the food chain
have been declining.

How can I be exposed to PCBs?

Since PCBs are found throughout the environment, it is likely that everyone has been
exposed to them.

PCBs can enter the body by eating or drinking contaminated food, through the air we
breathe, or by skin contact.

PCBs are easily absorbed by the body and are stored in fatty tissue.

PCBs are not eliminated well, so they can accumulate in the body.

Most people are exposed to PCBs by eating contaminated fish, meat, and dairy products.
Catfish, buffalo fish, and carp usually have the highest PCB levels. Plants take up only small
amounts of PCBs from the soil, so amounts in grazing animals and dairy products are
generally lower than in fish.

Dust contaminated with very small levels of PCBs may be found on the outer surfaces of
fruits and vegetables.

PCBs do not dissolve well, so exposure to them from water is usually not a concern.

Some private wells may use old submersible pumps that contain PCB oil.

If the pump seal fails, PCBs can leak into the well and contaminate the drinking water.

Older fluorescent lights found in schools, offices and homes may still contain transformers
or ballasts that contain PCBs.

If the ballasts fail, PCBs can leak out and contaminate exposed surfaces and the air.

190 | P a g e
191

PCB levels measured in the air after a light ballast failure can be significant. The workplace
also may be a source of PCB exposure.

How can PCBs affect my health?

Coming in contact with PCBs does not mean you will get sick or have health problems.

Getting sick from being exposed to PCBs depends on: the amount of PCBs that entered
your body, how long you were exposed to PCBs, and how sensitive your body is to PCBs.

In people, PCBs can affect the skin and may cause chloracne--small, pale, yellow skin
lesions that may last from weeks to years.

PCBs also can cause short-term changes in the activity of the liver, but without any
noticeable symptoms.

These liver changes are similar to those resulting from the consumption of alcoholic
beverages or smoking cigarettes.

Animal studies also have suggested that PCBs can affect the immune, endocrine and
reproductive systems, but these effects are uncertain in humans.

Large amounts of PCBs given to laboratory animals over a short time can cause cancer.

Studies of human workers exposed to high levels of PCBs for long periods have not
consistently shown that PCBs cause cancer in humans.

USEPA classifies PCBs as probable human carcinogens (cancer-causing chemicals), but

there is no evidence that PCBs cause cancer at the low levels found in the environment.

Birth defects have been linked to mothers who have been exposed to PCBs.

Developing fetuses and young children are the most vulnerable to PCBs, therefore,
children and women who may become pregnant, are pregnant, or nursing should limit
their exposure to PCBs.

A pregnant woman can pass these chemicals to her unborn child.

Mothers who eat highly contaminated fish before giving birth may have children who have
slower mental development.

PCBs also can be passed to a baby through breast milk. However, the significant benefits of
breastfeeding far outweigh the risks.

Young children also may experience developmental health effects.

191 | P a g e
192

Is there a medical test for PCBs?

Most people have a measurable amount of PCBs in their bodies.

A blood test is best for measuring exposure to large amounts of PCBs.

Although measuring PCBs in the body is possible, the analysis is expensive and not
generally recommended because the results do not predict health effects or treatment.

How can I reduce or prevent my exposure to PCBs?

Avoiding contact with contaminated soils and sediments can reduce your exposure to
PCBs.

Another way to avoid exposure to PCBs is to wash fruits and vegetables before eating
them.

Old fluorescent lights containing PCBs should be replaced and discarded before they fail
and leak.

If an oily film or fuel odor is noticed in your well water and you have a submersible pump,
check to see if the pump has failed.

If it has, replace it and contact the Illinois Department of Public Health for instructions on
how to clean the well.
PAHs

Polycyclic aromatic hydrocarbon

A polycyclic aromatic hydrocarbon (PAH) is a hydrocarbon—a chemical

compound containing only carbon and hydrogen—that is composed of multiple aromatic
rings.
The group is a major subset of the aromatic hydrocarbons. The simplest of such chemicals
are naphthalene, having two aromatic rings, and the three-ring
compounds anthracene and phenanthrene.
The terms polyaromatic hydrocarbon[1] or polynuclear aromatic hydrocarbon[2] are also
used for this concept.[3]
PAHs are uncharged, non-polar molecules, with distinctive properties due in part to
the delocalized electrons in their aromatic rings.
Many of them are found in coal and in oil deposits, and are also produced by the
combustion of organic matter—for example, in engines and incinerators or when biomass
burns in forest fires.

