Chapter 3: Quality of waste water

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Introduction
• Sewage contains large amount of water ( about 99.9 %) and solid matter is suspension
and dissolved state (about 0.1 %)
• Sewage consists of residential, public and industrial mixtures of wastewater
• Contain organic and inorganic materials in dissolved or suspended, or colloidal form
• Contain various microorganisms useful and harmful to human life.
• before designing any sewage treatment system to work efficiently we analysis of
characteristics of sewage is needed.
3.1 Constitutes of Waste water
1. Inorganic Suspended Solids
• Small, relatively dense, often abrasive, and chemically inert particles. Consists of such
material as silt, sand, gravel, metal and glass.
2. Organic Suspended Solids
• Consists of animal excreta, vegetable, fruits wastage etc. As the substances are
organic they are normally capable of biodegradation.
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3.1 Constitutes of Waste water
3. Colloidal Solids
• Extremely fine solids (1-500 n.m.( 10-9 m) particle size), neither truly suspended nor
truly dissolved in the body of the liquid.
• Colloidal solids have the property of scattering light and causing the turbidity of waste
water
4. Dissolved Solids
• Solids, both organic and inorganic, which are smaller than 1 n.m in dimension
5. Inorganic Components
• Sodium Chloride ,Potassium ,Sulphate, Ammonium ,Phosphate ,Calcium ,Bicarbonate
,Magnesium, Carbonate etc
6. Organic components
Fats, carbohydrates, proteins, detergents etc

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3.1 Constitutes of Waste water
7. Biochemical oxygen demand (BOD)
• It is the amount of oxygen required for the decomposition of organic compounds by
aerobic bacteria in presence of oxygen at standard temperature.
• 5 days BOD at 20 c is taken as standard BOD.
8. Chemical oxygen demand (COD)
• amount of oxygen required for oxidation of organic matter, chemical, carbonaceous
matter
9. Pathogens
• Pathogens are organisms or viruses that are capable of causing disease like E-coli

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Aerobic and Anaerobic Decomposition
1. Aerobic decomposition:
• Fresh sewage is decomposed by the aerobic bacteria in the presence of free oxygen
is called aerobic decomposition.
• organic matter broken and oxidized to stable and non-objectionable products as CO2,
nitrates, sulphates etc.
• aerobic decomposition takes place in aeration tanks, trickling filters, contact beds,
oxidation ponds etc.
• Carbohydrates + O2 aerobic bacteria CO2 + H2O
• Fats + O2 aerobic bacteria CO2 + H2O
protein + O2 aerobic bacteria NH3 + H2O + CO2

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Aerobic and Anaerobic Decomposition
2. Anaerobic decomposition
• Organic matters are decomposed by anaerobic bacteria in absence of free oxygen and
light. This reaction is called hydrolysis.
• Aerobic bacteria survive by extracting and consuming bounded molecular oxygen
present in the oxygen radicals of organic compounds such as nitrites, nitrates,
sulphates etc.
• Organic matter broken into solids, liquids and gases such as CH4, H2, CO2, N2, NH3,
H2S, alcohols etc and produces bad odour, toxic end products and sewage becomes
septic.
• Occurs in septic tank, Imhoff tanks, sludge digestion tanks etc.

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Characteristics Of waste water
1. Physical 2. Chemical 3.Biological
1. Physical characteristics:
a. Colour:
• Colour of sewage due to suspended and other matters. Fresh sewage has light brown
colour, with passage of time sewage undergoes decomposition due to which its colour
changes to dark grey or black Colour
• Colour is tested by Tintometer represents in terms of platinum cobalt scale
b. Odour
• Fresh sewage is of sightly soapy or oily odour while Septic sewage has offensive odour
due to product of anaerobic decomposition like H2S, CH4 etc. it represents in
Threshold Odour Number
c. Temperature:
• Temperature of sewage is slightly higher temperature than the water. On increasing the
temperature of sewage biological activities increases and tested by thermometer.

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d. Turbidity:
• very turbid due to the presence of high suspended and organic matters.
• Test by turbidity meter
e. Solids:
• contains >99.9%of water and 0.1%of solids.
2. Chemical Characteristic
• Sewage contains complex compounds from urine, hospital and industrial wastage,
inorganic chemicals etc.
• Chemical characteristics affects the selection and operation of various treatment
component

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a. PH :
• Fresh sewage is alkaline and pH is between 7.3 and 7.5. With respect to time due to the
production of acids by bacterial action and become acidic. After oxidation again becomes
alkaline.
• Very lesser and very higher pH indicates industrial sewage.
• Tested by pH meter
b. Dissolved Oxygen (DO):
• amount of oxygen dissolved in wastewater.
• Presence indicates fresh sewage or oxidation after treatment.
c. BOD:
• Amount of oxygen required for the aerobic bacteria to oxidize the organic matter
present in the sewage.
d. COD:
• Amount of oxygen required for chemical oxidation of organic matters.

