WATER QUALITY AND

WATER POLLUTION

1
 Detergents-P
SS, Pesticides, NOM Human Waste: Organics,
N,,P& Pathogens
Industries:
Organics, Salinity
Eutrophication
Cr,Cd,Pb, Hg
River Pollution

Bioaccumulation &
Groundwater Pollution Natural Impurities: Biomagnification
Dissolved Solids: TDS:
Ca, Mg, HCO3, Fe, Mn,,
SO4, Cl, K, Mn, Even
Arsenic & Fluoride

2
IMPURITIES IN HYDROLOGIC CYCLE
 Size Classification of Impurities
Micrometer Scale
10-4 10-3 10-2 10-1 1.0 10 102 103

Aqueous Virus Protozoa Silt Sand

Salts
Metal Bacteria (Coliform)
Ions
Trihalomethanes Clay Cryptosporidium

Pesticides Humic Acid

Never Settle in Your

Ionized Lifetime Can be settled
Dissolved Colloids Suspended
Precipitation Coagulation & Flocculation Settling
Oxidation Ultrafiltration & Coagulation-Flocculation-Settling
Nanofiltration
Reverse Ultrafiltration, Microfiltration3
Osmosis Slow Sand Filtration Sand Filtration
How Much ?? (mg/L) Organic, Inorganic, Color,
Odor

Presence of impurities in such

quantity and of such nature
as to impair the use of water
for designated purpose
WATER POLLUTION
Drinking, Agriculture,
Bathing, Industrial use,
4
Fishing, Recreation
 Impurities in Water

• Physical
• Chemical
• Biological/Biochemical
• Bacteriological

5
Water Quality ????
Effective Use:
Only for Certain purpose

6
Water Quality ????
Effective Use:
Not fit for any use

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1. Physical Water Quality Parameters

Parameters respond to the senses of

• Sight: Suspended Solids: SS or TSS,
Turbidity, Color
• Touch: Temperature
• Taste: Taste
• Smell: Odor

8
 Suspended Solids

Suspended Solids:
– Volatile (Organic: Algae, bacteria)
– Inert/fixed (Inorganic: Clay, Silt)
• Generally used for Wastewater
– SS=0 (Clear groundwater)
– 300 mg/L (sewage)
– 1000 mg/L (Monsoon Rivers)
– 100,000 mg/L (Food Industry wastewater)

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 Suspended Solids
Natural Waters
 Direct hazard to aquatic life: Settled & Causes Anaerobic
Conditions
 Siltation- Reduce reservoir capacity.
Wastewaters
 Measure pollution strength.
 For measuring the treatment efficiency of wastewater Treatment
Plants
 Designing of Sludge Treatment Facilities in Wastewater Treatment
Plants
 Estimate of active biomass (VSS) or bacterial populations for
control of wastewater treatment Plants
 Regulatory control on effluent (TSS) Indian Standards < 100 mg/L
Drinking Waters
 Uses turbidity in place of TSS for Drinking Waters
 Aesthetics, interference with other processes, treatment doses &
sizing (Turbidity)
 Indian Standards Turbidity < 5 NTU (Nephelometric Turbidity
Units) 10
 Turbidity: Surrogate for TSS

• Normally used for

drinking water: Due
to very low TSS.
• Imparts
opaqueness & color.

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 Drinking Water
• Generally less than 1 NTU for clean water.
• India Standard : 5 NTU: turbidity of 5 NTU is just
noticeable in a glass of water. Developed Countries
<0.3 NTU
• highly turbid harbor microorganisms capable of
causing disease in humans, or if the particles have
adsorbed toxic organic or inorganic compounds.
• The 1993 WHO Guidelines indicate that a turbidity
above 5 NTU may give rise to consumer
complaints.
• The United States EPA regulations require turbidity
to be less than 5 NTU

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 Color
• By organic debris, leaves, tannins, humic acids:
Natural color
• Iron and Manganese: Brown & Blackish Color
• Different types of Industries.
• Measured by Spectrophotometer
• Aesthetic problem, Color causing substances
react with Chlorine and form carcinogenic THM
(Trihalomethanes); trichloromethane (Chloroform)
• Can be removed by Coagulation-Flocculation,
Activated Carbon Adsorption & Ozonation

13
 Taste & Odor

• Alkaline material: Bitter taste.

• Metallic Salts : Salty Taste.
• Organic Material: Reduced Products of
Sulphur: Rotten Eggs.
• Aesthetically displeasing for consumers.
• Removed by Activated Carbon Adsorption
& Ozonation.

