408-Environmental pollution and Industrial waste management

Wastewater treatment
ORIGIN OF WASTEWATER
Wastewaters can be classified by their origin as domestic wastewater and industrial
wastewater. Any combination of wastewaters that is collected in municipal sewers is
termed as municipal sewage. Domestic wastewater is that which is discharged from
residential and commercial establishments, whereas industrial wastewater is that which is
discharged from manufacturing plants. The pollutants in domestic wastewater arise from
residential and commercial cleaning operations, laundry, food preparation, body cleaning
functions, and body excretions. The composition of domestic wastewater is relatively
constant.
Industrial wastewater is formed at industrial plants where water is used for various
processes, and also for washing and rinsing of equipment, rooms, etc. These operations
result in the pollution of the nearby aquatic systems because some of the products and
byproducts are discharged, either deliberately or unintentionally into them.
Normally, wastewaters are conducted to treatment plants for removing undesirable
components which include both organic and inorganic matter as well as soluble and
insoluble material. These pollutants, if discharged directly or with improper treatment,
can interfere with the self-cleaning mechanisms of water bodies. The capacity for selfcleaning is due to the presence of relatively small numbers of different types of microorganisms in the water bodies. These micro-organisms use as food much of the organic
pollutants and break them down into simple compounds such as CO 2 or methane, and the
micro-organisms produce new cells also. But often either a pollutant does not degrade
naturally or the sheer volume of the pollutant discharged is sufficient to overwhelm the
self-cleaning process. Also, the microbial population can be destroyed by toxic wastes
discharged into the waterway. If that happens, the pollutant concentrations will build up
and reach high enough levels that will prevent re-establishment of a microbial population.
The water quality thus becomes permanently degraded.
Various constituents of wastewater are potentially harmful to the environment and to
human health. In the environment, the pollutants may cause destruction of animal and
plant life, and aesthetic nuisance. Drinking water sources are often threatened by
increasing concentration of pathogenic organisms as well as by many of the new toxic
chemicals disposed of by industry and agriculture. Thus, the treatment of these wastes is
of paramount importance.
Wastewater Composition
Depending on the amounts of physical, chemical, and biological constituents of
wastewaters, they may be classified as strong, medium, or weak.

Table 1. Typical composition of domestic wastewater

Constituent
Concentration
Strong
Medium
Solids, total
1200
700
Dissolved solid, total
850
500
fixed
525
300
volatile
325
200
Suspended solids, total
350
200
fixed
75
50
volatile
275
150
Settleable solids (ml/1)
20
10
Biochemical oxygen demand, 5-days, 20C
300
200
Total organic carbon (TOC)
200
135
Chemical oxygen demand (COD)
1000
500
Nitrogen (total as N)
85
40
Organic
35
15
Free ammonia
50
25
Nitrites
0
0
Nitrates
0
0
Phosphorus (total as P)
20
10
Organic
5
3
Inorganic
15
7
Chlorides
100
50
tt
Alkalinity (as CaCO3)
200
100
Grease
150
100
t
All values except for settleable solids are expressed in mg/l.
tt
Values should be increased by amount in carriage water.

Weak
350
250
145
105
100
30
70
5
100
65
250
20
8
12
0
0
6
2
4
30
50
50

Typical compositions for domestic wastewater are given in Table 1. The compositions
and concentrations are highly variable, and hence, the table is intended only to serve as a
guide and not as a basis for design. Data on typical characteristics of municipal sewage in
some urban cities of India are given in Table 2.
Table 2. Composition of sewage in some urban cities of India
Constituent
Delhi Kanpur
Madras
Hyderabad Ahmedabad
Suspended solids (mg/l)
354
560
550
985
148
TDS (mg/1)
803
1000
1170
723
1600
BOD, at 20C (mg/1)
203
255
352
339
133
COD (mg/1)
377
532

Nitrogen (total as N) (mg/1)
28.5
73.9
59.2
50.9
27.3
PO4 (mg/1)
13.7
2.5
25.3

Chlorides (mg/1)
147
114
259
104
300
pH
7.5
7.0
7.4
7.4
7.5
TDS = total dissolved solids; BOD = biochemical oxygen demand; COD = chemical
oxygen demand

The composition of industrial wastewater is quite varied, its constituents ranging from
organic solvents, oils, suspended solids to dissolved chemical compounds. Table 3 lists a
number of potentially polluting chemical substances released by different industries.
Most of the chemicals are toxic and some are even suspected of causing cancer. Such
"cancer suspect agents" include 4-nitrobiphenyl, 4-aminodiphenyl, - and -naphthylamine, methyl chloromethyl ether, benzidine, 3, 3'-dichlorobenzidine, propiolactone, 4-dimethylaminoazo-benzene, N-nitrosodimethylamine and vinyl chloride.
Another important aspect of industrial wastewaters is that some of the chemicals are
valuable enough to warrant recovery. This aspect of recovery has taken on a new
perspective in recent years and the recovered substance can either be recycled within the
plant, or offered to other companies for use as basic or intermediate chemicals.
Table 3. Major pollutants in various industries
Pollutants
Industry typet
Organic
Proteins
(1), (2), (3), (4), (13)
Carbohydrates
(1), (2), (3), (5), (6), (13)
Fats and oils
(1), (2), (3), (4), (7), (9), (10), (11), (12), (13)
Dyestuffs
(3), (4), (5), (6)
Organic acids
(6), (13)
Phenols
(3), (6), (7), (8), (9), (10), (11)
Detergents
(1), (3), (12), (13)
Organo-pesticides
(2), (13)
Inorganic
Acids
(3), (6), (10), (11)
Alkalies
(3), (6), (7), (8), (10), (11), (12)
Metals
(3), (5), (6), (10), (11), (13)
Metallic salts
(4), (5), (10), (11), (13)
Other salts
(1), (3), (4), (5), (6)
Phosphates, nitrates
(1), (3), (4), (5), (6)
Bleaches
(3), (5), (12)
Sulphides
(3), (4), (7), (8)
Cyanides, cyanates
(8), (10), (11)
Chromates
(4), (7), (10), (11)
Minerals (china clay and soil)
(1), (5), (13)
t

Industry type: (1) dairy, (2) food processing, (3) textiles, (4) tanning, (5) paper making,
(6) chemical, (7) petro-chemical, (8) coke ovens, (9) industrial oil
production, (10) engineering, (11) metallurgy, (12) laundry and (13)
agriculture.

Characterization of wastewaters (Dara 1, p.70)

Waste waters are characterized on the basis of various physical, chemical and biological
characteristics apart from flow data details:
(1) Physical Characteristics. Colour, odour, dissolved oxygen (D.O.), insoluble
substances (settleable solids, suspended solids), corrosive properties, radio-activity,
temperature range, foamability, etc.
(2) Chemical Characteristics. Chemical oxygen demand (C.O.D.), pH, acidity or
alkalinity, hardness, total carbon, total dissolved solids, chlorine demand, known organic
and inorganic components such as Cl-, S2, SO42-; N, P, Pb, Cd, Hg, Cr, As, surfactants,
phenols, hydrocarbons oils and greases.
(3) Biochemical characteristics. Biochemical oxygen demand (B.O.D.), presence of
pathogenic bacteria etc., and toxicity to man, aquatic organisms, plants and other life
forms.
The actual methods used for the treatment of a waste depend upon the characteristics of
the particular waste.
Suspended solids. The suspended solids are determined by filtering an aliquot of the
sample through a previously weighed sintered crucible or a tared Gooch crucible and
drying the crucible at 103 0C to 105 0C to constant weight. The difference in weight
indicated as mg/l gives the suspended solids content of the sample.
Settleable solids. The settleable solids content of a sample is obtained by allowing 1 litre
of the sample to settle for about 1 hour at 20 0C in an Imhoff cone, which is a tapered
conical tube. The volume of settleable matter in the cone is recorded as ml/1. The
settleable solids may also be expressed in mg/l which can be calculated by the difference
between mg/l suspended solids minus mg/l non-settleable matter determined by the
procedure described as above.
Total Solids. The total solids content of a sample is determined by evaporating a known
volume of the sewage or waste water sample, and drying the residue for 24 hours at 103
0
C to 105 0C, followed by weighing. This gives the total solids content of the sample,
which includes the dissolved as well as suspended solids.
Dissolved oxygen (DO). The measurement of DO gives a ready assessment of purity of
water. The determination of dissolved oxygen is the basis of BOD (Biochemical Oxygen
Demand) test, which is commonly used to evaluate the pollution strength of waste waters.
The determination of DO content is also essential for maintaining aerobic conditions in
the receiving waters and also in the aerobic treatment of sewage and industrial waste
waters.
Biochemical Oxygen Demand (BOD). Biochemical oxygen demand represents the
quantity of oxygen required by bacteria and other microorganisms during the biochemical
degradation and transformation of organic matter present in wastewater under aerobic
conditions. BOD test is a very valuable test in the analysis of sewage, industrial effluents
and grossly polluted waters. In spite of the inherent limitations, the BOD test is still
valued as the best test for assessing the organic pollution. BOD is considered as the major
characteristic used in stream pollution control. It gives very valuable information
regarding the purification capacity of streams and serves as a guide-line for the
Regulatory Authorities to check the quality of effluents discharged into such water
bodies.

Chemical Oxygen Demand (COD). The chemical oxygen demand (COD) is a measure
of the oxygen equivalent to that portion of organic matter present in the waste water
sample that is susceptible to oxidation by potassium dichromate. This is an important and
quickly measured parameter for stream, sewage and industrial waste samples to
determine their pollutional strength.
Wastewater Sampling and Analysis (CS Rao 3, p. 313)
Wastewater sampling and analysis form an important part of any water pollution control
programme because the identification of the pollutants and pinpointing their
concentrations are vital to the selection of a proper treatment process. The sampling
method used should be one that gives a representative picture of the quality of the waste
stream; otherwise, the time and effort involved in the analysis will be completely wasted.
SAMPLING
Generally, two types of samples can be taken: (1) the grab sample, and (2) the composite
sample.
The grab sample shows only the prevailing conditions at the time of sampling and cannot
represent average conditions. Hence, it should not be used as a basis for treatment.
However, grab samples are useful in determining the effects of extreme conditions of the
waste during the time composite samples are being collected or when the wastewater
flow is intermittent.
Composite samples provide more meaningful data when the composition of the waste
varies with either time or flow. A composite sample can be obtained by collecting
individual samples at frequent intervals and mixing them together. Composite samples
can be collected either manually or with automatic samplers on the basis of flow or time.
When wastewater flow and composition are relatively uniform, grab samples of a fixed
volume can be manually taken at given time intervals and composite sample obtained. If
the flow rate varies, the volume of the grab sample collected is proportional to the flow.
Usually, the flow rate of wastewater at sampling point is determined with a flow meter
each time a portion of the composite sample is collected. Manual sampling is particularly
advantageous when visible changes such as colour variation, suspended solids, floating
oil, etc., occur in the waste stream. When such changes do take place, operating personnel
can collect grab samples and analyze the effect of these changes on the waste stream.
Automatic devices can be used to obtain composite samples, particularly when there is a
need to collect wastewater samples at regular, frequent intervals throughout the day.
Some of these devices continuously collect one large composite sample, while others
collect small samples in individual containers. In automatic devices the sample pickup
line is generally placed below the surface of the water to obtain as representative a
sample as possible. Any contaminant which might form a stratified layer in the waste
stream is completely missed by such devices.
Depending on the type of analysis to be performed, a minimum volume of 1 to 2 litres is
collected in grab sampling, while the total composite volume is between 2 and 4 litres.
However, it is better to obtain a sample that is too large rather than one that is too small
as the analyst may wish to run additional tests or check the reliability of his earlier
results. The time allowed between collection and analysis of a sample depends on the
nature of the sample, the type of analysis to be made and the conditions of storage. It is of

prime importance that special preservation methods are used for samples that are not to
be analyzed immediately. This ensures that the characteristics to be analyzed are not
changed between collection and analysis. Table 8.1 gives special handling requirements
for several wastewater characteristics.
Table 8.1 Preservation of wastewater samples
Parameter

