Water

Water availability
Water availability across the globe
 The Hydrologic Cycle

Hydrologic cycle – The global system that supplies and removes water from the surface of the earth.
 Sources of water

Groundwater Surface water

Groundwater is located underground in Surface water is found in lakes, rivers and
large aquifers and must be pumped out streams and is drawn into the public water
of the ground after drilling a deep well. supply by an intake.
 General characteristics of Ground water and surface water

Ground water Surface water

Constant composition Varying composition
High mineralization Low mineralisation
Little turbidity High turbidity
Low or no colour Presence of colour
Bacteriologically safe Microorganisms present
No dissolved oxygen Dissolved oxygen
High hardness Low hardness
Little taste and odour Taste and odour
Little chemical toxicity Possible chemical toxicity
 Surface water hydrology

Precipitation

Once precipitation hits the ground, the following may happen.

1. Evaporation
2. Infiltration
3. Interception
4. Trapping

Abstractions = Evaporation + Infiltration + Interception + Trapping

 Surface water hydrology

Stream/River water

Direct run off

Base flow/Exfiltration

Watershed/Basin
A Watershed is an area of land where all of the water
that is under it, or drains off of gets collected into
the same place (e.g. The River).

Divide – Perimeter of the watershed

 Surface runoff estimate
(Rational formula – applicable to large watershed)

Storm water quantity, 𝑄 = 0.0028 𝐶𝑖𝐴

Q = Peak rate of storm water runoff, m3 sec-1

C = Coefficient of runoff
i = Mean rainfall intensity (mm h-1) (for a given time of concentration)
A = Drainage area of the basin (area of watershed) (ha, 100m x 100m)
0.0028 = conversion factor (From “mm h-1 ha” to “m3 sec-1”)
 Run off coefficients

Type of land cover Coefficient of runoff

Business areas 0.70 – 0.90
Apartment areas 0.50 – 0.70
Single family area 0.30 – 0.50
Parks, Playgrounds, Lawns 0.10 – 0.25
Paved Streets 0.80 –0.90
Water tight roofs 0.70 – 0.95
 Surface runoff estimate
Ex-1
The surface cover of a catchment area of 300 ha is given below. If the intensity
of the rainfall is 30 mm h-1, estimated the peak storm water run off rate.

Type of cover Coefficient of runoff Percentage

Roofs 0.90 15
Pavements and yards 0.80 15
Lawns and gardens 0.15 25
Roads 0.40 20
Open ground 0.10 15
Single family dwelling 0.50 10
Ex-1: Solution

Overall runoff coefficient, C

= [A1.C1 + A2.C2 + ….+ [Link]] / [ A1 + A2 + …+ An]

0.15 x 0.90 + 0.15 x 0.80 + 0.25 x 0.15 + 0.20 x 0.4 + 0.15 x 0.1 + 0.10 x0.5
=
0.15 + 0.15 + 0.25 + 0.20 + 0.15 + 0.10
= 0.44

I = 30 mm h-1
A = 300 ha
Therefore storm water run off rate, 𝑄 = 0.0028 𝐶𝑖𝐴 = 0.0028 ∗ 0.44 ∗ 30 ∗ 300 = 𝟏𝟏 𝒎𝟑 𝒔−𝟏
Ground water
 Ground water

unsaturated

saturated
 Ground water

Unsaturated zone
Vadose water + Soil water

Saturated zone
Ground water
Water table

Capillary fringe
Ground Water
 Ground Water

aquiclude &
aquitard
Schematic of Ground water aquifer
 Ground Water
Aquifer
Aquitard/Aquiclude

Unconfined aquifer/Water table aquifer

Confined aquifer/Artesian aquifer

Piezometric/Potentiometric surface

Artesian well

Flowing artesian well

Perched water table

Gravity or seepage spring

 Porosity
Porosity
Ratio of the volume of voids (open spaces) in the soil or rock to the total
volume is called porosity.

It is a measure of the amount of water that can be stored in the spaces

between soil particles.

It does not indicate how much of this water is available for development/use.

Volume of voids
Porosity (η) =
Total volume of solids and voids
 Specific yield/Effective porosity

The percentage of water that can be actually be drained from an aquifer

under the influence of the gravity is called specific yield.

Specific yield is not equal to porosity because the molecular and surface
tension forces in the pore spaces keep some of the water in voids.

Specific yield reflects the amount of water available for development/use.

 Specific yield/Effective porosity

Volume of water
Speicific Yield % = × 100
Volume of soil
 Storage coefficient
Storage coefficient (S)
Volume of available water resulting from unit decline in the piezometric surface over
unit horizontal cross-sectional area.

For confined aquifer, estimated yield is sometimes affected by the pressure released
as water is removed. This is indicated by the term ‘storage coefficient’.

For unconfined aquifer, storge coefficient and specific yield may be used
interchangeably.

Value of S:
Confined aquifer – 10-3 to 10-5
Unconfined aquifer – 10-2 to 0.35
 Porosity - Typical values of aquifer parameters

Aquifer material Porosity (%) Specific yield (%) Hydraulic Conductivity (m s-1)
Unconsolidated
Clay (≤ 3.9 µm) 55 3 1.2 x 10-6
Fine sand (125-250 µm) 45 10 3.5 x 10-5
Medium sand (0.25-0.5 mm) 37 25 1.5 x 10-4
Coarse sand (0.5-1.0 mm) 30 25 6.9 x 10-4
Sand & gravel 20 16 6.1 x 10-4
Gravel (2-64 mm) 25 22 6.4 x 10-3
Consolidated
Shale <5 3 1.2 x 10-12
Granite <1 0 1.2 x 10-10
Sandstone 1.5 5 5.8 x 10-7
Limestone 1.5 2 5.8 x 10-6
Fractured rock 5 2 5.8 x 10-5
 Hydraulic gradient and Head

The slope of the piezometric surface is called

hydraulic gradient.

It is measured in the direction of the steepest

slope of the piezometric surface.

