CE102: Environmental Studies

Module IV: Water Resources

Dr. Pradhi Rajeev

Assistant Professor
Department of Civil and Environmental Engineering
Indian Institute of Technology Patna
Bihta, (Bihar) - 801106, India
1
Syllabus
Module IV: Water Resources – Hydrologic cycle and
its components, Groundwater and surface water,
Water quality (No. of contact hours: 07)

2
The distribution of water on, in, and
above the Earth

3
Water Resources in World

Source: australian museum

4
Source: australian museum
5
 Global Water Footprint by Sector

Global average numbers and composition of all national water footprints,

internal and external 6
Source: Earth Trends 2001, World Resources Institute 7
• Water stress occurs when the demand for water exceeds the available amount
during a certain period or when poor quality restricts its use. Water stress causes
deterioration of fresh water resources in terms of quantity (aquifer over-
exploitation, dry rivers, etc.) and quality (eutrophication, organic matter pollution,
saline intrusion, etc.).
• “Water stress” refers to the ability, or lack thereof, to meet human and ecological
demand for fresh water.
• Compared to scarcity, “water stress” is a more inclusive and broader concept.
• It considers several physical aspects related to water resources, including water
availability, water quality, and the accessibility of water (i.e., whether people are
able to make use of physically-available water supplies), which is often a function
of the sufficiency of infrastructure and the affordability of water, among other
things.
• Both water consumption and water withdrawals provide useful information that
offers insight into relative water stress.
 Level of Water Stress

Figure: Level of water stress by countries: freshwater withdrawal as a

proportion of available freshwater resources in 2018 (%).

Source: UN-Water, 2021: Summary Progress Update 2021 – SDG 6 – water and sanitation for all.
Version: July 2021. Geneva, Switzerland. 9
 Level of Water Stress

Figure: : Level of water stress in 2018, by region and globally.

Source: UN-Water, 2021: Summary Progress Update 2021 – SDG 6 – water and sanitation for all.
Version: July 2021. Geneva, Switzerland. 10
Source: UN-Water, 2021: Summary Progress Update 2021 – SDG 6 – water and sanitation for all.
Version: July 2021. Geneva, Switzerland. 11
Source: UN-Water, 2021: Summary Progress Update 2021 – SDG 6 – water and sanitation for all.
Version: July 2021. Geneva, Switzerland. 12
 Water Resources in India
Per capita water availability in India

Per capita water demand: ratio of the annual average water consumption of a
community to the total population for 365 days. Hence, Per Capita Demand is
the annual average amount of daily water required by one person.
Source: Government of India, 2009. 13
No water in Bundelkhand

14
Latur water train Maharashtra

15
New Delhi Demands Water

16
Water train from Vellore arrives in Chennai
17
Water Stress in India

Source: World Resources Institute, 2014 18

 Water Stress in India
 India ranks a dismal low 120th out of 122 nations
for its water quality as per NITI Aayog and 133rd
out of 180 nations for its water availability as per
Forbes India.

 In addition, water scarcity in India is expected to

worsen as the overall population is expected to
increase to 1.6 billion by the year 2050.

 The water obtained from any of the surface

sources of water needs to be purified before it can
be supplied to the public.

Data source: NITI Aayog, Forbes India, [Link] 19

Hydrogeological
map of Bihar

Source: CGWB, Ministry of

Water Resources, Govt. of
India
20
 Variation depth of water level

May-2014 May-2016

May-2019
0-2 m bgl
2-5 m bgl
5-10 m bgl
10-20 m bgl
Source: CGWB, Ministry of
Water Resources, Govt. of
India 21
 Hydrology

The science that deals with the depletion and replenishment of

water resources, both surface and sub-surface waters including
spatial and temporal characteristics of the water in all its aspects
such as occurrence, circulation, distribution, physical and
chemical properties and impact on environment and living things.

22
Hydrologic Cycle

The entire phenomenon of evaporation and precipitation that continues

forever and maintain the balance between the loss of water to the
atmosphere as vapor from the earth and in gain of water by precipitation
such as rain, snow, hail, dew etc. is referred to as hydrologic cycle.
23
Hydrologic Cycle

This cycle of water amongst earth,

oceans, and atmospheric systems
is known as Hydrologic cycle
where Sun and Coriolis force play
important role in its completion

24
Salient Features of the Hydrologic Cycle
 Water is conserved: it is neither created nor destroyed.
 The earth’s total water content in the hydrologic cycle is not equally distributed.
 The oceans are the largest reservoirs of water, but since it is saline it is not
readily usable for requirements of human survival. The freshwater content is just
a fraction of the total water available.
 The fresh water distribution is highly uneven, with most of the water locked in
frozen polar ice caps.

Total global water content Global fresh water distribution 25

Hydrologic cycle and its components
The hydrologic cycle consists of following four key components:
• Evaporation
• Condensation
• Precipitation
• Surface Runoff
• Infiltration
• Storage
• Transpiration or Evapotranspiration

Surface and sub-surface

components of hydrologic cycle

26
 Common forms of precipitation
• Drizzle or mist (water droplets of diameters less than 0.5
mm),
• Rain (water drops of size between 0.5 mm and 6.0 mm),
• Snow (ice crystals combining to form flakes with average
specific gravity of about 0.1),
• Sleet (rain water drops, falling through air at or below
freezing temperatures, turned to frozen rain drops),
• Hail (precipitation in the form of ice balls of diameter more
than about 8 mm).
• Most of the precipitation, generally, is in the form of rains.
Therefore, the terms precipitation and rainfall are
considered synonymous.
• Rainfall, i.e., liquid precipitation, is considered light when
the rate of rainfall is up to 2.5 mm/hr, moderate when the
rate of rainfall is between 2.5 mm/hr and about 7.5 mm/hr,
and heavy when the rate of rainfall is higher than about 7.5
mm/hr. 27
 Groundwater and Surface water
• Groundwater:
• Water located below the water
table
• saturated conditions
• Recharge zones
• Locations where surface waters
move into the groundwater
• Discharge zones
• Locations where water flows or
seeps out of groundwater
• Vadose zone
• Area where water seeps through
pore spaces
• Aquifer
• Underground zone from which
groundwater can be obtained
• Cone of Depression
• Forms in water table elevation
when water is pumped from an
aquifer 28
Groundwater and Surface water
• Streams

