CHAPTER ONE

INTRODUCTION TO WASTEWATER TREATMENT

1.1 General

Wastewater is water whose physical, chemical or biological properties have been changed as a
result of the introduction of certain substances which render it unsafe for some purposes such as
drinking. The day-to-day activities of man is mainly water dependent and therefore discharge
‘waste’ into water. Wastewater treatment is the process and technology that is used to remove
most of the contaminants that are found in wastewater to ensure a sound environment and good
public health.
Wastewater collected from urban areas and from different industries must ultimately be returned
to receiving water bodies or to the land. The complex question of which contaminants in
wastewater must be removed is to protect the environment and to what extent must be answered
specifically for each case. This requires analyses of local conditions and needs together with the
application of scientific knowledge, engineering judgment based on past experience, and
consideration of federal, state and local requirements and regulations.
The presence of different pollutants in the wastewater makes it almost impossible to treat all the
wastewater in the same manner. Some important contaminants/pollutants of concern in
wastewater treatment are given in the Table 1.1.
The contaminants (pollutants) in wastewater are removed by physical, chemical and/or biological
means, and the individual methods usually are classified as physical, chemical and biological
unit processes or operations.
Treatment methods in which the application of physical forces predominates are known as
physical unit operations. Typical physical unit operations are: screening, mixing, flocculation,
sedimentation, flotation, and filtration and membrane filter operations.
Treatment methods in which the removal or conversion of contaminants is brought about by the
addition of chemicals or by other chemical reactions are known as chemical unit processes.
Neutralization, oxidation, reduction, precipitation, gas transfer, adsorption, ion-exchange,
electro-dialysis etc. are the most common examples of these processes used in wastewater
treatment.
Treatment methods in which the removal of contaminants is brought about by biological activity
are known as biological unit processes.
Biological treatment is used primarily to remove the biodegradable organic substances (colloidal
or dissolved) in wastewater. Basically, these substances are converted into gases that can escape
to the atmosphere and into biological cell tissue that can be removed by settling. The most
common approaches in the biological wastewater treatments are: aerobic processes such as

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trickling filters, activated sludge, oxidation ponds (or lagoons), and anaerobic processes such as
anaerobic lagoons, sludge digestion, etc.
Usually in the municipal wastewater treatment, but also in other wastewater processing the entire
above mentioned unit operations and processes are grouped together to provide what is known as
primary, secondary and tertiary (or advanced) treatment.
The term primary refers to physical unit operations and in some cases to chemical unit processes;
secondary refers to biological unit processes; and tertiary refers to combinations of all three.
The contaminants of major interest in wastewater and the unit operations and processes or
methods applicable to the removal of these contaminants are shown in Table 1.1.
In addition to the above mentioned classical basic processes, some new directions are also
evident in various specific areas of wastewater treatment, including:
(i) modification in treatment operations, processes and concepts
(ii) the changing nature of the wastewater to be treated
(iii) the problem of industrial wastes
(iv) wastewater treatability studies
(v) environmental and energy concerns
(vi) land treatment
(vii) small and individual onsite systems

Table 1.1 Important contaminants of concern in wastewater treatment

Contaminants Reason for importance
Suspended Suspended solids can lead to the development of sludge deposits and
solids anaerobic conditions when untreated wastewater is discharged in the aquatic
environment
Biodegradable Composed principally of proteins, carbohydrates and fats, biodegradable
organics organics are measured most commonly in terms of BOD and COD. If
discharged untreated to the environment, their biological stabilization can
lead to the depletion of natural oxygen resources and to the development of
septic conditions
Pathogens Communicable diseases can be transmitted by the pathogenic organisms in
wastewater
Nutrients Both nitrogen and phosphorus, along with carbon, are essential nutrients for
growth. When discharged to the water these nutrients can lead to the growth
of undesirable aquatic life. When discharged in excessive amounts on land
they can also lead to the pollution of groundwater
Refractory These organics tend to resist conventional methods of wastewater treatment.

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 organics Typical examples include surfactants, phenols, and agricultural pesticides
Heavy metals Heavy metals are usually added to wastewater from commercial and
industrial activities and may have to be removed if the wastewater is to be
reused
Dissolved Inorganic constituents such as calcium, sodium, and sulfate are added to the
inorganic solids original domestic water supply as a result of water use and may have to be
removed if the wastewater is to be reused
Source: Metcalf & Eddy, Wastewater engineering

Table 1.1 Unit operations, processes, and treatment systems

Unit Operation, Unit Process, or
Contaminant Classification
Treatment System
Suspended solids Screening and comminution P
Sedimentation P
Flotation P
Filtration P
Coagulation / sedimentation C/P
Land treatment P
Biodegradable Activated sludge B
Organics Trickling filters B
Rotating biological contactors B
Aerated lagoons B
Oxidation ponds B
Intermittent sand filtration P/B
Land treatment B/C/P
Physical / chemical P/C
Pathogens Chlorination C
Ozonation C
Land treatment P
Nutrients: Suspended-growth nitrification and denitrification B
Nitrogen Fixed-film nitrification and denitrification B
Ammonia stripping C/P
Ion exchange C
Breakpoint chlorination C
Land treatment B/C/P
Phosphorus Metal salt coagulation/sedimentation C/P
Lime coagulation / sedimentation C/P
Biological/chemical C/P
phosphorus removal B/C
Land treatment C/P
Refractory organics Carbon adsorption P

