UEMX3653 Water and Wastewater Treatment

Topic 5.1: Chemical Treatment

Processes
Dr. Lee Khia Min
Department of Civil Engineering

Objectives

Review some basic concepts of the chemistry

involve in chemical treatment processes.

To discuss types of chemical processes and their

roles within treatment systems.

Inorganic Chemicals and Compounds

Valence the combining power of an element relative to that of

the hydrogen atom which has an assigned value of 1.

An element with a valence of 2+ can replace two hydrogen atoms in a

compound.

An element with a valence of 2- can react with two hydrogen atoms.

Equivalent or combining weight of an element is equal to its

atomic weight divided by the valence.

For example, the EW of calcium equals 40 g divided by 2, or 20 g.

Equivalent weight of a molecule is equal to its molecular

weight divided by the number of positive or negative electrical
charges.

For example, the EW of sulfuric acid equals 98.1 g divided by 2, or 49 g.

3

Units of Expression

mg/g

ppm

%1

1 mg/L = 8.34 lb/million gal

Units of Expression
(mg/L as CaCO3)
The

concentration given in milligrams of

weight may not relate to specific element
whose concentration is being expressed.

Hardness: Ca2+ and Mg2+

Alkalinity: OH-, CO32-, and HCO3-

The common units is given in mg/L as CaCO3.

Ammonia,

nitrate, and organic nitrogen

expressed as mg/L as N.

Phosphates

expressed as mg/L as P.

Units of Expression (meq/L)

The term milliequivalents per liter (meq/L) expresses

the concentration of a dissolved substance in terms of its
electrical charge or its combination in reaction.
Milliequivalents are calculated from milligrams per liter
for elemental ions by the following equation:
valence
mg/L
meq/L mg/L

atomic weight
EW

and for radicals or compounds by the following equation:

electrical charge mg/L
meq/L mg/L

molecular weight
EW

Milliequivalents-per-Liter Bar Graph

For better visualization of the chemical composition, meq/L bar graph is

used.
The top row consists of major cations arranged in the order of Ca 2+, Mg2+,
Na+, K+. Anions in the bottom row are aligned in the sequence of carbonate
(if present), bicarbonate, sulfate, and chloride.
The sum of the positive meq/L must equal the sum of the negative meq/L.
Hypothetical combinations of + and ions can be written from a bar
graph, and are useful in evaluating a water for lime-soda ash softening.

10

11

Example 11.2

The results of a water analysis are Ca 40 mg/L, Mg 10

mg/L, Na 11.7 mg/L, K 7 mg/:, HCO3- 110 mg/L, SO42- 6.2
mg/L, and Cl- 11 mg/L. Draw a meq/L bar graph and
express the hardness and alkalinity in units of mg/L as
CaCO3.

Answer:
Hardness = 141 mg/L
Alkalinity = 90 mg/L

12

13

Alkalinity and pH Relationships

14

Coagulation

15

Definitions
Coagulation

is

The

addition and rapid mixing of coagulants

The

destabilization of colloidal and fine particles

The

initial aggregation of destabilized particles

Flocculation

is

The

gentle agitation to aggregate destabilized

particles to form rapid-settling floc

16

Colloidal Characteristics

What are colloidal particles

1nm

10-8 10-7
Molecules
ions

1m
10-6 10-5
colloids

10-4

10-3
silt

10-2

10-1
sand

cm

Colloids
Have

particle size between 0.001 to 1.0 micron

Colloids do not settle by the force of gravity

Are stable in suspensions because

Extremely small size

State of hydration (chemical combination with water)

Surface electrical charge

17

Colloidal Characteristics

Have large surface area per unit volume

surface phenomena such as electrostatic repulsion
and hydration become important.

Adsorb substances from surrounding water.

Have electrostatic charge (mostly negatively

charged).

Can be hydrophilic (organic colloids) or hydrophobic

(inorganic colloids).

Attract ions of opposite charge to its surface (fixed

layer and diffused layer).
18

Coagulation Theory

Colloid particles are in constant motion in

water and tend to collide each other.
Forces on the colloid

Electrostatic repulsive forces

When the two particles collide

F12 k

q1q2
q1q2

k
R2
(r1 r2 ) 2

Attractive force: Van der Waals force

19

Attractive

Energy/Force

Repulsive

Coagulation Theory Force

between particles
Electrostatic force ~ 1/r2,
Repulsive
Net force
Energy barrier

Van der Waals force ~ 1/r

Distance
20

Stabilization/Destabilization

Destablization of hydrophobic colloids can be

accomplished by double layer compression, charge
neutralization, enmeshment, and interparticle bridging.

1.

Adding electrolytes into the solution (Figure 11.10b)

destablizes colloids by double layer compression.
Counterions of the electrolyte suppress the double-layer
charge of the colloids to permit particles to contact due to
excession van der Waals forces.

2.

Charged species adsorb to (attach to the surface of) of the

colloid and reduce the surface charge (Figure 11.11a).
Trivalent metals hydrolyze in water to produce hydroxo
complexes that carry positive charge and have an affinity to
attach to negatively charged colloids, thereby reducing overall
colloidal charge and resulting in aggregation.
21

Stabilization/Destabilization

A colloidal suspension is stable when the dispersion shows little

or no tendency to aggregate (Figure 11.10a).

The repulsive force disperses particle and prevents aggregation.

Particles with a high zeta potential produce a stable sol.

Factors tending to destabilize a sol are van der Waals forces of

attraction and Brownian movement.

Van der Waals are the molecular cohesive forces of attraction

that increase in intensity as particle approach each other.

Brownian motion is the random motion of colloids caused by their

bombardment by molecules of the dispersion medium. This
motion has a destabilizing effect on a sol because aggregation
may result.
22

Figure 11. 10 Schematic representations of coagulation and bridging of

colloids. (a) A stable suspension of particle where forces of repulsion
exceeds forces of attraction. (b) Destablization and coagulation
23
caused by counterions of a coagulant suppressing the double-layer

Stabilization/Destabilization
3.

At particular pH conditions and high enough Al or Fe

concentrations, the metal will precipitate. Colloids
tend to adsorb to these solids and become
enmeshed in the resulting solid (Figure 11.11b). This
mechanism is called sweep floc coagulation.

4.

Interparticle bridging is the adsorption of colloids to a

relatively large molecule, such as organic polymer,
to destablize and aggregate the colloidal suspension.
The long polymer molecule attaches to absorbent
surfaces of colloidal particles by chemical or physical
interactions, resulting in aggregation.
24

Figure 11.11 Coagulation mechanisms: (a) charge neutralization, (b)

sweep floc, (c) agglomeration of destablized particle by attachment of
coagulant ions and bridging of polymers.