Preservation method

Maximum
holding period
0
BOD
Refrigeration at 4 C
6 hours
COD
2 ml H2SO4/L
7 days
0
Colour
Refrigeration at 4 C
24 hours
Cyanide
pH of the sample raised to 10 or higher with NaOH 24 hours
Fluoride
None required
7 days
Metals
No specific preservation, sample should be 6 months
acidified
Nitrogen (Kjel- Add 40 mg, HgCl2/L; refrigeration at 4 0C
7 days except
dahl, ammonia,
for
Kjeldahl
nitrite)
nitrogen which
is unstable
Phenol
1.0 g CuSO4/L+H3PO4 to lower pH to less than 4; 24 hours
refrigeration at 4 0C
Phosphorus
40 mg HgCl2/L; refrigeration at 4 0C
7 days
Sulphide
2 ml zinc acetate/L
7 days
0
Odour
Refrigeration at 4 C
7 days
Turbidity
None available
7 days
Caliform
Sterilized bottle, no specific preservative, 36 hours
bacteria
refrigeration at 4 0C
The sample from industrial wastewaters should be representative of the industry. For
example, in case there are great variations in flow and/or characteristics, the sampling
frequency should be so adjusted as to obtain a representative sample. Often, industries
find it desirable to continuously monitor water quality of rivers and lakes which are used
as sources for water supply or for disposal of waste effluents. In the latter case,
monitoring is done so that the quality and quantity of the discharge can be proportioned
according to the assimilative capacity of the water body and for maintaining its quality
standards. Several municipalities also use continuous monitoring systems for their
treatment facilities. Many continuous monitors are so sophisticated that not only the
analyses can be performed automatically and continuously, but also the analytical data
can be processed and translated by a computer for further use and application.
METHODS OF ANALYSIS
Various methods are available for analyzing wastewaters. These methods largely involve
standardized procedures that are often complicated and time-consuming. Sometimes
simpler rapid methods can be substituted with little, if any, loss in either precision or

accuracy. Test procedures often followed in practice are illustrated here briefly for
specific constituents. Detailed individual procedures are available in standard references.
DETERMINATION OF ORGANIC MATTER
Dissolved Oxygen (DO)
Surface waters of good quality should be saturated with dissolved oxygen. A fall in DO
level is one of the first indications that a water body is polluted by organic matter. The
DO level in water depends on physical, chemical and biochemical activities prevailing in
the water body and, thus, it is one of the important parameters for assessing the purity of
the water body. It is usually determined by Winkler's methods, which is based on the
reaction of dissolved oxygen with manganese ions to form a precipitate of manganese
dioxide.
Mn2+ + O2 MnO2
(8.1)
The manganese dioxide is then treated with iodide ions when iodine is liberated in an
amount chemically equivalent to the original dissolved oxygen.
MnO2 + 2I + 4H+ Mn2+ + I2 + 2H2O
(8.2)
The liberated iodine is determined, usually by titrating it with sodium thiosulphate.
2S2O3 2 + I2 S4O62 + 2I
(8.3)
The presence of nitrites or iron in +2 oxidation state in the solution can interfere with the
original DO determination. To eliminate these interferences, several modifications of the
basic method have been proposed. These include the use of azide, permanganate and the
alum to remove interferences due to nitrite, ferrous iron and suspended solids,
respectively.
The interference problems can also be overcome by using DO analyzers with membrane
electrodes. The plastic membrane has the selective ability of allowing oxygen to diffuse
through but preventing interfering ions, such as nitrites. The dissolved oxygen, after
diffusing through the membrane, reacts with the metal electrode and causes a cell current
which is directly proportional to the oxygen concentration in the sample. The analyzer is
calibrated by measuring, the DO of a sample of known oxygen content, which is
determined by the Winkler method.
Biochemical Oxygen Demand (BOD)
The most widely used and accepted measure of biodegradable organic content of
wastewater is the 5-day, 20 0C BOD value. The brief analytical procedure is outlined
below:
1. Two standard 300-ml BOD bottles are filled completely with the wastewater
of which the BOD is to be measured and the bottles are sealed.
2. Oxygen content of one bottle is determined immediately.
3. The other bottle is incubated at 20 0C for 5 days in total darkness, after
which its oxygen content is measured.
4. The difference between the two DO values is the amount of oxygen that is
consumed by microorganisms during the 5 days and is reported as the BOD,
(5-day BOD) value of the sample.

In practice, however, BOD measurements are more complicated than the simple
procedure given above. The wastewaters may have a high oxygen demand, high enough
to deplete all the dissolved oxygen in the sample before the end of 5 days, thus making
the test indeterminate. So, often the sample is diluted with high purity water to prevent
total depletion of DO. The diluting water is made up of deionized water to which
appropriate nutrients, phosphate buffer, trace elements, and seed organisms (usually
settled domestic sewage) are added. A blank is run on the diluting water so that the
oxygen demand of the seem material can be subtracted from the results. The BOD 5, is
calculated from the following equation:
BODs (in mg/L) = D* [(DOt=0 DOt=5) (DOt=0 DOt=5)]
(8.4)
sample
blank
where D* = dilution factor.
When the standard 5-day/20 0C conditions are used, approximately two-thirds of the
carbonaceous material is broken down; an incubation of about 20 days is needed for
nearly complete breakdown. Nitrogenous nutrients can create problems in the BOD test.
Because of the slowness of the nitrification process, the oxygen demand of the nitrifying
bacteria is assumed to be negligible in the standard 5-day incubation period at 20 0C. The
actual environmental conditions of temperature, biological population, oxygen
concentration, etc., are impossible to reproduce in the test; hence, care must be exercised
in extrapolating the test results to the actual stream oxygen demands. In addition, many
industrial wastewaters contain toxic materials which interfere with the growth of
microorganisms thus making the BOD test unreliable or even inapplicable without the
addition of suitable inoculum. Similarly, the presence of algae in the wastewater affects
the BOD test by leading to higher BOD values even when the test is performed in
darkness.
The BOD analysis, despite its limitations, has been in use for many years for monitoring
the quality of stream pollution involving oxygen sag, but it is now being replaced by the
chemical oxygen demand (BOD) test for research and plant control purposes.
Chemical Oxygen Demand (COD)
In the COD test, the oxidizing bacteria of the BOD test are replaced by a strong oxidizing
agent under acidic conditions. A sample of the wastewater containing organic material is
mixed with an excess of potassium dichromate and sulphuric acid and the mixture is
heated under total reflux conditions for a period of 2 hours. During digestion, the
chemically oxidizable organic material reduces a stoichiometrically equivalent amount of
dichromate, the remaining dichromate is titrated with standard ferrous ammonium
sulphate solution. The amount of potassium dichromate reduced gives a measure of the
amount of oxidizable organic material. Dichromate has advantages over other oxidants in
oxidizing power and applicability to a wide variety of samples.
The COD test does not distinguish between organic materials that are biodegradable and
those that are not, and, hence, gives a measure of the total oxidizable organic material in
the sample. Due to this, the COD test results are higher than those of BOD tests carried
out on the same sample. If inorganic substances such as chlorides and nitrites are present
in the wastewater, they interfore with the COD test since they are also oxidized by
dichromate and create an inorganic COD that leads to an error in the measurement.

Chloride interference can be eliminated by adding mercuric sulphate to the sample prior
to the addition of other reagents, and nitrite interference can be overcome by adding
sulphamic acid to the dichromate solution.
Total Organic Carbon (TOC)
Total organic carbon test is based on the oxidation of the carbon of the organic matter to
carbon dioxide, which is measured by a non-dispersive infrared analyzer. Alternatively,
the carbon dioxide can be reduced to methane, which is then measured by a flame
ionization detector.
In this test, a few micro-litres (5 to 10 1) of the aqueous sample are injected into a
combustion tube containing a catalyst and heated to 900C in a constant flow of air.
Water is vaporized and the carbonaceous matter is oxidized to CO 2 and steam. Outside
the combustion tube, the steam is condensed and removed. CO 2 is swept into a nondispersive infrared analyzer, which measures the amount of CO2. The concentration of
CO2 is directly proportional to the concentration of total carbon present in the original
sample and it includes both organic and inorganic carbon. Inorganic carbon can be
measured separately using an acid catalyst at 150 0C, which is below the temperature at
which organic matter is oxidized. Organic carbon content can then be obtained by
subtracting the inorganic carbon from the total result. A flow diagram for a dual
combustion tube total carbon analyzer is shown in Fig. 8.1.
The TOC test can be performed in a relatively short period of time (few minutes)
compared to BOD and COD measurements and, hence, offers a valuable supplement to
BOD and COD estimations. Because of this advantage, an empirical correlation between
TOC and COD or BOD, that is specific to a particular plant operation, can be established
and from this it is possible to obtain a tentative estimate of the plant performance quickly.
DETERMINATION OF INORGANIC SUBSTANCES
Nitrogen
The important chemical species containing nitrogen in wastewater systems are ammonia,
organic nitrogen, nitrite and nitrate. Ammonia exists in aqueous solution as one of the
intermediate compounds formed due to microbiological activity. Nitrogen, which is tied
up in high energy compounds such as amino acids and amines, is known as organic
nitrogen. Usually, organic nitrogen is a potential source of ammonia because deamination
reactions that occur during the metabolism of organic compounds release ammonium
ions. These two forms of nitrogen are often combined in one measure, known as Kjeldahl
nitrogen.
Aerobic decomposition eventually leads to nitrogen in the nitrite (NO 2) and finally
nitrate (NO3) forms. For domestic wastewaters in U.S.A., the normal proportion of
nitrogen-containing compounds is relatively constant: NH 4+ 5060%; organic nitrogen
4059%; and nitrites and nitrates 05%. Although the contribution of nitrites and
nitrates in domestic wastewaters is negligible, there may be a measurable concentration
of these ions following biological treatment due to the occurrence of nitrification. All the
above forms of nitrogen can be measured analytically by colorimetric techniques.