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 Tertiary ozonation C
Land treatment systems P
Heavy metals Chemical precipitation C
Ion exchange C
Land treatment C/P
Dissolved inorganic Ion exchange C
Solids Reverse osmosis P
Electrodialysis C
*B = biological, C = chemical, P = physical

1.2 Wastewater sources and quantity

The design of a wastewater treatment plant requires knowledge of the quantity or flow rate of the
wastewater, the quality of the untreated or raw wastewater, and the quality required for the
effluent.
Wastewater may be classified into the following components
♥ Domestic or sanitary wastewater (from residential and commercial districts and
institutional facilities) is the liquid wastewater discharged from sanitary facilities within a
building, such as residence, business building, and institutions.
♥ Industrial wastewater is the liquid wastewater discharged from an industry, such as a
papermaking plant or food processing.
♥ Storm sewage or storm water is the storm runoff that occurs from rainfall.
♥ Infiltration is the groundwater or rainfall seepage that enters sanitary sewers through
cracks in pipe joints and manholes, service connections, and defective pipes.
♥ Inflow is relatively unpolluted water that enters through such sources as manhole covers,
roof downspouts, yard drains, foundation drains, and cooling-water discharge from air
conditioners and industries.

1.3 Objectives of Wastewater Treatment

1. To introduce fundamentals of the wastewater treatment plants and their unit operations
and processes
2. To provide basic design skills and knowledge on the wastewater treatment plants and
their unit operations and processes
3. To experience a design project on a hypothetical wastewater treatment plant
a. Identify kinds and sources of wastewater
b. Describe hazards in wastewater
c. Describe ways of treating wastewater

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 d. Describe the products of wastewater treatment, including the production and use
of biosolids
The overall objectives of wastewater treatment are associated with the removal of pollutants and
the protection and preservation of our natural resources.
Specific concern is protection of human health by the destruction of pathogenic organisms
present in wastewater prior to treated effluent being discharged to receiving water bodies and
land.

1.4 Wastewater Treatment Standards

Effluents from different establishments should be treated before being discharged to receiving
bodies so that it should be:
1. Free from materials and heat in quantities, concentrations or combinations which are
toxic or harmful to human, animal, aquatic life.
2. Free from anything that will settle in receiving waters forming putrescence or otherwise
objectionable sludge deposits, or that will adversely affect aquatic life.
3. Free from floating debris, oil, scum and other materials in amounts sufficient to be
noticeable in receiving waters;
4. Free from materials and heat that alone, or in combination with other materials will
produce color, turbidity, taste or odour in sufficient concentration to create a nuisance or
adversely affect aquatic life in receiving waters;
5. Free from nutrients in concentrations that create nuisance growths of aquatic weeds or
algae in the receiving waters.
A significant element in wastewater disposal is the potential environmental impact associated
with it.
Environmental standards are developed to ensure that the impacts of treated wastewater
discharges into ambient waters are acceptable. Standards play a fundamental role in the
determination of the level of wastewater treatment required and in the selection of the discharge
location and outfall structures.
Regulations and procedures vary from one country to another and are continuously reviewed and
updated to reflect growing concern for the protection of ambient waters. The United States
Environmental Protection Agency (USEPA) developed the National Pollutant Discharge
Elimination System (NPDES) permit program in 1972 to control water pollution by regulating
point sources that discharge pollutants into waters. Accordingly, industrial, municipal, and other
facilities are required to obtain permits if their discharges go directly into surface waters. Under
this program, secondary treatment standards were established by USEPA for publicly owned

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treatment works, governing the performance of secondary wastewater treatment plants. These
technology-based regulations, which apply to all municipal waste-water treatment plants,
represent the minimum level of effluent quality attainable by secondary treatment in terms of
BOD5 and TSS removal.
Specific Limits
Effluents discharged to receiving water bodies should achieved the following minimum
wastewater quality limits:
Parameter Effluent Limit
BOD5 20mg/l
TSS 30mg/l
Nitrates (as Nitrogen) 30mg/l
Phosphate 10mg/l
COD 100mg/l
pH 6–9
Residual chlorine 1.5mg/l
MPN- Most Probable Number

1.5 Flow Sheets for Wastewater Treatment Systems

Depending on the contaminants to be removed, an almost limitless number of process

combinations can be developed using the unit operations and processes. The term "flow sheet" is
used to describe a particular combination of unit operations and processes used to achieve a
specific treatment objective. Apart from the analysis of the technical feasibility of the individual
treatment methods, the exact flow-sheets configuration will depend on factors such as:
(1) the needs of the client's needs,
(2) the designer's past experience,
(3) regulatory agency policies on the application of specific treatment methods,
(4) the availability of equipment suppliers,
(5) what use can be made of existing facilities,
(6) the availability of qualified operating personnel,
(7) initial construction costs, and
(8) future operation and maintenance costs
Conventional flow sheets for the treatment of wastewater are presented and discussed below.
The choice of a set of treatment methods depends on several factors, including discharge permits
and available disposal facilities. For example, where an ocean discharge is used, removal of large
debris by screens and of settleable solids by sedimentation may be the only treatment steps that