25

Destabilization

Two basic destabilization mechanisms:

Coagulation reduces the net electrical repulsive forces at

particle surfaces by adding coagulant chemicals.
Flocculation is a agglomeration of the destabilized
particles by chemical joining and bridging.

In water treatment, both are used to destabilize

turbidity, color, odor-producing compounds,
pathogens, etc.
In wastewater treatment, coagulation precedes
tertiary filtration necessary to clarify a biologically
treated effluent for effective chemical disinfection.
26

Coagulation process

The common unit operations and chemical additions in

the treatment of surface waters for a potable supply
(Figure 11.12).

27

Coagulants

Mainly aluminum and iron salts

Aluminum sulfate (most common)

Ferric sulfate (second most common)

Ferric chloride

Lime [Ca(OH)2]

Aluminum salts are cheaper, but iron salts are more effective
over wider pH range (pH 4-9), and are more effective at
removing NOM.

For some waters, cationic polymers are effective as a primary

coagulant (the higher the charge on the cation, the more
effective is the coagulant), but polymers are more commonly
applied as coagulant aids.
28

Aluminum Sulfate (Filter Alum)

Aluminum sulfate reacts with natural alkalinity in water to form

soluble Al hydroxo complexes or Al hydroxide floc:

Al2 (SO 4 ) 3 14.3H 2 O 2H 2 O 2Al(OH)2 2H 3SO 24- 14.3H 2 O

The production of H+ will tend to depress the pH. So, the types
of hydrolysis products formed depend on the pH. Addition of
base to control the pH shift may be required.

If sufficient alum is added, and pH = 6-8, aluminum hydroxide

precipitate is formed for the sweep floc coagulation
mechanism:

Al2 (SO 4 ) 3 14.3H 2 O 6H 2 O 2Al(OH)3 6H 3SO 24- 14.3H 2 O

Each mg/L of alum decreases water alkalinity by 0.5 mg/L as

29

Aluminum Sulfate (Filter Alum)

Lime or soda ash is added to provide necessary alkalinity

and control the pH of the coagulation process:

Al2 (SO 4 )3 .14.3H 2 O 3Ca(OH) 2 2Al(OH)3 3CaSO 4 14.3H 2 O

Al2 (SO 4 )3 .14.3H 2O 3Na 2 CO 3 3H 2 O
2Al(OH)3 3Na 2SO 4 3CO 2 14.3H 2 O

Soda ash does not increase hardness, only

corrosiveness, but lime is more popular and less
expensive.

Dosage range : 5-50 mg/L; optimum pH: 5.5-8.0.

30

Ferric Sulfate

It reacts with alkalinity presents in water:

Fe 2 (SO 4 ) 3 3Ca(HCO3 ) 2 2Fe(OH)3 3CaSO 4 6CO 2

Fe(OH)3 is dense and settle fast.

If alkalinity is not enough, hydrated lime is used.

Optimum pH is between 4 and 12.

31

Ferric Chloride

It reacts with natural alkalinity

2FeCl3 3Ca(HCO3 ) 2 2Fe(OH)3 3CaCl 2 6CO 2

If alkalinity is insufficient, lime is added

2FeCl3 3Ca(OH) 2 2Fe(OH)3 3CaCl 2

Each of the above equation has an optimum pH

range.

32

Advantages of Ferric Coagulation

Coagulation

is possible over a wider pH

range, generally 4-9 for most waters.

The

floc settes better than alum floc.

more

effective in the removal of NOM, taste,

and odor compounds.

33

Synthetic Polymers

Are water-soluble high-MW organic compounds that have

multiple electrical charges along a molecular chain of C
atoms.

Three types:

Cationic polymer: the ionization groups have a positive charge

Anionic polymer: the ionization groups have a negative charge

Nonionic polymer: no charges are exhibited or if the net charge is

zero

Are extensively used as coagulant aids with aluminum and

iron coagulants in treatment of turbid waters to build larger
floc by bridging mechanism.

34

Synthetic Polymers

Cationic polymers can be effective for coagulation, without

hydrolyzing metals, by producing destablization through
charge neutralization and interparticle bridging.

Common dosage: 0.5-1.5 mg/L

Anionic and nonionic polymers are effective coagulant

aids. After destablizing the colloidal suspension by
hydrolyzing metals such as alum, polymers promote larger
floc by a bridging mechanism (Figure 11.11c).

Common dosage: 0.1-0.5 mg/L

35

pH Adjustment
Used

if pH of water to be treated is not within

the optimum pH of the coagulant.

pH

is increased using lime, sodium

hydroxide, and soda ash.

pH

is reduced using sulfuric acid,

phosphoric acid.

36

Factors Affecting Coagulation

1.

Coagulant

2.

Coagulant aids

3.

pH

4.

Alkalinity

5.

Temperature

6.

Time

7.

Velocity

8.

Zeta potential
37

Water Softening

38

Causes of Hardness
Water

hardness is principally caused by:

calcium

ions
magnesium ions
Source

of calcium and magnesium ions

geological

formations

39

Types of Hardness
Carbonate

hardness - carbonates and

bicarbonates of calcium, magnesium and sodium,
which can be removed and settled by boiling of
water.
CO32-,

HCO3-

Noncarbonate

hardness - metallic cations of

iron, manganese and strontium
SO42-,

Total

Cl-, NO3-

hardness = carbonate + noncarbonate

40

Water Hardness

The maximum level of hardness considered for public

supply is 300 to 500 mg/l, though many customers object
to water harder than 150 mg/l.

Disadvantages of hardness
excessive soap consumption during laundering
scale-formation in hot water heaters and pipes.

The use of synthetic detergents and pipe linings can

overcome those problems.
41

Hardness Ranges
Degree of Hardness
Soft

Hardness Concentration (mg/L as CaCO3)

US

International

0 60

0 50

Moderate Soft

51 100

Slightly Hard

101 150

Moderately Hard

61 120

151 200

Hard

121 180

201 300

Very Hard

> 180

> 300

42

Softening

In precipitation softening, lime (CaO) and soda ash

(Na2CO3) are used to precipitate calcium and magnesium
form water. Lime treatment can also:
kill

bacteria

remove
help

iron

in clarification of surface water (coagulant)

Lime treatment will raise the pH value, so recarbonation

by carbon dioxide is used to lower the pH by converting
the hydroxide and carbonate ions to bicarbonate ion.
43

Lime

Lime is commercially available in the forms of:

quicklime
hydrated

lime

Quicklime
available

in granular form
contains minimum of 90% CaO
magnesium oxide is the primary impurity

Hydrated Lime
contains

about 68% CaO

Slurry lime is written as Ca(OH)2.