192 | P a g e
193

Polycyclic aromatic hydrocarbons are discussed as possible starting

materials for abiotic syntheses of materials required by the earliest forms of life.[4][5]

Nomenclature and structure

By definition, polycyclic aromatic hydrocarbons have multiple cycles,
precluding benzene from being considered a PAH.
Some sources, such as the US EPA and CDC, consider naphthalene to be the simplest PAH.[6]
Other authors consider PAHs to start with the tricyclic
species phenanthrene and anthracene.[7]
Most authors exclude compounds that include heteroatoms in the rings, or
carry substituents.[8]
A polyaromatic hydrocarbon may have rings of various sizes, including some that are not
aromatic.
Those that have only six-membered rings are said to be alternant.[9]
The following are examples of PAHs that vary in the number and arrangement of their rings:

 Examples of polycyclic aromatic hydrocarbons



Naphthalene

Biphenyl

Fluorene

Properties
Physicochemical
PAHs are nonpolar and lipophilic. Larger PAHs are generally insoluble in water, although
some smaller PAHs are soluble.[21][22]
The larger members are also poorly soluble in organic solvents and in lipids. The larger
members, e.g. perylene, are strongly colored.[16]

193 | P a g e
194

Polycyclic aromatic compounds characteristically yield radical anions upon treatment with
alkali metals.
The large PAH form dianions as well.[23] The redox potential correlates with the size of the
PAH.

Half-cell potential of aromatic compounds against the SCE (Fc+/0)[24]

Compound Potential (V)

benzene −3.42

biphenyl[25] −2.60 (-3.18)

naphthalene −2.51 (-3.1)

anthracene −1.96 (-2.5)

phenanthrene −2.46

perylene −1.67 (-2.2)

pentacene −1.35

Sources
Natural
Fossil carbon
Polycyclic aromatic hydrocarbons are primarily found in natural sources such
as bitumen.[26][27]
PAHs can also be produced geologically when organic sediments are chemically
transformed into fossil fuels such as oil and coal.[28]
The rare minerals idrialite, curtisite, and carpathite consist almost entirely of PAHs that
originated from such sediments, that were extracted, processed, separated, and
deposited by very hot fluids.[29][13][30]

194 | P a g e
195

Natural fires
PAHs may result from the incomplete combustion of organic matter in
natural wildfires .[31][32]
Substantially higher outdoor air, soil, and water concentrations of PAHs have been
measured in Asia, Africa, and Latin America than in Europe, Australia, the U.S., and
Canada.[32]
High levels of such PAHs have been detected in the Cretaceous-Tertiary (K-T) boundary,
more than 100 times the level in adjacent layers.
The spike was attributed to massive fires that consumed about 20% of the terrestrial
above-ground biomass in a very short time.[33]
Extraterrestrial
PAHs are prevalent in the interstellar medium (ISM) of galaxies in both the nearby and
distant Universe and make up a dominant emission mechanism in the mid-infrared
wavelength range, containing as much as 10% of the total integrated infrared luminosity
of galaxies[34].
PAHs generally trace regions of cold molecular gas, which are optimum environments
for the formation of stars[35]
NASA's Spitzer Space Telescope and James Webb Telescope include instruments for
obtaining both images and spectra of light emitted by PAHs associated with star
formation.
These images can trace the surface of star-forming clouds in our own galaxy or identify
star forming galaxies in the distant universe.[36]
In June 2013, PAHs were detected in the upper atmosphere of Titan, the
largest moon of the planet Saturn.[37]
Minor sources
Volcanic eruptions may emit PAHs.[28]
Certain PAHs such as perylene can also be generated in anaerobic sediments from
existing organic material, although it remains undetermined whether abiotic or
microbial processes drive their production.[38][39][40]
Artificial
The dominant sources of PAHs in the environment are thus from human activity: wood-
burning and combustion of other biofuels such as dung or crop residues contribute
more than half of annual global PAH emissions, particularly due to biofuel use in India
and China.[32][31]
As of 2004, industrial processes and the extraction and use of fossil fuels made up
slightly more than one quarter of global PAH emissions, dominating outputs in industrial
countries such as the United States.[32]
A year-long sampling campaign in Athens, Greece found a third (31%) of PAH urban air
pollution to be caused by wood-burning, like diesel and oil (33%) and gasoline (29%).

195 | P a g e
196

It also found that wood-burning is responsible for nearly half (43%) of annual PAH
cancer-risk (carcinogenic potential) compared to the other sources and that wintertime
PAH levels were 7 times higher than in other seasons, especially if atmospheric
dispersion is low.[41][42]
Lower-temperature combustion, such as tobacco smoking or wood-burning, tends to
generate low molecular weight PAHs, whereas high-temperature industrial processes
typically generate PAHs with higher molecular weights.[43]
PAHs are typically found as complex mixtures.[28][43]