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 Temperature/Thermal Pollution
• Life threatening: Trout & Salmon
• Beneficial: for some fishes
• Within certain limits- promotes fish growth,
fishing may improve
• Sudden change in temperature undesirable

With increase in temp.:

• Metabolic rate increases by a factor of 2 for
each 10 degree C rise in temp.
• DO requirement increases & Available DO
reduces

15
2. Chemical Water Quality Parameters
Major & Minor Ions in Water
Major constituent (1.0 to 1000 Secondary Constituents (0.01 to
mg/L) 10.0 mg/L)
Calcium and Potassium
Magnesium
Sodium Iron and Manganese
Bicarbonate Fluoride
Sulphate Nitrate and Phosphates
Chloride

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 Major Cations and Anions
CATIONS ANIONS
Calcium (Ca2+) Bicarbonate (HCO3-)/
Carbonate (CO3--)
Magnesium (Mg2+) Sulphate (SO4--)
Sodium (Na+) Chloride (Cl-)
Potassium (K+)

Ca++ Mg++ Na+ K+

HCO3- SO4-- Cl-
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Major Ions Some Primary Sources
Calcium Amphiboles, feldspars, gypsum, pyroxenes,
aragonite, calcite, dolomite, clay minerals
Magnesium Amphiboles, olivine, pyroxenes, dolomite,
magnesite, clay minerals
Sodium Feldspars, clay minerals, halite, mirabilite,
industrial wastes
Potassium Feldspars, feldpathoids, some micas, clay
minerals
Bicarbonate/ Limestone, dolomite
Carbonate
Sulphate Oxidation of sulphide ores, gypsum,
anhydrite
Chloride Sedimentary rock, igneous rock
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 Ion Balancing
• Sum of the positive ions (cations) must equal the
sum of the negative ions (anions).

• Error in a cation-anion balance can be written as:

% balance error = Σ cations – Σ anion ×100
Σ cations + Σ anions

• Where the ions are expressed in meq/L

• For groundwater and surface water, the absolute %

error should be less than 5. If it is greater, the
analysis may not be correct
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Exercise:
A laboratory measures the following concentrations of ions in a
sample of water. Perform the validation check
Cation Conc (mg/l) Anion Conc (mg/l)
Ca2+ 93.8 HCO3- 164.7
Mg2+ 28.0 SO4-2 134.0
Na+ 13.7 Cl- 92.5
K+ 30.2

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Exercise: A laboratory measures the following concentrations of
ions in a sample of water. Perform the validation check.
Cation Conc (mg/l) Anion Conc (mg/l)
Ca2+ 93.8 HCO3- 164.7
Mg2+ 28.0 SO4-2 134.0
Na+ 13.7 Cl- 92.5
K+ 30.2
Solution:
1. First the concentrations of cations and anions must be
converted from mg/l to meq/l.
a) This conversion is made using the mg/meq value for each
major ion species. This value is equal to the atomic weight of
the species divided by the ion charge.
For Calcium (Ca+2):
• Atomic weight = 40
• Ion charge = 2
• mg/meq = 40/2 = 20
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 Contd.
Dividing the concentration (mg/l) by the
mg/meq value for each species result in
meq/l.
• For Calcium (Ca2+):
• Concentration (mg/l) = 93.8
• mg/meq = 20
• 93.8/20 = 4.69 meq/l

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Cation Concentration (mg/l) (mg/meq) (meq/l)
Ca+2 93.8 20.0 4.69
Mg+2 28.0 12.2 2.30
Na+ 13.7 23.0 0.60
K+ 30.2 39.1 0.77
Total Cations 8.36 meq/l

Anion Concentration (mg/l) (mg/meq) (meq/l)

HCO3 - 164.7 61.0 2.74
SO4-2 134.0 48.0 2.79
Cl- 92.5 35.5 2.61
Total Anions 8.14meq/I
4.69

6.99

8.36
7.59
0
Ca2+ Mg2+ Na+ K
+
2- -
HCO3- SO4 Cl
23
0
Check accuracy (% balance error)

% balance error = Σ cations – Σ anions ×100

Σ cations + Σ anions

= 8.36 - 8.14 ×100 = 1.3 %

8.36 + 8.14

This is less than the allowed error, so the sample results can be
accepted. If error > 5% then check results, and possibly re-
analyse samples.
Note: An accurate ion balance does not necessarily mean that the
analysis is correct. There may be more than one error and these
may cancel each other out. 24
 Calcium & Magnesium: Determine
Hardness of Water

A term often used to characterize the ability of a

water to:
cause soap scum
Ca2+ + (Soap)-  Ca(Soap)2 (s)
increase the amount of soap needed
cause scaling of pipes
Ca(HCO3)2 CaCO3(s) (at high pH)
Mg(HCO3)2 MgCO3(s) (at high pH)
cause valves to stick due to the formation
of calcium carbonate crystals
leave stains on plumbing fixtures
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 Formation of Hardness
Hard Water
Precipitation