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are required. Where treated effluent is to be discharged to an inland stream, complete treatment
may be required. Discharges to environmentally sensitive lakes, streams, and estuaries may
require additional treatment to remove specific constituents.
Treatment schemes are often identified as primary, secondary, or advanced (also known as
tertiary). In primary treatment, a portion of the suspended solids and organic matter is removed
from the wastewater. This removal is usually accomplished with physical operations such as
screening and sedimentation. The effluent from primary treatment will ordinarily contain
considerable organic matter and will have a relatively high BOD. The further treatment of the
effluent from primary treatment to remove the residual organic matter and suspended material is
known as secondary treatment. In general, biological processes employing microorganisms are
used to accomplish secondary treatment. The effluent from secondary treatment usually has little
BOD5 and suspended solids and may contain several milligrams per liter of dissolved oxygen.
When required for water reuse or for the control of eutrophication in receiving waters, advanced
(tertiary) treatment is used for the removal of suspended and dissolved materials remaining after
secondary treatment.
Actually, the distinction between primary, secondary, and advanced treatment is rather arbitrary,
as many modern treatment methods incorporate physical, chemical, and biological processes in
the same operation. A more rational approach would be to drop these arbitrary distinctions and to
focus instead on the optimum combinations of operations and processes that must be used to
achieve the required treatment objectives.
Typical flow sheets for the treatment of wastewater are presented in Error: Reference source not
found

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Figure 1.1 Flow chart for wastewater treatment processes
The diagram demonstrates how the treatment plant works and how the different processes are
inter-connected to work as one. Each treatment process in the flow sheet will be discussed in
chapter 3 and 4.

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 CHAPTER TWO
CHARACTERISTICS OF WASTEWATER
Wastewater contains many different substances that can be used to characterize it. The specific
substances and amounts or concentrations of each will vary depending on the source. It is
difficult to precisely characterize wastewater. Instead, wastewater characterization is usually
based on and applied to an average domestic wastewater.
Note: Keep in mind that other sources and types of wastewaters can dramatically change the
characteristics.

2.1 Physical, Chemical and Bacteriological Characteristic of Wastewater

Wastewater is characterized in terms of its physical, chemical, and biological characteristics.

A. Physical Characteristics
The physical characteristics of wastewater are based on color, odor, temperature, and flow.
1. Turbidity
Sewage is normally turbid, resembling dirty dish water or wastewater from baths having other
floating matter like fecal matter, pieces of paper, cigarette-ends, match-sticks, greases, vegetable
debris, fruit skins, soaps, etc. The turbidity increases as sewage becomes stronger.
The degree of turbidity can be measured and tested by turbidity rods or by turbid-meters, as is
done for testing raw water supplied.
2. Color
Fresh wastewater is usually a light brownish-gray color. However, typical wastewater is gray and
has a cloudy appearance. The color of the wastewater will change significantly if allowed to go
septic (if travel time in the collection system increases). Typical septic wastewater will have a
black color.
3. Odor
Odors in domestic wastewater usually are caused by gases produced by the decomposition of
organic matter or by other substances added to the wastewater. Fresh domestic wastewater has a
musty odor. If the wastewater is allowed to go septic, this odor will significantly change to a
rotten egg odor associated with the production of hydrogen sulfide (H2S).
4. Temperature
The temperature of wastewater is commonly higher than that of the water supply because of the
addition of warm water from households and industrial plants. However, significant amounts of
infiltration or storm water flow can cause major temperature fluctuations.

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The temperature has an effect on the biological activity of bacteria present in sewage, and it also
affects the solubility of gases in sewage. In addition, temperature also affects the viscosity of
sewage, which, in turn, affects the sedimentation process in its treatment.
The normal temperature of sewage is generally slightly higher than the temperature of water,
because of additional heat added during the utilization of water. The ideal temperature of sewage
for the biological activities is 20°c. However, when the temperature is more, the dissolved
oxygen content (DO) of sewage gets reduced.
B. Chemical Characteristics
In describing the chemical characteristics of wastewater, the discussion generally includes topics
such as organic matter, the measurement of organic matter, inorganic matter, and gases. For the
sake of simplicity, chemical characteristics can be described in terms of alkalinity, BOD,
chemical oxygen demand (COD), dissolved gases, nitrogen compounds, pH, phosphorus,
chloride and solids (organic, inorganic, suspended, and dissolved solids).
1. Total Solids, Suspended Solids and Settle able Solids
Most pollutants found in wastewater can be classified as solids. Wastewater treatment is
generally designed to remove solids or to convert solids to a form that is more stable or can be
removed. Sewage normally contains very small amount of solids in relation to the huge quantity
of water (99.9%). It only contains about 0.05 to 0.1 percent (i.e. 500 to 1000 mg/l) of total solids.
Solids present in sewage may be in any of the four forms: suspended solids, dissolved solids,
colloidal solids, and settleable solids.
Suspended solids are those solids which remain floating in sewage. Dissolved solids are those
which remain dissolved in sewage just as salt in water. Colloidal solids are finely divided solids
remaining either in solution or in suspension. Settleable solids are that portion of solid matter
which settles out, if sewage is allowed to remain undisturbed for a period of 2 hours. The
proportion of these different types of solids is generally found to be as given below:
Inorganic matter consists of minerals and salts, like: sand, gravel, debris, dissolved salts,
chlorides, sulphates, etc.
Organic matter consists of:
(i) Carbohydrates such as cellulose, cotton, fiber, starch, sugar, etc.
(ii) Fats and oils received from kitchens, laundries, garages, shops, etc.
(iii) Nitrogenous compounds like proteins and their decomposed products, including
wastes from animals, urea, fatty acids, hydrocarbons, etc.
As a general rule, the presence of inorganic solids in sewage is not harmful. They require only
mechanical appliances for their removal in the treatment plant. On the other hand, suspended and

