Chapter 1 Sem 20192020 Updated 24.9.2019

Faculty of Civil & Environmental Engineering
ENVIRONMENTAL ENGINEERING
BFC32403
CHAPTER 1
WATER QUALITY
Topics on Water Quality (9
hours lecture)
1.1 Introduction to Water Quality

1.2 Interim National Water Quality Standards
1.3 Water Quality Parameters (Physical,
Chemical & Microbiology)
1.4 Sampling (River Monitoring)
1.5 DO Sag Curve
1.1 Introduction to Water
Quality
1.1.1 Beneficial Water Uses
 Municipal Uses
 Agricultural Uses
 Industrial Uses
 Rural Uses
Quality
1.1.2 Water Resources
 Snow / Rain
 Surface Water
i) Watershed
ii) Lake /River /Reservoir
 Groundwater
o Sub-surface water, or groundwater, is fresh water located in the pore
space of soil and rocks.
o Flowing within aquifers below the water table.
 Desalination
o Saline water is converted to fresh water.
Quality
1.1.3 Definition
Is the technical term that is based upon the characteristics of water in relation to
guideline values of what is suitable for human consumption and for all usual
domestic purpose.
1.1.4 Objective
To control the discharge of pollutants so that water quality is not degraded to an

unacceptable extent below the natural background level.
Quality
1.1.5 Water Quality Parameters
• Are the natural and man-made chemical, biological and microbiological

characteristics of rivers, lakes and groundwater.
• It provides important information about the health of a water body.
- Are the natural and man-made chemical, biological and microbiological
characteristics of rivers, lakes and groundwater.
- It provides important information about the health of a water body.
 Are used to find out if the quality water is good enough for drinking
water, recreation, irrigation and aquatic life.
Quality
Two types of water pollution:
POINT SOURCE NON-POINT SOURCE

 pollution flowing from a  pollution collected by rain
single and identifiable source falling over a larger watershed
such as discharge pipe from a which is then carried by
factory, roadway, or leaking runoff to a nearby lake or
underground storage tank stream, or by infiltration into
the groundwater
Point Source Pollution (PS)
Point Source Pollution (PS)
Hazardous and toxic materials from

manufacturing and industry
discharged directly into the water -
usually through a pipe or a leaky
underground tank
o Oil and gasoline
o Solvents (toxic liquids)
o Toxins and poisons
o Heavy metals (arsenic, lead,
mercury, etc.)
o THERMAL POLLUTION - heated
water causes the dissolved
oxygen (DO) content in a body
of water to decrease - can result
in fish kills
Non-Point Source Pollution (NPS)
A HARDER PROBLEM TO SOLVE

Non-Point Source Pollution - THE CHANGING URBAN LANDSCAPE
• Changing the landscape changes

the amount of runoff in a
watershed
• NON-POINT SOURCE
POLLUTION (NPS) is pollutants
being collected by rainwater
falling over a large watershed
and carried directly to a river,
lake or stream
• Gas, oil, chemicals, detergents
containing phosphorus, trash
and other pollutants collected
off driveways, roads and city
streets flow directly down drains
and storm sewers to a nearby
body of water untreated
Non-Point Source Pollution - THE CHANGING RURAL LANDSCAPE
MODERN FARMING IS A MAJOR SOURCE

OF NON-POINT SOURCE POLLUTION
o Pesticides (bug killer) and herbicides
(weed killer) can wash into nearby
lakes and rivers
o Crop fields, especially after harvest,
can wash large amounts of dirt and
sediment into nearby lakes and rivers
o Animal waste and manure can be a
source of nutrients and harmful
bacteria
o Fertilizer can be a source of nutrients,
such as nitrogen and phosphorus,
entering nearby lakes and rivers
leading to the serious problem of
EUTROPHICATION
BIGGER FARM = BIGGER PROBLEM
Non-Point Source Pollution - CONSTRUCTION & MINING
• Clear-cutting trees and plowing

a field to create a mining or
construction site can be a
major source of non-point
source pollutants
• Without the trees and the plants
in the field to hold the soil in
place, large amounts of dirt and
sediment can be discharged into a
nearby lake or stream
• Can be a source of toxic
chemicals, acids, or heavy metals
used in the construction or mining
process
1.2 Interim National Water Quality
Standards (INWQS)
 INWQS used for classification of rivers

or river segments based on 5 classes of
water quality.
 INWQS helps Department of

Environment (DOE) to identify problem
areas & develop appropriate strategies
for water quality management.
 It is important to maintain high quality

level for natural water.
 Therefore, the DOE has set up the

minimum quality standard that reflects
its beneficial uses.
Interim National Water Quality Standards (INWQS)
Parameter Classes
Unit
I IIA IIB III IV V
Ammoniacal
mg/L 0.1 0.3 0.3 0.9 2.7 >2.7
Nitrogen
Biochemical
mg/L 1 3 3 6 12 >12
Oxygen Demand
Chemical Oxygen
mg/L 10 25 35 50 100 >100
Demand
Dissolved
mg/L 7 5-7 5-7 5-9 5-9 -
Oxygen
pH - 6.5-8.5 6-9 6-9 5-9 5-9 -
Color TCU 15 150 150 - - -
Electrical
μS/cm 1000 1000 - - 6000 -
Conductivity*
Floatables - N N N - - -
Odor - N N N - - -
Salinity % 0.5 1 - - 2 -
Taste - N N N - - -
Total Dissolved
mg/L 500 1000 - - 4000 -
Solid
Total Suspended
mg/L 25 50 50 150 300 300
Solid
Normal Normal
Temperature C
o
- - - -
+ 2 oC + 2 oC
Turbidity NTU 5 50 50 - - -
Count/ 5000 5000
Fecal Coliform** 10 100 400 -
100ml (20000)a (20000)a
Count/
Total Coliform 100 5000 5000 50000 50000 >50000
100ml
Source: Environmental Quality Report 2010

Classification of Water Based on INWQS
Class
Parameter Unit
I II III IV V
Ammoniacal Nitrogen mg/L <0.1 0.1-0.3 0.3-0.9 0.9-2.7 >2.7
Biochemical Oxygen Demand
mg/L <1 1-3 3-6 6-12 >12
Chemical Oxygen Demand mg/L <10 10-25 25-50 50-100 >100
Dissolved oxygen mg/L >7 5-7 3-5 1-3 <1
pH - >7 6-7 5-6 <5 >5
Total Suspended Solid mg/L <25 25-50 50-150 150-300 >300
Water Classes and Uses