Topsoil

Subsoil

CO2 + H2O  H2CO3

Limestone CaCO3(s) + H2CO3  Ca(HCO3)2

MgCO3(s) + H2CO3  Mg(HCO3)2

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 Types of Hardness
• Total Hardness= Ca 2+ + Mg 2+
• Carbonate Hardness= Hardness
Associated with HCO3 and CO3
• Non Carbonate Hardness = Hardness
Associated with other anions

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 Find out different types of
Hardness from previous problem
Total
hardness
Carbonate Noncarbonate
hardness hardness

Ca-CH Ca-
NCH Mg-NCH
4.69

6.99

8.36
7.59
0
Ca2+ Mg2+ Na+ K
+
2- -
HCO3- SO4 Cl
5.53
2.74

0
8.14 28
 Sodium
• All natural waters contain sodium ions (Na+) as the element is one
of the most abundant on the planet.
• High concentrations in inland waters, however, are normally
associated with pollution from industrial discharges or sewage
effluent or, in coastal areas, sea water intrusion. Normally, however,
sodium concentrations are below 200 mg/L .
• Na (non- toxic): Bitter taste and health hazard to cardiac and kidney
patients. Standard (250 mg/L)
• Have a negative effect on soil structure by defloculating it, which can
affect plant growth.
• To evaluate the suitability of water for irrigation the Sodium
Adsorption Ration (SAR) is used as follows:

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 SAR
• SAR < 3 the water is suitable for irrigation use.
• 3 to 9 represent some use restrictions
• SAR values in excess of 9 normally mean that water
cannot be used for irrigation.
• In India, however, the SAR standard for irrigation water
is set to 26 which reflects the fact that sodium does not
build up in the soil and cause damage because every
monsoon season the soil is thoroughly flushed and
renewed

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 % Na and RSC
• Sodium percentage (%Na) = [Na 100/(Na + K + Ca +
Mg)], where all values are expressed in meq/L.
• It is recommended that sodium percentage should not
exceed 60.
• In waters where the bicarbonate content is high, there is
a tendency for calcium and magnesium if present, to
precipitate out as carbonates, thus increasing SAR. The
residual sodium carbonate (RSC) is defined as:

If its value exceeds 2.5 meq/L the water is not suitable, 2.5 to
1.25 is marginal and less than 1.25 is safe. 31
Exercise: Problem: A water sample is known to contain calcium, sodium
chloride and bicarbonate. The result of an analysis were as follows:
Calcium 60 mg/L, Sodium 46 mg/L, Chloride 71 mg/L
(Mol. wt. Ca++ 40, Na+ 23, Cl- 35.5, HCO3 - 61.)
Calculate % Na, RSC and comment on suitability of water for
irrigation

1.0 Estimate the concentration of bicarbonates.

(2) Calculate percent sodium and residual sodium carbonate

3. Comment on the suitability of water for irrigation.

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Exercise: A water sample is known to contain calcium, sodium chloride
and bicarbonate. The result of an analysis were as follows:
Calcium 60 mg/L, Sodium 46 mg/L, Chloride 71 mg/L
(Mol. wt. Ca++ 40, Na+ 23, Cl- 35.5, HCO3 - 61.). Calculate % Na, RSC
and comment on suitability of water for irrigation
Solution:
1.0 Estimate the concentration of bicarbonates.
Calculate concentrations in meq/L
Ca++ = 60/20 = 3, Na+ = 46/23 = 2, Cl- = 71/35.5 = 2
Sum of cations = 5 meq/L
Therefore, for ion balance sum of anions is also = 5 meq/L
Hence HCO3- = 5 - 2 = 3 meq/L, or 3 x 61 = 183 mg/L

(2) Calculate percent sodium and residual sodium carbonate

Percent sodium = [2/(3 + 2)] x 100 = 40
RSC = 3 - 3 = 0

3. Comment on the suitability of water for irrigation.

The water is safe for irrigation, since both the parameters % Na and
RSC do not exceed the limits. 33
 Potassium
• The concentration of potassium ions (K+) in
natural fresh waters is generally low (normally
less than 10 mg/L).
• Sea water and brines contain much higher
concentrations,
• Potassium ions are highly soluble and are
essential for most forms of life.
• Potassium in the water environment is readily
taken up by aquatic life.