Distribution in the environment

Aquatic environments
Most PAHs are insoluble in water, which limits their mobility in the environment,
although PAHs sorb to fine-grained organic-rich sediments.[44][45][46][47]
Aqueous solubility of PAHs decreases approximately logarithmically as molecular
mass increases.[48]
Two-ringed PAHs, and to a lesser extent three-ringed PAHs, dissolve in water, making
them more available for biological uptake and degradation.[47][48][49] Further, two- to
four-ringed PAHs volatilize sufficiently to appear in the atmosphere predominantly in
gaseous form, although the physical state of four-ring PAHs can depend on
temperature.[50][51]
In contrast, compounds with five or more rings have low solubility in water and low
volatility; they are therefore predominantly in solid state, bound to particulate air
pollution, soils, or sediments.[47]
In solid state, these compounds are less accessible for biological uptake or degradation,
increasing their persistence in the environment.[48][52]
Human exposure
Human exposure varies across the globe and depends on factors such as smoking rates,
fuel types in cooking, and pollution controls on power plants, industrial processes, and
vehicles.[28][32][53]
Developed countries with stricter air and water pollution controls, cleaner sources of
cooking (i.e., gas and electricity vs. coal or biofuels), and prohibitions of public smoking
tend to have lower levels of PAH exposure, while developing and undeveloped countries
tend to have higher levels.[28][32][53]
Surgical smoke plumes have been proven to contain PAHs in several independent
research studies.[54]
A wood-burning open-air cooking stove.

Smoke from solid fuels like wood is a large source of PAHs globally.
Burning solid fuels such as coal and biofuels in the home for cooking and heating is a
dominant global source of PAH emissions that in developing countries leads to high

196 | P a g e
197

levels of exposure to indoor particulate air pollution containing PAHs, particularly for
women and children who spend more time in the home or cooking.[32][55]
In industrial countries, people who smoke tobacco products, or who are exposed
to second-hand smoke, are among the most highly exposed groups; tobacco
smoke contributes to 90% of indoor PAH levels in the homes of smokers.[53]
For the general population in developed countries, the diet is otherwise the dominant
source of PAH exposure, particularly from smoking or grilling meat or consuming PAHs
deposited on plant foods, especially broad-leafed vegetables, during growth.[56]
PAHs are typically at low concentrations in drinking water.[53]
Smog in Cairo. Particulate air pollution, including smog, is a substantial cause of human
exposure to PAHs.
Emissions from vehicles such as cars and trucks can be a substantial outdoor source of
PAHs in particulate air pollution.[28][32]
Geographically, major roadways are thus sources of PAHs, which may distribute in the
atmosphere or deposit nearby.[57]
Catalytic converters are estimated to reduce PAH emissions from gasoline-fired vehicles
by 25-fold.[28]
People can also be occupationally exposed during work that involves fossil fuels or their
derivatives, wood-burning, carbon electrodes, or exposure to diesel exhaust.[58][59]
Industrial activity that can produce and distribute PAHs includes aluminum, iron,
and steel manufacturing; coal gasification, tar distillation, shale oil extraction;
production of coke, creosote, carbon black, and calcium carbide; road paving
and asphalt manufacturing; rubber tire production; manufacturing or use of metal
working fluids; and activity of coal or natural gas power stations.[28][58][59]
Environmental pollution and degradation
PAHs typically disperse from urban and suburban non-point sources through
road runoff, sewage, and atmospheric circulation and subsequent deposition of
particulate air pollution.[60][61]
Soil and river sediment near industrial sites such as creosote manufacturing facilities can
be highly contaminated with PAHs.[28]
Oil spills, creosote, coal mining dust, and other fossil fuel sources can also distribute
PAHs in the environment.[28][62]
Two- and three-ringed PAHs can disperse widely while dissolved in water or as gases in
the atmosphere, while PAHs with higher molecular weights can disperse locally or
regionally adhered to particulate matter that is suspended in air or water until the
particles land or settle out of the water column.[28]
PAHs have a strong affinity for organic carbon, and thus highly organic sediments
in rivers, lakes, and the ocean can be a substantial sink for PAHs.[57]
Algae and some invertebrates such as protozoans, mollusks, and many polychaetes have
limited ability to metabolize PAHs and bioaccumulate disproportionate concentrations

197 | P a g e
198

of PAHs in their tissues; however, PAH metabolism can vary substantially across
invertebrate species.[61][63]
Most vertebrates metabolize and excrete PAHs relatively rapidly.[61]
Tissue concentrations of PAHs do not increase (biomagnify) from the lowest to highest
levels of food chains.[61]
PAHs transform slowly to a wide range of degradation products. Biological degradation
by microbes is a dominant form of PAH transformation in the environment.[52][64]
Soil-consuming invertebrates such as earthworms speed PAH degradation, either
through direct metabolism or by improving the conditions for microbial
transformations.[64]
Abiotic degradation in the atmosphere and the top layers of surface waters can produce
nitrogenated, halogenated, hydroxylated, and oxygenated PAHs; some of these
compounds can be more toxic, water-soluble, and mobile than their parent
PAHs.[61][65][66]
Urban soils
The British Geological Survey reported the amount and distribution of PAH compounds
including parent and alkylated forms in urban soils at 76 locations in Greater London.[67]
The study showed that parent (16 PAH) content ranged from 4 to 67 mg/kg (dry soil
weight) and an average PAH concentration of 18 mg/kg (dry soil weight) whereas the
total PAH content (33 PAH) ranged from 6 to 88 mg/kg
and fluoranthene and pyrene were generally the most abundant PAHs.[67]
Benzo[a]pyrene (BaP), the most toxic of the parent PAHs, is widely considered a key
marker PAH for environmental assessments;[68]
the normal background concentration of BaP in the London urban sites was 6.9 mg/kg
(dry soil weight).[67]
London soils contained more stable four- to six-ringed PAHs which were indicative of
combustion and pyrolytic sources, such as coal and oil burning and traffic-sourced
particulates.
However, the overall distribution also suggested that the PAHs in London soils had
undergone weathering and been modified by a variety of pre-and post-depositional
processes such as volatilization and microbial biodegradation.
Peatlands
Managed burning of moorland vegetation in the UK has been shown to generate PAHs
which become incorporated into the peat surface.[69]
Burning of moorland vegetation such as heather initially generates high amounts of two-
and three-ringed PAHs relative to four- to six-ringed PAHs in surface sediments,
however, this pattern is reversed as the lower molecular weight PAHs are attenuated by
biotic decay and photodegradation.[69]