Class Uses
I Conservation of natural environment.
Water Supply I – Practically no treatment necessary.
Fishery I – Very sensitive aquatic species.
IIA Water Supply II – Conventional treatment required.
Fishery II – Sensitive aquatic species.
IIB Recreational use with body contact.
III Water Supply III – Extensive treatment required.
Fishery III – Common, of economic value and tolerant species; livestock
drinking.
IV Irrigation
V None of the above
Source: Environmental Quality Report 2010
1.3 Water Quality Parameters
1. Physical
parameters 2. Chemical
parameters
3. Biological
parameters
1.3.1 Physical Parameter
• This parameter responds to the sense of sight, touch, taste or smell
Solids
Temperature
Turbidity
1.3.1 Physical Parameter - SOLIDS
 Total Solid (TS) are the total of all solids in a water

sample. They include the total suspended solids, total
dissolved solids, and volatile suspended solids.
 Dissolved solids (DS) = calcium, chlorides, nitrate,

phosphorus, iron, sulfur, and other ions and particles
that will pass through a 2 micron filter.
 Suspended solids (SS) = silt, clay, plankton, algae, fine

organic debris, and other particulate matter that will
not pass through a 2-micron filter
Interrelationships
of solids
Determination of Suspended Solids
Example 1
The following test were conducted for a wastewater sample taken from a
headwork to a WTP. All the test were performed using sample size of 50 mL.
Determine the concentration of total solids (TS), total volatile solids (TVS),
suspended solids (SS), volatile suspended solids (VSS), total dissolved solids (TDS)
and volatile dissolved solids.
Data:
Tare mass of evaporating dish = 53.5433 g
Mass of evaporating dish + residue after evaporation at 105oC =53.5794 g
Mass of evaporating dish + residue after ignition at 550oC = 53.5625 g
Tare mass of Whatman GF/C filter after drying at 105oC = 1.5433 g
Mass of Whatman GF/C filter + residue after drying at 105 oC = 1.5554 g
Mass of Whatman GF/C filter + residue after ignition at 550 oC = 1.5476 g
Solution:
1) Determine total solids (TS)
TS = (mass of dish + residue, g)-(mass of dish, g)
sample size, Liter
TS = ((53.5794-53.5433) g)(103 mg/g) = 722 mg/L
0.050 L
2) Determine total volatile solids (TVS)
TVS = (mass of dish + residue, g)-(mass of dish + residue after ignition, g)
sample size, Liter
TVS = ((53.5794-53.5625) g)(103 mg/g) = 338 mg/L
0.050 L
3. Determine total suspended solids (TSS)

TS = (residue on filter after drying, g)-(tare mass of filter after drying, g)
sample size, Liter
TS = ((1.5554-1.5433) g)(103 mg/g) = 242 mg/L

0.050 L
4. Determine total volatile solids (TVS)

TVS = (residue on filter after drying, g)-(residue on filter after ignition, g)
sample size, Liter
TVS = ((1.5554-1.5476) g)(103 mg/g) = 156 mg/L

0.050 L
1.3.1 Physical Parameter - TURBIDITY
• Is a measure of the amount of particulate matter that is

suspended in water or the measurement of water
clarity.
• Measured by Turbidity meter.
• Unit-NTU (Nephelometric Turbidity Unit)
• Water that has high turbidity appears cloudy / opaque .
• High turbidity can cause increased of water temperature
and decreased DO
WHY???
1.3.1 Physical Parameter - TURBIDITY
It is because…
• More suspended particles will absorb more heat from
solar radiation than water molecules will. This heat is then
transferred to the surrounding water by conduction.
• Such particles (SS – clay, silt, finely divided organic
material, plankton) can also prevent sunlight from reaching
plants below surface hence decrease the rate of
photosynthesis. So, less O2 is produced by plant
1.3.1 Physical Parameter - TEMPERATURE
• It is a major factor in determining which species are present in the

stream
• Temperature will impacts:
(i) the rates of metabolism and growth of aquatic organism
(ii) rate of plant photosynthesis
(iii) solubility of O2 in water [0C, DO = 14.6 mg/l; 20C, DO = 9.1 mg/l]
(iv) organism’s sensitivity to disease, parasites and toxic materials
• Temperature affects rate of chemical and microbiological reactions
• The most suitable drinking waters are consistently cool and do not have
temperature fluctuations of more than a few degrees
• Groundwater and surface water from mountain area generally meet
these criteria
1.3.2 Chemical Parameter
pH Hardness
Alkalinity Nitrogen & Phosphorus
Chemical Oxygen
Demand (COD)
Biochemical Oxygen
Demand (BOD)
1.3.2 Chemical Parameter - pH
• affects chemical and biological reactions

• It is a measure of the concentration of hydrogen ions
[H+]
• The term pH was derived from the manner in which
the hydrogen ion concentration is calculated
pH= -log[H+]
pH=1 :
[H+]=1 x 10-1 moles/liter (acidic)
1.3.2 Chemical Parameter – pH Acid – Base Concentrations
10-1
pH = 3 pH = 11
concentration (moles/L)
H3O+ OH-
pH = 7
10-7
H3O+ OH-
OH- H3O+
10-14
[H3O+] > [OH-] [H3O+] = [OH-] [H3O+] < [OH-]
acidic neutral basic
Timberlake, Chemistry 7th Edition, page 332
solution solution solution
Example 1
Calculate the concentration of hydrogen ion (H+) for a water sample with pH of 10.
pH = -log [H+]
10 = -log [H+]
Therefore, [H+]= antilog -10
= 10-10 mol/liter
Example 2
Calculate the pH value of a water sample which has hydrogen ion concentration of 1 x 10 -6.4
mol/liter.
pH = -log [H+]
= -log (1 x 10-6.4)
= -[log 1 + log 10-6.4]
= -[0 + (-6.4)log 10]
= 6.4
Example 3
Find the hydrogen ion ( H+) concentration and the hydroxide ion (OH-)
concentration in tomato juice having a pH of 4.1. Prepare answer in unit
mol/L and mg/L
pH + pOH = 14
pH = -log [H+] pOH = 14-4.1 = 9.9
4.1 = -log [H+] pOH = -log [OH-]
Therefore, 9.9 = -log [OH-]
[H+] = antilog -4.1
= 10-4.1 mol/L Therefore,
[OH-] = antilog -9.9
= 10-9.9 mol/L
mol/L to mg/L
• H+ == atomic weight = 1 g/mol ( refer Periodic Table)
• OH- == atomic weight = 17 g/mol (refer Periodic Table)
• mol/L (conc. ) x g/mol (atomic weight) x 1000mg/1g = mg/L
---------------------------------------------------------------------------------------------------------------------------
Therefore,
[H+] = 10-4.1 mol/L