44

CO2
Carbon

dioxide is:

gas
colorless
clear
produced

by burning fuel such as coal, oil, or gas

used to recarbonate lime-softened water
applied through diffusers immersed in the treatment
tank

45

Removal of hardness with soda ash and lime

Ca(OH) 2 CO 2 CaCO 3 H 2 O....(1)
Ca(OH) 2 Ca(HCO 3 ) 2 2CaCO 3 2H 2 O.....(2)
2Ca(OH) 2 2Mg(HCO 3 ) 2 Mg(OH) 2 2CaCO 3 2H 2 O.....(3)
Ca(OH) 2 MgCO 3 CaCO 3 Mg(OH) 2 .....(4)
Ca(OH) 2 MgSO 4 CaSO 4 Mg(OH) 2 .....(5)
Ca(OH) 2 MgCl 2 CaCl 2 Mg(OH) 2 .....(6)
Na 2 CO 3 CaSO 4 Na 2SO 4 CaCO 3 .....(7)
Na 2 CO 3 CaCl 2 2 NaCl CaCO 3 .....(8)
Free of hardness?
Minimum practical limits of precipitation softening are 30 mg/L of Ca2+ and
10 mg/L Mg2+ expressed as CaCO3.

46

Reactions
From

Hardness?

the reaction equations, it can be seen that:

Lime

reacts first with free carbon dioxide (eq. 1)

Next,

lime reacts with calcium bicarbonate (eq. 2)

Lime

also reacts with magnesium carbonate and bicarbonate

(eqs. 3 and 4)

Noncarbonate

hardness (magnesium sulphate and chloride)

requires the addition of soda ash for precipitation (eqs. 5 and
6)

Noncarbonate

hardness (calcium sulphate and chloride)

requires the addition of soda ash only for precipitation (eqs. 7
and 8)
47

Pros and Cons of Softening

Advantage

of precipitation softening:

the

lime added is removed along with the hardness taken

out of solution.

TDS

of the water are reduced.

the

chemical reactions can be used to estimate the quantity

of sludge produced.

Disadvantage

of precipitation softening:

sodium

ions, from the addition of soda ash, remain in the

finished water.
48

Recarbonation

Recrabonation is used to stabilize lime-treated water, and thus

reducing its scale-forming potential.

Carbon dioxide is used for the recarbonation process. It

converts lime to calcium carbonate. Further recarbonation will
convert carbonate to bicarbonate.

49

Recarbonation Reactions
Recarbonation for removal of excess lime and pH control
(pH 9.5)
CO 2 Ca(OH) 2 CaCO 3 H 2 O
CO 2 Mg(OH) 2 MgCO 3 H 2 O
Recarbonation for pH control (pH 8.5)
CO 2 CaCO 3 H 2 O Ca(HCO 3 ) 2
50

Stoichiometric Requirement

Based on the above equations, the stoichiometric

requirement for lime and soda ash expressed in equivalent
per unit volumes are

Lime required (eq/m 3 ) CO 2 HCO 3- Mg 2 excess

Soda ash required (eq/m 3 ) Ca 2 Mg 2 alkalinity

Approximately 1 eq/m3 of lime in excess of the

stoichiometric requirement must be added to bring the pH
to above 11 to ensure Mg(OH)2 complete precipitation.
After precipitation, recarbonation is needed to bring pH
down to a range of 9.2 to 9.7.
51

Example

Water has the following composition: calcium = 82 mg/L,

magnesium = 33 mg/L, sodium = 14 mg/L, bicarbonate = 280 mg/L,
sulfate = 82 mg/L, and chloride = 36 mg/L. Determine carbonate
hardness, noncarbonate hardness, and total hardness, all in terms of
mg/L of CaCO3.

Solution:
The species concentration in meg/L is computed as
mg/L
100
meq/L

50 for CaCO 3
equivalent weight
2
The species concentration in mg/L of CaCO3 is calculated as
mg/L as CaCO 3 meq/L of species 50

mg/L of species 50
equivalent weight of species

52

Solution

Construct a table for ions in mg/L as CaCO3:

Ion species

MW

EW

Ca2+

40

Mg2+
Na+
HCO3-

Concentration
mg/L

meq/L

mg/L as CaCO3

20

82

200

24.3

12.2

33

2.7

135

23

23

14

0.6

30

Total: 7.3

365

61

61

280

4.6

230

Cl-

35.5

35.5

36

50

SO42-

96.1

48

82

1.7

85

Total: 7.3

65
53

Solution

Construct an equivalent bar diagram for the cationic and anionic

species of the water:

The diagram shows the relative proportions of the chemical species

important to the water softening process.

Cations are placed above anions on the graph.

The calcium equivalent should be placed first on the cationic scale and
be followed by magnesium and other divalent species and then by the
monovalent species sodium equivalent.

The bicarbonate equivalent should be placed first on the anionic scale

and immediately be followed by the chloride equivalent and then by the
sulfate equivalent.
0

200

335

Ca2+

Mg2+

HCO30

Cl230

365

Na+
SO42-

280

365

54

Solution

Compute the hardness distribution:

Total hardness = 200 + 135 = 335 (mg/L as CaCO3)

Alkalinity = bicarbonate = 230 mg/L as CaCO3

Carbonate hardness = bicarbonate = 230 mg/L as CaCO3

Noncarbonate hardness = 335 230 = 105 mg/L as CaCO3

55

Process Variations in Lime-Soda

Ash Softening

Depend on the degree of hardness and types and amount of

chemical added.

Include

Excess-lime treatment

Selective calcium removal

Split treatment

56

Excess-Lime Softening

Carbonate hardness associated with Ca ion can be

effectively removed to the practical limit of CaCO3
solubility by stoichiometric additions of lime.

Precipitation of Mg ion needs additional 35 mg/L of CaO

(1.25 meq/L) above stoichiometric requirements.

The practice of excess-lime treatment reduces the TH to

about 40 mg/L (i.e., 30 mg/L of CaCO3 and 10 mg/L of Mg
hardness).

57

Excess-Lime Softening

In excess-lime softening:
After

excess lime addition, the water is flocculated and settled to

remove CaCO3 and Mg(OH)2 precipitates.

After

that, recarbonation is carried out in two stages.

In

the first stage, CO2 is added to lower the pH to 10.3 and

converts excess lime to CaCO3.