198 | P a g e
199

Evaluation of the PAH distributions using statistical methods such as principal

component analyses (PCA) enabled the study to link the source (burnt moorland) to
pathway (suspended stream sediment) to the depositional sink (reservoir bed).[69]
Rivers, estuarine and coastal sediments
Concentrations of PAHs in river and estuarine sediments vary according to a variety of
factors including proximity to municipal and industrial discharge points, wind direction
and distance from major urban roadways, as well as tidal regime which controls the
diluting effect of generally cleaner marine sediments relative to freshwater
discharge.[60][70][71]
Consequently, the concentrations of pollutants in estuaries tends to decrease at the
river mouth.[72]
Understanding of sediment hosted PAHs in estuaries is important for the protection of
commercial fisheries (such as mussels) and general environmental habitat conservation
because PAHs can impact the health of suspension and sediment feeding organism. [73]
River-estuary surface sediments in the UK tend to have a lower PAH content than
sediments buried 10–60 cm from the surface reflecting lower present day industrial
activity combined with improvement in environmental legislation of PAH.[71]
Typical PAH concentrations in UK estuaries range from about 19 to 16,163 µg/kg (dry
sediment weight) in the River Clyde and 626 to 3,766 µg/kg in the River Mersey.[71][74]
In general estuarine sediments with a higher natural total organic carbon content (TOC)
tend to accumulate PAHs due to high sorption capacity of organic matter.[74]
A similar correspondence between PAHs and TOC has also been observed in the
sediments of tropical mangroves located on the coast of southern China.[75]

Human health
Cancer is a primary human health risk of exposure to PAHs.[76] Exposure to PAHs has also
been linked with cardiovascular disease and poor fetal development.
Cancer
PAHs have been linked to skin, lung, bladder, liver, and stomach cancers in well-
established animal model studies.[76]
Specific compounds classified by various agencies as possible or probable human
carcinogens are identified in the section "Regulation and Oversight" below.

NANO MATERIALS:

What are Nanomaterials?

Nanomaterials are materials with at least one external dimension that measures 100
nanometers (nm) or less or with internal structures measuring 100 nm or less.
The nanomaterials that have the same composition as known materials in bulk form may
have different physico-chemical properties.

199 | P a g e
200

Materials reduced to the nanoscale can suddenly show very different properties compared
to what they show on a macroscale.
For instance, opaque substances become transparent (copper); inert materials become
catalysts (platinum); stable materials turn combustible (aluminum); solids turn into liquids
at room temperature (gold); insulators become conductors (silicon).
Nanomaterials are not simply another step in the miniaturization of materials or particles.
They often require very different production approaches.

There are several processes to create various sizes of nanomaterials, classified as ‘top-down’
and ‘bottom-up’.
Nanomaterials can be constructed by top down techniques, producing very small structures
from larger pieces of material, for example by etching to create circuits on the surface of a
silicon microchip.

They may also be constructed by bottom up techniques, atom by atom or molecule by

molecule.
One way of doing this is self-assembly, in which the atoms or molecules arrange themselves
into a structure due to their natural properties.
Crystals grown for the semiconductor industry provide an example of self assembly, as does
chemical synthesis of large molecules.
Although this 'positional assembly' offers greater control over construction, it is currently
very laborious and not suitable for industrial applications.

200 | P a g e
201

Applications of nanomaterials
If you check our links in the right column of this page you can explore lots of areas where
nanotechnology and nanomaterials are currently used.
So we don't have to repeat this here.
Suffice it to say that nanotechnology already has become ubiquitous in daily life through
commodity products and growth rates are strong.
The chart below shows how products involving nanomaterials and nanotechnology are
distributed across industries:

Global nanotechnology market by industry branches. (Source:

doi:10.1021/acsnano.1c03992)

Analyzing nanotechnology revenues by sector reveals that materials and manufacturing

contributed the most to total nanotechnology revenue. Such a trend is expected considering
that the first stage of development in creating any general purpose technology includes
foundational interdisciplinary research, which in case of nanotechnology translates into the
discovery of material properties and synthesis of nanoscale components.
However, in the upcoming years we can expect this trend to shift more toward application
sectors as nanodevices are amalgamated with existing technologies.