= 10-4.1 mol/L x g/mol (1) x 1000mg/1g
= 0.0794 mg/L
[OH-] = 10-9.9 mol/L

= 10-9.9 mol/L x g/mol (17) x 1000mg/1g
= 2.14 x 10-6 mg/L
1.3.2 Chemical Parameter - Hardness
 Stream water hardness is the total concentration of cation,

specifically calcium (Ca2+ ),magnesium (Mg2+), iron (Fe2+),
manganese (Mn2+) in the water.
 Water rich in these cation is said to be ‘hard’. Stream water
hardness reflects the geology of the catchment area.
 Sometimes it also provides a measure of the influence of
human activity
 For instance, acid mine drainage often results in the release
of iron into a stream. The iron produces extraordinarily high
hardness which is a useful water quality indicator.
 Hardness is a reflection of the amount of calcium and
magnesium entering the stream through the weathering of
rock such as limestone (CaCO3).
1.3.2 Chemical Parameter – Hardness (Carbonate hardness)
• Source: Combination of Ca2+ and Mg2+ ions with ions of CO32-, or

HCO3-.
• These carbonate components can be eliminated by softening
methods such as boiling, or by adding lime
• When the carbonate components settled then the water have
become soft water.
1.3.2 Chemical Parameter – Hardness (Carbonate hardness)
+
Ca 2 +
Mg 2 + -
HCO3 -
CO32
Ca(HCO3)2 CaCO3 Mg(HCO3)2 MgCO3

1.3.2 Chemical Parameter – Hardness (Non- Carbonate hardness)
+
Ca 2 +
Mg 2 -
Cl -
SO42 -
NO3
CaCl2 CaSO4 Ca(NO3)2 MgCl2 MgSO4 Mg(NO3)2
 Source: Combinations of Ca and Mg ions with ions of Cl-, SO42-, or NO3-.

 The non-carbonate ions cannot be eliminated by ordinary softening methods
as done on carbonate hardness.
 Usually elimination of non carbonate hardness is done chemically by adding
softening soda (soda ash or sodium carbonate)
1.3.2 Chemical Parameter – Hardness (Total hardness)
•Because calcium and magnesium predominate, it is often

convenient to define total hardness as the sum of Calcium
and Magnesium elements.
•Therefore Total Hardness as CaCO3 :

Total Hardness = Ca2+ + Mg2+
•Total hardness is measured in mg/L CaCO3:
mg/L material X = Conc. of X (mg/L)  (50 mg CaCO3/meq)
as CaCO3 (Equivalent wt of X (mg/meq))
1.3.2 Chemical Parameter – Hardness (Total hardness)
•Total hardness is broken down into two components:

(1) that associated with the HCO3- anion (carbonate
hardness, CH) and
(2) that associated with other anions (non-carbonate
hardness, CH).
Total hardness, then may also be defined as:

TH= CH + NCH
1.3.2 Chemical Parameter – Hardness
• Water hardness is stated in equivalent unit of CaCO3

• Hardness classification:
Hardness Concentration Range

(mg/L eq CaCO3)
Soft <50
Medium 50-150
Hard 150-300
Very Hard >300
Example 1
Find the equivalent weight (EW) of each of the following:

i) Ca2+, ii) CO32-, and iii) CaCO3.
Solution:
Equivalent weight was defined as
EW = [atomic or molecular weight] / [n] (valence)
units: grams/equivalent (g/eq) or milligrams/milliequivalent (mg/meq)
i) For calcium, n=2 (valence or oxidation state in water).

Atomic weight = 40.08 ( refer Periodic table)
Therefore the EW is then

EW of Ca2+ = 40.08/2 = 20.04 g/eq or mg/meq
ii) For carbonate ion (CO32-), the oxidation state of 2- is used for n since the
base CO32- can potentially accept 2H+. The molecular weight (MW) is 60.01.
Therefore,
EW of CO32- = 60.01/2 = 30 g/eq or mg/meq
iii) In CaCO3, n=2 since it would take 2H+ to replace the cation (Ca2+) to
form carbonic acid, H2CO3. The MW of CaCO3 is 100.
Therefore,
EW of CaCO3 = 100/2 = 50 g/eq or mg/meq
Example 2
A sample of groundwater has 100 mg/L of Ca2+ and 10 mg/L of

Mg2+. Express it hardness in unit of mg/L as CaCO 3.
Solution: Since;
mg/L of X = concentration of X (mg/L)  (50 mg CaCO3/meq)
as CaCO3 (equivalent weight of X (mg/meq))
1. Convert Ca2+ and Mg2+ to mg/L as CaCO3

Ca2+ : MW = 40, n=2, EW=40/2 = 20 g/eq or mg/meq
Mg2+ : MW = 24.3, n=2, EW=24.3/2 = 12.2 g/eq or mg/meq
2. Now, find the mg/L as CaCO3 of cations
Use formula;
mg/L of X = concentration of X (mg/L)  (50 mg CaCO3/meq)
as CaCO3 (equivalent weight of X (mg/meq))
=>Ca2+ = 100 x 50 = 250 mg/L as CaCO3

20
=>Mg2+ = 10 x 50 = 41 mg/L as CaCO3
12.2
Total Carbonate Hardness = Ca2+ + Mg2+
= 250 + 41
= 291 mg/L as CaCO3
Example 3
From the water analysis below determine the total hardness of the water sample given the following
water composition; (50/(40/2))
Ca2+ = 95.2 mg/L HCO3 = 241.49 mg/L