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 Sulphate
• Sulphate is present in all surface waters as it arises from
rocks and from sea water which contains a high sulphate
concentration.
• High concentrations of sulphate make the water
– corrosive to building materials (e.g., concrete),
– associated with scale-formation,
– palatability
– and are capable of being reduced to hydrogen sulphide (a toxic,
foul-smelling gas) when zero dissolved oxygen conditions prevail in
the water body.
• Normally, sulphate concentrations in surface waters are
between 2 and 80 mg/L although they may exceed 1000 mg/L
if industrial discharges or sulphate-rich minerals are present.
• Indian Standard is SO4 – 200 mg/L

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 Chloride
• Chlorides in fresh waters generally come from rocks, the
sea or sewage, agricultural and industrial effluents.
• Fresh water concentrations of chloride are normally less
than 40 mg/L and can be as low as 2 mg/L in waters,
which have not been subject to pollution.
• Chloride concentrations over 100 mg/L give the water a
salty taste and thereby make it unsuitable for drinking by
humans or animals.
• The Drinking Water Standard of Chloride is -250 mg/L

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 Minor Ions
• Iron & Manganese
• Fluoride
• Nutrients: Phosphates and Nitrates
• Heavy Metals

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 IRON & MANGANESE
• Iron & Mn Comprises 5 % and 0.1 % of Earth Crust
• FeCO3 (Rocks) + CO2 ---- (Dissolved) Fe 2+

• Iron exist in minerals as Ferrous Sulphide and manganese

exist as manganese dioxide—both are insoluble—But in the
presence of CO2 soluble as Ferrous iron (Fe++) and
Manganous manganese (Mn++)

• Ferrous iron (Fe++) and manganous manganese (Mn++) -------

Soluble & invisible (Well water and Anaerobic Reservoir) -------
Expose to air ------ Oxidize ------- Insoluble, visible (brown color)
Ferric iron (Fe+++) and manganic manganese (Mn+++)

• Drinking Water Standard:

– Iron=0.3 mg/L
– Mn = 0.05 mg/L 38
 Effects

• No harmful effect on human body but iron

impart taste.
• Unaesthetic conditions
• Growth of iron bacteria in distribution system –
(Autotrophs & Obtained energy by oxidation of
ferrous to ferric, form slime layer)- foul taste &
odors – red water in distribution system
• Strains to plumbing fixtures,
• Interfere laundering operations

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 Fluoride
• The fluoride occurs in water as; Sellaite, fluorspar, Ca
F2; Cryolite, Na3 Al F6;
• Many rivers flowing through more than half a dozen
states in India reported to have fluoride contents
varying from 0.1 to 12.0 ppm.
• Similarly occurrence of fluoride bearing waters was
reported by many in A.P., Rajasthan, Punjab and
Haryana, Maharastra,Tamilnadu,Karnataka, Madhya
Pradesh, Gujarat and Uttar Pradesh.
• Generally higher conc. In deeper wells – Fluoride rich
rocks

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 Fluoride Significance
• Fluoride- Beneficial for dental caries
• Low fluoride concentrations stabilize the skeletal
systems by increasing the size of the apatite
crystals and reducing their solubility.
• Fluoride- Linked to dental fluorosis
• Above 2 mg/L "children are likely to develop
objectionable dental fluorosis"
• Above 4 mg/L, individuals are at risk of
developing "crippling skeletal fluorosis.
• Limit is 1 mg/L (more than 1.5 mg/L disturb tooth
mineralization, and more than 4 mg/L cause
skeletal fluorosis)

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 Arsenic
• This is a metalloid. The most commonly found valence
states in the groundwater are As(III) and As(V).

• Over-exploitation of underground water causes the geo-

chemical leaching of arsenic from the arsenic-bearing
rocks into the groundwater used for drinking purposes
in many places in India

• It is by far one of the most toxic substances found in

groundwater.

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 Arsenic
• Ingestion of arsenic at a level higher than 10
micro-g/L for a prolonged time causes severe
disorders. The manifestation starts with
pigmentation in the skin, soon followed by skin
lesions, keratosis, and damage to the internal
organs causing cancers and often becomes
fatal.

• In India, more than seven states have

dangerous levels of arsenic concentration in
public drinking water, often in the range of
100-500 micro-g/L (10 to 50 times the
regulatory limit). Currently, about 10 million
people are directly affected and many more are
at risk.
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 Nitrate

• Common contaminant in water supplies especially

shallow wells. Fertilizer is the largest contributor to
nitrate pollution.
• Some sources say that poorly managed crops may
only utilize 10% of the nitrate that is actually
spread on the field.
• The runoff from these fields ends up in surface
water sources. Nitrate is highly soluble in water
Nitrate can also percolate down through the soil
and end up in the drinking water aquifers.
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 Nitrate Sources
• From livestock manure
run-off,
• From septic tanks
leaching into ground
water.
• Industrial waste
• Lack of proper
underground drainage
and sewerage systems

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 Nitrate

• Nitrate levels fluctuate seasonally,

seemingly based on rainfall.
• Shallow wells are more quickly and
adversely affected than deep well-
constructed wells.
• If your area or well is prone to nitrate
contamination, regular water analysis is
recommended.