What is classification of nanomaterials?

Nanomaterials can be categorized into four types [9, 10] such as:
(1) inorganic-based nanomaterials;
(2) carbon-based nanomaterials;
(3) organic-based nanomaterials; and

201 | P a g e
202

(4) composite-based nanomaterials.

Generally, inorganic-based nanomaterials include different metal and metal oxide
nanomaterials.

The Environmental Impact of Nanotechnology

A potential solution to these problems is to use nanomaterials.

Nanomaterials can be used to assist with cleaning the environment and even provide
efficient energy solutions, such as nanomaterial based solar cells.

In addition to this, nanomaterials help to improve the quality and performance of many
consumer products.

As a result of this, the exposure to manufactured nanomaterials is increasing day-by-day.

However, there are both positive and negative impacts on the environment due to
nanotechnology.

Positive Impacts

With the help of nanotechnology, water quality can be improved. Some of the
nanomaterials that can be used for remediation of water are carbon nanotubes (CNTs),
zeolites, nanoparticles of zero valent iron (ZVI), silver nanoparticles, etc.

Other nanomaterials like zinc oxide (ZnO), titanium dioxide (TiO2), tungsten oxide, serve as a
photocatalyst.

These photocatalysts can oxidize organic pollutants into harmless materials.

TiO2 is the most preferred material as it has high photostability, high photoconductivity,
easily available, inexpensive and non-toxic.

Silver nanoparticles have antimicrobial effect. Also, many polymeric nanoparticles are being
used for wastewater treatment.

Another new technology is known as nanofiltration which can be used in water treatment in
homes, offices, and industries.

202 | P a g e
203

Molybdenum disulphide (MoS2) nonporous membrane is used for energy efficient

desalination of water which filters five times more than the conventional ones.

To clean oil spills in the water bodies, a nanofabric paper towel has been developed which
are woven from tiny wires of potassium manganese oxide that can absorb oil 20 times its
weight.

Thus, nanotechnology provides a solution to clean the contaminated water and

With the help of nanotechnology, toxic gases in the air can be cleaned.

But first, we have to detect the pollutants at the molecular level using precise sensors.

A sensor called nanocontact sensor has been developed which can detect the heavy metal
ions and radioactive elements.

These sensors have a small size, are inexpensive and are easy to use on-site.

Currently, single-walled nanotubes (SWNTs) are being used for the detection of NO2 and
NH3 gases. Also, SWNTs sensor can accomplish high sensing activity at room temperature
when compared to the conventional sensors which work at 200 to 600 ◦C.

Cantilever sensors have been developed to sense VOCs, heavy metals and pesticides.

A mixture of CNTs with gold particles helps adsorb toxic gases like NOx, SO2 and CO2.

Another porous nanomaterial manganese oxide has better adsorption of toxic gases due to
its large surface area.

Therefore, by detecting pollutants by specific sensors, we can help protect the sustainability
of human health and the environment.

Thus, nanotechnology provides us with a new approach to cut down the waste production,
reduce the emission of greenhouse gases and discharge of hazardous chemicals in water
bodies.

203 | P a g e
204

Negative Impacts

Nanomaterials can also have a negative impact.

Currently there is very little information describing the relative environmental risk of the
manufactured nanomaterials.

Only a few studies have been conducted with the aim of discovering the direct and indirect
exposure to nanomaterials and there are no clear guidelines to quantify the effects.

Recently, a workshop, conducted by the National Science Foundation and the US

Environmental Protection Agency, was undertaken to identify the critical risk issues
concerning nanomaterials.

Specifically, the workshop aimed at determining the exposure and toxicity of manufactured
nanoparticles, ability to extrapolate manufactured nanoparticles toxicity using existing
particle and fiber toxicology database, and recyclability and overall sustainability of the
manufactured nanomaterials.

The Applications of Nanomaterials

Materials with grain sizes in the order of a billionth of a meter are called nanomaterials, or
nanocrystalline materials. They exhibit very attractive and useful properties, which can be
used for a range of structural and non-structural applications.

Applications

As nanomaterials have exclusive, advantageous physical, chemical, and mechanical

properties, they can be applied in a host of applications including, but not limited to, those
listed below.

Next-Generation Computer Chips

The microelectronics sector has paid special attention to miniaturization, which involves
reducing the size of circuits like transistors, capacitors, and resistors.

A considerable reduction in their size enables microprocessors developed using these parts,
to operate much faster, thus allowing computations at much greater speeds.

204 | P a g e
205

However, there are a number of technical obstacles to achieving these advancements, such
as the lack of ultrafine precursors to make these parts, inadequate dissipation of huge
amounts of heat generated by these microprocessors because of faster speeds, poor mean
time to failures (poor reliability), etc.

Nanomaterials help the industry to overcome these obstacles by offering manufacturers

materials with better thermal conductivity, nanocrystalline starting materials, ultra-high-
purity materials, and longer-lasting, durable interconnections (connections between
different parts in the microprocessors).