• Effluent stream
• All streams do not necessarily begin as runoff water,
but they can emanate from the underlying water table.
• An effluent river system, also known as a gaining
stream, is a river whose water originates from the
groundwater beneath the surface, the local aquifer,
and it increases in volume further downstream.
• Examples of effluent rivers include the Amazon River in
South America, the Mississippi River in the United
States, and the Columbia River in the Pacific North
West of North America.

29
Groundwater and Surface water
• Streams

• Influent stream
• An influent river, also known as a losing stream, a sinking
stream, or a disappearing stream, is a type of stream that
loses water as it flows downstream.
• Influent river systems lose most of their water to the
underlying bedrock through percolation and enriching the
underlying aquifer.
• Water loss is not only limited to percolation, but it can also
occur through evaporation, plant use, and human or
animal consumption.
• Some losing streams include the Nile River, which is one
of the longest rivers in the world emanating from Lake
Victoria in East Africa and draining into the Mediterranean
Sea, as well as the Colorado River in the southwestern
United States.

30
Groundwater and Surface water

31
 Interactions Between Surface Water and
Groundwater
 Should be
considered part of
the same resource
 Nearly all surface
water environments
have linkages with
ground water
 Ex: withdrawal
of groundwater
can lower
stream flow or
lake levels
 Pollution can
spread from
one source to
the other

32
Water Use
 Off-stream use
 Refers to water removed from its source for use
 May be returned to source after use
 Consumptive use- water is not returned to its source
 Plant or animals water use (evaporates in the tissue, or
is used to make new organs)
 Industrial use
 In-stream use

 Water left in its source for use

 Navigation, hydroelectric power, fish and wildlife habitats,

and recreation

33
Water Conservation
 Careful use and protection of water resources
 Involves both quantity and quality of water
 Important component of sustainable water use
 Three components
 Agricultural Use
 Domestic Use
 Industrial Use
 Advanced planning of Water Management may include
 Reuse of wastewater
 Develop surface water and use groundwater in dry years
 In wet years pump excess surface water underground to
recharge groundwater

34
Assignment
 The Indus Water Treaty?
 The Cauvery Water Dispute?
 The Satluj-Yamuna Link Canal Dispute?
 Water conflict in the Middle East?
 Water privatization in Cochabamba, Bolivia?

35
Water Quality and Testing

36
Water Quality

Water Quality Parameters

Chemical:
Physical:
1. pH
1. Solids
2. Alkalinity
2. Turbidity
3. Hardness Microbiological:
3. Color
4. Dissolved Oxygen 1. Coliforms
4. Taste and
5. Chemical Oxygen Demand (COD) (Total & Fecal)
Odor
6. Biochemical Oxygen Demand (BOD)
5. Temperature
7. Total Organic Carbon (TOC)
[Link] [Org.-N, NH4+, NO2-, NO3-, (TKN)]
9. Phosphorous
10. Cations including heavy metals (Na, K,
Ca, Mg, Al, Cu, Cr, Cd, Pb, As, Hg, etc.)
11. Anions (F-, Cl-, SO42-, S2-, CN-)

37
Water Quality
Physical water quality parameter are as follows:

Suspended solids

Turbidity

Color

Odor and Taste

Temperature

38
 Solids

 Solids in water is due to the presence of the following:

• Inorganic particles like silt, clay etc.
• Organic particles like plant fibres, algae, etc.
• Immiscible solids like oil, grease etc.
 The possible effects of solids in water are as follows:
• It gives water a muddy appearance.
• It provide adsorption sites for chemical and biological agents.
• It leads to incrustation in pipes.
• Suspended organic solids may be degraded biologically, resulting
in objectionable by products.
• Biologically active suspended solids may include disease-causing
organisms

39
Solids
• Solids are defined as the matter that remains as residue upon
evaporation and drying at 103°C to 105°C overnight.
• Total Solids in a sample consist of total dissolved solids and
total suspended solids.
• Total dissolved solids are materials in liquid that will pass
through a filter paper with 0.45 µm or smaller pore size and
remains as residue upon evaporation and drying at 103°C to
105°C overnight.
• Fixed solids correspond to the matter that remains as residue
upon muffling (ignition) at 550°C to 600°C for 1 h.
• While Volatile solids correspond to the matter loss upon
muffling or high temperature oxidation and volatilization.

40
(Cont…)

Fixed solids: After the ignition for a specific duration at a certain temperature, the total
suspended or dissolved solids remaining in the sample.

Total dissolved solids (TDS): Under the specific condition, the part of total solids that pass
through a filter 0.45 µm (or smaller) nominal pore size.

Total solids: The material left in a sample vessel after evaporation and oven drying at a
specified temperature.

Total suspended solids (TSS): The part of total solids in the form of an aqueous sample which
is retained on the filter.

