CHAPTER 1

WATER QUALITY
Dr Nor Adila Ab Aziz
Prof Madya Dr Rafidah Hamdan
 Content
PART 1: INTRODUCTION TO WATER QUALITY
i) Beneficial Water Use
ii) Water Resources
iii)Definition
iv) Objectives
v) Water Quality Parameters

PART 2:INTERIM NATIONAL WATER QUALITY STANDARDS

PART 3: WATER QUALITY PARAMETERS

i) Physical (Suspended Solids, Turbidity and Temperature)
ii) Chemical (pH, Alkalinity, Hardness, Dissolved Oxygen (DO), Biochemical Oxygen
Demand (BOD), Chemical Oxygen Demand (COD), Nitrogen and Phosphorus)
iii) Microbiological (Total Coliforms, Fecal Coliforms, E.Coli, Macroinvertebrate
Bioindicator)

PART 4: SAMPLING (RIVER MONITORING)

PART 5: DO SAG CURVE

2
 PART 1
INTRODUCTION TO WATER QUALITY

3
Beneficial Water Uses

• Municipal Uses
• Agricultural Uses
• Industrial Uses
• Rural Uses

4
 Water Resources
1. Snow / Rain
2. Surface Water
i) Watershed
ii) Lake /River /Reservoir
3.Groundwater
- Sub-surface water, or groundwater, is fresh water located in
the pore space of soil and rocks.
- Flowing within aquifers below the water table.
4. Desalination
- saline water is converted to fresh water.

5
 Water Quality 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

6
Objective of Water Quality

To control the discharge of

pollutants so that water quality is
not degraded to an unacceptable
extent below the natural
background level

7
 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.

8
 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 used to find out if the quality water is good
enough for drinking water, recreation, irrigation
and aquatic life.

9
 TYPES OF WATER POLLUTION
POINT SOURCE
 pollution flowing from a single and identifiable
source such as discharge pipe from a factory,
roadway, or leaking underground storage tank

NON-POINT SOURCE
 pollution collected by rain falling over a larger
watershed which is then carried by runoff to a
nearby lake or stream, or by infiltration into the
groundwater
POINT SOURCE POLLUTION
POINT SOURCE POLLUTION
• Hazardous and toxic materials
from manufacturing and
industry discharged directly into
the water - usually through a
pipe or a leaky underground
tank
• Oil and gasoline
• Solvents (toxic liquids)
• Toxins and poisons
• Heavy metals (arsenic, lead,
mercury, etc.)
• 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

A HARDER PROBLEM TO SOLVE

THE CHANGING URBAN LANDSCAPE
• Changing the landscape
changes the amount of runoff
in a watershed
• NON-POINT SOURCE
POLLUTION 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
THE CHANGING RURAL LANDSCAPE
• MODERN FARMING IS A MAJOR
SOURCE OF NON-POINT SOURCE
POLLUTION
• Pesticides (bug killer) and
herbicides (weed killer) can wash
into nearby lakes and rivers
• Crop fields, especially after harvest,
can wash large amounts of dirt and
sediment into nearby lakes and
rivers
• Animal waste and manure can be a
source of nutrients and harmful
bacteria
• Fertilizer can be a source of
nutrients, such as nitrogen and
phosphorus, entering nearby lakes
and rivers leading to the serious
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
 PART 2
Interim National Water Quality
Standards (INWQS)

18
 Interim National Water
Quality Standards
• 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.
19
 Malaysia : Interim National Water Quality
Standard (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 Oxygen mg/L 7 5-7 5-7 5-9 5-9 -
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 Dissolve
mg/L 500 1000 - - 4000 -
Solid
Total Suspended
mg/L 25 50 50 150 300 300
Solid
oC Normal Normal
Temperature - - - -
+ 2 oC + 2 oC
Turbidity NTU 5 50 50 - - -
Count/ 5000 5000
Faecel Coliform** 10 100 400 -
100ml (20000)a (20000)a
Count/
Total Coliform 100 5000 5000 50000 50000 >50000
100ml
Source: Environmental Quality Report 2010
20
 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
mg/L <1 1-3 3-6 6-12 >12
Demand
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
21
Source: Environmental Quality Report 2010
 PART 3
WATER QUALITY
PARAMETERS