Kjeldahl nitrogen is determined by digesting the sample in sulphuric acid when the
organic nitrogen is converted to ammonia. The total ammonia content is measured after
neutralizing the excess sulphuric acid. The standard technique employed for the
determination of ammonia is the Nessler methods. In this technique, the neutralized
sample is first distilled to separate the ammonia from interfering substances. The
ammonia in the distillate is reacted with Nessler's reagent (potassium mercuric iodide,
K2HgI4), which produces a yellowish-brown colloidal dispersion. The colour intensity is
directly proportional to the amount of NH 3 present. The colour can be compared visually
to standards or can be estimated photometrically.
Another method of measuring the ammonia content in the sample is the phenolhypochlorite method. In this method, ammonia is treated with phenol and hypochlorite in
the presence of a catalyst to produce the blue coloured solution of indophenol. The
intensity of colour is proportional to the ammonia concentration.
Determination of nitrogen present as nitrite is based on the diazotization of sulphanilic
acid with nitrite followed by its combination with N-(1-napthyl)-ethylenediamine
dihydrochloride to form a purple azo-dyes. The intensity of the purple colour is directly
proportional to the nitrite concentration and can be read on a photometer. The method is
very sensitive but is time consuming. A simple and rapid method consists of the addition
of 1,5-dimethyl-2-phenyl-3-pyrazolone to the nitrite solution which forms a nitroso
derivative, the extinction coefficient of which can be measured spectrophotometrically.
Nitrogen present as nitrate can be analyzed by reducing it to nitrite or ammonia, which is
then determined by employing one of the sensitive methods previously described. One
such method in popular use is the cadmium reduction method where the nitrates are
quantitatively reduced by cadmium to nitrite. The nitrite thus produced is measured by
the diazotization method. Since this method gives the sum of nitrate and nitrite nitrogen,
a separate analysis of the nitrite is required so that this value can be subtracted from the
results of the cadmium procedure. Nitrates can also be reduced to nitrites with zinc under
controlled conditions and the nitrites determined colorimetrically. Other techniques of the
determination of nitrogen are the Brucine, phenoldisulphonic acid, and the chromotropic
acid methods.
Phosphorus
Phosphorus exists in wastewaters as orthophosphate (PO 43, HPO42, H2PO4),
polyphosphate, and organic phosphate. Orthophosphates are assimilated by bacteria
during their-growth process. However, polyphosphates must undergo enzymatic
hydrolysis to the ortho form before they can be assimilated. The organic phosphate is
present in molecules. such as RNA, DNA and nucleotides. This is also an important
constituent of industrial wastes.
The orthophosphate is determined using colorimetric methods. These methods involve
treating the sample with ammonium molybdate under acidic conditions to form
molybdophosphoric acid, which is reduced using vanadium, or stannous chloride or
ascorbic acid when a coloured complex is formed. The intensity of the colour is
proportional to the phosphate concentration in the solution. The vanadium method is
quite useful for determining phosphate concentrations in the range of 0.218 mg. The
stannous chloride method is highly sensitive and concentrations as low as 3 g/L can be

detected. The ascorbic acid method on the other hand is slightly less sensitive and the
minimum detectable concentration is approximately 20 g/L.
Polyphosphates are hydrolyzed into orthophosphates in an acidic medium and the excess
acid is neutralized before the addition of ammonium molybdate solution. The amount of
polyphosphate is obtained by subtracting the amount of orthophosphate originally present
in the sample from the result.
The measurement of organic phosphorus is done by first oxidizing the organic matter so
that phosphorus is released as phosphate ion. The total phosphorus can be measured by
the procedure previously outlined for orthophosphate and the amount of the organic
phosphorus present is obtained by subtracting the inorganic content from the result.
Trace Elements
The standard methods used for determination of toxic heavy metals like cadmium,
chromium, lead and zinc are the atomic absorption spectrophotometry and colorimetry.
The atomic absorption system consists of a light source which emits light of a particular
wavelength, an atomizer burner unit for introducing the sample into the flame, a prism to
separate and isolate the emission lines, and a detector. A schematic diagram of an atomic
absorption spectrophotometer is given in Fig. 8.2. In this technique, light from a source
lamp of an exact wavelength necessary to excite the atoms of a particular trace element
traverses the sample which is atomized in a flame, and passes through a prism where the
desired wavelength is isolated. The light intensity passing through the flame is reduced as
light is absorbed by each atom of the element; the amount absorbed is detected by the
photomultiplier tube. This decrease in intensity with the sample is a measure of the
concentration of the element. The technique is quite rapid, highly selective, and
automated for monitoring effluent streams. The detection limits for some selected toxic
metals are given in Table 8.2.
In using colorimetric method for determining the concentration of individual metals, care
must be taken to eliminate interference from other metals occurring simultaneously in the
waste sample. Since metals form complex ions with organic matter present in wastewater,
it is generally necessary to destroy the organic matter with acid digestion. Acid digestion
also eliminates possible interference from cyanide, nitrite, sulphide, sulphite, etc.
Diphenylthio-carbazone (dithizone) is the colorimetric reagent used for the determination
of cadmium, lead and zinc. These metals give a red/pink coloured complex which
can be extracted in a suitable solvent such as carbon tetrachloride or chloroform. The
colour intensity is then determined by a colorimeter or spectrophotometer. Chromium
determination involves oxidation of the metal to the hexavalent state and its reaction with
diphenylcarbazide in acidic medium when a red-violet product is obtained whose
intensity can be measured photometrically.
Alkalinity
Alkalinity in wastewaters is due to the presence of bicarbonates, carbonates and
hydroxides of metal ions such as calcium, magnesium, sodium and potassium. Of these,
bicarbonates are most common, since they are formed by the action of carbon dioxide on
the basic materials such as the salts of calcium and potassium in the soil. In addition, salts
of weak acids and ammonia present in wastewaters also contribute to the total alkalinity.

Alkalinity is measured by titrating the sample with a standard acid such as N/50 H 2SO4;
the results are expressed in terms of CaCO3. If the pH of the original sample is higher
than 8.3, the titration is carried out using phenolphthalein indicator until it becomes
colourless. This occurs at a pH value of 8.3. This end point is known as phenolphthalein
alkalinity or bicarbonate equivalence point, which is observed in the case of hydroxide,
or carbonate, or both.
Usually, bicarbonates are present in the original sample along with hydroxides and
carbonates. In such cases the sample is titrated with methyl orange indicator and the
titration is carried out beyond the phenolphthalein end point. When a pH of about 4.5 is
reached, there occurs a colour change from yellow to red indicating carbonic acid
equivalence point. This result is used to calculate the total alkalinity, which may be due to
any of the three alkaline ions, bicarbonates, carbonates or hydroxides.
Determination of alkalinity is of importance in water softening, chemical treatment of
wastewater, corrosion control, and in removal of ammonia by air stripping.
PHYSICAL CHARACTERISTICS
Suspended Solids
The determination of suspended matter is extremely important in the analysis of
wastewaters. The suspended matter contained in domestic wastewaters and in many
industrial wastes is largely organic and is, therefore, responsible for a significant portion
of the oxygen demand. Hence, it is one of the major parameters used to evaluate the
quality of domestic and industrial wastes.
Analytically, the term total solids in wastewater refers to the matter that remains as
residue after evaporation and drying at 103 to 105 0C. The total solids can he classified as
filterable solids and suspended solids. The filterable solids are those that are able to pass
through a specified filter and consist of colloidal and dissolved solids. The colloidal
solids range in size from 10-3 to 10-6 mm, while dissolved solids are smaller than 10 -6 mm
and exist as molecules and ions in solution. The suspended solids are retained on the filter
and their minimum diameter is about 1 m. Of the suspended solids, the settleable solids
are those which settle in a cone shaped container (Imhoff cone) in a definite time period.
The suspended solids (also filterable solids) may be further classified on the basis of their
volatility at 600 0C. The organic matter that is oxidized at this temperature is known as
"volatile suspended solids" (VSS), and the inorganic fraction that remains as ash is
termed "fixed suspended solids" or "non-volatile suspended solids" (NVSS). Fig. 8.3
gives an approximate classification of solids found in medium strength wastewaters.
The suspended solids concentration is an easily measured parameter. In almost all the
cases gravimetric methods are used such as filtration through a Gooch crucible, but the
determination is subject to considerable error if proper precautions are not taken. An
alternative procedure for measurement of suspended solids makes use of a continuous
flow nephelometer. The measurement of light transmitted or light scattered by suspended
particles can be correlated with the actual suspended solids concentration.
Colour and Odour
Colour and odour are important parameters from the standpoint of aesthetics. Colour may
be of organic or mineral origin. Organic sources include algae, tannins, humic
compounds, etc.; inorganic sources are iron and manganese compounds, chemicals and

dyes from various industries. Objectionable odours in water are caused by algae and
decaying vegetation. Some inorganic substances such as mercaptans, amines and
sulphides also cause bad odour.
Colour is measured by comparison with known standards. Coloured water made with
potassium chlorophtinate when tinted with cobalt chloride closely resembles colour of
many natural waters which are yellow-brownish in appearance. A stock solution
containing 500 mg/l of potassium chloroplatinate, with cobalt chloride added as a tinting
material, is usually prepared and this is assigned colour of 500 units. Then a series of
working standards is prepared from it by dilution. The intensity of colour in water is
measured against these standards by direct visual comparison.
Suspended matter in water can interfere with the measurement of colour. In such cases
the sample is centrifuged to separate the solids and analysis is made on the clear portion.
Removal of the suspended matter from the sample by filtration is not recommended
because of the possibility that the filter may adsorb some colour and thereby cause error
in the measurement.
The odour causing substances are usually present in very small quantities and are often
very complex. It is, therefore, often impossible and impractical to isolate and identify
positively the odour causing materials. Evaluation of odour is, thus, dependent on the
olfactory senses of the tester and on his ability to distinguish between different levels and
kinds of odours. The testing is based entirely on arbitrary comparison since no absolute
unit or base exists for odour.
The standard test method is the threshold dilution method in which the odour bearing
sample is diluted successively with odour-free water, until a dilution is obtained which
has a barely perceptible odour. The result is expressed in terms of the "threshold odour
number (TO)", which is given by,
ml of sample + ml odour-free water
TO = -----------------------------------------------ml of sample
It has been recommended that odour tests be run at 40 and 60 0C. Since TO is a function
of temperature, the test temperature should be reported in all cases.
BACTERIOLOGICAL MEASUREMENTS
From public health standpoint the bacteriological quality of water is as important as the
chemical quality. A variety of procedures have been devised to measure the
bacteriological quality, but the most popular method is based on determining the content
of "indicator organisms" in it. The principal indicator organisms used are the coliform
group of bacteria. This group is normally nonpathogenic, present in polluted waters when
pathogens are, or might be present, unable to multiply under conditions when pathogens
do not multiply, and readily identified and enumerated by simple laboratory techniques.
The coliform group of bacteria has the ability to ferment lactose or lauryl tryptose broth
and produce gas. This offers a simple test of the presence of coliform organisms.
However, some other organisms also ferment the broth under certain conditions and,
therefore, additional growth reactions must be carried out to confirm the presence of
coliform group. The test is conducted by inoculating the broth by multiple portions of
a series of decimal dilutions of the water sample. The result is usually expressed as the
number of coliform organisms per unit volume of the sample.