Water

is then flocculated and settled.

If

needed, soda ash is added at this stage to remove noncarbonate

hardness.

In

the second stage, CO2 is added to further lower the pH to the

range of 8.5 to 9.5 to convert most of the remaining carbonate ion
to bicarbonate ion in order to stabilize the water against scale
formation.
58

Figure 11.13 Schematic flow diagram for a two-stage excess-lime softening plant.
59

Example 11.6

Water defined by the following analysis is to be softened by excess-lime

treatment in a two-stage system (Figure 11.13):
CO2 = 8.8 mg/L as CO2
Alk(HCO3-) = 115 mg/L as CaCO3
Ca2+ = 70 mg/L

SO42- = 96 mg/L

Mg2+ = 9.7 mg/L

Cl- = 10.6 mg/L
Na+ = 6.9 mg/L
The practical limits of removal can be assumed to be 30 mg/L of CaCO 3
and 10 mg/L of Mg(OH)2, expressed as CaCO3.
a)

b)

c)

Sketch a meq/L bar graph and list the hypothetical combinations of

chemical compounds in the raw water.
Calculate the quantity of softening chemicals required in lb/Mgal of
water treated and the theoretical quantity of CO 2 needed to provide a
finished water with one-half of the alkalinity converted to bicarbonate
ion.
Draw a bar graph for the softened water after recarbonation and
filtration.

60

Solution
Figure 11.14 Meq/L bar
graph.
(a) Bar graph and
hypothetical chemical
combinations in the raw
water.
(b) Bar graph of the water
after lime and soda ash
additions and settling but
before recarbonation.
(c) Bar graph of the water
after two-stage
recarbonation and final
filtration.
61

Selective Calcium Removal

If the water to be treated contains low concentration of magnesium

(< 40 mg/L as CaCO3), selective calcium removal can be used.

Magnesium hardness of more than 40 mg/L as caCO3 is not

recommended due to the possible formation of hard magnesium silicate
in high temperature waters (180F).

Enough lime is added to precipitate calcium hardness without

providing any excess for Mg removal.

Soda ash may be used depending on the extent of noncarbonate

hardness.

If precipitation of CaCO3 is not satisfactory, alum or a polymer can be

used to aid flocculation.

Recarbonation is used to reduce scale formation on the filter and to

produce stable water.

62

Figure 11.15 Schematic diagram for a single-stage calcium-carbonate

softening plant.

63

Example 11.7

Determine the chemical dosages needed for selective calcium softening

of the water described in Example 11.6. Draw a bar graph of the
processed water.

64

Solution

Figure 11.16 Bar graph of the softened water after selective calcium removal.

65

Iron and Manganese

Removal

66

Iron (Fe) and Manganese (Mn)

Fe and Mn in concentrations greater than 0.3 mg/L of

Fe and 0.05 mg/L of Mn stain plumbing fixtures and
laundered clothes.

Foul tastes and odors can be produced by growth of

Fe bacteria in water distribution mains. These
filamentous bacteria, using reduced Fe as an energy
source, precipitate it, causing pipe encrustations. Decay
of the accumulated bacterial slimes creates offensive
tastes and odors.

67

Chemistry of Fe and Mn

Fe and Mn are abundant elements in the earths crust. They get into
natural water from dissolution of rocks and soil, from acid mine
drainage, and from corrosion of metals.

Under reducing conditions (absence of DO and low pH), ferrous

iron Fe2+ and manganous manganese Mn2+ are
chemically

reduced

soluble
complexed

with NOM

When exposed to air, they are oxidized to ferric iron Fe3+ and
manganic manganese Mn4+, which are:
oxidized
stable
insoluble

68

Chemistry of Fe and Mn

Oxygen, chlorine, and potassium permanganate

(KMnO4) are the most frequent oxidizing agents.

Oxidation reactions using KMnO4 are

3Fe+ + MnO4- 3Fe3+ + MnO2

3Mn2+ + 2MnO4- 5MnO2
MnO2

acts as catalysts that increase the rate of Mn

oxidation.

69

Fe and Mn Removal Process

The techniques for removing Fe and Mn are based on the

oxidation of Fe2+ and Mn2+ to the Fe3+, Mn3+ and Mn4+,
and the oxidation of any organic-complex compounds.
This is followed by filtration to remove insoluble
compounds.
Four major techniques for Fe and Mn removal from water
are:

Aeration-Filtration
Aeration-Chemical Oxidation-Sedimentation-Filtration
Water Softening
Greensand Filtration
70

Aeration-Filtration

Aeration (air oxidation) is the simplest oxidation

treatment in removing iron.
The reaction that takes place is in the form of:
2Fe(HCO3)2 + 0.5O2 +H2O 2Fe(OH)3 + 4CO2

Aeration alone cannot remove manganese effectively.

Increasing the pH to 8.5 can enhance the oxidation
process. If manganese is not effectively removed from the
water, it can cause problems with post-chlorination.
When oxidized:
it

can clog the solution-feed chlorinator

it cause a staining water

71

Aeration-Chemical OxidationSedimentation-Filtration

This is a common method for removing iron and manganese

from well water without softening treatment.

Contact tray aeration is designed to displace dissolved gases

(i.e., CO2) and initiate oxidation of the reduced Fe and Mn.

Chlorine, potassium permanganate, ozone, chlorine dioxide

can oxidize Fe and Mn.

72

Aeration-Chemical OxidationSedimentation-Filtration

When Cl2 is used, a free available chlorine residual is

maintained throughout the treatment process.

The KMnO4 oxidation is many times faster than Cl2 for the
oxidation of Mn. Potassium permanganate oxidizes iron and
manganese at rates faster than dissolved oxygen and its
reaction is relatively pH independent.

Ozone oxidizes Mn faster than other oxidants, but if the

dosage is too high, it may convert the manganese to
permanganate and thereby cause the water to turn pink (the
color of permanganate solution).

Since iron and manganese can not be completely removed by

sedimentation, effective filtration is required.
73

Oxidation of Iron and Manganese with

Oxygen, Chlorine, and Chlorine Dioxide
4Fe 2 O 2 10H 2 O 4Fe(OH)3 8H
2Fe 2 Cl 2 6H 2 O 2Fe(OH)3 6H 2Cl
Fe 2 ClO 2 3H 2 O Fe(OH)3 ClO 2 3H
2Mn 2 O 2 2H 2 O 2MnO 2 4H
Mn 2 Cl 2 2H 2 O MnO 2 4H 2Cl
Mn 2 2ClO 2 2H 2 O MnO 2 2ClO 2 4H
74

Water Softening

Lime-soda ash softening will also remove Fe and Mn.