Volatile solids— At a defined time and temperature, the total, dissolved, or solids are removed
from a sample after ignition.
41
Some common instruments/apparatus/glassware

Electronic balance is an instrument

used in the accurate measurement of
weight of materials

A crucible is a ceramic or metal

container in which metals or other
substances may be melted or subjected
to very high temperatures

A hot air oven is a laboratory instrument

that uses dry heat to sterilize laboratory
equipment and other materials

Muffle furnaces are chambers that are

used in laboratories and industries to
create an environment of high
temperatures
42
Some common instruments/apparatus/glassware
Filter paper is a semi-permeable paper barrier
used to separate fine solid particles from liquids or
gases

A beaker is a glass container with a flat bottom

that used to hold liquids

Vacuum filtration is faster than gravity

filtration, because the solvent or solution and
air is forced through the filter paper by the
application of reduced pressure

43
(Cont…)
 Water quality can be defined as a measure of the suitability of
water for a particular use.

 In order to assess the quality of water, few essential steps are

required to be followed.

 Sampling
 Preservation of samples
 Storage of samples
 Analysis of samples

 The parameters which help in determining the quality of raw water

are called water quality parameters, which can be classified as
follows:

• Physical Parameters
• Chemical Parameters
• Biological Parameters

44
(Cont…)
Measurement of solids
Gravimetric analysis
Note down the
Switch on the balance initial dry weight
Switch on
the balance of the crucible
along with filter
Note down the
paper
initial dry weight
of the crucible

Take the filter paper

and place it on the
Place the Filter 50 mL of field
evaporating dish
crucible water sample using
inside the filter paper
Take 20 mL of
oven at
water sample in
103 oC
the crucible
Place the
evaporating
dish inside the
Cool it to
oven at 103 oC
room
Cool it to
temperature
room
in desiccator
temperature
in desiccator

Note down the final dry

Note down the weight of the filter
final dry weight paper
of the crucible

Total solids (TS) Total suspended solids (TSS)

45
(Cont…)
Switch on the Note down the Portable TDS meter
balance initial dry weight of
the crucible  It is best suited for filed
measurements.

Take 20 mL of
water sample in the
crucible Filter 50 mL of
field water
sample using
filter paper

Place the
crucible inside
the oven at
Cool it to room
103 oC
temperature in
desiccator

Note down the

final dry weight
of the crucible

Total dissolved solids (TDS) Portable TDS meter 46

SUSPENDED SOLIDS EXAMPLE PROBLEM
Calculate suspended and volatile suspended solids in mg/L
given the following data:

Sample Volume = 25 mL
Weight of Crucible + Filter Paper = 18.1450 grams
Weight of Crucible + Filter Paper & Dry Solids = 18.1482 grams
Weight of Crucible + Filter Paper & Ash = 18.1456 grams

Suspended Solids, mg/L = Wt. Dry Solids, grams

X 1,000,000
Sample Volume, mL

= 18.1482 g- 18.1450 g
X 1,000,000
25 mL

0.0032 g
= X 1,000,000
25 mL

= 128 mg/L 47
 SUSPENDED SOLIDS EXAMPLE PROBLEM
Calculate suspended and volatile suspended solids in mg/L
given the following data:

Sample Volume = 25 mL
Weight of Crucible + Filter Paper = 18.1450 grams
Weight of Crucible + Filter Paper & Dry Solids = 18.1482 grams
Weight of Crucible + Filter Paper & Ash = 18.1456 grams

Volatile Sus. Solids, mg/L = Wt. Volatile Solids, grams X 1,000,000

Sample Volume, mL

= 18.1482 g- 18.1456 g
X 1,000,000
25 mL

0.0026 g
= X 1,000,000
25 mL

= 104 mg/L 48
SUSPENDED SOLIDS PRACTICE PROBLEMS

Calculate suspended and volatile suspended solids in mg/L

given the following data:

Weight of Crucible + Filter Paper = 21.0256 grams

Weight of Crucible + Filter Paper & Dry Solids = 21.0301 grams
Weight of Crucible + Filter Paper & Ash = 21.0263 grams
Volume of Sample Filtered = 50 mL

49
 SUSPENDED SOLIDS PRACTICE PROBLEM
Calculate suspended and volatile suspended solids in mg/L
given the following data:

Weight of Crucible + Filter Paper = 21.0256 grams

Weight of Crucible + Filter Paper & Dry Solids = 21.0301 grams
Weight of Crucible + Filter Paper & Ash = 21.0263 grams
Volume of Sample Filtered = 50 mL

Suspended Solids, mg/L = Wt. Dry Solids, grams

X 1,000,000
Sample Volume, mL

= 21.0301 g - 21.0256 g
X 1,000,000
50 mL

0.0045 g
= X 1,000,000
50 mL

= 90 mg/L 50
 SUSPENDED SOLIDS PRACTICE PROBLEM
Calculate suspended and volatile suspended solids in mg/L
given the following data:

Weight of Crucible + Filter Paper = 21.0256 grams

Weight of Crucible + Filter Paper & Dry Solids = 21.0301 grams
Weight of Crucible + Filter Paper & Ash = 21.0263 grams
Volume of Sample Filtered = 50 mL

Volatile Sus. Solids, mg/L = Wt. Volatile Solids, grams X 1,000,000

Sample Volume, mL

= 21.0301 g - 21.0263 g
X 1,000,000
50 mL

0.0038 g
= X 1,000,000
50 mL

= 76 mg/L 51
 Turbidity
 A direct measurement of suspended solids is not usually performed on
samples from natural bodies of water or on potable (drinkable) water
supplies.
 The nature of the solids in these waters and the secondary effects
they produce are more important than the actual quantity.
 Turbidity is a measure of the extent to which light is either absorbed or
scattered.
 Because absorption and scattering are influenced by both size and
surface characteristics of the suspended material, turbidity is not a
direct quantitative measurement of suspended solids.
 For example, one small pebble in a glass of water would produce
virtually no turbidity. If this pebble were crushed into thousands of
particles of colloidal size, a measurable turbidity would result, even
though the mass of solids had not changed.