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3. Biological characteristic
• Sewage contains large amount of micro-organism. Micro-organism plays fundamental
role in decomposition of organic matter present in sewage
• Bacteria present in sewage can be classified as:
1. Aerobic bacteria: it need oxygen to survive
2. Anaerobic bacteria: it can survive in absence of oxygen
3. Facultative bacteria: it can survive in presence as well as absence of oxygen
Bacteria present in sewage can also be classified as:
1. Pathogenic bacteria: disease causing bacteria
2. Non-pathogenic bacteria: do not cause any harm

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Sampling of waste water
• It is the process of collection sewage sample which are taken at frequent interval and
from different depths to obtain of true representative sample to determine
characteristics, nature and flow of sewage with time and depth.
• characteristics changes continuously with respect to time so 24 hours sample (100 to
150 cc) collection is done at one hour interval
• The sample should be tested without delay because sewage contains a number of
unstable compounds, which rapidly decompose. The sample is place in an ice-chest to
prevent the quick biological action.
• Type of sample:
1. Grab sample: the sample which is taken from below the surface where sewage
particles are fairly mixed due to turbulence is called grab sample. It represents the
condition of sewage at particular time and location. It is suitable for testing pH,
residual chlorine and dissolved oxygen. Grab sample are taken as 1 – 1 hour interval
without entrapping air.
2. Composite Sample: the sample which is prepared by mixing different grab samples
taken at different intervals in proportion to the flow of sewage is called composite
samples. It represents the average strength and composition of sewage

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Preservation and storing
• Sample is taken in a quartz bottle with capacity 200 - 300 ml and quartz bottle should
be cleaned, dried and sterilized and samples kept in a cool place to prevent bacterial
activity
• Suitable preservatives (chloroform, sulphuric acid, formaldehyde etc) to prevent
change in quality
• Sulphuric acid: should not be used for determination of alkalinity, acidity or PH
• Chloroform: should not be used to test organic matters
• for BOD: no preservatives are used.
• Each sample should have label with information as under:
• 1. Source 2.Date 3.Time 4. Preservatives used 5. Collector's identity
6.Temperature 7. Atmospheric pressure

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Biochemical oxygen demand (BOD)
• It is the amount of oxygen required for the decomposition of organic compounds by
aerobic bacteria in presence of oxygen at standard temperature.
• 5 days BOD at 20 ℃ is taken as standard BOD.
• Organic matter is utilized by bacteria as food and they derive energy and develop new
cells by decomposition of organic matter
• BOD depends upon biological activity and temperature.
• Generally after 5 days 60-70% decomposition takes place after 10 days 90%
decomposition and after 20 days 95-99% decomposition takes place
Bod can be divided into
1. First stage or carbonaceous biochemical oxygen demand
• First stage bod is defined as the amount of oxygen necessary for the micro-organisms
in the sample to decompose carbonaceous materials like carbohydrates, fats, sugar,
etc into CO2 and water

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2. Second stage or nitrification biochemical oxygen demand
• First stage bod is defined as the amount of oxygen necessary for the micro-organisms
in the sample to decompose nitrogenous materials like proteins, amino acids, etc into
nitrates and nitrites

BOD5

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BOD test are used for
• Determination o0f approximate quantity of oxygen required for decomposition of organic matter
• Determination of strength of sewage
• Determination of size of waste water treatment facilities
• Measurement of efficiency of treatment plant
Derivation of BOD equation
At a given temperature, rate of decomposition
Is directly proportional to the organic matter
present in sewage at that time.
= - K’ L
Where L = amount of BOD remaining in
the sample at any time t, in mg/l
K’ = rate constant which gives the rate
of oxidation of organic matter, per day
t = time in days

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e= 2.718
-2.303Kt -2.303Kt -Kt
e = 2.718 = 10

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• The amount of organic matter
decomposed by any time t is
yt = L0 – Lt
-K t
= L0 - L0 x10
-K t
= L0 ( 1 - 10 )
• This yt is also called
BOD of t days
y = BODt
t
• 5 days BOD at 20 ℃
taken as Standard BOD
-5k
BOD5 = y = L0 ( 1 - 10 )
5