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dissolved organic solids are responsible for creating nuisance, if disposed of, untreated. The
amounts of various kinds of solids present in sewage can be determined as follows:
(a) The total amount of solids (S1 in mg/l) present in a given sewage can be determined by
evaporating a known volume of sewage sample, and weighing the dry residue left. The mass
of the residue divided by the volume of the sample evaporated will represent the total solids
mr
in mg/l, S1. ( S1 = )
Ve
(b) The suspended solids (S2) are those solids which are retained by a filter of 1µm pores; and
they are, therefore, also called as filterable solids. Their quantity can be determined by
passing a known volume of sewage sample through a glass-fiber filter apparatus, and
weighing the dry residue left: The mass of the residue divided by the volume of sample
mr
filtered will represent the suspended solids, (S2), in mg/l. S2=
Vf
(c) The difference between the total solids (S 1) and the suspended solids (S2) will represent
nothing but dissolved solids plus colloidal, or non-filterable solids; S3 where S3 = S1 - S2,
(d) Now, the total suspended solids (S 2) may either be volatile or fixed. In order to determine
their proportion, the filtered dry residue of step (b) above, is burnt and ignited at about
550°c in an electric muffle furnace for about 15 to 20 minutes. Loss of weight due to
ignition will represent the volatile solids in the sample volume filtered through the filter. Let
the volatile suspended solids concentration be S4 (in mg/l).
(e) The difference S2 - S4 = S5 will evidently represent the fixed solids.
(f) The quantity of settleable solids (S6) can be determined easily with the help of a specially
designed conical glass vessel called Imhoff cone (Refer Figure 2.1). The capacity of the cone
is 1 liter, and it is graduated up to about 50 ml.

Figure 2.1 Imhoff cone

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Sewage is allowed to stand in this Imhoff cone for a period of two hours, and the quantity of
solids settled in the bottom of the cone can then be directly read out. However, in order to obtain
precise amount of settle able solids, the liquid from the cone should be decanted off, and the
settleable solids collected at the bottom of the cone should be dried and weighed. The quantities
of different types of solids when determined experimentally as above will help in detecting the
strength of sewage, as given in Table 2.2.
2. Alkalinity
This is a measure of the wastewater’s capability to neutralize acids. It is measured in terms of
bicarbonate, carbonate, and hydroxide alkalinity. Alkalinity is essential to buffer (hold the
neutral pH) of the wastewater during the biological treatment processes.
3. pH
This is a method of expressing the acid condition of the wastewater. pH is expressed on a scale
of 1 to 14. For proper treatment, wastewater pH should normally be in the range of 6.5 to 9.0.
The determination of pH value of sewage is important, because of the fact that efficiency of
certain treatment methods depends upon the availability of a suitable pH value.
It may also be mentioned here that the fresh sewage is generally alkaline in nature (with pH more
than 7); but as time passes, its pH tends to fall due to production of acids by bacterial action in
anaerobic or nitrification processes. The pH, however, rises upon treatment of sewage.
4. Chloride Contents
Chlorides are generally found present in municipal sewage and are derived from the kitchen
wastes, human feces, and urinary discharges, etc. The normal chloride content of domestic
sewage is 120mg/l, whereas, the permissible chloride content for water supplies is 250mg/l.
However, large amounts of chlorides may enter from industries like ice cream plants, meat
salting, etc., thus, increasing the chloride contents of sewage. Hence, when the chloride content
of a given sewage is found to be high, it indicates the presence of industrial wastes or infiltra tion
of sea water, thereby indicating the strength of sewage.
The chloride content can be measured by titrating the wastewater (i.e. sewage) with standard
silver nitrate solution, using potassium chromate as indicator as is done for testing water sup-
plies.
5. Dissolved gases
These are gases that are dissolved in wastewater. The specific gases and normal concentrations
are based upon the composition of the wastewater. Typical domestic wastewater contains oxygen
in relatively low concentrations, carbon dioxide, and hydrogen sulfide (if septic conditions exist).