Groundwater flows in the direction of the

hydraulic gradient and at a rate proportional to
the slope.
The level up to which water would rise if an
well is dug up to confined aquifer is called
piezometric surface. At this surface, water
pressure is in equilibrium. For unconfined
aquifer, the piezometric surface is water table.
 Hydraulic gradient

Hydraulic head = Elevation head + Pressure head

Elevation head represents the height

of the water at the base of the well.

The pressure head is the height to

which the water rises within the
well.

The hydraulic head is the vertical

distance from some reference datum
plane (usually, mean sea level, MSL)
to the water table.

Unit: m of water
Change in head ℎ2 − ℎ1 𝑑ℎ
Hydraulic gradient = = ≅
Horizontal distance 𝐿 𝑑𝐿
 Flow net

Flow net head, h2 > head, h1

Combination of streamlines/flowlines and equipotential line
𝒙1 𝒚1
Streamline/Flow line Streamline 1
Direction along which flow takes place

Equipotential line 𝒙2 𝒚2
Line joining locations of equal head Streamline 2

𝒙3 𝒚3
Streamline 3
Difference in head
Hydraulic gradient =
Horizontal distance betweeen equipotential lines
Equipotential line 1 Equipotential line 2

ℎ2 − ℎ1 𝑑ℎ (A two dimensional flow net consisting

Hydraulic gradient = ≅
𝐿 𝑑𝐿 of streamlines and equipotential lines)
Flow net
 Hydraulic Conductivity, K

The discharge that occurs through a unit cross-section of aquifer under a

hydraulic gradient of 1.

It is the property of an aquifer.

It is a measure of its ability to transmit water under a sloping piezometer

surface.

Unit of speed: m s-1

 Transmissibility, T

The coefficient of transmissibility, T,

is a measure of the rate at which
water will flow through a unit width
vertical strip of aquifer extending
through its full saturated thickness
under a unit hydraulic gradient.

Unit of T: m2 s-1

Range of T: 1 x 10-4 to 1.5 x 10-1 m2 s-1

T= Discharge that occurs through unit width and total aquifer height D
= Discharge through cross-section RSUT
K = Discharge that occurs through unit cross-section 1 m2
= Discharge through cross-section PQRS
 Hydraulic Conductivity
Darcy’s Law
Basic equation governing the groundwater flow.

Formulated by the French hydraulic Engineer, Henri Darcy in 1856.

Quantity of fluid passing through a porous media is directly proportional

to the head loss and inversely proportional to the length of the flow
path.

Obtained from a laboratory experiment involving flow of water through

sand filter.

Flow rate is Q is proportional to the cross-sectional area A times the

hydraulic gradient.
 Darcy’s Law

Flow rate is Q is proportional to the cross-sectional area A times

the hydraulic gradient.

𝑑ℎ 𝑉
Flow rate (m3 d-1), 𝑄=
𝑄∝𝐴 𝐴
𝑑𝐿
𝑑ℎ
= Hydraulic gradient
𝑑ℎ 𝑑𝐿
𝑄 = 𝐾𝐴
𝑑𝐿
A = Cross-sectional area (m2)

K = Hydraulic conductivity or
Better known as Darcy’s Law for flow coefficient of permeability (m d-1)
through porous media.
 Darcy’s Law

𝒅𝒉
𝑸 = 𝑲𝑨
𝒅𝑳
Assumption of linearity between flow rate and hydraulic gradient is not valid
when flow is turbulent (Ex: at immediate vicinity of a pumped well).

The expression is also invalid when water passes through extremely fine grained
material , such as colloidal clays.

It should be used only when the medium is fully saturated with water.

K value can vary by order of magnitude, depending on:

Difference in particle orientation
Difference in shape
Relative amount of silt and clay
 Hydraulic conductivity and Aquifer

Homogenous aquifer – Aquifers that have same hydraulic conductivity

throughout

Heterogenous aquifer – Aquifers in which hydraulic conductivity varies from

place to place
 Hydraulic conductivity and Aquifer

Conductivity can depend on direction of flow:

It is quite common to have higher hydraulic conductivities in horizontal
direction than in vertical direction.

Isotropic aquifer – Aquifers having same hydraulic conductivity in any flow

direction

Anisotropic aquifer – Aquifers where hydraulic conductivity depends on the

direction of flow.

Flow modelling – Mathematically we assume homogenous and isotropic

aquifer; however, such aquifer hardly exists
 Flow velocity

It is important to estimate the rate at which groundwater is moving through aquifer when
a toxic plume exist.

Flow velocity – The rate at which groundwater is moving through an aquifer

𝑑ℎ
𝑄 = 𝐾𝐴
𝑑𝐿
𝑄 𝑑ℎ
=𝐾
𝐴 𝑑𝐿
𝑑ℎ
𝑣=𝐾
Darcy velocity 𝑑𝐿
 Flow velocity

Darcy velocity assumes that flow cross-sectional area A is

available for water to flow. 𝑄 𝑑ℎ
=𝐾
𝐴 𝑑𝐿
However, much of the cross-sectional area is made up of
solids and therefore actual area available for flow is much
less. 𝑑ℎ
𝑣=𝐾
𝑑𝐿
Therefore, Darcy velocity is not the real velocity of flow.

Real groundwater velocity is considerably faster than Darcy

velocity.
 Flow velocity

Flow rate, Q, remaining constant (known),

we can calculate actual velocity.