46
 Nitrate Contamination
•over-exploitation, contamination and drought
•Karnataka,
•Aurangabad,
•Jaipur, Udaipur, Muzaffarnagar
•Andhra Pradesh

•Many Places, almost mandatory for drinking water

quality analysis

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 Nitrate Health Effects

• Methemoglobinemia, a sometimes fatal blood

condition in infants also known as "blue baby
syndrome".
• This condition reduces the blood's oxygen
carrying ability in infants and fetuses..
• Standard- 10 mg/L as NO3-N (India)
• and ?? mg/L WHO
• It causes algae to bloom resulting in
eutrophication in surface water.

48
 Phosphates

• Phosphorus is typically the limiting nutrient in lakes,

and algae growth is linked to phosphorus inputs.

• Sources: Fertilizers, Human and industrial waste.

• Problems
– aesthetic
– taste and odor in drinking water
– can be toxic, especially to farm animals
– fouling
– diurnal DO cycles
49
 Heavy Metals
•Important ones- Hg, Pb, Cd, As
•Toxic Non-degradable
•Essential nutrients-Cr, Fe
•Cr, Cd in higher doses – nervous system /
kidney damage, creation of mutation , induction
of tumors
•Inhaled / Ingested: Absorption –depends on
particular metal and form .
•Ex. Liquid Hg- not very toxic
•Hg Vapor- Highly Toxic/ enters lungs./ diffused
in to blood stream/ can pass in to the brain /
damage the central nervous system
50
 Heavy Metals
• Kidney/complex filter/ eliminate toxic
substance from body.
• Kidney- Contain millions of excretory
units-nephrons,
• Chemicals toxic to kidney-
nephrotoxins
• Example Of nephrotoxic metals-Cd, Pb,
Hg

51
ENDOCRINE Endocrine disruptors are chemicals that, at certain doses, can
interfere with the endocrine (or hormone) system in mammals.
DISRUPTION These disruptions can cause cancerous tumors, birth defects,
and other developmental disorders.

52
 • EDCs mimic a natural
hormone, fooling the body
into over-responding to the
stimulus (e.g., a growth
hormone that results in
increased muscle mass), or
responding at inappropriate
times (e.g., producing insulin
when it is not needed).

• They block the effects of a

hormone from certain
receptors (e.g. growth
hormones required for
normal development).

• They directly stimulate or

inhibit the endocrine system
and cause overproduction or
http://web.bryant.edu/~dlm1/sc372/readings/to underproduction of
xicology/endocrinedisrupter.jpg hormones
53
 Endocrine Disruption
• Endocrine system secretes hormones into the
blood stream and works in conjunction with the
nervous system.

• Endocrine disrupting chemicals (EDCs) mimic

hormones and interfere with synthesis, secretion,
transport, binding, action or elimination of natural
hormones.

• EDCs are bad for adults, worse for children and

worst for unborn children of parents who are
exposed. 54
 Total Dissolved Solids (TDS) or
Salts
• Total Dissolved Solids: Summation of All ions

• Typically measures as Total Dissolved Solids

(TDS)
• Water classification
– freshwater < 1500 mg/L TDS
– brackish water 1500 – 5000 mg/L
– saline water >5000 mg/L
– sea water 30-34 g/L

55
 Total Dissolved Solids

• The palatability of drinking water has been rated according to TDS

concentrations as follows :

– mg/L quality
– 120-200 Excellent- Ganga Canal/All Imp Rivers
– 200-500 Good- IIT Roorkee
– 500-800 Fair- NCR Region/Punjab/Haryana
– 800-1000 Poor- NCR Region
– >1000 Unacceptable-Agra

56
TDS Standards (Drinking Water)

• Water with extremely low TDS may taste flat and

insipid (tasteless).
• High TDS associated with excessive scaling in
pipes, fittings and household appliances.
• Based on taste, TDS < 500 mg/L is regarded as
good quality water
• TDS up to 1000 mg/L is acceptable to many
communities

57
 Electrical conductivity:
Surrogate for TDS

• TDS or Total Dissolved Solids is a measure of

the total ions in solution.
• EC is actually a measure of the ionic activity of
a solution in term of its capacity to transmit
current.
• In dilute solution TDS and EC :
• TDS (mg/L) = A x EC (μS/cm)
• where A = 0.5

58
Conductivity Values

59
 High TDS

Irrigated Land Damaged by

Country Salt
(million Ha)
7.0
India
6.7
China
4.2
Pakistan
4.2
USA
2.4
Uzbekistan
1.7
Iran
1.0
Turkmenistan
0.9
Egypt
28.1
Subtotal
World Estimate
47.7
60
 DRINKING WATER QUALITY STANDARDS
Characteristics Standard Remarks
Color Colorless Generally cause by decaying vegetation or
industries
Odor Unobjectionable Caused by biological reactions and sewage