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6. Dissolved Oxygen (DO)
The determination of dissolved oxygen present in sewage is very important, because: while
discharging the treated sewage into some river stream, it is necessary to ensure at least 4ppm of
DO in it; as otherwise, fish are likely to be killed, creating nuisance near the vicinity of disposal.
To ensure this, DO tests are performed during sewage disposal treatment processes.
The DO test performed on sewage before treatment helps in indicating the condition of sewage.
It is well known by now that only very fresh sewage contains some dissolved oxygen, which is
soon depleted by aerobic decomposition. Also, the dissolved oxygen in fresh sewage depends
upon temperature. If the temperature of sewage is more, the DO content will be less. The
solubility of oxygen in sewage is 95% of that in distilled water.
The DO content of sewage is generally determined by the Winkler's method which is an
oxidation- reduction process carried out chemically to liberate iodine in amount equivalent to the
quantity of dissolved oxygen originally present.
7. Bio-Chemical Oxygen Demand (BOD)
Biochemical oxygen demand is used as a measure of the quantity of oxygen required for
oxidation of biodegradable organic matter present in the wastewater by aerobic biochemical
action. The rate of oxygen consumption in a wastewater is affected by a number of variables:
temperature, pH, the presence of certain kinds of microorganisms, and the type of organic and
inorganic material in the wastewater. BOD directly affects the amount of DO within the
wastewater.
The greater the BOD, the more rapidly oxygen is depleted in the water body, leaving less oxygen
available to higher forms of aquatic life. The consequences of high BOD are the same as those
for low DO: aquatic organisms become stressed, suffocate, and die.
BOD is one of the most important and useful parameters (measured characteristics) indicating
the organic strength of a wastewater. BOD measurement permits an estimate of the waste
strength in terms of the amount of dissolved oxygen required to break down the wastewater.
8. Chemical Oxygen Demand (COD)
COD measures the total quantity of oxygen required for oxidation of organics into carbon
dioxide and water. The oxygen required to oxidize the organic matter present in a given
wastewater can be theoretically computed, if the organics present in wastewater are known.
Thus, if the chemical formulas and the concentrations of the chemical compounds present in
water are known to us, we can easily calculate the theoretical oxygen demand of each of these

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compounds by writing the balanced reaction for the compound with oxygen to produce CO 2, H2O
and oxidized inorganic components.
Hence, if the organic compounds and their concentrations are known, the theoretical oxygen
demand of the water can be accurately calculated, but it is virtually impossible to know the
details of the organic compounds present in any natural raw water or a waste water.
9. Total Organic Carbon
Another important method of expressing organic matter is in terms of its carbon content. Carbon
is the primary constituent of organic matter, and hence the chemical formula of every organic
compound will reflect the extent of carbon present in that compound. Known concentrations of
such chemical compounds in a given wastewater will thus enable us to theoretically calculate the
carbon present in that wastewater per liter of solution.
C. Biological Characteristics
The bacterial characteristics of sewage are due to the presence of bacteria and other living micro-
organisms, such as algae, fungi, protozoa, etc. The former are more active.
Most of the vast number of bacteria present in sewage (of the order of 5 - 50 billion per liter of
sewage) is harmless non-pathogenic bacteria. They are useful and helpful in bringing oxidation
and decomposition of sewage. A little number of bacteria, however, is disease producing
pathogens, and it is they who constitute the real danger to the health of the public.
In case of sewage, the routine bacteriological tests as performed on water supply samples are
generally not performed, because of the high concentration of bacteria present in it. But at the
times of epidemiological investigations, certain tests may be useful for separating the pathogenic
bacteria. The bacteriological counts may also be useful where the treatment processes are likely
to be affected adversely by bactericidal industrial wastewaters.

Table 2.2 Summary of typical domestic wastewater characteristics

Concentration
Contaminants
Unit Weak Medium Strong
Total solids (TS) mg/l 350 720 1200
Total dissolved solids
(TDS) mg/l 250 500 850
Fixed mg/l 145 300 525
Volatile mg/l 105 200 325
Suspended solids mg/l 100 220 350
Fixed mg/l 20 55 75
Volatile mg/l 80 165 275
Settleable solids mg/l 5 10 20
BOD5, 20⁰c mg/l 110 220 400

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 TOC mg/l 80 160 290
COD mg/l 250 500 1000
Nitrogen (total as N) mg/l 204 40 85
Organic mg/l 81 153 35
Free ammonia mg/l 12 25 50
Nitrites mg/l 0 0 0
Nitrates mg/l 0 0 0
Phosphorus (total as P) mg/l 4 8 15
Organic mg/l 13 3 5
Inorganic mg/l 3 5 10
Chlorides mg/l 30 50 100
Sulfate mg/l 20 30 50
Alkalinity (as CaCO3) mg/l 50 100 200
Grease mg/l 50 100 150
6 7 7 8
Total coli forms No/100 ml 10 - 10 10 - 10 107- 109
Volatile organic compounds µg/l < 100 100 - 400 > 400
Source: Adapted from Metcalf and Eddy Inc., Wastewater Engineering, 3rd edition.

2.2 Measurement of Concentration of Contaminants in Wastewater

Contaminants in wastewaters are usually a complex mixture of organic and inorganic

compounds. It is usually impractical, if not nearly impossible to obtain complete chemical
analysis of most wastewaters.
However, since it is comparatively easy to measure the amount of oxygen used by the bacteria as
they oxidize the wastewater, the concentration of organic matter in the wastewater can easily be
expressed in terms of the amount of oxygen required for its oxidation. The most important
standard methods for analysis of organic contaminants are:

1. Theoretical Oxygen Demand (ThOD)

This is the theoretical amount of oxygen required to oxidize the organic fraction of the
wastewater completely to carbon dioxide and water. The equation for the total oxidation of, say,
glucose is:

With C = 12, H = 1 and O = 16, C 6H12O6 is 180 and 6O2 is 192; we can thus calculate that the
192
ThOD of, for example, a 300 mg/l solution of glucose is ∗300=321mg/l . Because
180
wastewater is so complex in nature its ThOD cannot be calculated, but in practice it is
approximated by the chemical oxygen demand.