22
 Water Quality Parameters

1. Physical 2. Chemical
parameters
parameters

3. Biological
parameters

23
 Physical Parameters
• This parameters respond to the sense of
sight, touch, taste or smell

24
Solids

25
 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

27
 Determination of
Suspended Solids

28
Example 1
The following test were obtained for a wastewater 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), suspende 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 105oC = 1.5554 g
Mass of Whatman GF/C filter + residue after ignition at 550oC = 1.5476 g

29
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
30
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
31
• 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 (Nephlometric Turbidity Unit)
• Water that has high turbidity appears cloudy
/ opaque .
• High turbidity can cause increased of water
temperature and decreased DO
WHY???
32
 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
33
• 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
34
• 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
35
 CHEMICAL PARAMETERS
pH Hardness
Nitrogen &
Alkalinity Phosphorus

Biochemical Oxygen Chemical Oxygen

Demand (BOD) Demand (COD)

36
 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+]
[H+] = [H3O+]
pH=1 : [H+]=1 x 10-1 moles/liter (acidic)

37
pH

38
 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-]
Timberlake, Chemistry 7th Edition, page 332
acidic neutral basic
solution solution solution
 pH
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
40
 pH
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

41
42
 pH
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
= 0.794 mg/L

[OH-] = 10-9.9 mol/L

= 10-9.9 mol/L x g/mol (17) x 1000mg/1g
= 21.4 x 10-6 mg/L
43
 Hardness

- Stream water hardness is the total

concentration of cations, specifically
calcium (Ca2+ ),magnesium (Mg2+), iron
(Fe2+), manganese (Mn2+) in the water.
- Water rich in these cations 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
44
 Hardness

• 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).

45
 Hardness: Carbonate hardness
• Source: Combination of Ca and Mg 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.

46
Hardness: Carbonate hardness

Ca 2+ Mg 2+ + HCO3- CO32-

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

47
Hardness: Carbonate hardness

• Source: Combination of Ca and Mg

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.

48
Hardness: Noncarbonate hardness

• 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)

49
Hardness: Carbonate hardness

Ca 2+ Mg 2+ + Cl- SO42- NO3-

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

50
 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))

51
 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

52
 Hardness
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

53
 Hardness
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

54
 Hardness
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 CaCO3.

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

55
 Hardness
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

56
 Hardness
Example 3

From the water analysis below determine the total hardness of the water sample given the following water
composition;
Ca2+ = 95.2 mg/L HCO3 = 241.49 mg/L (50/(40/2))
2+ 2-
Mg = 13.44 mg/L SO4 = 53.77 mg/L
Na+ = 25.76 mg/L Cl- = 67.81 mg/L

Solution:
Ion mg/L as EW mg/L as EW CaCO3 =
ion CaCO3/ CaCO3 50 mg/meq
EW ion EW ion =
Atomic wt
Ca2+ 95.20 2.50 238.00 valence

Mg2+ 13.44 4.12 55.37 (50/(24.3/2))

Na+ 25.76 2.18 56.16
HCO3 241.46 0.82 198.00
(50/61)
SO4 2- 53.77 1.04 55.92
Cl- 67.81 1.41 95.61
(50/(96/2))
Total Hardness (TH) = 293.37 mg/L as CaCO3
Carbonate Hardness (CH) = 198.00 as CaCO3
Non-carbonate Hardness (NCN) = TH-CH = 95.37 mg/L as CaCO3
57
 Alkalinity
• Alkalinity is defined as the quantity of ions in water
that will react to neutralise hydrogen ions (H+).
Alkilinity is thus the measure of the ability of water to
neutralise 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+)
58
 Alkalinity
• 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.

59
 Alkalinity
Example 1
A sample of water having a pH of 7.2 has the
following concentrations 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.

60
 Alkalinity
Solution
Ion Conc. M.W. Eq. Wt. Conc. Conc.
n
mg/L mg/mole mg/meq meq/L mg/L as
CaCO3
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 0.510 25.7
K+ 7.0 39.1 1 39.1 0.179 8.95
HCO3- 110.0 61.0 1 61.0 1.800 90.2
SO42- 67.2 96.1 2 48.05 1.400 69.9
Cl- 11.0 35.5 1 35.5 0.031 15.5

61
 Alkalinity
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 CaCO3)
= (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
62
= 141 mg/L as CaCO3
 Alkalinity
• 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

63
 Alkalinity
Bar chart

64
 ThOD
(Theoretical oxygen demand )

Oxygen Demand

Measurements in form of
i) Biochemical oxygen demand
ii) Chemical oxygen demand
iii) Nitrogenous oxygen demand
65
 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 