𝑄 = 𝐴𝑣 = 𝐴′ 𝑣 ′

A’ = Area of voids or cross-sectional area

available for flow

v’ = Actual average linear velocity (also

called “seepage velocity’)

Total volume = AL
Void (filled with water) volume = A’L
A’ < A
 Flow velocity
𝑄 = 𝐴𝑣 = 𝐴′ 𝑣 ′
𝐴𝑣 𝐴𝐿𝑣
𝑣′ = ′ = ′
𝐴 𝐴𝐿
Total volume
= ×𝑣 Put picture here
Void volume
𝑣 Void volume
= Porosity =
Porosit𝑦 Total volume

Darcy velocity
=
Porosity
𝑣
=
𝜂
 Flow velocity

𝑄 = 𝐴𝑣 = 𝐴′ 𝑣 ′ 𝑑ℎ
𝑄 = 𝐾𝐴
𝑑𝐿
𝑑ℎ
𝐴𝑣 = 𝐾𝐴
𝑑𝐿
𝑑ℎ
𝑣=𝐾
𝑑𝐿
𝑣 𝐾 𝑑ℎ
=
𝜂 𝜂 𝑑𝐿

𝐾 𝑑ℎ 𝑣
𝑣′ = ′
𝑣 =
Actual average linear flow velocity 𝜂 𝑑𝐿 𝜂
 Water quality

Palatable water
Pure water

Pure water, also known as purified Potable water is not pure water Palatable water means water that is
water, is water from a source that has because it almost always contains pleasant to drink. Palatable water is at a
removed all impurities. Distilled water dissolved impurities. For water to desirable temperature, completely
is the most common form of pure be potable, it must have transparent and free from tastes,
water. sufficiently low levels of dissolved odours and colours, but is not
salts. Sodium chloride, common necessarily free from disease-causing
salt, is one such compound. agents.
 Water quality

wholesome water Polluted water Contaminated water Mineral water

Safe water/Wholesome water

Aesthetically
acceptable

Free from Chemically

bacteria safe
Safe Water/
Wholesome
Water

Organic Radioactive
substances elements
absent absent
 Water pollution

Point sources
A point source is a single, identifiable source of
pollution, such as a pipe or a drain.
Industrial wastes discharge, sewerage
discharge (commonly discharged to rivers) are
examples of point sources.
 Water pollution
Non-point sources
Non-point sources of pollution are often termed ‘diffuse’
pollution. They refer to inputs and impacts which occur over a
wide area and are not easily attributed to a single source.
They are often associated with particular land uses, as opposed
to individual point source discharges.

Urban land use

Stormwater from street surfaces is often contaminated with
car oil, dust, animal faeces, and soil and sediment run-off
from construction sites.
Agricultural land use
In farming areas non-point sources of pollution include
pesticides, fertilisers, animal manure and soil washed into
streams in rainfall run-off
Forestry land use
Forestry operations may contribute to non-point source
pollution of streams by increasing soil erosion and sediment
run-off.
 Water pollution

Water withdrawn from the natural source are returned after the intended use.

These water carry substances that is injurious to health of animals, plants and
can damage the material.

Agriculture – Water returns with pesticides, fertilizers and salts

Municipal use – Water carries human sewage
Industry use – water contains wide range of chemical pollutants and organic
wastes
Power plant – Discharge water has high temperature
 Types of water pollutants

1. Oxygen demanding waste

2. Disease-causing agents
3. Synthetic organic compounds
4. Plant nutrients
5. Inorganic chemicals and minerals
6. Sediments
7. Radioactive substances
8. Thermal discharges
9. Oil and grease
Water quality parameters
 Physical characteristics of water

Related to quality of water for domestic use

Associated with appearance, taste and temperature of water
Some of the parameters are turbidity, colour, taste and odour, temperature.
 Chemical characteristics of water

Evidenced by observed reaction of water for domestic as well as industrial use.

Some of the parameters are:

Dissolved solids and suspended solids
pH
Hardness
Chloride
Nitrogen
Heavy metals
 Biological/Microbiologica characteristics of water

Important in relation to public health

Microbes in water can modify physical and chemical characteristics of water.

The microbes include:

Bacteria
Protozoa
Viruses
Worms
Fungi
 Radiological characteristics of water

Important in area where possibility of water coming in

contact with radioactive substance exist.
It is a public health concern.
 Temperature

Surface water temperature governs biological species present in water and their rate of activity.

Temperature has an effect on most chemical reactions that occur in natural water system

Temperature has pronounce effect on solubility of gases in water.

Water having temperature between 10℃ and 15℃ is most palatable to majority individuals.

Sources of temperature

Ambient temperature (Shallow water bodies are more affected.)

Localized sudden temperature change at industrial water discharge points of the receiving water bodies.
 Temperature
Impact

Low temperature – Biological activity (utilization of food, reproduction, etc.) is slow.

As temperature increases –
Biological activity increases.
Increase of 10℃ - double the biological activity provided essential nutrients are
present.
However, number of some species may decline and eventually they may die.
Organisms that are more efficient in food utilization and reproduction at
elevated temperature may also cause problem (algal bloom).
Oil secretion by algae and dead cells of algae may result taste and odour
problem.
 Temperature
Impact

As temperature increases –
Higher order species (fish) get more affected as Dissolved oxygen solubility
decreases.
Game fish requires cooler temperature and higher DO level.
Reaction rate is accelerated and gas solubility decreases with elevated temperature.

Viscosity of water increases with decreasing temperature.

Maximum density of water is at 4℃; density decreases on either side of this temp.
 Suspended solids

Solids that remain dispersed in water/solution.

Particles are large enough to settle out of the solution or be removed by
filtration. Therefore SS is also called filterable material.
They can also be removed by sedimentation or centrifugation.
Typical size range: 0.1 – 100 µm

Suspended solids are commonly found in surface water and are materials
resulting from erosion action of water flowing through the surface.

Suspended solid is seldom a constituent of ground water because of

filtering capacity of soil.
 Suspended solids
Inorganic solids – clay, silt and other soil constituents
Organic solids – plant fibers, biological solids (algal cells, bacteria)

Domestic use results organic suspended solids.

Organic suspended solids, such as decomposing matter or sewage
effluent often naturally include high levels of microorganisms such
as protozoa, bacteria and viruses.
Such pathogens contribute to waterborne diseases like
cryptosporidiosis, cholera and giardiasis.
Industrial use results both organic and inorganic suspended solids.