2. Chemical Oxygen Demand (COD)

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The chemical oxygen demand (COD) of a raw water or a wastewater is determined by
performing a laboratory test on the given wastewater with a strong oxidant like dichromate
solution; and the theoretical computations of COD are only performed on water solutions
prepared with the known amounts of specific organic compounds in laboratory situations to
compare the theoretical and test results, and to establish the limitations of the test procedures.
The laboratory determination of COD, as said above, lies in using a strong oxidant like
potassium dichromate (K2Cr2O7) or potassium permanganate (KMnO4) solution to stabilize the
organic matter to determine the molecular oxygen used from the oxidant solution in oxidizing the
organic matter present in the given wastewater.
In order to perform this test, a known quantity of wastewater is mixed with a known quantity of
standard solution of potassium dichromate, and the mixture is heated. The organic matter is
oxidized by K2Cr2O7 (in the presence of H2SO4 (helps to digest/break down the complex
molecules)). The resulting solution of K2Cr2O7 is titrated with standard ferrous ammonium
sulphate [Fe (NH4)2.(SO4)2.6H2O)], and the oxygen used in oxidizing the wastewater is
determined. This is called the chemical oxygen demand (COD) and is a measure of organic
matter present in sewage.
The advantage of COD measurements is that they are obtained very quickly (within 3 hours), but
they have the disadvantages that they do not give any information on the proportion of the
wastewater that can be oxidized by bacteria, nor on the rate at which bio-oxidation occurs.

3. Biochemical Oxygen Demand (BOD)

Oxygen demand of wastewaters is exerted by three classes of materials:

(1) Carbonaceous organic materials usable as a source of food by aerobic organisms
(2) oxidizable nitrogen derived from nitrite, ammonia, and organic nitrogen compounds
which serve as food for specific bacteria (e.g., Nitrosomonas and Nitrobacter).
(3) Chemical reducing compounds, e.g., ferrous ion (Fe 2+), sulfites (SO32-), and sulfide (S2-)
which are oxidized by dissolved oxygen.
For domestic sewage, nearly all oxygen demand is due to carbonaceous organic materials and is
determined by BOD dilution test. For effluents subjected to biological treatment, a considerable
part of the oxygen demand may be due to nitrification.
BOD Dilution Test
Procedure is given below.
1. Prepare several dilutions of the sample to be analyzed with distilled water of high purity.
Recommended dilutions depend on estimated concentration of contaminants responsible for
oxygen demand. For highly contaminated waters, dilution ratios (ml of diluted sample/ml of
original sample) may be of 100:1. For river waters, the sample may be taken without dilution

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 for low pollution streams, and in other cases dilution ratios of 4:1 may be utilized.
2. Incubation bottles (250ml to 300ml capacity), with ground-glass stoppers are utilized.
In the BOD bottle one places:
(a) the diluted sample (i.e., the “substrate")
(b) a seed of microorganisms (usually the supernatant liquor from domestic sewage), and
(c) Nutrient solution for the microorganisms.
This solution contains sodium and potassium phosphates ammonium chloride (nitrogen and
phosphorus are elements needed as nutrients for microorganisms). The pH of the solution in
the BOD bottle should be about 7.0 (neutral). Phosphate solution utilized is a buffer. For
samples containing caustic alkalinity or acidity, neutralization to about pH 7 is made with
dilute H2SO4 or NaOH prior to the BOD test.
For each BOD bottle a control bottle which does not contain the substrate is also prepared.
Bottles are incubated at 20°c for 5 days. Light must be excluded from the incubator to
prevent algal growth that may produce oxygen in the bottle. The DO content before the
incubation and after the incubation is thus determined. The difference between
concentrations of dissolved oxygen (mg/liter) in control bottle and in sample bottle
corresponds to the oxygen utilized in biochemical oxidation of contaminants.
When the dilution water is not seeded:
DO1 −DO2
BOD5 , mg/lit= 2.1
P
When the dilution water is seeded:
( DO 1−DO2 ) −( DO S 1−DO S 2 )∗f
BOD5 , mg/lit= 2.2Where, DO1 – dissolved oxygen of the
P
diluted sample immediately after preparation, mg/l
DO2 – dissolved oxygen of the diluted sample after 5 day incubation at 20ºc, mg/l
DOS1 – dissolved oxygen of seed control before incubation, mg/l
DOS1 – dissolved oxygen of seed control after incubation, mg/l
f – fraction of seeded dilution water volume in sample to volume of seeded dilution
water in seed control
P – fraction of wastewater sample volume to total combined volume
 Seeding: a process in which the microorganisms that oxidize organic matter are added to
the BOD bottle
As pointed out earlier, this test is conducted to determine the oxygen demand for the first five
days on a number of samples, and their average value is taken as the BOD 5 at the test
temperature.