Two methods are generally used for obtaining the number density of coliform organisms
in the test sample. One is the memrobrane-filter technique and the other is the most
probable number (MPN) technique. In the membrane-filter technique, a known volume of
water sample is passed through the filter that has a very small pore size. The coliform
bacteria are captured .by the filter and the filter is then exposed to nutrients which
promote the growth of coliform while inhibiting that of other organisms. After 24 or 48
hours of incubation, the number of coliform colonies is counted and their density is
determined. The caliform colonies appear pinkish in colour and their count is made with
the aid of an optical device. The coliform density is reported in terms of (total) coliforms
per 100 ml.
The most probable number of coliform organisms is a statistical estimate of their density
and is based on the examination of a number of portions of different sizes of the water
sample for the presence of coliforms. From a knowledge of the number of portions of
different sizes giving positive or negative results for coliforms, the MPN can be
determined from the following equation13,
From the above result, the most probable number is 0.47 per mi at which aY is maximum.
In other words the MPN per 100 ml is 47.
Although the coliform bacteria meet some of the criteria for indicator organisms, they do
have certain limitations. Coliforms often grow in treatment facilities or water bodies and
the tests can reveal higher populations even though pathogens are far less likely to
multiply under the same environmental conditions. In addition, some viruses and several
other organisms may survive for longer periods than coliforms, and reduction of
coliforms to low concentrations or even to zero may not always indicate that the water is
safe. Nevertheless, in spite of these and other limitations, the coliform test has provided a
valuable and reliable technique for evaluating water purity.
WATER QUALITY STANDARDS
The analyses required of water samples depend on the intended use of the water. For
example, if its intended use is drinking, water should meet certain quality criteria with
respect to the appearance (turbidity, colour), potability (taste, odour), health (bacteria,
nitrates, chlorides, etc.) and toxicity (metals, organics). These and similar criteria are
established by health or other regulating agencies to ensure that the water quality in a
resource is suitable for the proposed use.
Based on the criteria, quality standards are set, which reflect the current state of
knowledge of various water constituents. These standards are continuously revised as
more and more is learnt about the effects of water constituents on proposed uses. Hence,
these standards should not be used as absolute limits, but only as guidelines that can be
used for preliminary judgements. Table 8.3 summarizes several quality criteria and their
standards for drinking water as suggested by the following agencies:
(1) Indian Council of Medical Research (ICMR)
(2) World Health Organization (WHO)
(3) United States Public Health Service (USPHS)
Standards have been prepared for raw waters to be used as a source for various industrial
applications. The specific purpose for which the water is used usually controls the
requisite water quality. Water used in food and beverage industries will need to meet
standards similar to those for drinking water, while water for cooling purposes can

contain much higher concentrations of impurities. Table 8.4 illustrates the water quality
characteristics of raw surface waters that have been used as source for various industrial
operations. The values listed are the maximum concentrations of different constituents in
the raw surface waters used in the specified industry, and not the maximum
concentrations that could be tolerated.
Table 8.3
Table 8.4

3. Wastewater treatment
Origin of wastewater [3, p.282]; Characterization of wastewaters [1, p.70];
Wastewater sampling and methods of analysis [3, p.313]; Methods and equipment
used in wastewater treatment: Preliminary treatment; Primary treatment
(sedimentation, coagulation, equalization, neutralization) [2, 1];. Secondary
(Biological) treatment (aerobic: aerated lagoons, trickling filters, activated sludge
process, oxidation ditch process, oxidation pond; anaerobic: sludge digestion, sludge
treatment and disposal) [2,1], Sludge treatment and disposal [3]; Advanced or tertiary
treatment (evaporation, ion exchange, adsorption, chemical precipitation,
electrodialysis, electrolytic recovery, reverse osmosis) [2,1], Recovery of materials
from process effluents [3].
Book Reference
1. Environmental chemistry and pollution control, S.S. Dara, p. 70-87.
2. Waste water treatment, M.N. Rao and A.K. Datta, P. 197.
3. Environmental pollution control engineering, C.S. Rao, p. 282-285, 313-327.
5. Wastewater from some typical industries (Wastewater sources, characteristics,
effects and treatment options): Pulp and paper, tanneries, fertilizer, sugar industry,
pharmaceuticals, textile, soap and detergent manufacturing, chloro-alkali industry,
iron and steel manufacturing, thermal and nuclear power plants, photochemical
industry.
(Wastewater sources; characteristics; effects and treatment options):
Book Reference
1. Waste water treatment, M.N. Rao and A.K. Datta, P. 197.
Multichoice questions; True/ False questions
Book Reference
1. Environmental chemistry, B. K. Sharma, p. water pollution -41.
6. Current industrial environmental status. Guidelines and discharge standards of various
industries permit system for discharge/emission. Procedures for undertaking EIA and
their evaluation.
Book Reference
1. Environmental management EIA, S.S. Dara, p. 251

-------------------------------Chapter 3: Wastewater treatment (CS Rao 3, p. 333 )

BASIC PROCESSES OF WATER TREATMENT
The purpose of wastewater treatment is to remove the contaminants from water so that
the treated water can meet the acceptable quality standards. The quality standards usually
depend upon whether water will be reused or discharged into a receiving stream.
Available wastewater treatment processes can be broadly classified as physical, chemical
or biological. These processes, which consist of a series of unit operations, are applied in
different combinations and sequences depending upon the prevailing situations of
influent concentration, composition and condition and specifications of the effluent.
Physical processes are based on exploitation of the physical properties of the
contaminants and are generally the simplest forms of treatment. These principally
comprise screening, sedimentation, flotation and filtration. Chemical processes utilize the
chemical properties of the impurities or of the added reagents. Commonly used chemical
processes are precipitation, coagulation, and disinfection. Other physical and chemical
processes such as air stripping, carbon adsorption, oxidation and reduction, ion exchange
and membrane processes like reverse osmosis and electrodialysis are also important in
certain particular cases. Biological processes utilize biochemical reactions; typical
examples are biological filtration and the activated sludge process.
The wastewater treatment processes are generally grouped according to the water quality
they are expected to produce. These processes are usually grouped as the primary
treatment, the secondary treatment, and the tertiary or the advanced waste treatment.
Primary treatment removes identifiable suspended solids and floating matter. In the
secondary treatment, also known as the biological treatment, organic matter that is
soluble or in the colloidal form is removed. Advanced waste treatment may involve
physical, chemical or biological processes or their various combinations depending on the
impurities to be removed. These processes are employed to remove residual soluble nonbiodegradable organic compounds, including surfactants, inorganic nutrients and salts,
trace contaminants of various types, and dissolved inorganic salts. The advanced waste
treatment processes are expensive, and are used only when water produced is required to
be of higher quality than that produced by conventional secondary treatment so that the
treated water can be reclaimed and put to some form of direct re-use.

Chapter 4: Wastewater treatment of various industries

INDUSTRIAL WASTE TREATMENT
9.0. Introduction:
While a huge amount of water is required for different industrial processes, only a small
fraction of the same is incorporated in their products and lost by evaporation; the rest
finds its way into the water courses as waste water. Thus the industries join the
municipalities to contribute to the "pollution" of the natural bodies of water.
The industrial wastes either join the streams or other natural water bodies directly, or are
emptied into the municipal sewers. Thus these wastes affect in some way or other, the
normal life of a stream or the normal functioning of sewerage and sewage treatment
plants. Much attention is now given in India on the treatment of industrial wastes, due to

its growing pollution potential arising out of the rapid industrialization of the country.
Streams can assimilate certain amount of wastes before they are "polluted", and the
municipal sewage treatment plants can be designed to handle any kind of industrial
wastes. Thus we have three alternatives for the disposal of the industrial wastes viz (i)
The direct disposal of waste into the streams without any treatment, (ii) discharge of the
wastes into the municipal sewers for combined treatment, and (iii) separate treatment of
the industrial wastes before discharging the same into the water bodies. The selection of a
particular process depends on various factors like the following:
(i) Self purification capacity of the streams,
(ii) Permissible limits of the pollutants in the water bodies, established by law,
(Tolerance limits for the inland surface waters, subjected to pollution, as given by ISI are
shown in Table 1.3)
(iii) Economic interests of both the municipalities and the industries,
(iv) Technical advantages, if any, in mixing the industrial wastes with domestic
sewage. After a thorough economic and technical appraisal, if it is decided to treat the
industrial waste either independently or along with the domestic sewage, the treatment
plants are to be designed after (i) a thorough investigation of the characteristics of the
wastes, and (ii) a cost study for the final choice of the particular method of treatment.
9.1. Characteristics of the Industrial Wastes:
Unlike the domestic sewage, the industrial wastes are very difficult to generalize. The
characteristics of the industrial wastes not only vary with the type of the industry, but also
from plant to plant producing same type of end products. Different types of liquid wastes
originate from various types of industrial processes. The pollutants include the raw
materials, process chemicals, final products, process intermediates, process by-products,
and impurities in raw materials and process chemicals. Broadly, these pollutants can be
classified as follows:
(a) Organic substances that deplete the oxygen content of the receiving streams
and impose a great load on the biological units of the sewage treatment plant.
(b) Inorganic substances like carbonates, chlorides, nitrogen etc. that render the
water body unfit for further use and some times encourage the growth of some
undesirable micro-plants in the body of water.
(c) Acids or alkalis which make the receiving stream unsuitable for the growth of
fish and other aquatic life there, and cause serious difficulties in the operation of sewage
treatment plants.
(d) Toxic substances like cyanides, sulphides, acetylene, alcohol, petrol etc. which
cause damage to the flora and fauna of the receiving streams, affect the municipal
treatment processes and some times endanger the safety of the workmen. A list of the
toxic substances from some selected industries is given in Table 9.1.
(e) Colour-producing substances like dyes, which though not toxic, are
aesthetically objectionable when present in the water supplies.
(f) Oil and other floating substances, which not only render the streams unsightly,
but interfere with the self-purification of the same, and the operations of the sewage
treatment plants. Whenever an industrial waste is decided to be discharged into a sewage
treatment plant, special attention must always be given to toxic components of the waste,
if there are any.