Immiscible liquids such as oil and grease are treated under

suspended solids.
 Suspended solids

Colloidal particles:
Particles having size between dissolved solids and suspended solids
Typical size range: 0.01 - 10 µm
Colloidal particles are in solid state and therefore can be removed by
physical means
High-force centrifugation
Filtration through membrane with very small pores (normal
filtration is not effective)
Colloidal particles exhibit Tyndall effect, i.e., Light is reflected by colloidal
particles in solution.
Colloidal particles contribute to Turbidity – The degree to which a colloidal
solution/suspension reflects light at 90° to the entering light beam.
 Suspended solids

Impacts
Aesthetically unpleasant, undesirable taste and odour
Can block light from reaching submerged vegetation
Provides adsorption sites for chemical and biological agents
Higher concentrations of bacteria, nutrients, pesticides
Biologically active suspended solid (bacteria) may result disease causing organisms
Organic solids may degrade biologically to produce objectionable by-products.
Can cause problems for industrial use, because the solids may clog the pipes and
machinery.
 Suspended solids
Measurement
Filtration, followed by drying the residue and weight at a constant temperature (104 ℃ ± 1℃)
Expressed as mg of solid per liter of water (mg l-1)

Dissolved solid usually pass through the filter.

Filterable residue – Pass through the filter along with water

Relate more closely to dissolved solids
Nonfilterable residue – Retained on the filter
Relate more closely to suspended solid

Filtration of water sample does not exactly divide the solids into suspended and dissolved
fraction, because:
Some colloids may pass through filter and be measured as dissolved solids
Some dissolved solids may get absorbed on filter surface
 Suspended solids

How to know organic and inorganic suspended solid

Use glass-fibre (G/F) filter paper for filtration (G/F does not decompose at high temperature).
Dry the suspended solid collected on the filter paper and subject it to a temperature
of 600 ℃ for 1 hour.
Organic suspended solid converts to CO2 and H2O vapour and other gases and escape.
Remaining part is inorganic residue.
 Dissolved solids

The substance is truly in solution.

Homogenously dispersed in the liquid.
Results from solvent action of water.
Can be in the form of organic (Decay products of vegetation and organic
chemicals) or inorganic (minerals, metals, gases).
Can be in the form of simple atom or complex molecular compound.
Cannot be removed from the liquid without accomplishing phase change.
 Dissolved solids

Phase change is accomplished by:

Distillation – Either the liquid or the substance is changed from

liquid phase to gas phase in order to achieve separation.
Precipitation – Substance in liquid phase combines with another
chemical to forma solid phase and is separated from water.
Adsorption – Dissolved substance reacts with a solid particle to form a
solid particle substance complex
Liquid extraction – Dissolved substance is separated from water by extracting
it into another liquid.

Under no circumstance can physical method such as filtration, sedimentation or

centrifugation remove dissolved substance.
 Dissolved solids

Impacts
Aesthetically unpleasing
Affects taste of water
Increases the water hardness
May be toxic or carcinogenic
Two or more halogen group substance combine to produce more
harmful effect

Measurement
Evaporate to dryness the water free from suspended solid
Residue weight and TDS expressed as mg l-1
 Alkalinity

Quantity of ion in water that will react to neutralise hydrogen ions

(H+) without significant pH change.

It is the ability of the water to neutralize acids.

Principal constituents of alkalinity:

Hydorxide (OH-)
Carbonante (CO3-)
Bicorbonate (HCO3-)

Other compounds:
HSiO3-, H2BO3-, HPO42-, HPO4-, HS-, NH30
 Alkalinity
In natural water, alkalinity is due to CO2.
Process

𝐶𝑂2 + 𝐻2 𝑂 ⇌ 𝐻2 𝐶𝑂3 [Dissolved CO2 and carbonic acid]

𝐻2 𝐶𝑂3 ⇌ 𝐻+ + 𝐻𝐶𝑂3− [Bicarbonate]

𝐻𝐶𝑂3 ⇌ 𝐻+ + 𝐶𝑂32− [Carbonate]

Weak reaction
𝐶𝑂32− + 𝐻2 𝑂 ⇌ 𝐻𝐶𝑂3 + 𝑂𝐻− [Hydroxide] Algae utilizes bicarbonate ion as a carbon source
Water with heavy algal growth has pH value about 9 to 10

Alkalinity = [𝐻𝐶𝑂3− ] + [𝐶𝑂32− ] + [𝑂𝐻 − ] − [𝐻 + ]

 Alkalinity
Measurement

Alkalinity is measured by titrating the water with an acid and determining the hydrogen equivalent.

Expressed as mg l-1 of CaCO3.

If 0.02N H2SO4 is used in titration, then 1 ml of H2SO4 will neutralize 1 mg of alkalinity as CaCO3.

H+ ion from the acid react with alkalinity according to the following equations:

𝐻 + + 𝑂𝐻− ⇌ 𝐻2 𝑂

𝐶𝑂32− + 𝐻 + ⇌ 𝐻𝐶𝑂3−

𝐻𝐶𝑂3− + 𝐻+ ⇌ 𝐻2 𝐶𝑂3
 Alkalinity titration curve
Decolourisation of phenolphthalein indicator
Neutralisation of OH- and ½ CO32-
Conversion of carbonate to bicarbonate is complete.
14 However, bicarbonate is an alkalinity species, so equal amount of acid must be added to
13 Inflection point complete the neutralisaion.
12 Therefore, neutralisaion of CO32- is only half complete at pH=8.3
11
Conversion of OH- is however complete.
10
9
8.3 Phenolphthalein alkalinity: Conversion of OH- is full + one half of carbonate
8 1 2−
𝑂𝐻 − + 𝐶𝑂
7 2 3
6
Inflection point
pH

5 4.5
Methyl orange alkalinity: Methyl orange indicator changes
1 from yellow to pink. All HCO3- converted to carbonic acid.
4 𝐶𝑂32− + 𝐻𝐶𝑂3−
2
3
2 𝑂𝐻 − + 𝐶𝑂32− 𝐻𝐶𝑂3−
1

ml of titrants (acid) Thus amount of acid required titrate a sample to pH 4.5

is equivalent to the total alkalinity of water.
Total alkalinity = Phenolphthalein alkalinity + Methyl Orange alkalinity
 Alkalinity

Source
Dissolution of mineral substance in water/soil
From atmosphere (mainly CO2)
Phosphate may originate from detergents
HS- and NH30 may result from microbial decomposition of organic
material

Impact
Imparts bitter taste to water
Reaction that can occur between alkalinity and certain cations in the
water and can damage the pipe
 Alkalinity

Standard
Indian drinking water standard [IS:10500 – 2012]
200 mg l-1 [Max]; Beyond this, the taste becomes unpleasant
600 mg l-1; Permissible in the absence of alternate source

Use
Alkalinity measurement of natural water determines its buffering capacity.
Alkalinity is used as a process control variable in water and wastewater treatment.
 Hardness
Hardness is defined as concentration of multivalent metallic cations
in solutions.