Kinetic Energy Penetrators with Improved Lethality

The Department of Defense (DoD) has been using depleted uranium (DU) projectiles
(penetrators) for its battle against hardened targets and armored vehicles of enemies. But
DU has residual radioactivity;

therefore, it is explosive, harmful (carcinogenic), and lethal to personnel who use them.

However, some of the key reasons for the sustained use of DU penetrators are that they
have an exclusive self-sharpening mechanism on impact with a target, as well as the lack of
an appropriate non-explosive, non-toxic alternative for DU.

Nanocrystalline tungsten heavy alloys can be used for such self-sharpening mechanisms due
to their exclusive deformation characteristics, for example, grain-boundary sliding.

Therefore, nanocrystalline tungsten heavy alloys and composites are being assessed for use
as alternative DU penetrators.

Better Insulation Materials

Nanocrystalline materials manufactured by the sol-gel method give rise to foam-like

structures known as “aerogels.”

In spite of being extremely lightweight and porous, these aerogels can hold loads equal to
100 times their weight.

Aerogels are made up of continuous 3D networks of particles with air (or any other fluid,
such as a gas) trapped at their interstices.

205 | P a g e
206

Since aerogels are porous and include air trapped at the interstices, they are used for
insulation in homes, offices, etc.

This considerably reduces the cooling and heating bills, thus saving power and decreasing
the associated environmental pollution.

They are also being employed as materials for “smart” windows, which darken when the sun
is very bright (same as in changeable lenses in sunglasses and prescription spectacles), and
lighten when the sun is not shining very brightly.

Phosphors for High-Definition TV

The resolution of a monitor or television is subject to the size of the pixel.

These pixels are fundamentally composed of materials known as “phosphors,” which glow
when struck by a stream of electrons within the cathode ray tube (CRT).

The resolution enhances with a reduction in the pixel size or the phosphors.

Nanocrystalline zinc selenide, cadmium sulfide, zinc sulfide, and lead telluride prepared
through the sol-gel methods are potential materials for enhancing the resolution of
monitors.

The use of nanophosphors is intended to lower the cost of these displays to make personal
computers and high-definition televisions (HDTVs) affordable for an average household in
the United States.

Low-Cost Flat-Panel Displays

In the laptop (portable) computer industry, the demand for flat-panel displays is high.

Japan is leading in this area, mainly due to its R&D efforts on the materials for these
displays.

The resolution of these display devices can be significantly improved by synthesizing

nanocrystalline phosphors, while considerably bringing down the manufacturing costs.
Furthermore, the flat-panel displays manufactured using nanomaterials have far higher

206 | P a g e
207

contrast and brightness compared to the traditional ones due to their improved magnetic
and electrical properties.

Tougher and Harder Cutting Tools

Cutting tools made of nanocrystalline materials like carbides of tantalum, tungsten, and
titanium, are a lot harder, much more erosion-resistant and wear-resistant, and last longer
than their traditional (large-grained) equivalents.

They also allow the manufacturer to machine several materials much faster, thereby
boosting productivity and largely minimizing manufacturing costs.

Moreover, miniaturizing microelectronic circuits necessitates microdrills (drill bits having

diameters lesser than the thickness of an average human hair [100 µm]) with improved edge
retention and much better wear resistance.

Nanocrystalline carbides are being used in these micro drills since they are much harder,
stronger, and wear-resistant.

Elimination of Pollutants

Nanocrystalline materials have very large grain boundaries corresponding to their grain size.

Therefore, they are very active with regards to their physical, chemical, and mechanical
properties.

Owing to their improved chemical activity, nanomaterials can be employed as catalysts to

react with toxic and noxious gases such as nitrogen oxide and carbon monoxide, in power
generation equipment and automobile catalytic converters, to avoid environmental
pollution caused when gasoline and coal are burnt.

High Energy Density Batteries

Traditional and rechargeable batteries are used in nearly all applications that necessitate
electric power.

These applications include laptop computers, automobiles, toys, electric vehicles, personal
stereos, cordless phones, cellular phones, watches, and next-generation electric vehicles
(NGEV) that reduce environmental pollution.

207 | P a g e
208

The energy density (storage capacity) of these batteries is very low, necessitating frequent
recharging. The life of traditional and rechargeable batteries is also low.

Nanocrystalline materials produced using sol-gel methods have a foam-like (aerogel)

structure that can store significantly more energy than their traditional equivalents.

Hence, they are highly suitable for separator plates in batteries. Moreover, nickel-metal
hydride (Ni-MH) batteries made of nanocrystalline nickel and metal hydrides have been
predicted to necessitate much lesser recharging and to last considerably longer because of
their large grain boundary (surface) area and improved chemical, physical, and mechanical
properties.

High-Power Magnets

A magnet’s strength is measured in terms of saturation magnetization and coercivity values.

These values will increase when there is a decrease in the grain size and an increase in the
specific surface area (surface area per unit volume of the grains) of the grains.