Lime treatment has been used to remove organically bound Fe

and Mn from surface water. The process scheme aerationcoagulation-lime treatment-sedimentation-filtration can
treat surface waters containing color, turbidity, and organically
bound Fe and Mn.

75

Greensand Filtration

The mineral glauconite, commonly known as greensand, can be used

in pressure filters with either continuous or periodic addition of
permanganate to remove Fe and Mn.
Oxides on the greensand surface can oxidize Fe and Mn.
Permanganate oxidizes Fe and Mn and regenerates the greensand.

76

Greensand Filtration

KMnO4 is applied prior to filtration.

The filter is a dual-media filter with anthracite filter medium is

placed on top of the manganese zeolite.

Iron and manganese are oxidized by KMnO4.

The upper layer will remove the insoluble metal ions.

Any iron and manganese ions not oxidized, it will be captured

by the lower layer of manganese zeolite.

Any surplus KMnO4 will regenerate the greensand.

When the bed becomes saturated, it is backwashed by KMnO4

to remove particles from the upper layer and regenerate the
greensand.
77

Reaction Equations
Oxidation
Z MnO 2 Fe 2 Z Mn 2 O 3 Fe3
Z MnO 2 Mn 2 Z Mn 2 O 3 Mn 3
Regeneration
Z Mn 2 O 3 KMnO 4 Z MnO 2

78

Disinfection

79

Disinfection

Definition: the process of destruction or inactivation of waterborne

pathogens or living pathogenic microorganisms.

Post-disinfection to disinfect filtered water and leave an adequate

disinfectant residual in the treated water to ensure its safety in the
distribution system until its use by the farthest consumer

Disinfection depends on:

The physico-chemistry of the disinfectant

The cyto-chemical nature and physical state of the pathogens

The interaction of the above

Temperature

pH

Electrolytes

Interfering substances
80

Disinfection
Most

chemical disinfectants form harmful DBPs:

Chlorine: THMs and HAAs

Chloramines: cyanogen chloride and chloropicrin

Chlorine dioxide: chlorites and chlorates

Ozone: bromates and aldehydes

The

balance between proper disinfection and

disinfection byproducts is the goal of each water
utility.
81

Disinfection Methods
Chlorine
Alternative

disinfectants and oxidants:

Ozone
Chlorine

dioxide
UV irradiation
High pH
Other halogens (iodine and bromine)
Reasons:

DBPs, greater disinfection efficiency

Disadvantages: Typically more costly, etc.
82

(1) Chlorine and Chloramines

Chlorine (Cl2) is widely used

Effective

at low concentration

Cheap
Helpful

in controlling taste and odor, Fe, Mn, cyanides, and

phenols
Forms

residual if applied in sufficient dosages

Chlorine is applied as:

Gas

(most common)

hypochlorite

Chlorine is a strong oxidizing agent

It

reacts with various organic substances, ammonia, and metals.

It

inactivates microorganisms by reacting with their enzymes.

83

Chlorination Reaction

Chlorine gas reacts with water (hydrolyzes) to form (lower the

pH)
Hypochlorous

acid (HOCl) the principal disinfecting form of

chlorine.
H+

and Cl- (no disinfection potential)

Cl 2 H 2 O HOCl H Cl

At pH above 7.5, HOCl dissociates to hypochlorite ion (OCl) (

a function of pH); thus, it becomes less and less effective.

The higher the pH, the higher the ionization, the less effective the
Cl2.

HOCl H OCl

So, ACID!!!

84

Figure 11.21
85

Chloramines

Reaction with ammonia (a function of pH, [Cl2]/[NH3],

temperature)
NH 3 HOCl NH 2 Cl H 2 O
monochloramine
NH 2 Cl 2HOCl NHCl 2 2H 2 O
dichloramine

pH

NHCl 2 3HOCl NCl3 3H 2 O

trichloramine

At pH 4.5-8.5, monochloramine and dichloramine are formed.

At pH > 8.5, monochloramine predominates.
At pH about 4.5, dichloramine predominates.
At pH 4.4, trichloramine predominates
Chloramines are effective against bacteria but not viruses.

86

Chlorination Reaction
Reaction

with organics

Reaction

with phenol produces chlorophenols

Reaction

with humic substances (or NOM) produces

trihalomethanes (THMs)

Chloroform (CHCl3)

Bromodichloromethane (CHCl2Br)

Dibromochloromethane (CHClBr2)

87

Dosages, Demand and Residuals

Dosage: the amount of chlorine added.

Demand: the amount of chlorine needed to oxidize materials,

or the difference between the amount added and the quantity
of free and combined available chlorine remaining at the end
of a specified contact period.

Residual: the amount of chlorine remaining after oxidation.

Assume we used 3 mg/L chlorine dose in a sample, and after 30 min

there was 2 mg/L residual.
Chlorine demand is therefore 3 mg/L 2mg/L = 1 mg/L.

88

89

Combined and Free Available

Residual
Chlorine

Combined available residual chlorine

residual chlorine existing in chemical combination with

ammonia (chloramines) or organic nitrogen compounds.

Free available residual chlorine

residual chlorine existing in water as hypochlorous acid or
hypochlorite ion. (Note: some say +Cl2)

90

Chlorine Residual Curve

When chlorine is added to water containing reducing agents
and ammonia, residual develop that yield a curve as shown in
the next slide.
A-B When chlorine is added to water, chlorine first reacts with
reducing agents, such as nitrites, ferrous ions, and H2S.
B-C The excessive addition of chlorine results in the formation
of chloramines (combined available residual chlorine)
which are much less effective than the free chlorine
(faster and higher disinfection capacity).
C-D The previously produced chloramines are oxidized to
produce nitrogen compounds, such N2, N2O, NO3-.
D
Once most of the chloramines are oxidized, additional
chlorine creates an equal residual. Point D is referred to as
the breakpoint.
91
Beyond point D, all added residual is free available chlorine.

Completion of
chlorination
reactions

N2, N2O, NO3-

HOCl

C
Hump

Reducing
agents
A

No residual

Free residual chlorine /

breakpoint residual

Breakpoint or dip

92

Reactions of Chlorine with Reactants in

Water

Reactions in sequence:

Reducing agents

Fe, Mn, H2S and nitrites neutralize Cl2 into chlorides.

Red water, black water, tastes and odors are removed.

No residual chlorine at this stage.

Ammonia

Choramines are formed until hump.