Mg2+ = 13.44 mg/L SO42- = 53.77 mg/L
Na+ = 25.76 mg/L Cl- = 67.81 mg/L Ion mg/L as EW CaCO3/ mg/L as CaCO3
ion EW ion
Solution: Ca2+ 95.20 2.50 238.00

EW CaCO3 = 50 mg/meq
Mg2+ 13.44 4.12 55.37
EW ion = Atomic wt
Na+ 25.76 2.18 56.16 (50/(24.3/2))
valence
HCO3 241.46 0.82 198.00
SO42- 53.77 1.04 55.92 (50/61)
Cl- 67.81 1.41 95.61
Total Hardness (TH) = 293.37 mg/L as CaCO3 (50/(96/2))

Carbonate Hardness (CH) = 198.00 as CaCO3
Non-carbonate Hardness (NCH) = TH-CH = 95.37 mg/L as CaCO3
1.3.2 Chemical Parameter – Alkalinity
• Alkalinity is defined as the quantity of ions in water that will

react to neutralize hydrogen ions (H+). Alkalinity is thus the
measure of the ability of water to neutralize acids.
• Therefore alkalinity is the buffer capacity of the water to
remain neutral.
• The carbonate species that contribute to alkalinity are:
• Hydroxyl ions (OH-), Carbonate ions (CO32-), Bicarbonate
ions (HCO3-),
Alkalinity (mol/L) = [HCO3-] + 2[CO32-] + [OH-] – [H+]
Alkalinity (mg/L as CaCO3) = (HCO3-) + (CO32-) + (OH-) – (H+)
• Is measured to determine the ability of a stream to resist changes in

pH.
• Alkalinity results from the dissolution of calcium carbonate (CaCO3)
from limestone bedrock which is eroded during the natural processes
of weathering
• Alkalinity values of 20-200 ppm are common in freshwater ecosystems.
Alkalinity levels below 10 ppm indicate poorly buffered streams.
• In large quantities, alkalinity imparts bitter taste to water.
• Reactions that can occur between alkaline water and certain ions
resulting in precipitation of solids which can foul pipes and other water
system appurtenances.
Example 1
A sample of water having a pH of 7.2 has the following concentration
of ions:
Ca2+ 40 mg/L Mg2+ 10 mg/L
Na+ 11.8 mg/L K+ 7.0 mg/L
HCO3- 110 mg/L SO42- 67.2 mg/L
Cl- 11 mg/L
Calculate the TH, CH, NCH, Alkalinity, and construct a bar chart of the
constituents.
Solution
1 2 3 4 5 6 7
Conc. M.W. Eq. Wt. Conc. Conc. of X
Ion
(mg/L) (mg/mole) n (mg/meq) (meq/L) mg/L as CaCO3
(3/4) (2/5) (6 x 50)

Ca2+ 40.0 40.1 2 20.05 1.995 99.8*
Mg2+ 10.0 24.3 2 12.15 0.823 41.2
Na+ 11.8 23.0 1 23.0 0.513 25.7
K+ 7.0 39.1 1 39.1 0.179 8.95
HCO3- 110.0 61.0 1 61.0 1.803 90.2
SO42- 67.2 96.1 2 48.05 1.398 69.9
Cl- 11.0 35.5 1 35.5 0.031 15.5
mg/L of X as CaCO3 = concentration of X (mg/L)  (50 mg

CaCO3/meq)
Sample Calculation:
Conc in meq/L ( refer to Ca2+)

meg/L = mg/L x meq/mg
= 40.0 /20.05
= 1.995
Concentration of Ca2+ in mg/L as CaCO3

= (Concentration in meq/L)*(Equivalent Weight of CaCO 3)
= (1.995 meq/L) X (50 mg/meq)
= 99.8 mg/L as CaCO3
Check Solution
(Cation) s = (Anion)s
175.6 = 175.6
Note: to within  10% mg/L as CaCO3
Total Hardness
=  of multivalent cations
= (Ca2+) + (Mg2+)
= 99.8 + 41.2
= 141 mg/L as CaCO3
•Alkalinity = (HCO32-) + (CO32-) + (OH-) - (H+)

Alkalinity  (HCO32-) = (1.80 x 10-3) eq/L
Alkalinity = (1.80 x 10-3 eq/L)(50 g/eq)(1000 mg/g)
= 90.1 mg/L as CaCO3
•Carbonate Hardness (the portion of the hardness

associated with carbonate or bicarbonate)
Alkalinity = 90.1 mg/L as CaCO3
TH = 141 mg/L as CaCO3
CH = 90.1 mg/L as CaCO3
(Note: if TH > Alk then CH = Alk; and NCH = 0)
•Non-carbonate Hardness
NCH = TH - CH = 141 - 90.1 = 50.9 mg/L as CaCO3
Bar chart
1.3.2 Chemical Parameter – Oxygen Demand
ThOD
(Theoretical oxygen demand )
Oxygen Demand
Measurements in form of
i) Biochemical oxygen demand
ii) Chemical oxygen demand
iii) Nitrogenous oxygen demand
ThOD – theoretical oxygen demand

(i) It is the amount of O2 required to oxidize
a substance to CO2 and H2O
(ii) Calculated by stoichiometry if the chemical
composition of the substance is known
(iii) The ThOD of X in mg/L
 Molecular weight of O 2 in grams 

  Amount of X in mg/L   
 MW of X in grams 
Example 1
Compute the ThOD of 108.75 mg/L of glucose (C6H12O6)
• STEPS:
(i) write balanced equation for the reaction
(ii) Compute the grams molecular weights of the reactants
(iii) Determine ThOD
The balanced equation for the reaction

C6H12O6 + 6O2  6CO2 + 6H2O
The molecular weights (grams , refer Periodic Table) of the reactants
Glucose: 6C=72, 12H=12, 6O=96, = 180
Oxygen : 6(2)O=192
Thus, it takes 192 of O2 to oxidize 180 g of glucose to CO2 and H2O.
The ThOD of 108.75 mg/L of glucose is
 192 g of O 2 
 108.75 mg/L of glucose   
 180 g of glucose 
 116 mg/L O 2
Example 2
If concentration of glucose is 10 mg/L what is the
theoretical oxygen demand (amount of DO required?)
  