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Ultimate BOD
• The ultimate BOD of a sewage sample equal to the initial oxygen equivalent of the
organic matter present in the sample of waste water
When t = ∞, yt becomes yu ( ultimate BOD )is given by
-K ∞
yu = L0 ( 1 - 10 ) = L0
Rate Constant
• The value of rate of reaction constant K, depends on the organic matter of sewage and
temperature. The value of K at temperature
KƟ = Ko x 1.047T-20
Where Ko = rate reaction constant 20 = K20 = 0.1 /day

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Chemical oxygen demand ( COD )
• COD is defined as the amount of oxygen required for chemical oxidation of organic
matter present in sewage by a strong chemical oxidizing agent used in an acidic
medium.
• Potassium dichromate K2Cr2O7 in presence of concentrated sulphuric acid is used as
oxidizing agent.
• COD can be determined in 3 hours whereas BOD test takes 5 days.
• COD value is always greater than or equal to the BOD value.
• A higher value of COD than BOD indicates that the sewage is difficult to biodegrade.
• COD can be used for control and operating of treatment plants.

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Examination of Total Solids, Fixed Solids and Volatile Solids
• Take a dry crucible of weight 'W1’ in milligram and put ‘V’ milliliter volume of well
• mixed sewage sample and evaporate to dryness in oven at 103 – 105°C for 24 hours.
• Cool the crucible and take weight as ‘W2'
W 1
• Then Total solids ( TS ) = x1000 mg/liter
V
• Place the crucible (W2 milligram) place in muffle furnace at temperature of 600 °C for
30 min. At this temperature volatile materials escape away.
• Cool the crucible in desiccator for 5 min and weigh W3 mg
• Then Fixed solids ( FS ) = x1000 mg/liter
V
• Volatile Solids ( VS ) = x1000 mg/liter
V

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Dissolved Oxygen (DO) Test
Procedure
1.Carefully fill a 300-mL glass Biological Oxygen Demand (BOD) stoppered bottle brim-full with sample
water.
2.Immediately add 2mL of manganese sulfate to the collection bottle by inserting the calibrated pipette just
below the surface of the liquid.
3.Add 2 mL of alkaline potassium iodide reagent in the same manner.
4.Mix the sample by inverting several times. Check for air bubbles; discard the sample and start over if any
are seen. If oxygen is present, a brownish-orange cloud of precipitate or floc will appear.
5.Add 2 mL of concentrated sulfuric acid via a pipette held just above the surface of the sample. At this
point, the sample is "fixed" and can be stored for up to 8 hours if kept in a cool, dark place.
6.In a glass flask, titrate 200 mL of the sample with N/ 40 sodium thiosulfate to a pale straw color. Titrate by
slowly dropping titrant solution from a calibrated pipette into the flask and continually stirring sample
water.
7.Add 2 mL of starch solution so a blue color forms.
8.Continue slowly titrating until the sample turns clear. As this experiment reaches the endpoint, it will take
only one drop of the titrant to eliminate the blue color. Be especially careful that each drop is fully mixed
into the sample before adding the next.
9.The concentration of dissolved oxygen in the sample is equivalent to the number of milliliters of titrant
used. Each 1 mL N/40 of sodium thiosulfate added in steps 6 and 8 equals 1 mg/L dissolved oxygen.
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Biochemical oxygen demand (BOD) test:
(1) Direct method (2)Dilution method
(2) 1 Direct method:
In this method, Dissolved oxygen ( DO) of sewage is measured before and after
incubation and BOD of sewage is determined
This method can only be used to measure very low BOD
Procedure
• Take suitable quantity of sample of sewage in BOD bottle and measure initial DO (DOi )
• Keep it in incubator at standard temperature of 20°C for standard time of 5 days
• Again measure final DO ( DOf ) after 5 days.
• Oxygen consumed in 5 days gives the BOD directly.
• Mathematically, BOD5,20 = DOi – DOf