Combined available residual chlorine

Destruction of combined residual chlorine

Chlorine reacts with combine chlorine, resulting in a drop of residual

chlorine.

Breakpoint chlorination therefore ensures a proper disinfection after

control of Fe, Mn, bacteria, tastes and odors.

93

Breakpoint Chlorination
The

purpose of breakpoint chlorination is to

produce and maintain free-residual chlorine in the
water after complete oxidation of substances that
react with chlorine.

94

Chloramination
Often

practiced in water treatment, particularly to

maintain a residual in the distribution system after
some other disinfectant (chlorine, ozone, or
chlorine dioxide) is used as the primary
disinfectant.

Effective

for bacteria, but not for viruses.

[Cl2]:[NH3]

= 3-6.

95

Manual-Control Chlorinator

96

Automatic Proportional-Control
Chlorinator

97

Factors Affecting Chlorination

pH
The

lower the pH, the more effective the free-residual

chlorine. Why?
The

amount of HOCl decreases at above pH 7.5 as it

ionizes into OCl-.

Type

of residual chlorine

HOCl

is more effective than the OCl-.

Temperature
The

higher the temperature, the quicker the

disinfection and the shorter the required contact time
is.
98

Factors Affecting Chlorination

Contact time period

Chlorine requires a certain amount of contact time at different

temperatures to react with microorganisms.
The longer the contact time, the more effective the disinfection
is. So, the concept of CT is used to ensure a proper disinfection.
CT stands for concentration of a disinfectant as mg/L and its
contact time in minutes.
Required CT is constant for each disinfection at different
temperatures.
In chlorination, it also takes into consideration the pH of the
water. The lower the pH, the better the disinfection, and the
lower the CT value is.
99

Factors Affecting Chlorination

Concentration
The

higher the concentration, the more effective the

disinfectant is.

Normally

0.5 to 1 ppm free-residual chlorine will

effectively disinfect the water.

According

to the SDWA, the maximum allowable

chlorine residual in the distribution system is 4 mg/L
and the minimum required is 0.2 mg/L.

100

CT and CT Ratio

C stands for the concentration of a disinfectant as mg/L, which is the

lowest residual value of the disinfectant at the highest flow at the
effluent site.
T stands for the contact time in minutes, which is the detention time of
a pipe or a basin at the highest flow during 24 hours.
CT value is CT as mg/L-minutes.
CT value takes into consideration the lowest C and its shortest T, and
vice versa.
CT calculation needs the disinfectant residual at the effluent end of
each pipe and basin and their detention times at the highest flow to
satisfy CT requirements.
The calculated CT for each part of the disinfection train divided by he
required CT (from the CT table provided by the EPA) for each
disinfectant is called available CT.
101
The higher the available CT value, the better the disinfection is.

Dechlorination
Chlorinated

effluents can have negative impacts

on receiving environment
Chemicals used for dechlorination include:
Sulfur

dioxide (most common)

Sodium sulfite
Sodium bisulfite
Sodium thiosulfate
Hydrogen peroxide
Ammonia
102

Sulfur Dioxide (SO2)

General characteristics
Has

solubility in water of 18.6% at 0C

When reacts with water, it forms a weak solution of sulfurous
acid (H2SO3)
Sulfurous

acid dissociates as follows:

H 2SO 3 H HSO

HSO 3 H SO 32

103

Sulfur Dioxide (SO2)

Free and combined chlorine forms react readily with sulfite

ion (SO32-) as follows:
SO 32 HOCl SO 24 Cl H
SO 32 NH 2 Cl H 2 O SO 24 Cl NH 4

Required mass ratio of SO2 to Cl2 is 1.1:1

104

(2) Chlorine Dioxide (ClO2)

ClO2

was originally used to remove taste and odor

from water
General characteristics of ClO2
More

powerful oxidant than chlorine

Its effectiveness is not affected by ammonia and pH
It is very effective when followed by chlorine or
chloramines
Does not react with water, so can be easily removed from
water by aeration
Readily decomposed by exposure to UV radiation
Maintains a stable residual
105

Preparation of ClO2

Produced onsite by mixing sodium chlorite and

(excessive) chlorine:

Cl 2 H 2 O HOCl HCl
HOCl HCl 2NaClO 2 2ClO 2 2NaCl H 2 O

Acid and sodium chlorite

NaClO 2 HCl ClO 2 NaCl H

Sodium hypochlorite and sodium chlorite

2NaClO 2 NaOCl 2HCl 2ClO 2 3NaCl H 2

106

Advantages of ClO2 Disinfection

ClO2

is strong bactericide and viricide over a wide

pH range.

ClO2

has longer lasting residual than HOCl.

In

wastewater, ClO2 use is limited to phenolic

wastes and the control of sulfide in wastewater
collection systems.

ClO2

does not produce measurable amounts of

THMs (trihalomethanes) or TOXs (total organic
halogens).

107

Disadvantages of ClO2 Disinfection

ClO2 is unstable compound that shortly reverts to

chlorine. Being short lived, it is generated onsite and
applied immediately.

It is explosive at a concentration above 10% in the air.

It is relatively expensive to generate.

It forms chlorites (can be reduced by ferrous ions) and

chlorates, which are toxic. Chlorite is regulated as a DBP
in the primary drinking water standards at 1 mg/L, and
ClO2s maximum residual disinfectant level leaving the
treatment plant is 0.8 mg/L. Chlorate is unregulated yet.
108

(3) Ozone

General characteristics of ozone (O3)

More reactive than Cl2 and ClO2.

The reactions are rapid in inactivating microorganisms,

oxidizing Fe, Mn, sulfide, and nitrite, and slower in
oxidizing organic compounds like humic and fulvic
substances, pesticides, and VOCs.

Does not react with water to produce DBPs, but

decomposes in water to produce O2 and OH.

Unstable in aqueous solutions, has a half-life of 10 to 30

minutes in distilled water; therefore, it is produced on-site
and cannot be stored.

109

Ozone Production
1.

2.

3.
4.

Air is refrigerated to remove moisture (dew point =

-40 to -60 C).
Air is dried through desiccants (silica gel and
activated alumina).
Air is passed between oppositely charged plates .
This process converts a small % of O2 to O3 (1-3%
from air, and 2-6 % from the O2 feed).

110

Ozonation Processes
Ozonation

treatment of water can be divided into

3 parts:
Preparation

of feed gas is mainly filtration of air to

remove dust particles and moisture. Pure O2 feed is
more efficient.