Characteristics of the wastes from some selected Indian Industries are given in Table 9.2.
9.2. Treatment of Industrial Wastes:
The treatment of industrial waste water may be accomplished in part or as a whole either
by the biological processes, as done in the case of sanitary sewage, or by processes very
special for the industrial waste water only. The important factors, which affect the
planning for a industrial waste water treatment plants are (1) the discontinuous and some
times seasonally discharged wastes, (2) high concentration of the waste, and (3) Nonbiodegradability and toxicity of some wastes. Depending upon the mode of discharge of
the waste, and the nature of the constituents present in it, the treatment may consist of any
one or more of the following processes.
(i) Equalization
(ii) Neutralization
(iii) Physical treatment
(iv) Chemical treatment
(v) Biological treatment.
The above processes may be carried .out partly or entirely in a municipal sewage
treatment plant along with the domestic sewage, or in a separate treatment plant.
When the characteristics of the waste vary in a day and also the discharge rate is not
uniform or continuous, the waste may require Equalization before it is subjected to the
treatment. Equalization consists of holding the waste for some pre-determined time in a
continuously mixed basin, which produces an effluent of fairly uniform characteristics.
When the waste contains excessive amount of acid or alkali (particularly acid), the waste
requires Neutralization in the neutralization tank. Neutralization may be carried out in the
Equalization Tank, when the conditions permit.
When the industrial waste is treated along with the municipal sewage or discharged into a
stream, the waste may be subjected to another prior unit operation, known as
proportioning. Proportioning consists of the control of the discharge of the waste into the
receiving sewer or stream, in a fixed proportion to the flow of domestic sewage or the
stream. This helps not only in protecting the treatment device from the shock load but
also in improving the sanitary quality of the treated effluent.
Before an industrial waste is subjected to a chemical or biological treatment, or both, it
may be required to separate the suspended matter by physical operations like
Sedimentation, and Floatation. Sedimentation tanks are to be provided only when the
waste contains high percentage of settleable solids. Floatation is employed to separate
fine particles with very low settling characteristics. Floatation consists of creation of fine
air bubbles in the waste body by the introduction of air to the system. The rising air
bubbles attach themselves to the suspended particles and thereby increase the buoyancy
of the particles. The particles thus lifted to the liquid surface are removed by skimming.
Some of the industrial wastes, amenable to biological treatment, may require prior
chemical treatment; some requires only chemical treatment without any biological
treatment. Some of the chemical and physicochemical processes, employed in the
Industrial wastes treatment, for the removal of dissolved inorganic materials are:
(i) Reverse osmosis (Hyper filtration),
(ii) Electrodialysis,
(iii) Chemical oxidation,

(iv) Chemical precipitation,

(v) Adsorption,
(vi) Ion exchange,
(vii) Thermal reduction,
(viii) Air stripping.
When a permeable membrane separates a dilute and a concentrated solution, the osmotic
pressure drives the water molecules from the dilute solution, through the membrane to
establish an equilibrium. This natural response is reversed in the reverse osmosis process,
where the waste water containing dissolved salts are filtered through a semi permeable
membrane such as cellulose acetate at a pressure higher than the osmotic pressure. In this
type of treatment, pre-treatment of the waste such as Activated carbon adsorption or
chemical precipitation followed by some kind of filtration is necessary.
In electrodialysis, the flow of ionic substances is initiated by providing an electrical
potential between two electrodes and the substances are filtered by using an ion-selective
membrane ahead of the electrodes. The separation of substances in this process requires
sets of alternate cation and anion permeable membranes in between the electrodes as
shown in the following schematic diagram (Fig. 9.1).
FId. 9.1 : Schematic Diagram of Electrodialysis Process.
When the waste water is passed through such cells, alternate cells of concentrated and
dilute wastes are formed. Electrodialysis also requires some pretreatment as in Reverse
Osmosis. The chemical oxidation consists of addition of chemicals like chlorine and
ozone to reduce the BOD loading on the subsequent biological process, or to reduce
substances like ammonia, cyanide etc. Chemical precipitation consists of coagulation
either by alum or ferric salts as well as treatment by lime.
Adorption involves the passage of pre-treated waste water through fixed bed Activated
Carbon column, and is used only as a tertiary treatment unit, to remove non-biogradable
organics like synthetic detergents, colour and odour. The regeneration of the exhausted
bed is accomplished by oxidizing and thus removing the adsorbed organics in a furnace at
a temperature of about 925C. Other commercially available materials like clay, fly ash
etc. are also recommended as potential adsorbents.
Ion exchange involves similar passage of waste water through a fixed bed synthetic ion
exchange resin bed, where some of the undesirable cations or anions of the waste are
exchanged for Sodium or Hydrogen ions of the resin. Ion exchange bed requires
regeneration, and special care should be taken for the treatment of the waste produced
due to regeneration.
Thermal reduction involves the burning and thereby oxidation of some refractory and
toxic substances (like organic cyanide).
Air stripping involves the passage (down flow) of a liquid waste through a packed tower,
which is equipped with an air blower at the bottom. This process is a modification of
aeration process used for the removal of gases from the waste water.
The chemical and physico-chemical treatments involve a significant recurring cost, and
chemical oxidation and precipitation required additional facilities for the treatment of
large quantity of sludge produced. So, the chemical treatment should be provided only
when it becomes unavoidable.

When the waste substances are biodegradable, with or without acclimatisation, the
biological process is by far the most desirable treatment process. The treatability of an
industrial waste may be assessed by conducting laboratory tests on BOD/COD ratio. If
the ratio is greater than 0.6, the wastes are bioiogically treatable without acclimatisation;
if the ratio ranges from 0.3 to 0.6, the waste needs acclimatisation for biological
treatment; if the ratio is less than 0.3, other methods are suggested for the treatment. The
acclimatisation involves the gradual exposure of the waste in increasing concentration to
the seed or initial microbiological population, under a controlled condition.
The design criteria for the conventional biological treatment processes may be different
for different types of industrial wastes. The system parameters for particular type of
industrial wastes may 'be determined by laboratory experiments. In the absence of any
actual test result, the performance data of similar type of waste may be used for design.
In some cases, while the commonly available microbiological population fails to achieve
the biological oxidation, some special type of microorganisms do well. So, for the
effective metabolism of some complex organic substances, development of suitable
microbial culture containing specific group of organisms is necessary. (As for example,
some micro organisms which are phenolytic in action, and often found in well manured
soil, have been identified, and are employed in the activated sludge treatment of coke
oven effluents).
Most of the industrial wastes do not contain sufficient amount of nutrients for good
microbial growth. For effective biological treatment of this type of wastes nutrients are
added to the reactors in the form of Urea, Superphosphate or any other compound
containing Nitrogen and Phosphorus. For a balanced growth of microorganisms in a
reactor, the BOD : N : P ratios .of 100 : 5 : L in aerobic systems and 100 : 2.5 : 0.5 in
anaerobic systems are to be maintained.
Special care should be taken in regard to the toxic wastes. Toxicity may be of acute or
chronic type, and may be to humans, plants, animals or to microorganisms responsible for
aerobic or anaerobic biological treatment. Some of the toxic wastes like phenols,
cyanides, formaldehydes etc. yield to acclimatised growths of normal or special type of
bacteria. Some other toxic metal ions like Copper, Zinc, Chromium etc. interfere with the
biological oxidation by tying up the enzymes essentially required for microbial growth.
As such these must he pretreated chemically before the waste is subjected to biological
treatment.
So far, only the principles of industrial waste treatment are described; the selection of the
particular process depends on the effluent requirements and the characteristics of the
waste. The methods of treatment of wastes from some typical industries, along with their
characteristics will be dealt with in the subsequent chapters. It must be borne in mind that
before a treatment policy is fixed up for a particular industry the age of recycling and
reclamation (recovery) of the waste must be considered, for a better management of
Industrial waste waters. Seggregation of strong wastes from the weak wastes some times
reduces the problem.

Methods and Equipment used in Waste Water Treatment (Dara p. 72)1

The various methods used in sewage and industrial waste water treatment are as follows:

(i) Preliminary Treatment.

The principal objectives of preliminary treatment are the removal of gross solids (i.e.
large floating and suspended solid matter, grit, oil and grease if they are present in
considerable quantities.
Large quantities of floating rubbish such as cans, cloth, wood and other larger objects
present in waste water are usually removed by metal bars, acting like strainers as the
waste water moves beneath them in an open channel. The velocity of the water is then
reduced in a grit-settling chamber of a larger size than the previous channel.
Removal of gross solids is generally accomplished by passing waste water through mixed
or moving screens. Different types of these screens are available, which include bar
screens (described above), hand raked or mechanical raked screens, drum screens and
wire rope screens.
The modern mechanical screens cum filters include rotary, self-cleaning, gravity type
units and circular overhead fed vibratory units. These are costlier, as compared to the
conventional bar screens, but are very effective in reducing the suspended solids and

BOD. Sometimes, instead of screening, the gross solids in the sewage are cut into small
pieces with the help of macerators or comminutors.
Grit (or detritus) is removed in the early stages of treatment in grit channels or tanks to
safeguard against any damage to pumps and other equipment by abrasion and also to
avoid settling in pipe bends and channels. Grit, being heavier than organic solids, can be
separated from organic solids by careful regulation of the flow velocity in the grit tanks.
The grit settling chambers are periodically disconnected from the main system to remove
the grit manually, for possible use in land-filling, road making and on sludge drying beds.
If the waste waters contain appreciable quantities of oil and grease, then it is advisable to
remove as much of these as possible, in the preliminary treatment itself to avoid adverse
effects on the rest of the plant. This is achieved by passing the waste water through
skimming tanks where oil and grease are skimmed off. This process can be rendered
more efficient by aeration, chlorination or vacuum flotation.
If the oil and grease are in emulsified condition, as in wool-scouring wastes, ordinary
skimming methods are ineffective. In such cases, they may be removed with the help of
chemical reagents in primary sedimentation tanks.
(ii) Primary Treatment
After the removal of gross solids, gritty materials and excessive quantities of oil and
grease, the next step is to remove the remaining suspended solids as much as possible.
This step is aimed at reducing the strength of the waste water and also to facilitate
secondary treatment.
Sedimentation. The suspended matter can be removed efficiently and economically by
sedimentation. This process is particularly useful for treatment of wastes containing high
percentage of settleable solids or when the waste is subjected to combined treatment with
sewage.
The clear liquid produced is known as the overflow and it should contain no readily
settleable matter. If the sedimentation tank is poorly designed the overflow may contain
solid particles or the underflow may be more dilute than desired.
The sedimentation tanks are designed to enable smaller and lighter particles to settle
under gravity. The most common equipment used include horizontal flow sedimentation
tanks and centre-feed circular clarifiers. The settled sludge is removed from the
sedimentation tanks by mechanical scrapping into hoppers and pumping it out
subsequently. In a well-designed continuous flow sedimentation tank, about 50% of the
suspended solid matter is settled out within two hours of detention time. An efficient
sedimentation system is expected to remove about 90% of the suspended solids and 40%
of organic matter (thus reducing the BOD).
In waste waters containing larger proportion of industrial wastes, a long detention time
helps in mixing and balancing (or equalizing) of the various wastes and safeguards
against unduly heavy loads being passed on to the biological purification plants
subsequently.
Sedimentation aids. Finely divided suspended solids and colloidal particles cannot be
efficiently removed by simple sedimentation by gravity. In such cases, mechanical
flocculation or chemical coagulation is employed.
In Mechanical flocculation, the wastewater is passed through a tank with a detention time
of 30 minutes and fitted with paddles rotating at an optimum peripheral speed of 0.43