  6 mmol O 2  32 mg O 2  
 mg glucose   mmol glucose  mmol O 2   mg O 2
 10    10.7
 L  mg glucose L
180 
 mmol glucose 
 
1.3.2 Chemical Parameter – Biochemical Oxygen Demand
 It is a measure of the quantity of oxygen used by microorganisms

(eg. aerobic bacteria) in the oxidation of organic matter.
 In other words: BOD measures the change in dissolved oxygen
concentration caused by the microorganisms as they degrade the
organic matter.
 High BOD is an indication of poor water quality
 The term “decomposable” may be interpreted as meaning that
the organic matter can serve as food for bacteria, and energy is
derived from its oxidation.
 The standard oxidation (or incubation) test period for BOD is 5
days at 20C or stated as a BOD5 and can be referred by using the
Standard Methods for the Examination for Water and Wastewater
(5210 B. 5- Day BOD Test).
• Take sample of waste; dilute with

oxygen saturated water; add nutrients
and microorganisms (for seeded BOD test)
• Measure dissolved oxygen (DO) levels over 5 days
• Temperature 20° C
• In dark (prevents algae from growing)
• Need at least 2 mg/L change in DO over 5 days
• Maximum allowable DO depletion over the test period is 5mg/L
Apply Eqn C to measure BOD5 for the sample

(unseeded BOD test).
BOD5 mg/L = Di – Df ( Eqn C)

P
Where
Di = initial DO ( mg/L)
Df = final DO (mg/L)
P = Volume of sample used / Total volume
Note for quality control of DO data:

1)DO in blanks should not deplete more than 0.2 mg/L
2)DO in sample should not less than 2 mg/L
3)Final DO in the samples should not less than 1 mg/L
A BOD measurement is to carried out for wastewater

sample.
The wastewater sample inserted to BOD bottle is 10 mL.
The 300 mL BOD bottle is filled up with dilution water.
Calculate the BOD5 for the wastewater by using the given data:
Concentration of DO (mg/L) Day 1 Day 5
7.5 5.0
Solution:
•
For each test bottle meeting the 2.0 mg/L minimum DO depletion
and the 1.0 mg/L residual DO, then the;
D1  D2
BOD5 , mg / L 
P
7 .5  5 .0

(10 / 300)
 75mg / L
Modeling BOD as a First-order Reaction
6
5
Conc. (mg/L)
4 Organic matter oxidized

3
2
1 Organic matter remaining
0
0 10 20 30
time (days)
Modeling BOD Reactions

Assume rate of decomposition of organic waste is proportional to
the waste that is left in the flask.
dLt
 - kLt
dt
where Lt  amount of oxygen demand left after time t
k  the BOD rate constant (time -1 )
Solving this equation yields :
Lt  Lo e  kt
where Lo is the ultimate carbonaceous oxygen demand
Ultimate BOD
6
L
5 Lo- Lt BOD exerted
Conc. (mg/L)
4 o
3
2 BODt
1 L
L remaining
0 t
0 10 20 30
time (days)
Ultimate Biochemical Oxygen Demand
Lt = amount of O2 demand left in sample at time, t

Lo = amount of O2 demand left initially (at time 0, no DO demand has
been exerted, so BOD = 0)
At any time, Lo = BODt + Lt

(that is the amount of DO demand used up and the amount of DO that could
be used up eventually)
Assuming that DO depletion is first order

BODt = Lo(1 - e-kt)
BOD Rate Reaction

Example 1
If the BOD5 of a waste is 102 mg/L and the BOD20
(corresponds to the ultimate BOD) is 158 mg/L, what is
k (base e)?

 kt
BOD t  L0 1  e   BOD t 
 ln 1  
BOD t  L 
1  e  kt k 0
L0 t
 BOD t   102 mg/L 
ln 1     kt  ln 1  
 L  158 mg/L
0
k  
5 day
k  0.21 day -1
BOD Rate Reaction

 Temperature dependence of BOD rate reaction
o As temperature increases, metabolism increases, utilization
of DO also increases
kT = k20T-20
 = 1.135 if T is between 4 - 20 oC
 = 1.056 if T is between 20 - 30 oC
BOD Rate Reaction

Example 1
The BOD rate constant, k, was determined empirically to be 0.20 days-1 at
20 oC.
What is k if the temperature of the water increases to 25 oC?
What is k if the temperature of the water decreases to 10 oC?
k 25   0.20 day -1 (1.056) 25 20

k 25  0.26 day -1
k10   0.20 day -1 (1.135)10 20
k10  0.056 day -1
BOD Rate Reaction

Graphical determination of BOD rate Constants
According to Thomas,
(1-e-kt) = kt (1+kt/6)-3
Therefore
BODt=Lo(1-e-kt)
BODt=Lo(kt)[1+(1/6)kt]-3 .....(1)
• By rearranging terms & taking the cube root of both sides, equation (1) can be transformed
to:
(t/BODt)1/3=(kLo)-1/3 + (k)2/3/6(Lo)1/3 (t) ....(2)
• A plot of (t/BODt)1/3 versus t is linear. The intercept is defined as:

A = (kLo)-1/3 ….(3)
BOD Rate Reaction

a slope is defined by:
B = (k)2/3/6(Lo)1/3 ….(4)
y=(t/BOD) 1/3
m=a/b = (k2/3/6Lo1/3)
a
b
A =(kLo)-1/3
x=t
• Recalled , y = c + mx
BOD Rate Reaction
• Solving Lo1/3 in Eq.(3) substituting into Eq. (4) and solving for k yields:
k= 6(B/A) …(5)
• Likewise, substituting Eq. (5) into Eq.(3) and solving for Lo yields:
Lo = 1/(6A2B) …(6)
Example 1
The following data were obtained from an experiment to determine the
BOD rate constant and ultimate BOD for an untreated wastewater:
Time (day) 2 4 6 8 10
BOD (mg/L) 125 200 220 230 237
Solution:
1. Calculate values of (t/BODt)1/3 for each day.
Time (day) 2 4 6 8 10
BOD (mg/L) 125 200 220 230 237
(t/BODt)1/3 0.252 0.271 0.301 0.326 0.348