52
 Turbidity
 Suspended and colloidal particles, such as clay, silt, finely divided
organic and inorganic matter, and plankton and other microscopic
organisms, causes turbidity in water.
 Turbidity of water samples is expressed in NTU.
 Turbidity is an important consideration in public water supply for three
main reasons:
• It makes water aesthetically displeasing.
• Increases load on filter beds.
• It reduces disinfection efficiency.

53
 Measurement of turbidity
Nephelometer
 This method works by comparing the intensity of light scattered by
the sample with the intensity of light scattered by a standard
reference suspension under similar conditions.
 Nephelometer is calibrated using stock solutions (0.02 NTU, 40 NTU,
4000 NTU) before actual sample is measured.

Standard solutions Nephelometer Water samples

54
Digital turbidity meter
 It can be conveniently used for field measurements. The turbidity
measurement range is 0-200 NTU.

Digital turbidity meter

55
COLOR
 Pure water is colorless, but water in nature is often colored by foreign
substances.
 Water whose color is partly due to suspended matter is said to have apparent
color.
 Color contributed by dissolved solids that remain after removal of suspended
solids is known as true color.

Sources
 Organic debris such as leaves, conifer needles, weeds, or wood, etc.
 Iron oxides and manganese oxides
 Industrial wastes from textile and dyeing operations, pulp and paper
production, food processing, chemical production, and mining, refining, and
slaughterhouse operations

Impact
 Colored water is not aesthetically acceptable to the general public.
 Highly colored water is unsuitable for laundering, dyeing, papermaking,
beverage manufacturing, dairy production and other food processing, and
textile and plastic production. 56
COLOR (Measurement)
 Although several methods
of color measurement are
available, methods
involving comparison with
standardized colored
materials are most often
used.

 Results are expressed in true color units (TCUs) where one unit is
equivalent to the color produced by 1 mg/L of platinum in the form of
chloroplatinate ions

Spectrophotometers

57
TASTE AND ODOR
 Substances that produce an odor in water will almost invariably impart
taste as well.
 The converse is not true, as there are many mineral substances that
produce taste but no odor.

Sources
 Substances such as minerals, metals, and salts from the soil, end products
from biological reactions, and constituents of wastewater.
 Inorganic substances are more likely to produce tastes unaccompanied by
odor.
 Alkaline material imparts a bitter taste to water, while metallic salts may
give a salty or bitter taste.
 Organic material, on the other hand, is likely to produce both taste and
odor.

Impacts
 Consumers find taste and odor aesthetically displeasing for obvious
reasons.
 Odors produced by organic substances may pose more than a problem of
simple aesthetics since some of those substances may be carcinogenic.
58
TASTE AND ODOR (Measurement)
TASTE
 Flavor threshold number (FTN)
𝐀+𝐁
 FTN =
𝐀

 A = volume of water sample in mL

 B = Volume of taste free water (or diluent) added in mL

ODOR
 Threshold odor number (TON)
𝐀+𝐁
 TON =
𝐀

 A = volume of water sample in mL

 B = Volume of odor free water (or diluent) added in mL

The drinking water should not have any objectionable taste and odor and
for this the flavor threshold number (FTN) and the threshold odor number
(TON) should not exceed 3 and should preferably be 1

59
TEMPERATURE
 Temperature is not used to evaluate directly either potable water or
wastewater.
 But one of the most important parameters in natural surface-water
systems.
 The temperature of surface waters governs to a large extent the
biological species present and their rates of activity.
 Temperature has an effect on most chemical reactions that occur in
natural water systems.
 Temperature also has a pronounced effect on the solubilities of
gases in water.

Sources
 Temperature of the surrounding atmosphere.
 Discharge of the heated water may result in dramatic temperature
change in receiving streams (though perhaps localized).

60
TEMPERATURE
Impacts
 An increase of 10 oC usually sufficient to double the biological
activity, if essential nutrients are present.
 Higher-order species, such as fish, are affected dramatically by
temperature and dissolved oxygen levels, which are function of
temperature.
 Temperature changes affect the reaction rates and solubility levels
of chemicals.
 Temperature also affects other physical properties of water such as
viscosity, density, etc.

61
(Cont…)
Drinking water specifications for physical water quality parameters
Permissible limit in the
Requirement
Parameter absence of alternate
(Acceptable limit)
source
Turbidity (NTU unit) 1 5
Colour (Hazen units) 5 15
Taste (FTN) Agreeable Agreeable
Odour (TON) Agreeable Agreeable
Total dissolved solids (mg/L) 500 2000
Source: IS 10500 : 2012

62
 Chemical water quality parameters
Chemical water quality parameter are as follows:

Total Dissolved Solids

pH

Alkalinity

Hardness

Dissolved Oxygen

Metals

Nutrients

Organics

63
 Total Dissolved Solids
• The material remaining in the water after filtration for the
suspended solids analysis is considered to be dissolved.

Sources

• Dissolved substances may be organic or inorganic in nature

• Inorganic substances - minerals, metals, and gases
• Organic substances - Materials from the decay products of
vegetation and from organic chemicals

Impacts
 Dissolved minerals, gases, and organic constituents may
produce aesthetically displeasing color, tastes, and odors.
 Dissolved solids can be toxic and carcinogen
 Objectionable by-products

64
 Total Dissolved Solids
Measurement
• A direct measurement can be done by gravimetric analysis.
• An approximate analysis for TDS is often made by determining
the electrical conductivity of the water.

• TDS (mg/L) = A × 𝐄𝐂 (𝛍𝐒/𝐜𝐦)

A = 0.55 to 0.90
(Depending on the ionic composition of water)

65
 Ion Balance
Common ions in natural waters

Major constituents Secondary constituents

(1.0 - 1000 mg/L) (0.01 - 10 mg/L)
Sodium Iron
Calcium Potassium
Magnesium Carbonate
Bicarbonate Nitrate
Sulfate Fluoride
Chloride Silica

As a check, the sum of the anions should equal the sum of the
cations because electroneutrality must be preserved. A significant
imbalance suggests that additional constituents are present or
that an error has been made in the analysis of one or more of the
ions.