Wastewater Treatment Lecture Note Page 17

If the oxygen supply is made available for periods more than 5 days, it is found that the oxygen
is consumed rapidly for 6 or 7 days, and then slows down until the end of about 20 days or more.
This value is called ultimate BOD denoted as BODu.
Thereafter, it may again accelerate for some time, and again slow down to a very low rate for an
indefinite period. The first demand during the first 20 days occurs due to the oxidation of organic
matter, and is called carbonaceous demand or first stage demand or initial demand. The latter
demand occurs due to biological oxidation of ammonia, and is called nitrogenous demand or
second-stage demand.
A typical BOD curve (BOD vs. incubation time) for oxidation of carbonaceous materials is
shown in Figure 2.2 In fact, a sanitary engineer is more concerned with the first stage demand,
since the oxygen consumed in its satisfaction is not recoverable. Hence, the term BOD is usually
used to mean the first stage BOD, i.e. the demand due to the presence of carbonaceous matter
alone.

Figure 2.2 Typical BOD curve for oxidation of carbonaceous materials

a. Ratio of COD and BOD

The value of BODu is generally lower than that for COD obtained by the standard dichromate
oxidation method. The reasons are that:
(1) many organic compounds which are oxidized by K2Cr2O7 are not biochemically oxidizable
(2) certain inorganic ions such as sulfide (S2-), thiosulfates (S2O32-), sulfites (SO32-), nitrites
(NO2-), and ferrous ion (Fe2+) are oxidized by K2Cr2O7, thus accounting for inorganic COD
which is not detected by the BOD test.
BOD
The ratio will always be less than 1.0; but this value shall approach towards 1.0 with the
COD
decreasing amount of non-biological organics.
If this ratio is found to be between 0.92 and 1.0 the wastewater can be considered to be virtually
fully biodegradable.

Wastewater Treatment Lecture Note Page 18

 BOD 5
Since, BODu is generally not measured and only BOD 5 is measured, the ratio usually
COD
BOD
referred to as ratio becomes more important. Since BOD 5 is about 68% of BODu, we can
COD
BOD 5
easily state that ratio should for fully-biodegradable wastes, vary between 0.92*0.68 =
COD
BOD
0.63 and 1.0*0.68 = 0.68. Any wastewater, having its ratio more than 0.63, can hence, be
COD
considered to be quite amenable to biological treatment, since it does not contain non-
biodegradable organics.
b. Effect of Seeding and Acclimation of Seed on the BOD Test
One of the most frequent reasons for unreliable BOD values is utilization of an insufficient
amount of microorganism seed. Another serious problem for industrial wastes is acclimation of
seed. For many industrial wastes, the presence of toxic materials interferes with growth of the
microorganism population. BOD curves obtained exhibit a time lag period.

Figure 2.1.3 Lag period in BOD test

Low BOD values are obtained if adequate corrective action is not taken. It becomes necessary to
acclimate the microorganism seed to waste. This is achieved by starting with a sample of settled
domestic sewage which contains a large variety of microorganisms, and adding a small amount
of industrial effluent. Air is bubbled through this mixture. The operation is performed in bench
scale reactors of either continuous or batch type.
The process is repeated with gradual increase in the proportion of industrial waste to domestic
sewage, until a microbial culture acclimated to the specific industrial waste is developed. This
may be a long and difficult procedure for very toxic industrial wastewaters. When an acclimated
culture has been developed, the BOD curve does not present a lag period.
c. Effect of Presence of Algae on the BOD Test
Presence of algae in the wastewater being tested affects the BOD test. If the sample is incubated
in the presence of light, low BOD values are obtained owing to production of oxygen by

Wastewater Treatment Lecture Note Page 19

photosynthesis, which satisfies part of the oxygen demand. On the other hand, if incubation is
performed in darkness, algae survive for a while. Thus, short-term BOD determinations show the
effect of oxygen on them. After a period in the dark, algae die and algal cells contribute to the
increase of total organic content of the sample, thus leading to high BOD values. Therefore, the
effect of algae on the BOD test is difficult to evaluate.

2.3 Mathematical Model for the BOD Curve

It is desirable to represent the BOD curve by a mathematical model. From kinetic considerations,
the mathematical model utilized to portray the rate of oxygen utilization is that of a first-order
reaction. Figure 2.4 reveals that the rate of oxygen utilization, given by the tangent to the curve
at a given incubation time, decreases as concentration of organic matter remaining unoxidized
becomes gradually smaller.
The rate at which BOD is satisfied at any time, (i.e. the rate of deoxygenation) depends on
temperature and also on the amount and nature of organic matter present in sewage at that time.

Figure 2.4 1st stage BOD curve

Thus, at a certain temperature, the rate of deoxygenation is assumed to be directly proportional to

the amount of organic matter present in sewage at that time (there is proportionality between the
rate of oxygen utilization and that of destruction of organic matter by biological oxidation); i.e.
dLt
=−K Lt 2.3
dt
Where, Lt = oxygen equivalent of carbonaceous oxidizable organic matter present in sewage
after t days from the start of oxidation, in mg/l.
dLt
= rate of disappearance of organic matter by aerobic biological oxidation
dt

Wastewater Treatment Lecture Note Page 20

 t = time in days.
K = rate constant signifying the rate of oxidation of organic matter, and it depends
upon the nature of organic matter and temperature. Its unit is per day.
Minus sign indicates that with the passage of time (i.e., increase in t) the value of L t decreases.