At supersaturated conditions, hardness cations will react with anion

in the water to form solid precipitate.

Source
Most abundant multivalent metallic cations in natural water –
Ca2+ and Mg2+

Other cations responsible for hardness of water – Fe2+, Mn2+,

Sr2+ and Al3+ [Found in very small quantities in respect to Ca2+
and Mg2+].
Therefore for all practical purpose, hardness may be
represented by the sum of the calcium and magnesium ions.
 Hardness

Temporary Hardness: Permanent Hardness:

If bicarbonates and carbonates of calcium and If sulphates, chlorides and nitrates of calcium or
magnesium are present in water, the water is render magnesium are present in water, they can not be
hard temporarily as this hardness can be removed to removed at al by simple boiling and therefore, such
some extent by simple boiling or to full extent by water require special treatment. Ions causing
adding lime to water. Such a hardness is known as permanent hardness of water can be removed
temporary hardness or carbonate hardness. using a water softener, or ion exchange column.
Such a hardness is known as permanent hardness
Mainly associated with HCO3- ions. It precipitates or non-carbonate hardness.
readily at high temperature.

∆
𝐶𝑎 𝐻𝐶𝑂3 2 → 𝐶𝑎𝐶𝑂3 + 𝐶𝑂2 + 𝐻2 𝑂
∆
𝑀𝑔 𝐻𝐶𝑂3 2 → 𝑀𝑔𝑂𝐻2 + 2𝐶𝑂2
 Hardness

Carbonate hardness = Total hardness or Alkalinity (which ever is less)

Carbonate hardness is equal to the total hardness or alkalinity which ever
is less

Non-carbonate hardness = Total hardness – Alkalinity

Non-carbonate hardness is the total hardness in excess of the alkalinity.
If the alkalinity is equal to or greater than the total hardness, there is no
non-carbonate hardness.
This is therefore called “remaining hardness”.

Total hardness (TH) = Carbonate hardness (CH) + Non-carbonate hardness (NCH)

If TH > alkalinity, then CH = Alkalinity

If TH ≤ alkalinity, then CH = TH, NCH = 0
 Hardness

Natural process by which water becomes hard:

Rain
Rain water enters the topsoil.

Topsoil Respiration of microorganisms increases the CO2 content of the water.

Bacterial action CO2

CO2 reacts with water to form H2CO3 (carbonic acid).

Subsoil CO2 + H2O H2CO3
Limestone made up of solid CaCO3 and MgCO3 reacts with carbonic acid to form:
CaCO3(s) + H2CO3 Ca(HCO3)2 Calcium bicarbonate, Ca(HCO3)2 and Magnesium bicarbonate, Mg(HCO3)2
Limestone
MgCO3(s) + H2CO3 Mg(HCO3)2
While CaCO3 and MgCO3 are insoluble in water,
Ca(HCO3)2 and Mg(HCO3)2 are quite soluble in water.

Gypsum (CaSO4) and MgSO4 may also go into solution to contribute to hardness.
 Hardness
Impact

Sodium soap reacts with multivalent cation to from precipitate, thereby

loosing surfactant properties. Soap consumption is high as soap is consumed
to soften the water. When all cations are consumed, leathering starts.

2NaCO2C17H33 + Cation 2+ Cation 2+ (CO2C17H33)2 + 2Na+

Soap Precipitate

Soap consumption by hard-water causes economic loss to water consumers.

 Hardness
Impact

Precipitate stains the water container, water tank, dishes and clothing.
Crusty deposits (scale) on coffee pots, tea kettle and water heaters. This scale
formed can reduce the life of equipment, raise the costs of heating the water,
lower the efficiency of electric water heaters, and clog pipes.

Scale in boilers - Carbonate hardness precipitates leads to scaling in boilers

which causes considerable economic loss.

Calcium hardness has no health effect.

Magnesium hardness, particularly sulphate hardness has a laxative effect.
Mg concentration up to 50 mg l-1 is desirable in potable water.
 Hardness

Environmental impacts:

One of the most common causes of cloudy dishes and glassware is hard
water.

For human consumption, the hard water is non-toxic but it acts as an irritant
to the digestion system and can lead to digestion problems.

Hard water can also leave mineral deposits in your hair, diminishing its natural
shine and leaving buildup on your scalp results in hair dullness.
 Hardness measurement principle

Total Hardness = Ca+2 hardness + Mg+2 hardness.

Ca+2 and Mg+2 ions develop wine red color when small amount of dye such as Eriochrome Black-T
(EBT) is added under alkaline condition.
In alkaline conditions Ethylene Diamine Tetra Acetic acid (EDTA) or its sodium salt (Na2EDTA)
reacts with Ca+2 and Mg+2 to form a soluble chelated complex.
When EDTA is added as titrant, the Ca+2 and Mg+2 form complex with EDTA resulting in sharp
change in color from wine red to blue. This indicates the end of the reaction.
 Hardness measurement principle

Hardness is expressed in the units of mg l-1 of equivalent weight of CaCO3.

𝐶×𝐷×𝑀×1000
Total Hardness = mg/l eq. wt of CaCO3
𝑉𝑜𝑙.𝑜𝑓 𝑆𝑎𝑚𝑝𝑙𝑒

Where,
C = Amount of EDTA required by the sample for titration (A-B).
D = Equivalent weight of CaCO3
M = Molarity of EDTA

If 0.1 M EDTA is used, then 1ml of titrant consumed ≈ 1 mg l-1 hardness as CaCO3
equivalent.
 Classification of water based on hardness

Classification Hardness in mg/L

Soft 0-75
Moderately hard 75-150
Hard 150-300
Very hard ≥ 300

Total Hardness permissible limit for drinking water 300 mg/L, may be
extended up to 600 mg/L of CaCO3 based on IS: 10500: 1991.
 Dissolved Oxygen
Dissolved oxygen (DO) is essential for sustaining the plant and animal life in any
aquatic system.