It has been demonstrated that magnets made of nanocrystalline yttrium-samarium-cobalt

grains have highly uncommon magnetic properties because of their extremely large surface
area.

Common applications for these high-power rare-earth magnets include ultra-sensitive

analytical instruments, quieter submarines, land-based power generators, automobile
alternators, motors for ships, and magnetic resonance imaging (MRI) in medical diagnostics.

High-Sensitivity Sensors

Sensors use their sensitivity to detect the variations in different parameters they are
programmed to measure.

The parameters include chemical activity, thermal conductivity, electrical resistivity,

magnetic permeability, and capacitance.

All of these parameters depend a lot on the microstructure (grain size) of the materials used
in the sensors.

208 | P a g e
209

A variation in the sensor’s environment is revealed by the sensor material’s physical,

chemical, or mechanical characteristics, which is leveraged for detection.

For example, a carbon monoxide sensor made of zirconium oxide (zirconia) applies its
chemical stability to identify whether carbon monoxide is present.

When carbon monoxide is present, the oxygen atoms in zirconium oxide react with the
carbon in carbon monoxide to reduce zirconium oxide partially.

This reaction activates a modification in the sensor’s characteristics, such as capacitance and
conductivity (or resistivity).

The rate and the degree of this reaction are significantly increased by a decrease in the grain
size.

Therefore, sensors made of nanocrystalline materials are highly sensitive to variations in

their environment.

Common applications for sensors made using nanocrystalline materials are ice detectors on
aircraft wings, smoke detectors, automobile engine performance sensors, etc.

Automobiles with Greater Fuel Efficiency

Existing automobile engines waste substantial amounts of gasoline, thus adding to

environmental pollution by burning the fuel incompletely.

A traditional spark plug is not made to burn the gasoline totally and efficiently. This problem
is amplified by faulty, or worn-out, spark plug electrodes.

Since nanomaterials are harder, stronger, and considerably more erosion-resistant and
wear-resistant, they are currently being proposed for use as spark plugs.

These electrodes extend the service life of the spark plugs and help burn fuel far more
efficiently and fully.

A totally new spark plug design known as the “railplug” is also in the prototype stage.

209 | P a g e
210

This railplug applies the technology derived from the “railgun”—a spin-off of the famous
Star Wars defense program.

However, these railplugs produce much stronger sparks (with an energy density of almost 1
kJ/mm2).

Hence, traditional materials erode and corrode very quickly, and quite often are not of any
practical use in automobiles.

By contrast, railplugs made of nanomaterials are much more long-lasting than even the
traditional spark plugs.

Furthermore, automobiles waste substantial amounts of energy by losing the thermal

energy produced by the engine.

This is particularly true with diesel engines.

Hence, plans have been proposed to coat the engine cylinders (liners) with nanocrystalline
ceramics, such as alumina and zirconia, so that they preserve heat in a more efficient
manner, thus ensuring full and efficient fuel combustion.

Aerospace Components with Enhanced Performance Characteristics

Owing to the hazards involved in flying, aircraft manufacturers aim to make the aerospace
components tougher, stronger, and last longer.

One of the main properties needed in aircraft components is fatigue strength, which
declines as the age of the component increases.

By manufacturing the components using more robust materials, the aircraft’s life can be
significantly increased.

The fatigue strength increases with the decrease in the grain size of the material.

Nanomaterials offer such a considerable reduction in the grain size over traditional
materials that fatigue life is increased by an average of 200%–300%.

210 | P a g e
211

Moreover, components made using nanomaterials are stronger and can work at higher
temperatures, enabling aircraft to fly faster and more efficiently (using the same quantity of
aviation fuel).

In spacecraft, higher-temperature strength of the material is critical as the components (for

example, thrusters, rocket engines, and vectoring nozzles) work at much higher
temperatures than aircraft and at greater speeds.

Nanomaterials are ideal contenders for spacecraft applications, as well.

Better and Future Weapons Platforms

Traditional guns, such as 155 mm howitzers, cannons, and multiple-launch rocket systems
(MLRS), use the chemical energy derived by burning a charge of chemicals (gun powder).

The penetrator can be propelled at a maximum velocity of about 1.5–2.0 km/second.

Conversely, electromagnetic launchers (EML guns), or railguns, utilize electrical energy, as

well as the concomitant magnetic field (energy), for propelling the penetrators/projectiles
at velocities of up to 10 km/second.

Such an increase in velocity causes greater kinetic energy for the same penetrator mass.

The amount of energy is directly proportional to the damage imparted to the target.
Therefore, the DoD (particularly the U.S. Army) has undertaken wide-ranging research on
the railguns.

Since a railgun works on electrical energy, the rails have to be excellent conductors of
electricity.

Furthermore, they need to be so strong and inflexible that the railgun does not sag while
firing and collapse due to its own weight.

Copper is the apparent choice when it comes to high electrical conductivity.

However, railguns made of copper wear out considerably faster because of the erosion of
the rails by the hypervelocity projectiles.