Production

of O3

Contaction

is contacting the microbes by the bubbling

of an O3 and O2/air mixture through the water by
dispersing it mostly by diffusers at the bottom of a
contact chamber for the maximum O3 transfer.
111

Ozonation System

Figure 11.25 Two-compartment ozone contactor with porous diffusers.

112

Ozone Reactions

A need to balance pathogen inactivation and DBP control.

Ozone reacts rapidly with NOM, producing small organic

compounds.

The biodegradability of the resulting organic carbon is increased.

This biodegradable organic matter (BOM), measured as

biodegradable dissolved organic carbon (BDOC) or assimilable
organic carbon (AOC), can cause problems of bacterial regrowth in
the distribution system, production of tastes and odors, and
increased residual chlorine demand.

Granular media filters can be operated in a biologically active state

(i.e., microbial growth is encouraged in the filter to biodegrade the
organics so they are not released to the distribution system.
113

Alternatives of Ozonation
Various

combinations of O3 and other

disinfectants:
Peroxone

is the use of H2O2 and O3 to accelerate the

oxidation of some organics by 2-6 times when
compared to O3 itself.

Soozone

is a combination of ultrasonic waves and O3,

where ultrasonic waves break organics particles, and
O3 oxidizes them.

114

Advantages of Ozonation
When

compared to chlorination:

Ozone degrades to O2, so no toxic residues.

Ozone has been used to remove tastes and odors,

color, algae, THMs precursors, phenols, cyanides,
sulfides, sulfites and heavy metals.

The required CT is very low.

115

Disadvantages of Ozonation
High

cost of production.
Short-lived with almost no residual effect.
On-site production.
Oxidizes bromide ion (Br-) to bromate (BrO3-)
(difficult to remove), a DBP regulated at 10 g/L.

Therefore, ozonation is less common than

chlorination. Generally, ozonation is followed by
chlorination or chloramination for the residual
effect.

116

(4) Ultraviolet (UV) Radiation

UV rays have wavelengths from 100 to 400 nm (Figure

11.26) and are produced by a variety of lamps (Table
11.6).

UV radiation is absorbed by and damages the nucleic

acids in DNA and RNA of microorganisms which
prevents their replication.

Although many microorganisms have enzymes that

enable them to repair the damaged nuclei acids, higher
UV doses and residual chemical disinfectants are
expected to inhibit the repair and maintain inactivation.
117

Figure 11.26 UV light in the electromagnetic spectrum

118

119

U-V Sterilizer

U-V Tube
120

Advantages and Disadvantages of UV

In wastewaters, SS can shield bacteria and viruses from the UV

radiation.

pH, temperature, alkalinity, and total organic carbon do not influence

the UV radiation.

Potable water systems have low SS and turbidity.

In potable water systems, chemical disinfection is used after UV

radiation to maintain a disinfectant residual. (LACK OF
DISINFECANT RESIDUAL)

For wastewaters where residual disinfectants are not allowed, UV

radiation has this particular advantage for disinfecting wastewaters.
(DISINFECANT RESIDUAL IS NOT REQUIRED)

Chemical disinfection may be used together with UV radiation to

inactivate viruses.
121

Factors Affecting UV Treatment

Turbidity

Turbidity shield microorganisms from radiation.

The higher the turbidity, the less effective the UV treatment is

TDS

Solids deposit on the lamp and foul it.

The less the TDS, the better the treatment is.

Dissolved organic matter

DOM absorbs the UV light and shields microbes from radiation.

The less the DOM, the better the treatment is.

Depth

The shallow the water, the more effective the UV treatment is

122

Relative Strength of Disinfectants

O3

> ClO2 > HOCl > OCl- > NH2Cl

123

Taste and Odor

Control

124

Causes of Taste and Odor

Taste and odor can be caused by:
Decaying

of natural organic compounds

Microbes: algae and bacteria
Dissolved gases (e.g., H 2S) in GW
Inorganic

salts
Metal ions (e.g., Fe, Mn, Pb, Cu, Zn)
Disinfectants
Organic compounds resulting from industrial activities
Sewage
125

Causes of Taste and Odor

In water systems, taste and odor problems are
unique in each system.
in

groundwater, odor is caused by dissolved gases that

can be stripped from water by aeration.
Aeration

in

surface water, odor is caused by nonvolatile

organic compounds which can not be removed by
aeration.
Breakpoint

chlorination and AC treatment

126

Prevention
Preventing taste and odor-producing substances
from reaching surface water should be given
priority.
if

the problem is caused by industrial waste discharge,

the source may be removed.

if

algal growth is causing the problem, copper sulfate

(one of the algaecides) or powered activated carbon
can be used to stop the growth of algae.

127

Treatment
Aeration

Oxidation

Activated

Carbon

128

(1) Aeration/Air Stripping

It

is effective for removing dissolved gases and

highly volatile odorous compounds.

Aeration

as the first step in processing well water

may acgieve any of the following:
Removal

of H2S, CO2 and CH4

Addition

of DO for oxidation of Fe and Mn

Rarely

effective in processing surface waters

since the odor-causing substances are nonvolatile.
129

(2) Oxidation
Oxidation

can be done by the use of:

chlorine

(formation of THMs must be considered)

chlorine

dioxide (has the stronger oxidative power as

chlorine without forming THMs)

potassium

permanganate (strong oxidizing agent but

forms MnO2, so filtration must be applied after
treatment with KMNO4)

Ozone

130

Adsorption
What

Attachment to interfaces between phases

water and solid

Air and solid

Effects

is adsorption?

removal of species

Uses

removal of contaminants

activated carbon removal of trace organic compounds

ion exchange resins for water softening
metal hydroxides coagulation in water treatment
131

Adsorption on AC

Adsorption on AC is the most effective treatment for the removal of taste and
odor from water.

Activated carbon (AC) adsorption

Main treatment for the removal of tastes and odors, volatile organic
compounds, and synthetic (pesticides) organic chemicals.

AC is a wood product made by burning plant matter to form charcoal

through carbonation and activation.

Carbonation is the burning of wood material at 550 to 700C in the

absence of air to form charcoal.

Activation is the further burning of charcoal at 800 to 900C in the

presence of steam and CO2 to produce pores and crevices in and on the
surface of the particles.

Two forms of AC in the water treatment:

Powdered Activated Carbon (PAC)

Granulate/Granular Activated Carbon (GAC)

The choice depends on the water quality and design of the plant.

132

Powdered Activated Carbon (PAC)

Power is mixed with water to form slurry. Slurry is added to the water at
several points, starting from intake to the filter influent.