2. Plot (t/BODt)1/3 versus t on graph paper and draw the line

of best fit by eye.
3. Determine the intercept (A) and slope (B) from the plot.
Y = (t/ BODt)1/3
0.5
0.4
Slope, B= (0.348-0.224)/(10-0)
0.3
=0.0125
0.2
A= 0.224
0.1
0
2 4 6 8 10 Time (t)
4. Calculate k and Lo using the following formula
k = 6 (B/A) Lo = 1/ 6(A)2(B)
k = 6(B/A)
= 6(0.0125/0.224)
= 0.335 / day
Lo = 1/(6A2B)
= 266 mg/L
1.3.2 Chemical Parameter – Chemical Oxygen Demand (COD)
• It is based on the fact that all organic compounds, with a few

exception, can be oxidized by the action of strong oxidizing agents
under acid condition (=Value usually about 1.25 times BOD)
• Chemical oxygen demand is to measure the oxygen requirement of a
sample that is likely to oxidation by strong chemical oxidant
( potassium dichromate).
• Organic matter in aqueous samples could be determined by oxidation
with dichromate.
• The amount of O2 that is chemically equivalent to the dichromate
consumed is defined as the COD of the sample.
• During the oxidation in which sample is heated with the known
excess of dichromate, organic matter is converted to carbon dioxide
and water while dichromate is reduced to Cr 3+.
• The excess dichromate is determined by means of an oxidation-
reduction titration with ferrous ammonium sulfate (FAS).
1.3.2 Chemical Parameter – Nitrogenous Oxygen Demand
 The total BOD of a wastewater is composed of two

components – a carbonaceous oxygen demand and
a nitrogenous oxygen demand.
 Traditionally, because of the slow growth rates of those
organisms (nitrosomonas and nitrobacter) that exert the
nitrogenous demand, it has been assumed that no
nitrogenous demand is exerted during the 5-day BOD5 test.
• Nitrification (2 step process)

2 NH3 + 3O2  2 NO2- + 2H+ + 2H2O (nitrosomonas)
2 NO2- + O2  2 NO3- (nitrobacter)
• Overall reaction:
NH3 + 2O2  NO3- + H+ + H2O
• Theoretical NBOD =
grams of oxygen used 4 x 16

  4.57 g O 2 /g N
grams of nitrogen oxidized 14
Untreated domestic wastewater

ultimate-CBOD = 250 - 350 mg/L
ultimate-NBOD = 70 - 230 mg/L
Ultimate NBOD  4.57 x TKN
TKN = is the sum of ammonia-nitrogen (NH3-N)
plus organic nitrogen ( protein and urea)
= 15 - 50 mg/L as N
(Total Kjeldahl Nitrogen = TKN)
1.3.2 Chemical Parameter – Nitrogen
 Nitrogen is often the limiting nutrient in ocean waters and some

streams
 Nitrogen can exist in numerous forms, but nitrate (NO3-), nitrite (NO2-),
ammonia (NH3) are most commonly measured
 Sources are primarily from fertilizers and acid deposition
 Human intervention in the nitrogen cycle
1. Additional NO and N2O in atmosphere from burning fossil fuels;
also causes acid rain
2. N2O to atmosphere from bacteria acting on fertilizers and
manure
3. Destruction of forest, grasslands, and wetlands
4. Add excess nitrates to bodies of water
5. Remove nitrogen from topsoil
Nitrogen Cycle in a Terrestrial Ecosystem with Major
Harmful Human Impacts
1.3.2 Chemical Parameter – Nitrogen
 Cycles through water, the earth’s crust, and living organisms

 Limiting factor for plant growth
 Impact of human activities
1. Clearing forests
2. Removing large amounts of phosphate from the earth to make fertilizers
3. Erosion leaches phosphates into streams
Phosphorus Cycle with Major Harmful
Human Impacts
Nitrogen & Phosphorus global concern
Eutrophication
1.3.3 Biological Parameter
Microbial Indicator
Macro-invertebrate indicators
1.3.3 Biological Parameter – Microbial indicators
 Microorganisms can be used as indicators of the presence of

pathogens or infectious agent that cause illness to aquatic or
terrestrial ecosystem health.
 Bacteria counting is a simple method to examine the microbial
status of a sample
 The most used indicator:
Microbial indicator Origin Indicator for
Total coliforms Soil, plant Finished drinking water
Fecal coliforms fecal Recreational water
Class 1: Primary contact recreational
200 cf/ 100 mL
Class 1: Secondary contact recreational
2000 cf/100 mL
E. coli Fecal of human and Freshwater recreational

warm-blood animal
Pathogenic Organisms
 Many organisms that cause human or animal diseases 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 organisms in very large numbers
 When water is contaminated by excreta, the organisms can be
transmitted to those who contact the water
1.3.3 Biological Parameter – Macro-invertebrate indicators
 Macroinvertebrate are useful and convenient

indicators of the ecological health of a water body or
river. They are almost always present, and are easy
to sample and identify
 Benthic refers to the bottom of a waterway. Example

of benthic macro-invertebrates include insects in
their larval or nymph form, crayfish, claims, snails
and worms.
 Most live part or most of their life cycle attached to

submerged rocks, logs and vegetation.
1.4 Water Sampling (River
Monitoring)
Why we sample??
• To verify compliance for INWQS, to classify the water body

1.4 Water Sampling (River Monitoring)
Sampling Preparation
 Sample bottles, preservatives, labels and marker pens

 Sample storage/transit containers and ice packs
 Filtering apparatus (if required)
 Samplers/sampling equipment
 Rubber boots, waders, etc.
 Standard operating procedures for sampling
 Spares of all above items if possible and when appropriate
Documentation
 Pens/wax crayons
 Sample labels
 Field notebook
 For on-site testing
 List of analyses to be performed on site
Collection &Preservation Of Water Samples
Standard Methods for the

Examinations of Water and
Wastewater
Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques
Sequence of Sampling Matrices and Analytes
Project deals with multimedia and/or multiple parameters use following sequence:
o Collect from least to most contaminated sampling locations
o If sediment and water is being collected, collect water first to minimize effects
from suspended bed materials
o For shallow streams, start downstream and work upstream to minimize
sediment effects due to sampling disturbances
o If sampling at different depths, collect surface samples first and then proceed
deeper
o Always collect VOCs first, followed by SVOCs (e.g. pesticides, PCBs, oil, etc.),
then total metals, dissolved metals, microbiological samples, and inorganic
nonmetals
Sample Amount
 Minimum sample required depends on the concentration of the

analytes present
 Should take enough for all analyses and additional for any QA/QC
work required
 Heterogeneous samples generally require larger amounts to be
representative of sample variations
 Taking too much sample can lead to problems with storage and
transportation
Sample Amount - Water
• 5 mL for total petroleum hydrocarbons (TPHs), 100 mL for metals, 1 L

for trace organics (pesticides)
• As a general rule the minimum volume collected should be 3-4 times
the amount required for analysis (EPA, 1995)
Sample Preservation and Storage
 Purpose – minimize physical, chemical and biological changes