66
 Oxygen Demand
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

67
 Oxygen Demand
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
68
 Oxygen Demand

Example 2
If concentration of glucose is 10 mg/L what is the
theoretical oxygen demand (amount of DO required?)

 mmol O  mg O 
  6 2
 32 2
 
 mg glucose   mmol glucose  mmol O 2   mg O 2
10    10.7
 L  180
mg glucose
 L
 mmol glucose 
 

69
 Biochemical Oxygen Demand
(BOD)
• 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

70
 Biochemical Oxygen Demand
(BOD)
• 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).
71
 Biochemical Oxygen Demand
(BOD)

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:
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
72
–
Biochemical Oxygen Demand
(BOD)
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
73
 Biochemical Oxygen Demand
(BOD): 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)?

BODt  L0 1  e kt   102 mg/L 
 ln 1  
k  158 mg/L 
BODt 5 day
1  e  kt
L0
k  0.21 day -1
 BODt 
ln 1    kt
 L0 
 50 mg/L 
 BODt   ln 1  
 ln 1   k  90 mg/L 
k  L0  8 day
t 74
 Biochemical Oxygen Demand
(BOD): BOD Rate Reaction

• Temperature dependence of BOD rate

reaction
! 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

75
 Biochemical Oxygen Demand
(BOD): 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?

 
k25  0.20 day -1 (1.056) 2520
k25  0.26 day -1


k10  0.20 day (1.135)
-1
 1020

k10  0.056 day -1

76
 Biochemical Oxygen Demand
(BOD): 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) 77
 Biochemical Oxygen Demand
(BOD): BOD Rate Reaction
a slope is defined by:
B = (k)2/3/6(Lo)1/3 ….(4)
y=(t/BOD) 1/3

a m=a/b = (k2/3/6Lo1/3)
b

C =(kLo)-1/3

x=t

• Recalled , y = c + mx
78
 Biochemical Oxygen Demand
(BOD): 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)

79
 Biochemical Oxygen Demand
(BOD)
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 125 200 220 230 237
(mg/L)
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
80
 Biochemical Oxygen Demand
(BOD)
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.

0.5
Y = (t/ BODt)1/3

0.4

0.3 Slope, B= (0.348-0.224)/(10-0)

=0.0125
0.2
A= 0.224
0.1
0
2 4 6 8 10 Time (t)

81
 Biochemical Oxygen Demand
(BOD)
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
82
 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).
83
 Chemical Oxygen Demand
(COD)
• 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).
84
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.
85
Nitrogenous Oxygen Demand

86
Nitrogenous Oxygen Demand
• 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 87
 Nitrogenous Oxygen Demand
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)

88
 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

89
 Nitrogen
• 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

90
Nitrogen Cycle in a Terrestrial Ecosystem with Major
Harmful Human Impacts
 Phosphorus
• 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

92
Phosphorus Cycle with Major Harmful
Human Impacts
• Nitrogen & Phosphorus global concern

Eutrophication
 BIOLOGICAL
PARAMETERS

Microbial Indicator

Macro-invertebrate indicators

95
 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.
- The most used indicator:
Microbial Origin Indicator for
indicator
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 96
E. coli Fecal of human and Freshwater recreational
 Microbial indicators

- Bacteria counting is a simple method to

examine the microbial status of a sample
Microbial Origin Indicator for
indicator
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

97
 Microbial indicators
Pathogenic Organisms
• Many organims that cause human or
animal diseases colonize the instinal 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
98
99
100
101
 Macro-invertebrate indicators

- Macroinvertebrate are useful and convenient

indicators of the ecological health of a waterbody
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.
102
Macroinvertebrata
104
 PART 4
WATER SAMPLING (RIVER
MONITORING)

105
 Sampling Preparations

• 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
106
 For documentation

• Pens/wax crayons
• Sample labels
• Field notebook
For on-site testing
• List of analyses to be performed on site

107
COLLECTION &PRESERVATION
OF WATER SAMPLES

Standard Methods for

the Examinations of
Water and Wastewater

108
 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:
– Collect from least to most contaminated sampling locations
– If sediment and water is being collected, collect water first to
minimize effects from suspended bed materials
– For shallow streams, start downstream and work upstream to
minimize sediment effects due to sampling disturbances
– If sampling at different depths, collect surface samples first and
then proceed deeper
– Always collect VOCs first, followed by SVOCs (e.g. pesticides,
PCBs, oil, etc.), then total metals, dissolved metals,
microbiological samples, and inorganic nonmetals
 Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques

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
 Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques

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)
 Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques

Sample Preservation and Storage

• Purpose – minimize physical, chemical and biological changes

• 3 approaches:
– Refrigeration
– Use of proper sample container
– Addition of preserving chemicals
 Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques

Sample Preservation and Storage

• Refrigeration is a universally accepted method to slow down loss

processes

• Container choice (material type and headspace) is critical to reduce

– Volatilization
– Adsorption
– Absorption
– Diffusion
– Photodegradation

• Addition of preservatives is critical to reduce losses due to chemical

reactions and bacterial degradation
 Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques

Sample Preservation and Storage

 Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques

Sample Preservation and Storage

• 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
 Environmental Sampling Techniques
General Guidelines of Environmental Sampling Techniques

Selection of Sample Containers

Water
• Glass vs. Plastics:
– Glass may leach boron and silica, metals may stick to walls
– Glass is generally used for organics and plastic for metals, inorganics
and physical properties
– For trace organics cap and liner should be made of inert materials
(teflon)

• Headspace vs. no Headspace:

– No headspace is allowed for VOC samples/DO
– 40 mL vial with a teflon-lined septum
– Oil and grease should only be half-filled in wide mouthed glass bottles

• Special containers:
– e.g. BOD/DO bottles and VOC vials
117
118
 PART 5
DO SAG CURVE

120
 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)

1. 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
2. As the amount of waste increase, the self purification capacity
can be exceeded, causing detrimental changes in plant and
animal life

121
Water purification system and DO sag curve

3. then, the stream losses its ability to clean itself and the DO level
DECREASES.
4. when the DO drops below 4 to 5 mg/L, most game fish will
have been driven out.
5. If the DO is completely removed, fish and other higher animals
are killed or driven
6. The water become blackish and foul smelling as the sewage and
dead animal life decompose under anaerobic condition (without
O2)

122
Dissolved Oxygen Depletion

(From: Environmental Science: A Global Concern, 3rd ed. by W.P

Cunningham and B.W. Saigo, WC Brown Publishers, © 1995)
123
Dissolved Oxygen Sag Curve

124
 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

125
 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
126
Selecting System Boundaries

127
 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)

128
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
129
 1. Determine Initial Conditions
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

130
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)

131
 2. Determine Re-aeration Rate
a. O’Connor-Dobbins correlation
1/ 2
3.9u
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
T  20
k r  k r , 20

where Θ = 1.024
132
Determine the Deoxygenation Rate
a. rate of deoxygenation = kdLt
where kd = deoxygenation rate coefficient
(day-1)
Lt = ultimate BOD remaining at
time (of travel downdstream) t
b. If kd (stream) = k (BOD test)
 kd t
Lt  L0e

and
rate of deoxygentation  kd L0e kd t
133
 3. Determine the Deoxygenation Rate

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
T  20
k r  k r , 20
where Θ = 1.135 (4-20ºC) or 1.056 (20-30ºC)

134
 4. DO as function of time
• Mass balance on moving element
dD
 kd Lt  kr D
dt
• Solution is

Dt  
k d La  kd t
kr  kd
  
e  e kr t  Da e  kr t

135
5. Calculate Critical time and DO
1  kr  k r  k d 
tc  ln  1  Da 
kr  kd  kd  kd La 

Dc 
kr  kd
e 
k d La  kd tc
e  k r tc

 Da e  k r tc

136
 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.

137
1. Determine Initial Conditions
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 138
1. Determine Initial Conditions
c. Initial ultimate BOD concentration
Qw Lw  Qr Lr
La 
Qw  Qr

La 
37 (28)  250 3.6
 6.75
mg
37  250 L

139
 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

140
 3. Determine the Deoxygenation Rate

• 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

141
5. Calculate Critical time (tc)
1  kr  k r  k d 
tc  ln  1  Da 
kr  kd  kd  kd 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

142
5. 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

143
5. Calculate DO critical (Doc)
(as asked)

DOc 
kr  kd
e 
k d La  kd tc

 e  kr tc  De kr tc

DOc 
0.616.75 0.611.07 0.761.07
e e  1.65e0.761.07
0.76  0.61
mg
DOc  2.85
L

144
6. Calculate DO deficit (Da) during
critical

Da  DOs  DOc
mg
D  8.5  2.83  5.67
L

145
 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 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.

146
END

147