66
 Equivalent Concept
 When ions or radicals react with each other to
form new compounds, the reactions may not
always proceed on a one-to-one basis.
 Compounds are formed by the combination of
elements or radicals on a one-to-one equivalent
basis.
 The equivalence of an element or radical is
defined as the number of hydrogen atoms that
element or radical can hold in combination or can
replace in a reaction.
 In most cases, the equivalence of an ion is the
same as the absolute value of its valence.

67
 Equivalent Concept
 An equivalent of an element or radical is its gram
molecular mass divided by its equivalence.
 A milliequivalent is the molecular mass expressed
in milligrams divided by the equivalence and is
often more useful in water chemistry because
concentrations of dissolved substances are more
often in the milligrams per liter range.
 Equivalents also provide a means of expressing
various constituents of dissolved solids in a
common term.
 An equivalent of one substance is chemically
equal to an equivalent of any other substance.
68
 Calculating equivalents
Example: How many grams of calcium will be required to combine with
90 g of carbonate to form calcium carbonate?

69
Determining equivalent concentrations
Example: What is the equivalent calcium carbonate concentration of
117 mg/L of NaCI?

70
Example of Routine Water Quality Analysis: Ion Balance and
Error Analysis

Problem Statement: Results are shown below from a routine

water quality analysis being run on a water sample -

Constituents Concentration Constituents Concentration

(mg/L) (mg/L)
Ca2+ 55.0 HCO3- 250.0
Mg2+ 18.0 SO42- 60.0
Na+ 98.0 Cl- 89.0
pH = 7.7

Perform the ion balance or charge balance based on the

analysis results and estimate the percent error induced in
the analysis. Also, construct a representative bar diagram of
the ion balance or charge balance.

71
Example of Routine Water Quality Analysis: Ion Balance and
Error Analysis

Solution: The ion balance or charge balance based on the

analysis results -
Cations Anions
Ion Conc. Eqv. Eqv. Conc. Ion Conc. Eqv. Eqv. Conc.
(mg/L) (mg/meq.) (meq./L) (mg/L) (mg/meq.) (meq./L)
Ca2+ 55.0 40/2 2.75 HCO3- 250.0 61/1 4.10

Mg2+ 18.0 24.3/2 1.48 SO42- 60.0 96/2 1.25

Na+ 98.0 23/1 4.26 Cl- 89.0 35.5/1 2.51

Total
8.49 7.86
Ions

Estimation of the percent error induced in the analysis:

(8.49 – 7.86) × 100 / 7.86 = 8% < 10% (Acceptable)

72
Example of Routine Water Quality Analysis: Ion Balance and
Error Analysis
Solution: The representative bar diagram of the ion balance or
charge balance -

Cations Anions
Ion Conc. Eqv. Eqv. Conc. Ion Conc. Eqv. Eqv. Conc.
(mg/L) (mg/meq.) (meq./L) (mg/L) (mg/meq.) (meq./L)
Ca2+ 55.0 40/2 2.75 HCO3- 250.0 61/1 4.10

Mg2+ 18.0 24.3/2 1.48 SO42- 60.0 96/2 1.25

Na+ 98.0 23/1 4.26 Cl- 89.0 35.5/1 2.51

Total
8.49 7.86
Ions

73
Practice problem: An analysis of water from a surface stream
yields the following results. If an error of 10 percent is
acceptable, should the analysis be considered complete?

Constituents
Ca2+ = 60 mg/L HCO3- = 115 mg/L
Mg2+ = 10 mg/L SO42- = 96 mg/L
Na+ = 7 mg/L Cl- = 11 mg/L
K+ = 20 mg/L NO3- = 10 mg/L

74
pH
 A pH is a measure to indicate the acidity or basicity of the water
sample. The range goes from 0 – 14.
pH = − 𝐥𝐨𝐠 [ 𝐇 + ]
pOH = − 𝐥𝐨𝐠 [ 𝐎𝐇 − ]
pH + pOH = 14

Measurement of pH
pH scale
• The pH scale measures the acidity or basicity of a solution. The pH scale ranges from 0 to
14. A pH of 7 is neutral. A pH less than 7 is acidic. A pH greater than 7 is basic.

• The acidic or basic/alkaline nature of a solution can be identified by measuring the pH

value. Pure water exists in a partially ionized state as depicted from the equation:

• H2O ↔ H+ + OH-

• Since a substance that produces hydrogen ions is known as acid and one that produces
hydroxyl ions is known as base, water may be classified as an acid and a base. The
presence of these ions is in the same quantity in pure water makes it neutral.
75
Importance of the pH of Drinking Water
 It alters the solubility and behavior of minerals and heavy
metals that water comes in contact with
 For instance, the pH of water may make certain elements in it,
such as minerals and metals, more or less available to the
body. Heavy metals in water with a lower pH tend to be more
toxic, as they are more available to the body. A high pH would
make heavy metals less available, and, therefore, less toxic.
 Water with a low pH may corrode metal pipes and extract
metal ions into the water, making it harmful to drink or use in
the home
 Aesthetic characteristics: At extreme levels, pH affects the
physical characteristics of water such as color, odor, turbidity,
or taste.
 Efficiency of disinfection: Chlorine is the most common water
disinfection agent in the world and pH impacts its
effectiveness.
76
Measurement of pH

pH indicator paper

pH strips with pH scale

77
(Cont…)
Potentiometer pH meter
 A potentiometer with calomel electrode  It is best suited for field measurements.
can be used for pH measurement.
 Buffer solutions having pH of 7, 4.01, 1.68,
10.01 can be used for calibration.