 3 approaches:
o Refrigeration
o Use of proper sample container
o Addition of preserving chemicals
Refrigeration is a universally accepted method to slow down loss processes
Container choice (material type and headspace) is critical to reduce

o Volatilization
o Adsorption
o Absorption
o Diffusion
o Photodegradation
Addition of preservatives is critical to reduce losses due to chemical

reactions and bacterial degradation

• Maximum Holding Time (MHT) is the length of time a sample can

be stored after collection and prior to analysis
• Immediate: pH, temperature, salinity, DO
• Within 1-2 days: careful pre-planning is required to avoid
sampling on Friday, Saturday or near holidays
Selection of Sample Containers
Water
 Glass vs. Plastics:
o Glass may leach boron and silica, metals may stick to walls
o Glass is generally used for organics and plastic for metals, inorganics and physical
properties
o For trace organics cap and liner should be made of inert materials (teflon)
 Headspace vs. no Headspace:

o No headspace is allowed for VOC samples/DO
o 40 mL vial with a teflon-lined septum
o Oil and grease should only be half-filled in wide mouthed
glass bottles
 Special containers:
o e.g. BOD/DO bottles and VOC vials
PART 5
DO SAG CURVE
112
Water purification system and DO sag curve
 The concentration of DO in river is an indicator of the general health of the river.

 All river have CAPACITY for water purification (self purification)
o As long as the discharge of oxygen demanding wastes is well within the self
purification capacity, the DO level remain HIGH and a diverse population of
plants and animals
o As the amount of waste increase, the self purification capacity can be
exceeded, causing detrimental changes in plant and animal life
o then, the stream losses its ability to clean itself and the DO level DECREASES.
o when the DO drops below 4 to 5 mg/L, most game fish will have been driven
out.
o If the DO is completely removed, fish and other higher animals are killed or
driven
o The water become blackish and foul smelling as the sewage and dead animal
life decompose under anaerobic condition (without O₂)
Dissolved Oxygen Depletion
(From: Environmental Science: A Global Concern, 3rd ed. by W.P Cunningham and B.W. Saigo, WC
Brown Publishers, © 1995)
Dissolved Oxygen Sag Curve
Mass Balance Approach
• Originally developed by H.W. Streeter and E.B. Phelps in 1925

• River described as “plug-flow reactor”
• Mass balance is simplified by selection of system boundaries
• Oxygen is depleted by BOD exertion
• Oxygen is gained through reaeration
Steps in Developing the DO Sag Curve
1. Determine the initial conditions

2. Determine the reaeration rate from stream
geometry
3. Determine the deoxygenation rate from BOD
test and stream geometry
4. Calculate the DO deficit as a function of time
5. Calculate the time and deficit at the critical
point
Selecting System Boundaries
Initial Mixing
Qw = waste flow (m3/s)

DOw = DO in waste (mg/L)
Lw = BOD in waste (mg/L)
Qr = river flow (m3/s) Qmix = combined flow (m3/s)

DOr = DO in river (mg/L) DO = mixed DO (mg/L)
Lr = BOD in river (mg/L) La = mixed BOD (mg/L)
1. Determine Initial Conditions

a. Initial dissolved oxygen concentration
Qw DOw  Qr DOr
DO 
Qw  Qr
b. Initial dissolved oxygen deficit
Da  DOs  DO
where D = DO deficit (mg/L)
DOs = saturation DO conc. (mg/L)
Qw DOw  Qr DOr
D  DOs 
Qmix
DOsat is a function of temperature. Values can be found

in Table A-3.
c. Initial ultimate BOD concentration
Qw Lw  Qr Lr
La 
Qw  Qr
Table A-3: Saturation values of DO in freshwater exposed to
saturated atmosphere containing 20.9% O2 under a pressure of
101.325kPa (Davis & Cornwell, 2013)
2. Determine Re-aeration Rate

a. O’Connor-Dobbins correlation
3.9u1/ 2
kr  3/ 2
h
where kr = reaeration coefficient @ 20ºC (day-1)
u = average stream velocity (m/s)
h = average stream depth (m)
b. Correct rate coefficient for stream temperature

k r  k r , 20T  20
where Θ = 1.024
3. Determine the Deoxygenation Rate
a. rate of deoxygenation = kdLt

where kd = deoxygenation rate coefficient (day-1)
Lt = ultimate BOD remaining at time (of travel
downstream) t
b. If kd (stream) = k (BOD test)
Lt  L0 e  k d t
and
 kd t
rate of deoxygentation  k d L0 e
c. However, k = kd only for deep, slow moving streams. For others,

u
kd  k  
h
where η = bed activity coefficient (0.1 – 0.6)
d. Correct for temperature
k r  k r , 20T  20
where Θ = 1.135 (4-20ºC) or 1.056 (20-30ºC)
4. DO as function of time
• Mass balance on moving element

dD
 k d Lt  k r D
dt
• Solution is
Dt  
k d La  kd t
kr  kd
 
e  e  kr t  Da e  kr t 
5. Calculate Critical time and DO
1  kr  k r  k d 
tc  ln  1  Da 
kr  kd  kd  k d La 
Dc 
kr  kd
e 
k d La  k d tc

 e  k r tc  Da e  k r tc
Example
A discharges 37.0 cfs of treated sewage having an ultimate BOD of
28.0 mg/L and 1.8 mg/L DO into a river with a flow of 250 cfs and
velocity of 1.2 ft/s. Upstream of the discharge point, the river has a
BOD of 3.6 mg/L and a DO of 7.6 mg/L. Determine the critical DO and
critical distance, and
Given :
The saturation DO (DOs) = 8.5 mg/L,
kd = 0.61 day-1,
kr = 0.76 day-1.
a. Initial dissolved oxygen concentration