m/s. Under this gentle stirring, the finely divided suspended solids coalesce into larger
particles and settle out. Specialised equipment such as Clariflocculator is also available,
wherein flocculating chamber is a part of a sedimentation tank.
In chemical coagulation, the sewage or other waste water is treated with certain
chemicals which form a floc (flocculent precipitate) that absorbs and entrains the
suspended and colloidal particles present. The coagulants in common use are (1)
Hydrated lime (2) Alum, Al 2(SO4)218H2O (3) Copperas FeSO4.7H2O (4) Ferric chloride
and (5) Chlorinated copperas, FeSO4.Cl (mixture of ferric sulphate and chloride). Alum is
the most popular coagulant used both in water and waste water treatment. For best
results, the chemicals used for coagulation are well mixed with the wastewater in baffled
channels followed by mechanical flocculation before sedimentation. Pre-aeration for
about 10 minutes before sedimentation is also found to help in the removal of entertained
gases like CO2 and H2S and improved flocculation and separation of oil and grease.
Coagulation is the most effective and economical means to remove impurities.
Sometimes, in addition to the coagulants, other chemicals called "coagulant aids" are
also used in very small quantities to promote the formation of large and quick settling
floc and thereby enhancing coagulation. Activated silica and polyeletrolytes (such as
polymers of cyanamide, acrylic or methacrylic acids and their derivatives, and
hydrolysed high molecular weight polymers having molecular mass of 10 4 to 106 of
acrylamide or acrylonitrile) are the most commonly used coagulant aids. Polyelectrolytes
are generally used in dilute solutions (~0.25 ppm). Owing to their selective property, care
should be taken in selecting the most suitable polyelectrolytes.
The synthetic coagulant aids work by the following two mechanisms:
(i) The coagulant aids, having long chain molecular structure, are absorbed on two or
more particles, thus drawing them together.
(ii) By reducing the charge on the particles and thus reducing the repulsive power of the
like charges on the particles.
The sequence of operations in the chemically aided coagulation are (a) Addition of lime,
if there is no sufficient alkalinity, (b) Addition of coagulants, followed by rapid mixing
for 4 to 6 minutes, (c) Addition of coagulant aids, followed by gentle agitation or slow
stirring for about 40 minutes.
Flotation
Flotation may be used in place of sedimentation, primarily for treating industrial
wastewaters containing finely divided suspended solids and oily matter. Flotation
technique is used in paper industry to recover fine fibres from the screened effluent and in
the oil industry for the clarification of oil-bearing waste. It is also used for treating
effluents from tannery, metal finishing, cold-rolling, and pharmaceutical industries. An
increasingly important application is the thickening of the sludge obtained from activated
sludge process.
Particles of density very close to that of water are very difficult to settle in normal
sedimentation tanks and take a long time for separation. In such cases, the separation can
be speeded up by aerating the effluent whereby air bubbles are attached to the suspended
matter. This has the effect of increasing the buoyancy of the particles; as a result, the
particles float to the surface where they can be readily removed. To aid in the flotation
process, chemical coagulants such as aluminium and ferric salts or polymer coagulant-

aids are often used. These chemicals increase the flocculent structure of the floated
particles so that they can easily entrap the air bubbles.
The residence time in the flotation tank is about half an hour.
Equalization. Some industries produce different types of wastes, having different
characteristics at different intervals of time. Hence, uniform treatment is not possible. In
order to obviate this problem, different streams of effluents are held in big holding tanks
for specified periods of time. Each unit volume of waste is mixed thoroughly with other
unit volumes of other wastes to produce a homogeneous and equalized effluent. Aeration
or mechanical agitation with paddles usually give better mixing of the different unit
volumes of effluents.
Neutralization. Highly acidic or highly alkaline wastes should be properly neutralized
before being discharged. Acidic wastes are usually neutralized by treatment with lime
stone or lime-slurry or caustic soda, depending upon the type and quantity of the waste.
Alkaline wastes may be neutralized by treatment with sulphuric acid or CO 2 or waste
boiler flue gas.
If both acidic and alkaline wastes are produced in the same plant or at nearby plants,
storing them in separate holding tanks and mutual neutralization by mixing them in
appropriate proportion is the cheapest method.
SECONDAR Y (BIOLOGICAL) TREATMENT
So far, only those materials were considered that might be removed by some type of
physical or mechanical action. Since much of the organic material in wastewater may be
colloidal or dissolved, the primary treatment processes are largely ineffective in removing
it. This organic material still represents a high demand for oxygen which must be reduced
further so that the effluent may be rendered suitable for discharge into the water bodies.
In secondary treatment, the dissolved and colloidal organic matter present in waste waters
is removed by biological processes involving bacteria and other micro-organisms. These
processes may be aerobic or anaerobic. In aerobic processes, bacteria and other microorganisms consume organic matter as food. They bring about the following sequential
changes:
i) Coagulation and flocculation of colloidal matter,
ii) Oxidation of dissolved organic matter to CO2, and
iii) Degradation of nitrogenous organic matter to ammonia, which is then
converted into nitrite and eventually to nitrate.
Thus, secondary treatment reduces BOD. It also removes appreciable amounts of oil and
phenol. However, commissioning and maintenance of secondary treatment systems are
expensive.
Biological or secondary treatment, as it is commonly referred to, is very similar in
concept to the natural biodegradation of organic matter by aerobic bacteria. In biological
treatment, oxygen supplied to the bacteria is consumed under controlled conditions so
that most of the BOD is removed in the treatment plant rather than in the watercourse.
Thus, the principal requirements of a biological waste treatment process are an adequate
amount of bacteria that feed on the organic material present in wastewater, oxygen, and
some means of achieving contact between the bacteria and the organics.

Two of the most commonly used systems for biological waste treatment are the activated
sludge system and biological-film system. In the activated sludge system the wastewater
is brought into contact with a diverse group of microorganisms in the form of a flocculent
suspension in an aerated tank. Whereas in the biological-film system, also known as
trickling filters, the wastewater is brought into contact with a mixed microbial population
in the form of a film of slime attached to the surface of a solid support medium . In both
cases the organic matter is metabolized to more stable inorganic forms. The most popular
means of treating domestic sewage has been the biological-film system because of its
ease of operation. However, the activated sludge process is gaining popularity and is
preferable to the biological-film system because of its reliability and suitability for
handling large volumes of wastewater, and because of the high degree of treatment
achieved.
The effluent from primary sedimentation tanks is first subjected to aerobic oxidation in
systems, such as aerated lagoons, trickling filters, activated sludge units, oxidation
ditches or oxidation ponds. Then the sludge obtained in these aerobic processes, together
with that obtained in the primary sedimentation tanks, is subjected to anaerobic digestion
in the sludge digesters.
Certain micro-organisms, in presence of dissolved oxygen and in proper environmental
conditions, utilise organic waste as their food, and convert into simpler compounds such
as CO2, H2O, nitrates and sulphates which are non-pollutants. This process, therefore, can
be used to remove organic substances from wastes. Almost all organic substances, with a
few exceptions, such as hydrocarbons and ethers, can be oxidised by aerobic biological
treatment. Complex cell tissues and protein materials are also synthesized during this
process, which are then agglomerated and removed from the waste by settling.
Germicidal and resistant organics, such as cyanides and phenols also can be destroyed by
special types of micro-organisms, after prolonged acclimatization periods.
Under anaerobic conditions (i.e., in the absence of dissolved oxygen or gaseous oxygen),
certain groups of micro-organisms, e.g., hydrolyte and methane forming organisms, can
carry out the digestion of complex organic wastes. The hydrolyte organisms convert
complex organic compounds to simple and low-molecular weight organic acids and
alcohols. These are then converted by methane bacteria to CO 2 and CH4. Anaerobic
treatment process can be carried out in depth without the need for large surface area. It
can take place in mixed or enriched cultures and can, therefore, be maintained easily on
large scale. The process can be applied to most types of substrates excepting a few like
lignin and mineral oil. The process is less expensive but the final effluent is less
satisfactory, as compared to that from aerobic treatment, because of the dark colour,
odour and higher residual BOD.
Anaerobic treatment is mainly employed for the digestion of sludges. However, organic
liquid wastes from dairy, slaughter house etc., were treated by this method economically
and effectively. The efficiency of this process depends upon pH, temperature, waste
loading, absence of oxygen and toxic materials.
Some of the commonly used biological treatment processes are described below:
(i) Aerated Lagoons. These are large holding tanks or ponds having a depth of 3-5 m
and are lined with cement, polythene or rubber. The effluents from primary treatment
processes are collected in these tanks and are aerated with mechanical devices, such as

floating aerators, for about 2 to 6 days. During this time, a healthy flocculent sludge is
formed which brings about oxidation of the dissolved organic matter. BOD removal to
the extent of 90% could be achieved with efficient operation. The operation and
maintenance are relatively simple. The major disadvantages are the larger space
requirements and the bacterial contamination of the lagoon effluent which necessitates
further biological purification in maturation pond or by secondary sedimentation and
sludge digestion.
(ii) Trickling Filters. The trickling filters usually consist of circular or rectangular beds,
1 m to 3 m deep, made of well-graded media (such as broken stones, PVC, coal, coke,
synthetic resins, gravel or clinkers) of size 40 mm to 150 mm, over which wastewater is
sprinkled uniformly on the entire bed with the help of a slowly rotating distributor (such
as a rotary sprinkler) equipped with orifices of nozzles. Thus, the waste water trickles
through the media. The filter is arranged in such a fashion that air can enter at the bottom,
counter current to the effluent flow and a natural draft is produced. A gelatinous film,
comprising of bacteria and aerobic micro-organisms known as "Zooglea", is formed on
the surface of the filter medium, which thrive on the nutrients supplied by the sewage or
the waste water. The organic impurities in the waste water are adsorbed on the gelatinous
film during its passage and then are oxidised by the bacteria and the other microorganisms present therein. When the thickness of the film on the medium increases, a part
of it gets detached and carried away along with the effluent. Hence, the effluent from the
trickling filters is allowed to settle in a settling tank to retain the sludge particles and is
then discharged. The sludge is then pumped to the sludge digestion unit.
A Schematic representation of a typical Trickling filtration process is given in Fig. 8.