Buffer solution for

calibration

Potentiometer with calomel electrode Portable pH meter

78
(Cont…)
Electrometrical evaluation of pH is carried out using pH sensitive glass tip electrodes. As
the glass electrode is put in a solution having different pH from the solution’s pH inside the
electrode, an electrical potential is generated between the reference electrode and glass
electrode. This potential, which is proportional to the difference in pH, is estimated, and the
instrument gives an output corresponding to the pH of the sample.

79
Nutrients: Nitrogen
 Nitrogen forms found in water (expressed as mg-N/L):
 Dissolved gaseous N2
 Dissolved free (unionized) ammonia (NH3)
 Ionized ammonia (NH4+)
 Nitrite ion (NO2-)
 Nitrate ion (NO3-)
 Organic nitrogen
 In surface water samples, nitrogen is present mainly as nitrate
(NO3-), which is the most oxidized form of nitrogen
 In groundwater samples nitrogen may be present as both nitrate
(NO3-) and nitrite (NO2-)
 In raw wastewater samples, and in water contaminated with
domestic and industrial wastes, nitrogen is mainly present as
ammonical nitrogen (NH4+-N or NH3-N), and organic nitrogen (Org.-
N)
 Total Kjeldahl Nitrogen (TKN) = NH4+-N + Org.-N and expressed in
mg NH4+-N/L
 Depending on pH (at 9.3) of water system, free and ionized
ammonia are in equilibrium according to the following equation:
NH4+ → NH3 ↑ + H+ 80
Nutrients: Phosphorous
 Phosphorous is mainly found in water as soluble mineral
phosphate (H2PO4-, HPO42-, PO43-), soluble organic P and
particulate P. Organic P can be mineralized into soluble
mineral phosphate by bacteria.
 Sources of phosphorous in wastewater are: detergent,
fertilizer and animal waste
 Phosphorous in water/wastewater is expressed as mg
PO43--P/L
 Excessive amount of nutrients i.e. N and P in water leads
to algae formation → Algal bloom → Eutrophication

 Blue baby syndrome- Nitrate poisoning?

 Eutrophication- Phosphate pollution?
81
Heavy metals
 Heavy metals such as mercury (Hg), cadmium (Cd), arsenic (As),
chromium (Cr), etc. can be measured by following methods:
• Atomic Absorption Spectroscopy (AAS)
• Inductively Coupled Plasma Mass Spectroscopy (ICP-MS)

AAS ICP-MS 82
Cations and anions

83
Cations and anions: Ion chromatography

84
Alkalinity
 Alkalinity is defined as quantity of ions in water that will react to
neutralize H+ ions.
 Major constituents of alkalinity are:
• 𝐂𝐎𝟐−
𝟑 : Carbonate alkalinity
• 𝐇𝐂𝐎− 𝟑 : Bi-carbonate alkalinity
• 𝐎𝐇 : Caustic alkalinity
−

 Alkalinity is expressed in terms of mg/L as CaCO3

 The possible effects of alkalinity are as follows:
• Alkalinity adds bitter taste to water.
• It reacts with certain cations and forms precipitate.
• It can cause fouling of pipes and other appurtenances.

85
Measurement of alkalinity
Titration
 Alkalinity measurements are done by
titrating the water with an 0.02 N
H2SO4, thereby determining the
hydrogen equivalent of alkalinity.

Methyl
orange
indicator

If 0.02 N H2SO4 is used in the titration,

then 1 mL of acid will neutralize 1 mg of
alkalinity as CaCO3. 86
Determining total alkalinity
Example: A 200 mL sample of water has an initial pH of 10. Thirty milliliters
of 0.02 N H2S04 is required to titrate the sample to pH 4.5. What is the total
alkalinity of the water in milligrams per liter as CaCO3?

87
 Hardness
 Hardness is defined as ability of the water to destroy
the surfactant property of the soap.

 It is the sum of all polyvalent cations, mainly calcium

(Ca2+) and magnesium (Mg2+).

 The common units of expression are mg/L as CaCO3 or

milliequivalents per liter (meq/L).

88
Cont.…
 Two components of total hardness are:

 Carbonate hardness

 It is associated with the presence of carbonate (CO2−

3 )
and bicarbonate (HCO− 3 ) anions.

 Carbonate hardness is termed as temporary hardness as

it can be removed by boiling the water.

 Noncarbonate hardness

 It is associated with the presence of other anions such

−
as Cl− , SO2−
4 , and NO3 .

 Noncarbonate hardness is termed as permanent

hardness because it cannot be removed by boiling.
89
Cont…
 Hardwater can be classified as follows:

Hardness range
Description
(mg/L as CaCO3)

0–50 Extremely soft

50–100 Very soft

100–150 Soft to moderately hard

150–300 Hard

>300 Very hard

Reference: Garg, S.K. 1977. Environmental Engineering Water Supply
Engineering, Khanna Publishers, India, Vol.1, ISBN-10: 9788174091208
90
 Issues of Hard Water
 Soap consumption by hard waters represents an economic
loss to the water user.

 The precipitate formed by hardness and soap adheres to

surfaces of tubs, sinks, and dishwashers and may stain
clothing, dishes, and other items.

 Residues of the hardness-soap precipitate may remain in

the pores making the skin feel rough.

 Boiler scale, the result of the carbonate hardness

precipitate may cause fouling of water heaters and hot-
water pipes.

91
Cont…

Cloudy solution formed in hard water Fouling and staining of appurtenances

Scaling inside household

Incrustations in pipes 92
geysers
Measurement of hardness
Titration Pipette out 20 mL
of the field sample
 Hardness is water sample can Add 2 mL of
ammonia buffer
be measured by titrating the
water with EDTA.