Turbidity 5 NTU Due to suspended solids

Dissolved solids 500 Beyond this palatability decreases and may

mg/L, Max cause gastro intestinal irritation From
minerals, metals

pH 6.5-8.5 Beyond this range, the water will affect the

mucous membrane and/or water supply
system
Total Alkalinity 200 mg/L Associated with hardness, bitter taste

Total hardness 300 Encrustation in water supply structure and

(as CaCO3) mg/L, adverse effects on domestic use
61
Max
 Characteristics Standard Remarks

Chlorides (as Cl) 250 Beyond this limit, taste, corrosion and
mg/L, max palatability are affected

Fluoride (as F) 1.0 Fluoride may be kept as low as possible.

mg/L, Max High chloride may cause fluorosis, Less
than 1 mg/L help to prevent dental
cavities in children.
Sulphate (as SO4) 200 Beyond this limit, taste/appearance are
mg/L, Max affected, has adverse effect on domestic
uses and water supply structures

Nitrate (as NO3-N) 45 as Beyond this methemoglobinemia takes

mg/L, Max NO3-N place. (bluish discoloration)
10 mg/L Methemoglobinemia (congenital or acquired) occurs
as NO3 when red blood cells (RBCs) contain methemoglobin
at levels higher than 1%. Methemoglobin results from
the presence of iron in the ferric form instead of the
usual ferrous form. This results in a decreased
availability of oxygen to the tissues.
Bacterial Counts: Nil 62
3. Biochemical/biological Water
Quality Parameters
Natural Sources and Human Activities (Anthropogenic)
CHNO

Biodegradabl Non-Biodegradable
Can be utilized byenaturally Resistant to biological
occurring Microorganisms degradation: Exceptionally strong
bonds

Starch, Fats, Proteins, Phenols, polysaccharides,

Alcohols, acids, aldehydes, benzenes, detergents, insecticides,
esters etc. pesticides etc.

63
 Equivalence of Organics

• Oxygen Equivalent of Total Organics: COD

• Oxygen Equivalent of Biodegradable
Organics: BOD
• Oxygen Equivalent of non-Biodegradable
Organics: COD-BOD

64
Oxygen-Demanding Material
• Increased Biochemical Oxygen Demand
(BOD) can result in
– anaerobic conditions.
– Anaerobic conditions lead to fish kills and bad
smell (H2S, NH3).
• High oxygen levels necessary for healthy stream
ecology
– trout require 5-8 mg/L dissolved oxygen (DO)
– carp require 3 mg/L DO
– aesthetic problem <1 mg/L
65
 Biochemical Reaction
New Cells/CO2

Oxygen

66
 Biodegradable organics
Oxygen-Demanding Material
• Measured in Terms of BOD
• BOD (Biochemical Oxygen Demand): amount of
oxygen (DO, Dissolved Oxygen) required for the
biological decomposition of organic matter. The
oxygen consumed is related to the amount of
biodegradable organics.
• When organic substances are broken down
in water, oxygen is consumed
Measure of BOD =
organic C + O2 → CO2 Initial oxygen-
Organic C : Protein, Carbohydrates, Final Oxygen after
Fats etc., in Human Waste 3/5 days 67
 Biochemical Oxygen Demand

• Amount of oxygen required by bacteria

while stabilizing the decomposable
organic matter under aerobic conditions.
• It involves the measurement of oxygen
consumed by living organisms.

68
Simple BOD Measurement

Measure DO of Put into 20oC Measure DO

the sample incubator for 5 days or after 3 or Five
27o C for 3 days days

69
 Biochemical Oxygen Demand
Measurement
• Take sample of waste; dilute with oxygen
saturated water; add nutrients and
microorganisms
• Measure dissolved oxygen (DO) levels over 5/3
day.
• Temperature 20/27° C.
• In dark (prevents algae from growing), Plastic
Bottle.
• Final DO concentration must be > 2 mg/L .
• Need at least 2 mg/L change in DO over 5/3 days.
70
 Calculations BOD
• If initial DO of a sample is 8 mg/L and final
DO after 5 days is 2 mg/L. What is the
BOD of the Sample.
• If initial DO of a sample is 8 mg/L and final
DO after 5 days is 0 mg/L. What is the
BOD of the Sample

71
 Exercise
• If the above sample is diluted 10 times, then
final DO after 5 days was 5 mg/L, What is the
BOD5 ?
• Undiluted: Initial DO - Final DO = BOD
• Diluted: ((Initial DO - Final DO))/ Dilution Factor

72
 Example 1
• A BOD test was conducted in the
laboratory using wastewater being
dumped into River Yamuna. The samples
are prepared by adding 3.00 mL of
wastewater to the 300.0 mL BOD bottles.
The bottles are filled to capacity with
seeded dilution water.