Although trickling filtration is classified as an aerobic process, it is indeed a facultative

system. Aerobic bacterial species, e.g., spore forming bacteria and bacillus are mostly
present in the upper layer of the filter, whereas anaerobic species, such as Desulfo vibrio,
are present in the interfaces of the stones. Facultative bacteria, such as Pseudomonas,
Alerligens, Flavo bacterium, Enterobactericeae and Micrococcus are also present in the
trickling filters. Algae, fungi, ciliates, protozoan, worms, senils, insect larvae that feed on
micro-organisms are also present.
By and large, smaller media give better results but they tend to choke easily. Synthetic
plastic media are found to be particularly useful for industrial wastes of higher loading.
Moreover, they can afford maximum surface area for the formation of microbial film and
their light weight helps in greater economy in laying the underdrain of the filter.
The microbial film formed is very sensitive to temperature. The metabolic activity is
proportional to the temperature of the waste water passing through the filter. Thus, the
efficiency of the filter decreases in winter season.
The efficiency of the filter depends upon the composition of the waste, strength of
hydraulic loading, temperature, pH, depth of the filter, the size and uniformity of the filter
medium, uniformity of waste water distribution over the filter and proper air supply.
The trickling filter has greater resistance to toxic waste, as compared to the "Activated
Sludge Process" and can recuperate more promptly from an overdose of toxic materials.
However, shock loads or sudden surges should be avoided lest the efficiency of the filter
might be impaired temporarily or even permanently.
Trickling filters are simple to operate and can produce BOD removal to the extent of 65
to 85%, depending upon the rate of filtration. Moreover, constant manual attention is not
needed for this process. Trickling filters produce effluents of consistent and better quality.
The disadvantages of the process include the cost of construction and the need for
ventilation ducts for the under drain system. The efficiency decreases with increased
loading of the waste water. To overcome this problem, the waste water may be diluted
with the effluent from the previous treatment.
Trickling filters are effectively used for the treatment of industrial wastes from dairy,
distillery, brewery, cannery, food processing, pulp and paper mills, pharmaceuticals,
petrochemicals, slaughter house and poultry processing industries.
(iii) Activated Sludge Process
This is the most versatile biological oxidation method employed for the treatment of
waste water containing dissolved solids, colloids and coarse solid organic matter. The
process flow diagram for a typical activated sludge plant is given in Fig. 9.14. The
essential features of the process are: an aeration stage, solids-liquid separation following
aeration, and a sludge recycle system. Wastewater after primary treatment enters an
aeration tank where the organic matter is brought into intimate contact with the sludge
from the secondary clarifier. This sludge is heavily laden with microorganisms which are
in an active state of growth. Air is introduced into the tank, either in the form of bubbles
through diffusers or by surface aerators. The microorganisms utilize the oxygen in the air
and convert the organic matter into stabilized, low-energy compounds such as NO3, SO4,
CO2, and synthesize new bacterial cells. The effluent from the aeration tank containing
the flocculent microbial mass, known as the sludge, is separated in a settling tank,
sometimes called a secondary settler or a clarifier. In the settling tank the separated

sludge exists without contact with the organic matter and becomes activated. A portion of
the activated sludge is recycled to the aeration tank as a seed; the rest is wasted. If all the
activated sludge is recycled, then the bacterial mass would keep increasing to the stage
where the system gets clogged with solids. It is, therefore, necessary to "waste" some of
the microorganisms, and this wasted sludge is the one which is processed and disposed.

The micro-organisms should be provided with essential nutrients, such as N and P, which
are supplied in the form of urea and mono-or di-ammonium hydrogen phosphate. Other
nutrients, e.g., K, Mg, Ca, etc are generally present in the waste. Other important factors
which determine the efficiency of the activated sludge are pH, temperature and oxidationreduction potential. The optimum pH range for the process is 6.5 to 9.0. Low temperature
slows down the rate of metabolism, while high temperature increases the metabolic
activity to such an extent that the oxygen is consumed fast, leading to anaerobic
conditions.
Activated sludge process produces a high quality effluent with relatively small areas. An
efficient aeration for 3 to 6 hours is adequate for sewage, whereas for industrial wastes, 6
to 24 hours of aeration is required for this process. With efficient systems, about 95%
BOD removal is possible. The disadvantages include high cost of operation and
maintenance, need for careful attention and sensitivity to shock loads of toxic and organic
substances.
Activated sludge process was used satisfactorily for the treatment of effluents from food
processing, sugar, textile processing, antibiotic manufacturing industries, etc.
Efficiencies of Activated Sludge Process
The activated sludge process, including pretreatment and primary settling, is an efficient
means of removing suspended solids and organic matter from wastewaters. Table 9.3
presents typical primary and secondary effluent characteristics. As is seen from the table,
most of the suspended solids and the BOD materials are removed after secondary
treatment. However, the activated sludge process does a poor job in removing both
nitrogen and phosphorus from wastewater. The total nitrogen content is reduced by
approximately one-third. The influent ammonia is oxidized by nitrifying bacteria and this
reduction is partially balanced by the production of ammonia by the sludge mass. The net
result is that there is a slight reduction in the ammonia concentration.
Table 9.3 Wastewater characteristics*

Suspended slids
BOD
Ammonia nitrogen
Total nitrogen
Phosphorus
Ultimate oxygen demand

Typical wastewater Primary effluent

(mg/l)
(mg/l)
230
85
200
135
18
16
30
25
13
11
383
276

Secondary effluent
(mg/l)
20
20
15
20
10
99

*Based on average treatment efficiencies. These values may vary from plant to plant, and
within any one plant with time.
Primary sedimentation in conventional treatment settles only a small percentage of the
phosphorus present in wastewater, since its major part is dissolved. In the activated
sludge process the microbial floc takes the soluble phosphate as a nutrient but the
removal efficiency is small (less than 30%), so that most of the phosphorus remains

uneffected by the secondary treatment. The ultimate oxygen demand (UOD) is reduced
by about 75% in the conventional secondary treatment. Most of this reduction is due to
the oxidation of the organic carbonaceous material and the remainder is due to removal of
ammonia. The extended aeration process may be expected to raise the removal efficiency
of UOD to about 90%.
Table 9.4 gives the major differences between conventional trickling filters and activated
sludge systems, and also lists their advantages and disadvantages.
Table 9.4 Comparison of trickling filters with activated sludge systems
1.
2.
3.
4.
5.
6.

Trickling filters
Bacterial growth is fixed on the media

Activated sludge systems

Bacterial growth is suspended as a
dispersed floc
All solids from the settler are wasted
Solids from the settler are partially
recycled
Less sensitive to shock loading, more More sensitive to shock loadings, require
stable
closer process control
Produce insects and odours
Produce spray clouds
Less effective in removing disease- More effective in removing pathogens
causing organisms
than trickling filters
Low operating costs
High operating costs

(iv) Oxidation Ditch. This can be considered as a modification of the conventional

Activated Sludge process. Oxidation ditch (Fig. 10) usually consists of an oval shaped
continuous channel, about 1 to 2 m deep and lined with plastic, tar or butyl rubber. Waste
water, after screening or comminution in the primary treatment, is allowed into the
oxidation ditch. The mixed liquor containing the sludge solids (MLSS) is aerated in the
channel with the help of mechanical rotors. Longer retention times are needed. The usual
hydraulic retention time is 12 to 24 hrs and for solids, it is 20-30 days. Most of the sludge
formed is recycled for the subsequent treatment cycle. The surplus sludge can be dried
without odour on sand drying beds.
The major advantages of the oxidation ditch include simplicity in operation, easy
maintenance, low cost of construction, operation and maintenance, overall efficiency and
flexibility. This process is generally used for wastes having low BOD.
Oxidation ditch process is used effectively for the treatment of waste water from beetsugar manufacture, vegetable and fruit canning industry, slaughter house and meat
packing industry and edible oil refineries.
(v) Oxidation Pond. An oxidation pond is a large shallow pond (0.5 m to 1.5 m depth)
with arrangements to measure the inflow and outflow. The wastes enter the pond at one
end and the effluent is removed at the other end. Stabilization of organic matter in the
waste is brought about mostly by bacteria, such as Pseudmonas, Flavo bacterium and
Alcaligenes, and to some extent by flagellated protozoa. The oxygen requirement for
their metabolism is provided by algae present in the pond. The algae, in turn, utilize the
CO2 released by the bacteria for their photo synthesis. Oxidation ponds are also called
waste stabilization ponds.

For efficient waste water treatment by this process, an adequate natural aeration, good
mixing by wind and proper penetration of sunlight required for photosynthesis of algae
are essential. This is the reason why oxidation ponds should be shallow.
Addition of nutrients may be necessary to enhance the growth of algae. This will enhance
the amount of oxygen released, which in turn increases the rate of purification of waste
water. Any deficiency of oxygen may lead to anaerobic conditions and consequent release
of bad odours due to putrefaction of wastes. This is the reason why mechanical aeration is
also provided at some places in addition to natural aeration.
Although waste water treatment in oxidation ponds is generally considered as an aerobic
process, the purification is performed by a combination of aerobic, facultative and
anaerobic processes. The waste water present in the upper part of the pond (which
constitutes the major portion of the waste) undergoes aerobic oxidation to CO 2 and H2O.
Solids present in the waste, which settle as a layer at the bottom, act as anaerobic phase.
Here, the organic matter is oxidised by anaerobic bacteria to CH 4, CO2, and NH3. The
facultative zone exists near the anaerobic phase.
Waste treatment by oxidation pond is cheap and the operation and maintenance are
simple. The process can be used for all types of wastes and any degree of purification can
be obtained. The process can withstand organic and hydraulic shock loads. The heavy
metal ions present in the waste water are precipitated as hydroxides (due to the high pH
of the waste water in the oxidation pond) which settle as sludge. However, oxidation
ponds require larger space. The effluent from the oxidation ponds may require
disinfection or further treatment in a separate maturation pond before final discharge.
(v) Anaerobic digestion. This treatment is mainly used for sludge digestion. Sludge is
the watery residue from the primary sedimentation tank and humus tank (from secondary
treatment). The constituents of the sludge undergo slow fermentation or digestion by
anaerobic bacteria in a sludge digester, wherein the sludge is maintained at a temperature
of 35 0C at pH 7-8 for about 30 days. CH4, CO2 and some NH3 are liberated as the end
products. The schematic representation of the anaerobic sludge digestion process is
shown in Fig. 11.
Fig. 11. Anaerobic sludge digestion process.
Species of Pseudomonas, Flavo bacterium, Aerobacter, Alcalagenes etc., convert complex
organic compounds to low molecular weight organic acids and alcohols. Methano
bacterium, Methanosarcina and Methanococcus types of bacteria are responsible for the
generation of CH, in this process. Desulfo Vibrio bacteria reduce sulphates to sulphides
and thus, H2S is released.
The anaerobic digestion process can be accelerated at higher temperatures.
The advantages of anaerobic digestion process are as follows:(1) Reduction in volume of the waste by about 65%.
(2) The digested sludge is safer to be used as manure than the undigested sludge.
(3) The digester gas obtained has the following percentage composition by volume : CH,
- 65 to 80%; CO2 - 5 to 30%, N2, H2, H2S and CO together - about 5%. About 0.6 to 1.25
m3 of the gas is produced per kg of the organic matter destroyed. The calorific value of
the gas is about 26 MJ/ m3 (i.e., about 700 BTU/ft3). The gas can therefore be used as a

fuel to provide the heat required to warm the digestion tanks. In large installations, it can
be used for power generation.
(4) Although anaerobic treatment is a slow process, it is useful for treating small
quantities of wastes, containing readily oxidisable dissolved organic solids in liquid form
or in finely divided form. The operation and maintenance costs are lesser with this
treatment. That is why some liquid wastes containing soluble organics from dairy,
slaughter house and paper mill industries have been economically and effectively treated
by this process.
Sludge Treatment and Disposal
Handling and disposal of sludge from biological wastewater treatment plants is an
important problem and represents about half the cost of most sewage treatment plants.
The concentration of solids in the primary sewage sludge is about 5%; the activated
sludge contains less than 1% solids; and the sludge from trickling filters has about 2%
solids. This means that the sludge is composed almost entirely of water and volume
reduction is the key to economic disposal. In addition to reducing its high water content,
the sludge must be stabilized so that its biological activity and tendency towards
putrefaction are reduced drastically.