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(b) Dilution method:
• In this method sewage sample is mixed with dilution water.
• Dilution water includes 1ml of MgSO4, 1 ml FeCl3, 1 ml CaCl2 and 1 ml Phosphate buffer
added to distilled water and is aerated to saturate it with oxygen before mixing with sewage
sample
Procedure
• Measure the initial Do (DOi) of diluted sample in mg/liter.
• Incubate it in incubator at 20°C for 5 days
• Again measure final DO (DOf) after 5 days in mg/liter
• Oxygen consumed in 5 days gives the BOD of sample indirectly by,
• BOD5,20 = (DOi – DOf) × Df
• where, Df = Dilution factor =
• Eg if 2ml of sewage is mixed with 98 ml of dilution water then
dilution factor = = 50
If dilution factor is given in % in question then BOD5,20 = (DOi – DOf) ×
Df %
• Df % = x100%

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(b) Dilution Method
• Alternative Procedure
• Measure the DO of undiluted sewage sample = DOs
• Mix dilution water and original sewage and incubate at 20 ℃ for 5 days
• Measure DO of diluted sample after 5 days = DOf
• Measure DO of diluted water (blank water ) after 5 days = DOb

• BOD = ( DOb – DOf ) x – (DOb – DOs )

Df %

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Chemical Oxygen Demand (COD) Test
Procedure
1. Take x ml of sewage sample in conical flask
2. Add 2x ml of potassium dichromate K2Cr2O7 so that all organic matter decomposed
and residual K2Cr2O7 is available
3. Add 3x ml of conc H2SO4
4. Titrate with N/40 ferrous ammonium sulphate [Fe(NH4)2(SO4)2 ] in burette
5. When the solution turns colorless add ferroin indicator which turn the solution to blue
green color
6. Continue with titration till the solution turns wine color
7. Note the amount of ferrous ammonium sulphate titrated = a ml
8. Repeat the titration with water only, amount of ferrous ammonium sulphate used in
this case = b ml

9. Then COD = mg/liter

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Numerical
Example 3.6 The following observations were made on 5% dilution sewage sample.
DO of blank water = 3.3 mg/ltr
DO of original sample = 0.55 mg/ltr
DO of diluted sample after 5 days of incubation at 20 ℃ = 0.89 mg/ltr
Calculate BOD and ultimate BOD
Solution
Dilution factor Df % = 5, DO of blank water DOb = 3.3 mg/ltr
DO of original sample DOs = 0.55 mg/ltr
DO of diluted sample after 5 days of incubation at 20 ℃ DOf = 0.89 mg/ltr
BOD = ( DOb – DOf ) x – (DOb – DOs )
Df %

= ( 3.3 – 0.89 ) x – (3.3 – 0.55 )

BOD5, 20 ℃ = 45.45 mg/ltr

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 -K t
• BOD5, 20 ℃ = L0 ( 1 - 10 )
-0.1x5
45.45 = L0 x(1 - 10 )
L0 = 66.47 mg/ltr
Ultimate BOD = L0 = 66.47 mg/ltr
Example 3.7 if 2.5 ml of raw sewage is diluted to 250 ml and DO concentration of the
diluted sewage at the beginning was 8mg/l and 5 mg/l after 5 days incubation at 20 ℃
find BOD of raw sewage and Kg of BOD concentration in 10 million liter of sewage?
Solution
Dilution factor Df = =
.
Doi = 8 mg/l
Dof = 5 mg/l
BOD of raw sewage = (DOi – Dof ) x Df = (8 - 5) x 100 = 300 mg/l
-6 6
BOD contained in 10 million liter of sewage = 300 x 10 kg x 10 x 10 = 3000 kg

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Example 3.8 the test of sewage for total solids indicates the following particulars
weight of dry crucible = 40 gm
volume of sewage sample = 100 ml
weight of crucible with residue after evaporation = 40.068 gm
weight of crucible with residue after ignition = 40.033 gm
determine total solids, volatile solids and fixed solids
Solution
weight of dry crucible W1 = 40 gm , volume of sewage sample V= 100 ml
weight of crucible with residue after evaporation W2= 40.068 gm
weight of crucible with residue after ignition W3= 40.033 gm
W 1 .
Total solids ( TS ) = gm/ml = x 1000 x1000 mg/ltr = 680 mg/ltr
V
W 1 .
Fixed solids ( FS ) = gm/ml = x 1000 x1000 mg/ltr = 330 mg/ltr
V
W 3 . .
Volatile solids ( VS ) = gm/ml = x 1000 x1000 mg/ltr = 350 mg/ltr
V

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Sulphur Cycle
• The Sulphur cycle corresponds
to biochemical decomposition
of sulphureous organic matter
and is also endless chain
connecting the process of
life and decay of animal and
plant world.

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Phosphorous Cycle
• Phosphorous cycle relates
to the maintenance of level
of phosphorous in the soil.

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