Integrating the above equation, we get

dL
∫ L t =∫− Kdt
t

log e Lt=− Kt +C 2.4

Where, C is a constant of integration, and can be evaluated from the boundary conditions at the
start i.e.
When t = zero (0), i.e. at start Lt = L (say). Substituting in the above equation, we have
log e Lt=− K∗0+C
C=log e L
Substituting this value of C in equation 2.4,
log e Lt=− Kt +log e L
log e Lt−log e L=−Kt
Lt Lt
log e =2.3∗log 10 =−Kt
L L
Lt −Kt
log 10 = =−0.434 Kt
L 2.3
0.434K = KD
Where, KD is the De-oxygenation constant or the BOD rate constant (on base 10) at the given
temperature = 0.434K.
We have
Lt
log 10 =−K D t
L
Lt −K t
=10 D
2.5
L
Now, L is the organic matter present at the start of BOD reaction, (expressed as oxygen
equivalent) and Lt is the organic matter left after t days; which means that during t days,
the quantity of organic matter oxidized = L - Lt.
If Yt represents the total amount of organic matter oxidized in t days (i.e. the BOD of t days),
then we have

Wastewater Treatment Lecture Note Page 21

 Y t =L−Lt =L 1− ( ) Lt
L
Yt Lt
=1−
L L
Lt Yt
=1−
L L
Substituting this value to the above equation, we get
Lt Yt −K t
=1− =10 D

L L
Yt −K t
=1−10 D

L
Y t =L∗( 1−10 ) 2.6
− K Dt

This is an important equation. Yt is the oxygen absorbed in t days, i.e. BOD of t days.
The ultimate first stage BOD (Yu) would be obtained from the above equation, when we
substitute t =  days in it.
Y u=L∗( 1−10−K ) D

(
Y u=L∗ 1−
1
10❑ )
=L 2.7

Hence, the ultimate first state BOD (Y u) of a given sewage is equa1 to the initial oxygen
equivalent of the organic matter present in this sewage (L). This is a fixed quantity, and does not
depend upon the temperature of oxidation.
The value of KD however, determines the speed of the BOD reaction, without influencing the
ultimate BOD, as shown in Figure 2.5:

Figure 2.5 BOD exertion as a function of KD

The figure shows that the coefficient of deoxygenation is different at different temperatures, but
finally, Yu is constant.
It is found to vary with temperature of sewage, and this relationship is approximately given by
the equation

Wastewater Treatment Lecture Note Page 22

 K D (T )=K D (20 )∗1.047T −20 2.8
Where, KD(20°) = Deoxygenation constant at 20°c. Its numerical value varies between (0.05 to
0.2) per day depending upon the nature of the organic matter present in
sewage. Simple compounds such as sugars and starches are easily utilized by
the micro-organisms, and have a high KD rate, while complex molecules such
as phenols are difficult to assimilate and hence have low K D values. Some
typical KD values are given in Table 2.3.
KD(T) = Deoxygenation constant at temperature Tºc.

Table 2.3 Typical values of KD at 20°c for various types of waters and wastewaters

Water type KD value per day

Tap waters < 0.05
Surface waters 0.05 - 0.1
Municipal wastewaters 0.1 - 0.15
Treated sewage effluents 0.05 - 0.1

Equation 2.8 shows that KD will be higher at higher temperatures, which means that the speed at
which BOD is consumed in the oxidation of the organic matter, is higher at higher temperatures.
This means that the entire carbonaceous organic matter will get oxidized quickly and in lesser
time at higher temperatures.
Equation 2.6 is called the first stage equation of BOD reaction, and is represented graphically by
the curve OAB of.

Figure 2.6 Combined BOD curve

By comparing Figure 2.4 and Figure 2.6, it can be seen that the curve of Figure 2.6 is nothing but
the reciprocal of curve in Figure 2.4. This is because the oxygen used in satisfying BOD is in

Wastewater Treatment Lecture Note Page 23

direct ratio of the amount of organic matter oxidized, which means reciprocal of the curve of
Figure 2.4.
The portion AC of the curve of Figure 2.6 represents the nitrification stage, which follows the
carbonaceous stage, so that the BOD curve for the complete oxidation is represented by OAC.
Note: The equations given above are only for the important first stage BOD, and have nothing to
do with the second stage BOD, with which we are not concerned here.
Example 1
The BODs of a wastewater is 150mg/l at 20°c. The k value is known to be 0.23 per day. What
would BOD8 be, if the test was run at 15°?
Example 2
The 5 day 30°c BOD of sewage sample is 1l0mg/l. Calculate its 5 days 20°c BOD. Assume the
deoxygenation constant at 20°c K20 as 0.1.
Exercise 1
Calculate 1 day 37ºc BOD of sewage sample whose 5 day 20°c BOD is 100 mg/l. Assume K D at
20°c as 0.1.
Exercise 2
The BOD5 of a waste has been measured as 600 mg/l. If K = 0.23/day (base e), what is the
ultimate BODu of the waste. What proportion of the BOD u would remain unoxidised after 20
days?

Wastewater Treatment Lecture Note Page 24