Four processes that affect the DO content in water:

Reaeration – Oxygen transfer from atmosphere to water. Solubility of oxygen
in fresh water at saturation point varies with temperature.
Photosynthesis – The green plants such as algae utilize CO and the inorganic
nutrients present in the water to synthesize organic materials and liberate
oxygen. Aquatic plants introduce oxygen into stream water as a byproduct of
photosynthesis.
Respiration – At night, bacterial and algal respiration produces CO2 and
leads to depletion of oxygen.
Oxidation of wastes – Organic substance during their breakdown by
microogranisms, exert oxygen demand. This depletes the DO content of
water.
Oxygen solubility at different temperature
 Dissolved Oxygen

If the oxygen present in water is found to be less than its

saturation level, it indicates presence of organic matter and
consequently making the waters suspicious.

Low dissolved oxygen levels can be the result of elevated

temperature and thus the inability of the water to hold the
available oxygen. Low dissolved oxygen levels can also indicate an
excessive demand on the oxygen in the system.

Fish growth and activity usually require 5-6 mg l-1 of dissolved

oxygen. Dissolved oxygen levels below 3 mg l-1 are stressful to
most aquatic organisms. Levels below 2 mg l-1 will not support fish
at all.
 Oxygen Demand

When biodegradable organic matter is released in to a water body, microorganisms,

especially bacteria, feed on wastes, breaking them down into simpler organic and
inorganic substances.

When the decomposition takes place in an aerobic environment, the process

produces non-objectionable, stable end products such as CO2, SO4, NO3 and PO4
(orthophosphate).

A simplified representation of the aerobic decomposition can be given as follows

Aerobic decomposition

Organic matter +O2 CO2 + H2O + New cells + Stable products (NO3, PO4, SO4, .....)
microbes
 Oxygen Demand

When the decomposition takes place in presence of insufficient oxygen, the

resulting anaerobic decomposition is performed by completely different
microorganismcs.

They produce end products that can be highly objectionable such as H2S, NH3 and
CH4.

A simplified representation of the anaerobic decomposition can be given as follows

Anaerobic decomposition

Organic matter CO2 + H2O + New cells + Unstable products (H2S, NH3, CH4, .....)
microbes
 Oxygen Demand
Biochemical oxygen demand or BOD is the amount of dissolved
oxygen needed by aerobic biological organisms in a body of water to break
down organic material present in a given water sample at certain temperature
over a specific time period.
BOD expressed as milligrams of oxygen required per liter of wastewater (mg l-1)

In receiving stream, high BOD level can cause depleted oxygen,

making it difficult for aquatic animal to survive.
Oxygen Demand: Definition and Notation
BOD Biochemical oxygen demand – the amount of oxygen utilized by microorganisms in oxidizing
carbonaceous and nitrogenous organic matter.
CBOD Carbonaceous biochemical oxygen demand – BOD where the electron donor is carbonaceous
organic matter.
NBOD Nitrogenous biochemical oxygen demand – BOD where the electron donor is nitrogenous organic
matter.
ThOD Theoretical oxygen demand – the amount of oxygen utilized by microorganisms in oxidizing
carbonaceous and / or nitrogenous organic matter, assuming that all of the organic matter is
subject to microbial breakdown, that is, it is biodegradable.
BOD5 5-day biochemical oxygen demand – the amount of oxygen consumed (BOD exerted) over an
incubation period of 5 days; the standard laboratory estimate of BOD. The BOD5 utilizes the
notation y5 , referring to the BOD exerted (y) over 5 days of incubation.
BODU Ultimate biochemical oxygen demand – the amount of oxygen consumed (BOD exerted) when all
of the biodegradable organic matter has been oxidized. The BODU utilizes the notation Lo, referring
to its potential for oxygen consumption when proceeding to complete oxidation.
COD Chemical oxygen demand – the amount of chemical oxidant, expressed in oxygen equivalent,
required to completely oxidize a source of organic matter; COD and ThOD should be near equal.

BOD = CBOD + NBOD

COD ≥ BOD
 Five-day BOD test

A test for oxygen required to completely degrade the waste in water will take
long time (e.g. several weeks).

Standard practice is to report oxygen demand over a period of 5 days at 20℃.

It is written as BOD5.

The test is conducted using a standard BOD bottle of 300ml.

70% to 80% waste is oxidized in 5 days.

Dissolved oxygen
(Laboratory test)
Question
The DO concentration of a waste water sample at the beginning of a
standard BOD test was 8 mg/L. The DO concentration was 5mg/L after
5-day incubation at 20 ̊C. What is the BOD of the sewage if there no
dilution was made for the test?

Answer
Loss of DO during test = Initial DO (DOi) – Final DO (DOf)
= 8-5 = 3 mg/L.
Therefore BOD of the waste water was 3 mg/L
Dilution factor
If there are too much of waste product in the water, then the entire amount of
DO may get exhausted during the 5 days.
In that case we do not know when the DO became zero and the test is invalid.
We therefore need some DO to remain at the end of the test period.
For that we add some pure water to the sample to dilute it so that after 5
days, the DO remains above zero.

BOD5 = (DOi – DOf )/ P

DOi = Initial dissolved oxygen
DOf = Final dissolved oxygen (after 5 days)
P= Dilution factor/Dilution fraction/Dilution ratio
= Volume of wastewater / volume of (wastewater + dilution
water)
Question
A raw sewage sample of 2.5 mL has been diluted to 250 mL during the BOD test.
The DO concentration of the diluted sample at the beginning of BOD test was 8
mg/L. The DO concentration was 5mg/L after 5-day incubation at 20 ̊C. What is
the BOD of the sewage?