73
 Example 1: Raw Data

Time (Days) Diluted Sample DO (mg/L)

0 7.95
1 3.75
2 3
3 2.75
4 2.15
5 1.8
74
Example1: Time–Concentration Plot

700
600
500
BOD (mg/L)

400
300
200
100
0
0 1 2 3 4 5 6
Time (days)

75
 Non-Biodegradable Organics
• Molecules with exceptionally strong bonds (some
polysaccharides) and ringed structures (benzene)
• Constituent of woody plants: tannic and lignin acids,
cellulose, phenols,
• Petroleum products, pesticides, industrial chemicals:
Toxic to microorganism.
• Total (Biodegradable+non Biodegradable) can be
measured in terms of Chemical Oxygen Demand
(COD).
• Individual Organics are Analyzed by GC &/or HPLC
and other sophisticated methods

76
 COD (Chemical Oxygen Demand)
• Oxygen equivalent of the organic matter of
a sample susceptible to oxidation by a
strong chemical oxidant.
• Uses a strong chemical oxidant in an acid
solution and heat to oxidize organic
carbon to CO2 and H2O.
• Oxygen demand is determined by
measuring the amount of oxidant
consumed using titrimetric or photometric
methods.
77
 Stochiometry of COD
2  3  a
Cn Ha Ob  Cr2 O  8H  nCO2  2 Cr   4    H2 O
7
 2
Organic Strong Sulphuric Carbon Chromic acid
Matter Oxidant Acid dioxide
(Potassium)
Dichromate

HEATING 2 HOURS 150 OC

Orange Green
Colored Colored

Where:  
2 n a b
 
3 6 3
78
Relationship BOD & COD
800

(1)
600
COD, (2)
mg/L
400
(3)

200

0
0 100 200 300 400

BOD, mg/L
(1) LARGE INDUSTRIAL CITY, KANPUR
(2) RESIDENTIAL CAMPUS, IIT, KANPUR
(3) BIOLOGICALLY TREATED SEWAGE, OKHLA, 79
 Biodegradable Fraction

DOMESTIC DAIRY SUGAR

DISTILLERY

FRACTION TANNERY
BIODEGRADABLE
PULP & PAPER

Natutal Waters

10 100 1000 10,000 100,000

COD, mg/L
80
 TOC

 Total organic carbon (TOC) is the amount of carbon

bound in an organic compound and is often used as a
non-specific indicator of water quality
 TOC = Total Carbon (TC) – Inorganic Carbon (IC)
 TOC = all carbon atoms covalently bonded in organic
molecules
 DOC = Carbon passed through 0.45 micrometer filter
 TC is a measure of all the carbon in the sample
 IC = carbonate, bicarbonate, and dissolved carbon dioxide
 IC is analyzed in liquid samples by acidifying with an
inorganic acid to pH 2 or lower, then sparging for a few
minutes with a stream of gas .

81
 COMPARISON: COD, BOD & TOC
Parameter COD BOD TOC
Oxidant Used K2Cr2O7 Oxidation by microbes O2, Heat
Suitable Use Rapid and frequent effects of organic compounds Measures total organic
monitoring on the DO content of carbon
receiving waters.
Time 1.5-3 hours 5 days (standard BOD test) Several min. to hour

Advantages Correlates with BOD Most closely models the Correlates with BOD
on waste with natural environment when on waste with constant
constant composition. used with proper “seed” composition, but not as
Toxic materials do closely as COD
not affect oxidant. Short analysis time
Short analysis time.

Disadvantages Interference from Toxic materials kill Requires expensive

chloride ions microorganisms. equipment.
Some organic Microorganisms do not Some organic
compounds are not oxidize all material in waste. compounds are not
oxidized completely Inaccuracies when used with oxidize completely.
improper seed. Measures Total
Lengthy test period Organic Carbon82not
oxygen demand
 Oxygen Demand
If 1 mg/L Glucose is completely oxidized to CO2 Find :
1. Theoretical Oxygen Demand (ThOD)
2. Chemical Oxygen Demand (COD)
3. Biochemical Oxygen Demand (BOD)
4. BOD5,
5. Total Organic Carbon (TOC)
C5H7NO2 + 5 O2 ------------ 5CO2 +NH3 + 2 H2O
mw = 113 mw =160
– ThOD = 160/113 = 1.42 mgO2/mg C5H7N
– COD = 1.42 mgO2/mg C5H7NO2
– BODult = COD
– BOD5 (5 days O2 Consumption) =0.68 BODult = 0.68 x 1.42 = 0.97
mg BOD5/ mg C5H7NO2
– TOC = 5 x 12 / 113 = 0.53 mg TOC/ mg C5H7NO2

83
 Natural Organic Matter
• Natural Organic Matter (NOM) is the organic material
present in surface or ground water.
• NOM includes both humic (humic and fulvic acids) and
non-humic (tannic acid) fractions.
• These substances are oxidized very slowly and their
solubility in water may vary with pH.
• The dissolved fraction of NOM may not be fully removed
using conventional water treatment practices and have
been shown to produce by-products such as
trihalomethane during chlorination.
• Dissolved organic carbon (DOC) is the most commonly
used parameter to quantify NOM.