Titrant:
Ethylenediaminetetraacetic acid
(EDTA) Fill the burette Add 2 drops of
with EDTA EBT indicator

Indicator:
Eriochrome Black T (EBT)

Continue the
titration till the
colour changes to
Titrate the
steel blue
contents against
EDTA solution
Calculate
the total
hardness

If 0.01 M EDTA is used in the titration,

then 1 mL of titrant measures 1 mg of
hardness as CaCO3. 93
Dissolved Oxygen (DO)
 Dissolved Oxygen (DO) concentration in natural waters is of great
importance as it is critical for the sustainability of aquatic ecosystems
 DO derives from atmosphere or oxygen-producing biological processes
(e.g., photosynthesis)
 The normal DO level of a healthy surface water body ranges from 8-10
mg/L, while the value for groundwater may be as low as 1-2 mg/L
 Reduction of DO values to less than 4 mg/L results in difficulties and even
death for aquatic animals
 Low DO values may indicate organic pollution and/or presence of
reduced species in the water bodies, resulting in DO depletion of the
water
 Following Henry’s Law, the rate of oxygen transfer in water is given by:

 K L aC S  C 
dC
dt
where, Cs = Saturated oxygen concentration, mg/L
C = Oxygen concentration at any time ‘t’, mg/L
KLa = Oxygen transfer rate coefficient, h-1
Cs – C = Dissolved oxygen deficit, mg/L 94
 Oxygen Demand
• It is a measure of the amount of organic and inorganic matter present
in water
• Relates to oxygen consumption in a river or lake as a result of a
pollution discharge
• Measured in several ways:
• Theoretical Oxygen Demand (ThOD)
• Chemical Oxygen Demand (COD)
• Biochemical Oxygen Demand (BOD)

95
Theoretical Oxygen Demand (ThOD)
Generalized balanced equation:
 a b 3  a 3 
C n H a Ob N c   n    c O2  nCO2    c  H 2 O  cNH 3
 4 2 4  2 2 
Example for Glucose:
C6H12O6 + 6O2 = 6CO2 + 6H2O
180 6×32

Oxygen Demand (OD)

6  M O2 6  32
  mg O2 / mg of Glu cos e  1.07mg O2 / mg of Glu cos e
M C6 H12O6 180
If glucose concentration in water is 360 mg/L, ThOD is:
1.07 × 360 mg/L = 385.2 mg/L

Practice for: Sucrose (C12H22O11), Acetic acid (CH3COOH), etc.

96
Theoretical Oxygen Demand (ThOD)
Generalized balanced equation:
 a b 3  a 3 
C n H a Ob N c   n    c O2  nCO2    c  H 2 O  cNH 3
 4 2 4  2 2 

97
Theoretical Oxygen Demand (ThOD)
Generalized balanced equation:
 a b 3  a 3 
C n H a Ob N c   n    c O2  nCO2    c  H 2 O  cNH 3
 4 2 4  2 2 

98
 Chemical Oxygen Demand (COD)
 COD value represents the amount of oxygen that will be
required to completely oxidize all organic matter in the sample
to CO2
 Measure of oxygen equivalent of the organic matter present in
the water sample that is susceptible to oxidation by a strong
chemical oxidant (acid + heat)
 Known (but excess) amount of Potassium dichromate
(K2Cr2O7), a strong oxidizing agent is added to the sample
under acidic conditions to find the amount of organic
compound in water sample
 Acidic condition is ensured by the addition of concentrated
sulphuric acid (H2SO4) in the presence of Ag2SO4 as catalyst
 The mixture is heated (digested) at 150±20C for 2 h
 COD is expressed in mg/L

99
 Biochemical Oxygen Demand (BOD)
• BOD is the amount of dissolved oxygen utilized by microbes for
the biochemical oxidation of organic (carbonaceous BOD) and
inorganic (nitrogenous BOD) matter
• BOD determination involves the measurement of the dissolved
oxygen (DO) used by microorganisms in the biochemical
oxidation of organic matter
• Biochemical oxidation is a slow process and theoretically takes
an infinite time for completion
• Within a 20-day period, the oxidation is about 95-99 percent
complete, and in the 5-day period used for the BOD test,
oxidation is 60-70 percent complete
• The five-day biochemical oxygen demand (BOD5) at 20oC is the
most widely used parameter for quantifying biodegradable
organic pollution, applied to both wastewater and surface
waters
• Five-day BOD at 20oC is equivalent to three-day BOD at 27oC
• BOD is expressed in mg/L
100
 Biochemical Oxygen Demand
y
NBOD
or

BOD
(mg/L) CBOD

Time

CARBONACEOUS NITROGENEOUS
OXYGEN DEMAND OXYGEN DEMAND BOD
(CBOD) (NBOD)

CBOD: NBOD:
COrg. + O2 CO2 + H2O NH3 NO2- NO3-
101
Nitrogenous BOD (NBOD)
 
NH3  15
. O2 
 NO  H2 O  H
Nitrosomonas
2

1
NO  O2  NO3
Nitrobacter
2
2
Complete Reaction:
 
NH 3  2O2 
 NO  H 2O  H 3

Oxygen Demand:
2 moles oxygen/mole of ammonia
i.e., 3.76 mg oxygen/mg ammonia

102
 Calculation of BOD5
BOD  DOi  DO f  D
DOi  DO f
BOD  OR
P
where:
DOi = initial dissolved O2 concentration
DOf = final or 5-day dissolved O2 concentration
P = volumetric fraction
D = dilution factor = 1/P
Example: 5 mL wastewater is added to a 300 mL BOD bottle and then
incubated for 5 days at 200C.
DOi = 8 mg/L DOf = 2 mg/L