Qw DOw  Qr DOr
DO 
Qw  Qr
DO 
 37 1.8   250 7.6  6.85 mg
37  250 L
b. Initial dissolved oxygen deficit
Da  DOs  DO
mg
Da  8.50  6.85  1.65
L
c. Initial ultimate BOD concentration

Qw Lw  Qr Lr
La 
Qw  Qr
La 
 37  (28)   250  3.6 
 6.75
mg
37  250 L
2. Determine Re-aeration Rate
• kr = 0.76 day-1 given
• no need to calculate from stream geometry
• assume given value is at the stream temperature (since not
otherwise specified), so no need to correct

• kd = 0.61 day-1 given
• no need to calculate corrections from stream geometry
• assume given value is at the stream temperature (since not
otherwise specified), so no need to correct
4. Calculate Critical time (tc)
1  kr  k r  k d 
tc  ln  1  Da 
kr  kd  kd  k d La 
1  0.76  0.76  0.61 

tc  ln  1  1.65 
0.76  0.61  0.61   0.61 6.75 
tc  1.07 day
4. Calculate critical distance (as asked)

 ft  s  hr  1 mi 
xc  1.07 d 1.2  3600  24  
 s  hr  d  5280 ft 
xc  20.9 mi
5. Calculate DO critical (Doc) (as asked)

DOc  d a  e  k d tc  e  k r tc   De k r tc
k L
kr  kd
DOc 
 0.61 6.75  0.61 1.07 
e  e  0.76  1.07    1.65e  0.76  1.07 
0.76  0.61
mg
DOc  2.85
L
6. Calculate DO deficit (Da) during critical

Da  DOs  DOc
mg
D  8.5  2.83  5.67
L
Try this!!
1.The town of State College discharges 17,630m3/d of treated wastewater into
the Bald Eagle Creek. The treated wastewater has a BOD5 of 12 mg/L and a k of
0.12d-1 at 20C. Bald Eagle creek has a flow rate of 0.43 m3/s and an ultimate
BOD of 5.0 mg/L. the DO of the river is 6.5 mg/L and the DO of the wastewater
is 1.0 mg/L. the stream temperature is 10C and the wastewater temperature
is 10C. Compute the DO and initial ultimate BOD after mixing.
2.Calculate the initial deficit of the Bald Eagle Creek after mixing with the
wastewater from the town of State College. The stream temperature is 10C
and the wastewater temperature is 10C.
3.Determine the deoxygenation rate constant for the reach of Bald Eagle Creek
below the wastewater outfall (discharge pipe). The average speed of the
stream flow in the creek is 0.03 m/s. the depth is 5.0 m and the bed-activity
coefficient is 0.35.
4.Determine the DO concentration at a point 5km downstream from the State
College discharge into the Bald Eagle Creek. Also determine the critical DO and
the distance downstream at which it occurs.

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Faculty of Civil & Environmental Engineering

1.1 Introduction to Water Quality

To control the discharge of pollutants so that water quality is not degraded to an

• Are the natural and man-made chemical, biological and microbiological

POINT SOURCE NON-POINT SOURCE

Hazardous and toxic materials from

A HARDER PROBLEM TO SOLVE

• Changing the landscape changes

MODERN FARMING IS A MAJOR SOURCE

• Clear-cutting trees and plowing

 INWQS used for classification of rivers

 INWQS helps Department of

 It is important to maintain high quality

 Therefore, the DOE has set up the

Source: Environmental Quality Report 2010

Water Classes and Uses

• This parameter responds to the sense of sight, touch, taste or smell

 Total Solid (TS) are the total of all solids in a water

 Dissolved solids (DS) = calcium, chlorides, nitrate,

 Suspended solids (SS) = silt, clay, plankton, algae, fine

3. Determine total suspended solids (TSS)

TS = ((1.5554-1.5433) g)(103 mg/g) = 242 mg/L

4. Determine total volatile solids (TVS)

TVS = ((1.5554-1.5476) g)(103 mg/g) = 156 mg/L

• Is a measure of the amount of particulate matter that is

• It is a major factor in determining which species are present in the

Alkalinity Nitrogen & Phosphorus

• affects chemical and biological reactions

[H+] = 10-4.1 mol/L

[OH-] = 10-9.9 mol/L

 Stream water hardness is the total concentration of cation,

• Source: Combination of Ca2+ and Mg2+ ions with ions of CO32-, or

Ca(HCO3)2 CaCO3 Mg(HCO3)2 MgCO3

CaCl2 CaSO4 Ca(NO3)2 MgCl2 MgSO4 Mg(NO3)2

 Source: Combinations of Ca and Mg ions with ions of Cl-, SO42-, or NO3-.

•Because calcium and magnesium predominate, it is often

•Therefore Total Hardness as CaCO3 :

•Total hardness is broken down into two components:

Total hardness, then may also be defined as:

• Water hardness is stated in equivalent unit of CaCO3

Hardness Concentration Range

Find the equivalent weight (EW) of each of the following:

i) For calcium, n=2 (valence or oxidation state in water).

Therefore the EW is then

A sample of groundwater has 100 mg/L of Ca2+ and 10 mg/L of

1. Convert Ca2+ and Mg2+ to mg/L as CaCO3

2. Now, find the mg/L as CaCO3 of cations

=>Ca2+ = 100 x 50 = 250 mg/L as CaCO3

Ca2+ = 95.2 mg/L HCO3 = 241.49 mg/L

Solution: Ca2+ 95.20 2.50 238.00

SO42- 53.77 1.04 55.92 (50/61)

Cl- 67.81 1.41 95.61

Total Hardness (TH) = 293.37 mg/L as CaCO3 (50/(96/2))

• Alkalinity is defined as the quantity of ions in water that will

• Is measured to determine the ability of a stream to resist changes in

(3/4) (2/5) (6 x 50)

Mg2+ 10.0 24.3 2 12.15 0.823 41.2

Na+ 11.8 23.0 1 23.0 0.513 25.7

K+ 7.0 39.1 1 39.1 0.179 8.95

HCO3- 110.0 61.0 1 61.0 1.803 90.2

SO42- 67.2 96.1 2 48.05 1.398 69.9

Cl- 11.0 35.5 1 35.5 0.031 15.5

mg/L of X as CaCO3 = concentration of X (mg/L)  (50 mg