84
 NOM
• UV absorbance at 254nm (UV254) is a useful surrogate measure
for DOC.
• This technique only requires very simple instrumentation and
can be performed by the operators in the treatment plant.
• NOM Can be removed by activated carbon adsorption

85
 4. Bacteriological Water Quality
Parameters
• Water Body Hosting Large number of
species with well balanced number of
individuals : Healthy System
• Fish: Trout: Higher Quality of Water than
Carp
• For Human Use and Consumption:
Pathogens: Capable of infecting or
transmitting disease to Humans

86
 Pathogens

• Bacteria, Virus, Protozoa, Helminths

• Cause Water-related diseases (e.g. gastro-intestinal,
typhoid, shigellosis, hepatitis and cholera)
• Main health concerns in the world.
• Often contamination through contact with water or via
food (e.g. via irrigated agriculture, or via fish/shellfish).

87
 Pathogenic Organisms
• Organisms colonize the intestinal tract but can live
for a period of time outside the body
• Carriers (who may or may not exhibit disease
symptoms) excrete these intestinal tract organism
in very large numbers.
• When water is contaminated by excreta, the
organisms can be transmitted to those who
contact the water.

88
Impacts on Human Health

89
 Pathogenic Organisms (Virus)
Virus (less than 1 micrometer, smallest Associated Disease
creature)
Poliovirus Poliomycetis
Hepatitis-A Virus Infectious Hepatitis
Adenovirus Respiratory, eye infections
Others Gastroenteritis, diarrhea

Nervous System disorders:

Immunization

Poliovirus

Bacteriophage
90
Pathogenic Organisms (Bacteria)
Bacteria (unicellular, <10 Associated Disease
micrometer)
Salmonella Typhi Typhoid fever
Shigella Bacillary dysentry
Vibrio Chlolera Cholera
Yesina Enterocolitica Gastroenteritis

Gastrointestinal Infections

Salmonella typhi

91
 Classification of Water
Associated Diseases
Transmission Description Examples of diseases
mechanism

Water borne Oral ingestion of pathogens in Cholera, typhoid,

water contaminated by urine or bacillary, trachoma,
feces
Water-washed Disease spread enhanced by Trachoma, dysentery
scarcity of water making
cleanliness difficult
Water -based Water provides habitat for Schistosomiasis
intermediate organism,
transmission to human through
water contact
Water Related Insect vectors (mosquitoes) rely on Malaria, yellow fever,
water for habitat, human water dengue
contact not needed 92
 Water Washed (Trachoma)
• Trachoma is caused by Chlamydia trachomatis
(Pathogenic Bacteria) and it is spread by direct
contact such as towels and/or washcloths, that
have had similar contact with these secretions.
• Flies can also be a route of mechanical
transmission.
• Untreated, repeated trachoma infections result in
entropion—a painful form of permanent blindness
when the eyelids turn inward, causing the
eyelashes to scratch the cornea.
93
 Water Based (Schistosomiasis)

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94
 Disease Rates and Risk

Disease Vector Morbidity Mortality Population at

Risk
Diarrheal Microorganisms > 1.5 billion 4 million > 2 billion
Diseases

Schistosomiasis Water snails 200 million 200,000 500-600

million
Malaria Mosquitoes 267 million 1-2 million 2.1 billion

Onchocerciasis Backflies 18 million 20-50,000 90 million

Source : UNEP 1993

95
 Indicator Organism

• Fecal Coliform groups: Principal strain is E

Coli.: Non pathogenic and longer survival time
outside the human body.
• Simple tests to determine the presence or
absence and enumeration.
• Membrane filter technique or multiple tube tests.

96
 (River Bathing Standards)

PARAMETERS PERMISSIBLE LIMIT

 BOD 3 mg/L (MAXIMUM)

 DO 5 mg/L (MINIMUM)
 COLIFORM (FECAL) 500 (DESIRABLE)
MPN
2500 (MAX. PERMISSIBLE) 100 ml

BOD - BIOCHEMICAL OXYGEN DEMAND

DO - DISSOLVED OXYGEN
MPN - MOST PROBABLE NUMBER
97
 Treated Water Quality Standards

INTO WATER BODY ON LAND

BOD (mg/l) 30 100

T S S (mg/l) 100 200

FECAL (MPN/100 ml) - (Desirable)

COLIFORMS
- (Maximum)

NRCP (National River Conservation Plan): BOD= 20 mg/L, TSS = 50 mg/L

Fecal coliforms 1000 MPN/100 ml Desireable and 10000 MPN/100 ml as
maximum 98