211 | P a g e
212

Moreover, they lack high-temperature strength. The erosion and wear of copper rails call for
very frequent barrel replacements.

To fulfill these necessities, a nanocrystalline composite material made of copper, tungsten,

and titanium diboride is being assessed as a potential candidate.

This nanocomposite exhibits the necessary electrical conductivity, satisfactory thermal

conductivity, outstanding high strength, hardness, high rigidity, and wear/erosion
resistance.

This results in erosion-resistant and wear-resistant railguns that last longer and can be fired
more often than their traditional equivalents.

Longer-Lasting Satellites

Satellites are being employed for both civilian and defense applications.

These satellites make use of thruster rockets to stay in or alter their orbits because of
various factors, such as the impact of gravitational forces applied by the earth.

Hence, thrusters are needed to reposition the satellites.

To a great extent, the life of these satellites is governed by the amount of fuel they can take
on board.

In reality, repositioning thrusters waste over one-third of the fuel carried aboard by the
satellites, caused by partial and inefficient burning of the fuel, such as hydrazine.

The partial and inefficient combustion occurs due to rapid wearing out of onboard ignitors
that stop performing effectively as a result.

Nanomaterials like nanocrystalline tungsten-titanium diboride-copper composite are

promising options for improving the performance features and life of these ignitors.

Longer-Lasting Medical Implants

In general, medical implants like heart valves and orthopedic implants are made of stainless
steel and titanium alloys.

212 | P a g e
213

These alloys are mainly used in humans as they are biocompatible, that is, they do not
adversely react with human tissue.

These materials are comparatively non-porous when used in orthopedic implants (artificial
bones for hip, etc.).

If an implant must mimic a natural human bone in an effective way, the adjacent tissue
must penetrate the implants, thus offering the implant the necessary strength.

Since these materials are comparatively impermeable, human tissue does not penetrate the
implants, thus minimizing their effectiveness.

Moreover, these metal alloys wear out fast, requiring frequent and very expensive
surgeries.

But nanocrystalline zirconia (zirconium oxide) ceramic is hard, corrosion-resistant (biological

fluids are corrosive), wear-resistant, and biocompatible.

It is also possible to make nanoceramics porous as aerogels (aerogels can endure up to 100
times their weight) if they are produced using sol-gel methods.

This would lead to much lesser implant replacements, and thus a substantial reduction in
surgical expenses.

Nanocrystalline silicon carbide (SiC) is a potential material for artificial heart valves mainly
because of its low weight, wear resistance, extreme hardness, high strength, corrosion
resistance, and inertness (SiC does not react with biological fluids).

Ductile, Machinable Ceramics

As such, ceramics are extremely hard, brittle, and tough to machine.

These properties of ceramics have dissuaded prospective users from leveraging their
advantageous properties.

However, these ceramics have been used more and more with reduced grain size.

213 | P a g e
214

Zirconia, a hard, brittle ceramic, has even been made a superplastic, that is, it can be
deformed to greater lengths (up to 300% of its initial length).

However, these ceramics must have nanocrystalline grains to be superplastic.

Actually, nanocrystalline ceramics like silicon carbide (SiC) and silicon nitride (Si3N4) have
been used in automotive applications such as ball bearings, high-strength springs, and valve
lifters.

This is because they have good machinability and formability, together with superior
physical, mechanical, and chemical properties.

They are also used as components in high-temperature furnaces.

It is possible to press and sinter nanocrystalline ceramics into different shapes at

considerably lower temperatures.

By contrast, it would be very hard, if not impracticable, to press and sinter traditional
ceramics even at high temperatures.

Large Electrochromic Display Devices

An electrochromic device comprises materials wherein an optical absorption band can be

added, or a current band can be modified by passing current through the materials, or by
applying an electric field.

Nanocrystalline materials like tungstic oxide (WO3⋅xH2O) gel are used in huge
electrochromic display devices.

The reaction controlling electrochromism (a reversible coloration process that is influenced

by an electric field) is the double-injection of ions (or protons, H+) and electrons, which form
tungsten bronze by combining with the nanocrystalline tungstic acid.

These devices are mainly used in ticker boards and public billboards to send information.

Electrochromic devices are analogous to liquid-crystal displays (LCD) generally used in

watches and calculators.

214 | P a g e
215

But electrochromic devices display information by changing in color in response to an

applied voltage.

The color gets bleached upon reversing the polarity.

The resolution, contrast, and brightness of these devices largely rely on the tungstic acid
gel’s grain size.

Therefore, nanomaterials are being investigated for this purpose.

Summary

From the examples provided in the article, it is quite clear that nanocrystalline materials
produced by the sol-gel method can be used in an extensive range of unique, new, and
existing applications.

It is also obvious that nanomaterials outclass their traditional counterparts by virtue of their
excellent physical, chemical, and mechanical properties, and by their outstanding
formability.

215 | P a g e
216

CNT-CARBON NANOTUBE:

216 | P a g e
217

217 | P a g e
218

218 | P a g e
219

219 | P a g e
220

220 | P a g e
221

221 | P a g e