Answer
• Volume of sample of sewage is 2.5mL
• Volume of diluted sample is 250mL
• Dilution factor, P = 2.5/250
BOD5 = (DOi – DOf )/ P = (8-5)/(2.5/250)
= 300 mg/L.
Example:
10.0 mL sample of sewage mixed with enough water to fill a 300 mL bottle has an initial DO
of 9.0 mg/L. To help assure an accurate test, it is desirable to have at least a 2.0 mg/ L drop
in DO during the five-day run, and the final DO should be at least 2.0 mg/L. For what range
of BOD5 would this dilution produce the desired results?

Answer:
The dilution fraction is P = 10 / 300.

To get at least a 2.0 mg/L drop in DO, the minimum BOD needs to be

BOD5 > (DOi-DOf)/P = 2/(10/300) = 60 mg/L

To assure at least 2.0 mg/L of DO remains after five days requires that

BOD5 > (9-2) mg/l/p = 2/(10/300) = 210 mg/L

This dilution will be satisfactory for BOD5 values between 60 and 210 mg/L.
Home work

Determine the BOD of the sewage when 2% solution of it is incubated

for 5 days at 20 ̊C. The depletion of oxygen was found to be 4 mg/L.
 BOD of Selected Waste Streams
Origin BOD5(mg/L)

River 2
Domestic Waste Water 200
Pulp and Paper mill 400
Commercial laundry 2,000

Sugar beet factory 10,000

Tannery 15,000

Brewery 25,000
Cherry – canning factory 55,000
 Modelling BOD as a first order reaction

Time
Bacteria oxidises waste.

Organic matter decreases with time.

Eventually it disappears.

Therefore, it is assumed that:

Rate of decomposition of organic waste ∝ Amount of the organic waste left

⇒Rate at which organics are utilized by microorganisms is a first order reaction.

 Modelling BOD as a first order reaction

Mathematically,
𝑑𝐿𝑡
∝ 𝐿𝑡
𝑑𝑡
Lt = Oxygen equivalent of organics at time t, mg l-1
𝑑𝐿𝑡
= −𝑘𝐿𝑡 L0 = Total oxygen equivalent of organics at time 0, mg l-1
𝑑𝑡
= Ultimate BOD
𝐿 𝑡
𝑑𝐿𝑡
න = −𝑘 න 𝑑𝑡 k = Reaction rate constant, d-1
𝐿
𝐿0 𝑡 0

𝐿𝑡
ln = −𝑘𝑡
𝐿0

𝐿𝑡 = 𝐿0 𝑒 −𝑘𝑡 Dissolve oxygen decay takes place exponentially.

 Modelling BOD as a first order reaction

𝑳𝟎
Ultimate oxygen demand
𝐿0 − 𝐿𝑡 = 𝑦𝑡
Organic matter oxidized
= Ultimate BOD
Oxygen equivalent of
organics/BOD, mg l-1

≈ BOD exerted
= Oxygen consumed in t days + Oxygen
remaining to be consumed
= 𝑦𝑡 (BODt)+ 𝐿𝑡
𝑦𝑡

𝒚 𝒕 = 𝑳𝟎 − 𝑳𝒕
𝐿𝑡

Organic matter remaining 𝒚𝒕 = 𝑳𝟎 − 𝑳𝒕 𝒆−𝒌𝒕

𝒚𝒕 = 𝑳𝟎 𝟏 − 𝒆−𝒌𝒕
Time, days

𝒚𝒕 approaches 𝑳𝟎 asymptotically, indicating that total or ultimate

BOD (𝒚𝒖 ) is equal to the initial oxygen equivalent of water, 𝑳𝟎 .
 Modelling BOD as a first order reaction

𝑳𝟎 𝑳𝟎
O2 depletion is rapid in first
BOD remaining Lt, mg l-1

𝐿𝑡
BOD utilized BODt, mg l-1
few days because of the
high concentration of
𝐵𝑂𝐷𝑡

organic matter present

𝐵𝑂𝐷𝑡 = 𝑦𝑡 = 𝐿0 1 − 𝑒 −𝑘𝑡
BOD5

𝐿𝑡 = 𝐿0 𝑒 −𝑘𝑡
𝐿𝑡

t 5 t
Time, days
Time, days
[BOD remaining as a function of time] [Oxygen already consumed as a function of time]
 BOD rate constant, k
Typical values of the BOD rate constant
k indicates rate of biodegradation of waste. Water type K (d-1) at 20℃
k increases implies,
Tap water < 0.1
Rate of utilization of dissolved oxygen increases
Ultimate DO requirement, L0, remains unchanged Surface water 0.1 – 0.23
Weak municipal water 0.35
Reaction rate, k, depends on: Strong municipal water 0.40
▪ Temperature [As temperature increases, rate of biodegradation Treated effluent 0.12 – 0.23
increases because of increase in rate of metabolism of microorganisms].
▪ Nature of wastewater [simple sugar and starch degrades easily;
cellulose, hair and fingernails are almost un-degradable]
▪ The ability of the available microorganisms to degrade the waste (not all
oganisms degrade a particular waste in same efficiency.
▪ Acclimatization of the organism to perform the job more efficiently (it
may take sometime for a healthy population of organism needing to
thrive on waste in water.)
 BOD rate constant, k

Ultimate BOD remains same

Value of k increases with increase in temperature.
𝑳𝟎
The change in k-value can be approximated

BOD utilized BODt, mg l-1

k3
by vant Hoff-Arrhenius model: k2
k1

𝒌𝑻 = 𝒌𝟐𝟎 𝜽 𝑻−𝟐𝟎

k3 > k2 > k1
T = Temperature of interest, ℃
Rate of BOD exerted is different
kT = BOD rate constant at the temperature of interest, d-1
k20 = BOD rate constant determined at 20℃, d-1
t
θ = Temperature coefficient Time, days
= 1.135 for temperature between 4℃ and 20℃
= 1.056 for temperature between 20℃ and 30℃
 BOD rate constant, k
Will have greater impact on DO in river water
because smaller fraction of BOD was exerted on
first 5 days due to lower rate constant.
500 L = 480 mg l-1
This is essentially carbonaceous
oxygen demand (CBOD), i.e., Amount 400
of O2 required by microorganisms to
oxidise the carbonaceous portion of

BOD, mg l-1
300 L = 290 mg l-1
the waste to simple CO2 and H2O.