Fig. 9.24
paths)

Sequence of operations for sludge treatment (Arrows indicate possible flow

The common unit operations of sludge treatment and disposal involve concentration or
thickening, digestion, conditioning, dewatering, oxidation and safe disposal. Fig.9.24
represents the general flow sheet of sludge treatment techniques in approximately the
order in which they could be applied in a treatment scheme.
Concentration
The purpose of concentration or thickening is to remove water from the sludge and
reduce its volume as much as possible so that the sludge can be handled more efficiently.
The common methods for thickening are gravity settling and flotation. In gravity
thickeners the sludge is subjected to gentle agitation by means of a slow stirrer which
enhances settling. In this manner the combined sludge from primary and secondary
settlers can be thickened so as to contain 5-9% solids. Often the thickening of activated
sludge is complicated by anaerobic action, particularly under warm conditions when the
bacteria in the sludge decompose organic matter and release gases. This also creates
settling and odour problems. The sludge can also be thickened by air flotation,
particularly the secondary sludge, which keeps the system aerobic. The flotation
technique can concentrate the sludge to bring its solids content to 4%.
Digestion
After concentration, the sludge is stabilized by digesting it under aerobic or anaerobic
conditions. Anaerobic digestion is the most common method in which the organic content
of the sludge decomposes to give mainly methane and carbon dioxide and at the same
time the bound water is released from the sludge. Properly digested sludge is black with a
faint smell of tar, and is stable. In a typical sludge digester, shown in Fig. 9.25, raw
sludge is fed into the active digestion zone and gas lifts the sludge particles and other
materials which form a supernatant layer on the top of the digestion zone. The gas is
collected at the top and the digested sludge is withdrawn from the bottom. The normal
detention period in standard digesters varies from 30 to 70 days depending upon the
temperature conditions.
Aerobic digestion is also used, and it may be considered similar to extended aeration. The
sludge is aerated in a tank for about 20 days at ambient temperatures. During the process
the bacterial cells are destroyed and a substantial portion of the sludge is oxidized
resulting in the reduction of the solid content by about 30%. Sometimes shallow lagoons
are employed as digesters. Large land areas are required for sludge lagoons and odour
problems may occur frequently.
Conditioning
The sludge after stabilization may be conditioned to improve its dewatering
characteristics. This is done by adding chemicals like iron salts, alum, lime and
polyelectrolytes. These chemicals bind the sludge particles together and encourage the
release of absorbed water. Physical conditioning methods such as heat treatment are
becoming popular. The sludge is heated under pressure and after a period of time the gel
structure of the sludge breaks down so that the water is released. Heat treatment has the
advantage of sterilizing the sludge; at the same time the sludge is partially oxidized and
completely stabilized.

Dewatering
The thickened sludge is dewatered for efficient handling and disposal. Dewatering is
accomplished by mechanical methods, the most common being centrifugation and
filtration, which includes pressure filtration and vacuum filtration. In centrifugation,
conditioned sludge is added to a rotating bowl that separates the sludge into a cake and a
dilute stream. The solid cake is transported within the bowl and is removed by a screw
conveyor at one end of the bowl; the liquid is removed at the opposite end (Fig. 9.26).
Centrifugation is a compact method which requires careful control of process variables.
Filtration, using plate-and-frame pressure filters or rotary drum vacuum filters, is widely
used for dewatering digested sludge. In pressure filtration, the sludge is pumped slowly
with increasing pressure into filter plates supporting a cloth, which retains the solids. It is
a batch process, and after the dewatering period the plates are separated and the sludge
cake removed. Pressure filtration can produce a cake with a solids content of 25-50%. In
contrast to pressure filtration, vacuum filtration is a continuous process where a rotating
drum, which is covered with filter cloth, is partially submerged in the sludge. On
applying a vacuum of 80-90 kPa inside the drum, the liquid is sucked into the drum. The
cake is deposited on the outside of the drum and is removed by a scraping mechanism.
Vacuum filtration yields a dewatered sludge with a solids content of about 25%.
Drying beds are also commonly used for dewatering. The bed consists of a filtering
medium on which the sludge is applied to a depth of upto 250 mm, depending on the
solids content. Dewatering takes place by a combination of drainage and evaporation.
Removal of dried sludge is carried out mechanically. Another technique, heat drying, may
be utilized in applications where the sludge is to be incinerated or when a saleable
commodity can be produced. A major problem associated with this process is the control
of gases and ash particles which may be generated in drying.
Oxidation
Before the final disposal, some sludges may be oxidized to reduce the organic content,
with the consequent destruction of bacteria and a significant reduction in their volumes.
Incineration and wet oxidation are the two common methods employed for sludge
oxidation. Incineration is usually performed in a multiple hearth furnace, although
fluidized beds or flash dryers may also be used. In the multiple hearth furnace the sludge
passes downward through a series of hearths. Vaporization of moisture occurs in the
upper hearths, followed by incineration in the lower ones. The combined efficiency of
evaporation and incineration in multiple hearth furnaces is about 55%. The fluidized bed
system consists of a bed of sand fluidized by air. When the sludge is introduced, the
sludge particles are dried almost instantly as they are dispersed, and are oxidized.
Wet oxidation is a process in which the sludge is ground, mixed with air in stoichiometric
proportions, and then subjected to high temperature
The sludge from the digester may contain about 90 to 93% water. The sludge is dewatered in drying beds, filter presses or vacuum filters. The de-watered sludge, after
chlorination, can be sent for ultimate disposal. The various methods used for ultimate
disposal include dumping in landfills, incineration, dumping at selected sites in sea, or
utilizing as a low grade fertilizer.

TERTIARY OR ADVANCED WASTEWATER TREATMENT

Table 15.1, indicates, not all of the impurities in a waste water stream are removed by
primary and secondary treatment. Ordinarily, the remaining quantities would be disposed
of naturally in the river which received the effluent, but the growth of population and
industry and its concentration along rivers require that most water be used many times
before it reaches the ocean. In many cases the increments of pollution remaining after
ordinary treatment are too large for natural removal prior to the next use. Thus, a number
of tertiary or advanced wastewater treatment techniques are becoming important,
although at present only a very small percentage of municipal systems use them (Table
15.1). Several of these methods are also applicable to industrial wastes where BOD and
suspended solids may not be the most important indicators of water quality, and indeed a
number of them find much greater use in such applications. In addition, they may be
employed at the beginning (water purification) as well as the end of the human water use
cycle.
Activated carbon adsorption
Ultrafiltration
Electrodialysis
Ion exchange
Removal of bacteria and viruses
Removal of nitrogen and phosphorus
Disposal of treated wastewater in spoils
Agricultural wastes
P. 84, Dara
Evaporation
Ion-exchange
Adsorption
Electrodialysis
Electrolytic recovery
Reverse osmosis
----------------------------------------------------------------------------------------------------

H-408 Environmental pollution and Industrial waste management

1. Deposition of Atmospheric pollutants and their effects. Acid rain, Some air pollutants
case (London smog, Bhopal disaster, Chernobnyl disaster, etc). Air quality standards.
Sampling and Monitoring.
2. Natural water-Eutrophication. Heavy metals and their removal, Sources and effects of
pollution by mercury, lead, Arsenic and chromium. Case studies-Bioamplification
(Minamata disease etc.).
3. Industrial monitoring, Concept of threshold limit value, time weighted average and
short term exposure limits. Methods of monitoring, exposure, active and passive,
diffusive monitors, Draeger tubes, portable/sampling device, Analytical techniques.
4. Wastewater treatment:

Origin of wastewater; Characterization of wastewaters; Sampling and methods of

analysis; Methods and equipment used in wastewater treatment: Preliminary
treatment; Primary treatment; Secondary (Biological) treatment, Sludge treatment and
disposal; Advanced or tertiary treatment, Recovery of materials from process
effluents.
5. Wastewater from some typical industries (Wastewater sources, characteristics, effects
and treatment options):
Pulp and paper, tanneries, fertilizer, sugar industry, pharmaceuticals, textile, soap and
detergent manufacturing, chloro-alkali industry, iron and steel manufacturing, thermal
and nuclear power plants, photochemical industry.
6. Current industrial environmental status; Guidelines and discharge standards of various
industries permit system for discharge/emission. Procedures for undertaking EIA and
their evaluation.
---------------------------4. Wastewater treatment
Origin of wastewater [3]; Characterization of wastewaters [2]; Sampling and methods
of analysis [3]; Methods and equipment used in wastewater treatment: Preliminary
treatment; Primary treatment (sedimentation, coagulation, equalization,
neutralization) [2,1];. Secondary (Biological) treatment (aerobic: aerated lagoons,
trickling filters, activated sludge process, oxidation ditch process, oxidation pond;
anaerobic: sludge digestion, sludge treatment and disposal) [2,1], Sludge treatment
and disposal [3]; Advanced or tertiary treatment (evaporation, ion exchange,
adsorption, chemical precipitation, electrodialysis, electrolytic recovery, reverse
osmosis) [2,1], Recovery of materials from process effluents [3].
Book Reference
1. Environmental chemistry and pollution control, S.S. Dara, p. 70-87.
2. Waste water treatment, M.N. Rao and A.K. Datta, P. 197.
3. Environmental pollution control engineering, C.S. Rao, p. 283-285, 313-327.
4. Environmental Chemistry, Fifth edition, A.K. De
5. Wastewater from some typical industries (Wastewater sources, characteristics,
effects and treatment options): Pulp and paper, tanneries, fertilizer, sugar industry,
pharmaceuticals, textile, soap and detergent manufacturing, chloro-alkali industry,
iron and steel manufacturing, thermal and nuclear power plants, photochemical
industry.
(Wastewater sources; characteristics; effects and treatment options):
Book Reference
1. Waste water treatment, M.N. Rao and A.K. Datta, P. 197.
6. Current industrial environmental status. Guidelines and discharge standards of various
industries permit system for discharge/emission. Procedures for undertaking EIA and
their evaluation.
Book Reference

1. Environmental management EIA, S.S. Dara, p. 251

Multi choice questions
True/ False questions
Book Reference
1. Environmental chemistry, B. K. Sharma, p. water pollution -41.