AC is also a reducing agent because it reacts with disinfectants such as

chlorine, chloramines, chlorine dioxide and ozone. It adsorbs them and
causes a higher disinfectant demand. Therefore, both should not be
applied at the same time or in sequence without proper time interval.

AC is mostly applied into the influents of presedimentation basin and the

final sedimentation basin. Other application points are rapid mix,
flocculation basin and influent of the primary sedimentation basin. It is
also applied to the influent of microfiltration and ultrafiltration processes.
It is also applied after the recarbonation of the softened water to prevent
the blocking of the adsorption sites by calcium carbonate.

A typical dose of PAC varies from 3 to 50 mg/L.

Low capital cost and dose, flexibility of application point, no required

regeneration, coagulation aid by providing particulate matter for
flocculation, but produces extra sludge.

133

Granulate/Granular Activated Carbon

(GAC)

Used for a continuous treatment when there is a need for

continuous removal of volatile and synthetic organics
compounds in addition to occasional taste and odor control.

It does filtration and adsorption.

GAC needs regeneration when GAC is exhausted and then

releases adsorbed substances.

More expensive than PAC due to regeneration and initial cost,

no flexibility of application at different points. So, PAC is
more popular.

134

Fluoridation

135

Fluoridation

Water fluoridation is the precise adjustment of the natural fluoride

concentration in a public water supply up to the level recommended
for preventing tooth decay.

Low levels of fluoride result in increasing incidence of caries, while

excessive fluoride results in mottled tooth enamel.

Recommended limits (Table 11.15) are based on air temperature,

since this influences the amount of water ingested by people.

The US EPA has set the maximum contaminant level for fluoride in
the drinking water at 4 mg/L.

To prevent dental decay, the optimum fluoride concentration has

been established at 1 mg/L (American Dental Association, 1980).
136

Table 11.15

137

Fluoridation
Most

common fluoride compounds (Table 11.16):

Sodium

fluoride (NaF) (45% F)

Sodium

silicofluoride (Na2SiF6) (61% F)

Most

common, economical, convenient, and safe.

Fluosilicic

acid (H2SiF6) (79% F)

Application

of fluoride is best in a channel or

water main coming from the filters, or directly to
the clear well.
If

it is applied prior to filtration, some of the fluoride

may be lost due to reactions with other chemicals.

138

139

Water Fluoridation Chemicals

Sodium Fluoride (NaF)

Crystalline powder
Relatively constant (low) solubility
pH 7.6
Saturator Systems

Sodium Fluorosilicate (Na2SiF6)

Crystalline powder
Solubility varies with water temperature
pH 3.5
Dry-feed Systems

Fluorosilicic Acid (H2SiF6)

Liquid
Infinite solubility
pH 1.2
Venturi Systems

140

Venturi Chemical Injector

Bypass venturi
injection device
for injection of
liquid chlorine,
liquid fertilizer or
acid.

throttling valve

chemical suction port

Cutaway of a
venturi injector
cross-section.
141

Example 11.14
The

fluoride ion concentration in a water supply is

increased from 0.3 mg/L to 1 mg/L by applying
98% pure sodium silicofluoride. How many
milligrams of chemical are required per liter of
water?

Solution:

From Table 11.16, Na2SiF6 is 61% F.

Dosage = (1 0.3)/(0.98 0.61) = 1.17 mg/L
142

Synthetic Organic
Chemical Removal

143

Removal of Synthetic Organic

Chemicals
Synthetic

organic compounds (SOCs) include a

large number of chemicals used in industrial,
agricultural, and household activities, e.g.,
pesticides, VOCs, and THMs.
Some of the SOCs are toxic substances and can
cause cancer or damage to vital organs, others can
impair the nervous system. The maximum
allowable level of SOCs in water range from
0.0002 to 0.1 mg/l.
144

Sources of SOCs
Groundwaters

can be polluted by:

leaching

of agricultural pesticides
seepage from improper disposal of industrial volatile
organic chemicals (VOCs)
Surface

waters can be polluted by SOCs through

runoff from:
agricultural

lands
discharge of industrial wastewater
spillage of chemicals
145

Treatment
Conventional

water treatment (coagulation sedimentation - filtration) is not effective in

removing SOCs.
Other alternatives that can improve the treatment
include:
changing

the coagulants
changing the polymers
adjustment of pH
use of activated carbon adsorption poor adsorption due to
pore structure of PAC, short contact time between carbon
particles and dissolved organic chemicals, and interference
by adsorption of other organic compounds.
146
use of filtration through a bed of granular activated carbon

Treatment
Granular

activated carbon (GAC) can be

reactivated by heating in a furnace.
Pilot plant studies need to be conducted in order
to:
select

the best type and dosage of carbon

determine the contact time
determine the effect of water quality variation
determine the effectiveness of reactivation

147

Chemical Precipitation for

Phosphorus Removal

Involves the incorporation of PO43- into TSS and the

subsequent removal of those solids.
Phosphorus can be incorporated into either biological
solid (microorganism) or chemical precipitates.
Phosphate precipitation can be brought about by the
addition of the salts of multivalent metal ions that
form precipitates of separingly soluble phosphates.
eg: Ca2+, Al3+, Fe3+.
148

Phosphate Precipitation with

Calcium
Ca

is added in the form of lime, Ca(OH)2.

When

lime is added to water, it reacts with

the natural bicarbonate alkalinity to CaCO3.
Ca(OH)2 + Ca(HCO3)2 2CaCO3 + 2H2O

When

pH > 10, excess Ca2+ will precipitate

out PO43- as hydroxylapatite.
10Ca2+ + 6PO43- + 2OH- Ca10(PO4) 6(OH) 2

149

Phosphate Precipitation with

Calcium
The

quantity of lime required depends on the

alkalinity of the water but not on the amount
of phosphate present.depends on the
alkalinity of the water but not on the amount
of phosphate present.
Quantity required to precipitate P is typically
~1.4 to 1.5 times the total alkalinity
expressed as CaCO3.
150

Phosphate Precipitation with

Aluminium and Iron
Phosphate

precipitation with Al:

Al3+ + HnPO43-n AlPO4 + nH+

Phosphate

precipitation with Fe:

Fe3+ + HnPO43-n FePO4 + nH+

Many competing reaction occur at the same time
when Al or Fe precipitate out the PO43-. This
causes the requires precipitant dosage cannot be
estimated.
151

Phosphate Precipitation with

Aluminium and Iron
Al

& Fe salts are added to the untreated

water, in the activated sludge aeration tank or
the final clarifier influent channel.
P is removed from the liquid phase through
precipitation, adsorption, agglomeration and
removed as 1 or 2 sludges.

152