P= 5 = 0.0167 D = 300/5 = 60
300

BOD5 = 8 – 2 = 360 mg/L

0.0167
103
 BOD Kinetics
 BOD5 only represents the oxygen consumed in 5 days and is about
60-70% of total BOD or ultimate BOD
 Total BOD or ultimate BOD or BOD at any time period can be
determined knowing the BOD kinetics
 Assumption: Organic matter utilization by the microorganisms is
first-order reaction i.e. rate at which organics utilized is
proportional to the amount available
 Mathematically, this can be expressed as:
dLt
 kLt (Note the –ve sign)
dt
where:
Lt = oxygen equivalent of the
organic matter at time ‘t’, mg/L
k = BOD reaction constant, d-1
104
 BOD Kinetics
 The equation can be rearranged and integrated as follows:

dLt
  k dt
Lt
Lt t
dLt
L Lt  k 0 dt
0

 Lt 
ln    kt
 L0 
 kt
Lt  L0 e
L0 = total oxygen equivalent of the organic matter at time 0 i.e. initially, mg/L
105
BOD Kinetics
 The oxygen equivalent remaining i.e. Lt is not the parameter of
primary importance
 However, the amount of oxygen used or consumed in the
degradation of organics i.e. BODt or yt is important and can be
found out from the Lt value
 Mathematically, the BOD exerted i.e. yt is:

y t  L0  Lt
 kt
y t  L0  L0 e

y t  L0 1  e  kt

 The value of yt approaches L0 asymptotically, indicating that
the total or ultimate BOD (yu or BODu) is equal to the initial
106
oxygen equivalent i.e. L0
 BOD Kinetics
 The final equation is:
 kt
BODt  yt  Lo (1  e )
 The value of BOD reaction constant i.e. k determines the
speed of the BOD reaction without influencing the magnitude
of BODu
 Values of k range from about 0.1 to 0.5 d-1 depending on the
nature of organic matter
 The value of k for any given organic compound is
temperature dependent and the change in k with
temperature can be approximated by the van’t Hoff-
Arrhenius model:

kT  k 20 T  200
(  1.047)
107
PROBLEM: The BOD5 measured for a wastewater sample is 500 mg/L. The
reaction rate constant for the sample was found to be 0.3 1/d. Determine the
ultimate carbonaceous BOD of this sample.

108
109
PROBLEM: A series of BOD tests were conducted in a lab with different
wastewater samples and the DO levels measured after 5 days were: Bottle A
= 5 mg/L, Bottle B = 1 mg/L, Bottle C = 0 mg/L, and Bottle D = 8 mg/L. All
samples were diluted by a factor of 1/100. Initial DO in all bottles was 8
mg/L. Are these results useful? If yes, determine the BOD5 in each bottle. If
the results are not useful, state the reasons. Hint: What are the criteria for
useful BOD5 results?

110
COD vs BOD
COD does not distinguish between biodegradable and non-
biodegradable organic matter whereas BOD only measures
biodegradable organic matter
COD is not specific to oxygen-consuming organics or
inorganic whereas BOD is specific to oxygen-consuming
organic or inorganic compounds
COD and BOD do not necessarily measure the same types of
oxygen consumption
COD determination requires less time (2-3 h) as compared to
BOD determination (5 d)

111
 Drinking water specifications for chemical water quality parameters

Permissible limit in the

Requirement
Parameter absence of alternate
(Acceptable limit)
source
pH 6.5-8.5 No relaxation
Total Hardness, mg/L (as
200 600
CaCO3)
Total alkalinity, mg/L (as
200 600
CaCO3)
Chlorides (as Cl− ), mg/L 250 1000
Sulphates (as SO2− 4 ), mg/L 200 400
Fluorides (as F − ), mg/L 1 1.5
Nitrates (as NO− 3 ), mg/L 45 No relaxation
Calcium (as Ca2+ ), mg/L 75 200
Iron (as Fe2+ ), mg/L 0.3 No relaxation
Manganese (as Mn), mg/L 0.1 0.3
Total arsenic (as As), mg/L 0.01 0.05
Total chromium (as Cr), mg/L 0.05 No relaxation
Lead (as Pb), mg/L 0.01 No relaxation
Source: IS 10500 : 2012 112
 Biological water quality parameters
Biological water quality parameter are as follows:

Bacteria

Protozoa

Helminth Coliforms
(Indicator organisms)
Algae

Virus

113
Microbes and methods for their identification and
quantification

114
 Biological water quality parameters
Selection of Microbiological Parameter(s): Indicator Organisms

In order to overcome the aforementioned difficulties, we use indicator

organisms which indicate the possible presence of pathogens. The
desirable properties of the indicator organisms are as follows:

• They should always be present along with the pathogens i.e. source of
pathogens and indicator organisms should be same.

• They should be present in large number compared to pathogenic

organisms.

• They should be easily measurable Time, resources (money) and skill.

• They should have same or more resistance to various water treatment

operations, particularly disinfection.

115
 Biological water quality parameters
 Indicator organisms
 An important biological indicator of water contamination is the group
of bacteria called coliforms.
 Water that has been recently contaminated with sewage will always
contain coliforms.
 A particular species of coliforms found in domestic sewage is
Escherichia coli or E. coli.
 It can be measured using techniques such as multiple-tube
fermentation and membrane filter method.

There are roughly 3

million of E. coli bacteria
in 100 mL volume of
untreated sewage.

116
 Measurement of coliforms
Multiple-tube fermentation
In this technique, replicate portions of the original sample are cultured to
determine the presence or absence of microorganisms in each portion. The
presence of bacteria is represented as most probable number (MPN)/100 mL.

117
MPN index for various combinations of positive results when
five tubes are used per dilution (10 mL, 1.0 mL, 0.1 mL)

118
Bacteriological Quality of Drinking Water

Source: IS 10500 : 2012 119

Thank You

120