The other components of the organics, 200

such as N and S, may also be oxidized BOD5 = 200 mg l-1
by microorganisms and their oxygen 100
demand is called NBOD. It starts after
almost all CBOD are exerted.
5 10 15 20 25
Time, days
[Effect of k on ultimate BOD for two wastewater with same BOD5]
 BOD rate constant, k

L0 = 50 mg l-1
50
BOD5 = 35 mg l-1
40
Ultimate BOD is same for the same
river water if temperature is

BOD, mg l-1
30
different.
20
However, BOD5 values vary due to
difference in BOD rate constant. 10 BOD5 = 20 mg l-1

5 10 15 20 25
Time, days

[Effect of k on BOD5 when the ultimate BOD is same]

Water borne diseases
 Biological water quality parameters
Microbial characterisation
Pathogen
Organisms capable of infecting or transmitting diseases to humans
Not native to aquatic system
Usually require an animal host for growth and reproduction
Can be transported by natural wate system
Maintain their infectious capabilities for significant period of time
Five types of pathogen (parasitic organisms) are generally known to be infective
to man and are found in water.
Bacteria
Viruses
Protozoa
Worms
Fungi
 Bacteria

These are the minute single cell organisms possessing no defined nucleus
and having no green material to help them manufacture their own food.

Lowest form of the life capable of synthesizing protoplasm from the

surrounding environment.

They are reproduced by binary fusion and may of various shapes and
sizes (1 to 4 µm), examined under microscope.

Usually colourless

Rod shaped (bacilli), spherical (cocci) and spiral shaped (spirilla)

 Bacteria

Non-disease causing bacteria – Non pathogenic bacteria.

Disease causing bacteria – Pathogenic bacteria.

Most common diseases by water borne bacteria: Gastrointestinal disorder

Others include: Cholera and Typhoid

 Classification of bacteria based on oxygen requirement:

Aerobic bacteria:
Those which require oxygen for their survival.

Anaerobic bacteria:
Those which flourish in the absence of free oxygen.

Facultative bacteria:
Those which can survive with or without free oxygen.
 Virus

Smallest biological structures known to contain all the genetic

information necessary for their own reproduction.

Obligate parasites that require host to live.

Diseases include waterborne viral infection:

Disorder of nervous system, rather than gastrointestinal problems
Hepatitis
 Protozoa

These are single cell animals and are the lowest and the simplest form of animal life.
Unicellular organisms, more complex in their functional activity than bacteria and virus.

Complete self-contained organisms that can be:

Free-living or Parasitic
Pathogenic or Nonpathogenic
Microscopic or Macroscopic

They are bacteria eaters and thus destroy Pathogens.

Diseases due to protozoa include:

Gastrointestinal disorder, milder that associated with bacterial infection
 Protozoa

Removal of protozoa

Under certain adverse environmental circumstances, aquatic protozoa forms cysts

and therefore difficult to deactivate by disinfection.
Complete treatment followed by filtration is necessary to remove protozoan cysts.
 Worms
These are the larva of flies.
One type of the parasitic worm is Helminth.

Helminth:
Sources include human and animal waste.
Snails and insects could be the host.

Persons at risk:
Who come in direct contact with untreated water(Ex – Sewage plant
operator; Farm labourers employed in agricultural and irrigation
operations)

Removal:
Modern water treatment methods are effective in destroying these
organisms.
 Fungi

These are those plants which grow without sunlight and live on other
plants or animals, dead or alive.

The presence of fungi in water distribution systems may cause

secondary metabolites produced by some species that can alter the
taste and smell of water, generating complaints from end- users.

Filamentous fungi are one of the most important producers of

secondary metabolites. Some of them can have a toxic effect on the
human body, leading to diseases.
 Test for Pathogenic bacteria

These can be tested and counted in the laboratories but with

great difficulty.

These tests are therefore, generally not performed in routine

to check up of the water quality.

The usual routine tests are generally conducted to detect and

count the presence of coliforms which in themselves harmless
organisms, but their presence or absence indicates the
presence or absence of pathogenic bacteria.
Methods to measure the presence of coliform bacteria:

Membrane filter technique (modern technique)

Mixing different dilution of a sample of water with lactose froth and
incubating them in test-tubes for 48 hours at 37 0 C.
The presence of acid or carbon dioxide gas in tubes will indicate the
presence of coliform bacteria.
Most probable number (MPN) represent the bacterial density.
Coliform index

It may be defined as the reciprocal of the smallest quantity of a sample

which would give a positive portion.

Coliform sometimes called bacteria coli (B-coli) or Escherichia (E-coli) are

harmless aerobic micro-organisms.

If not more than 1 coliform is present per 100ml of water, then water is said
to be safe for drinking.

𝑀𝑃𝑁 100 × 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑝𝑜𝑟𝑡𝑖𝑜𝑛

𝑚𝑙 =
100 𝑚𝑙 𝑖𝑛 𝑎𝑙𝑙 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑝𝑜𝑟𝑡𝑖𝑜𝑛 × (𝑚𝑙. 𝑖𝑛 𝑎𝑙𝑙 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑜𝑟𝑡𝑖𝑜𝑛)
Indian standard for Drinking water
IS 10500-2012 (Bureau of Indian Standards)
Indian standard for Drinking water
IS 10500-2012 (Bureau of Indian Standards)
Indian standard for Drinking water
IS 10500-2012 (Bureau of Indian Standards)
Indian standard for Drinking water
IS 10500-2012 (Bureau of Indian Standards)
Indian standard for Drinking water
IS 10500-2012 (Bureau of Indian Standards)
Indian standard for Drinking water
IS 10500-2012 (Bureau of Indian Standards)
Indian standard for Drinking water
IS 10500-2012 (Bureau of Indian Standards)
Designated Best Use Water Quality Criteria
(Central Pollution Control Board)
Thank you