Water treatment:

disinfection

Sudha Goel
Dept. of Civil Eng., IITKgp
Kharagpur 721 302

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Disinfection

Disinfection is the destruction or removal of vegetative
pathogens
 It is not sterilization which implies destruction of all life
forms (microbes, spores, cysts, viruses, etc.)

Autoclaving, membrane filtration

Physical methods
 Membrane Filtration
 Radiation: UV, X-rays, gamma rays

Chemical methods (disinfectants)
 Chlorinated compounds

chlorine, chloramines, chlorine dioxide

 Ozone (hydroxyl radical mechanism)

 Potassium permanganate
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Oxidation potentials and disinfection power of disinfectants

Oxidation potential
Disinfectant
(Volts)
Fluorine -3.06
Hydroxyl free radical (OH●) -2.80
Oxygen (atomic) -2.42
Ozone (O3) -2.07
Hypobromous acid (HOBr) -1.59
Hypochlorous acid (HOCl) -1.49
Chlorine (Cl2) -1.36
Oxygen (molecular) -1.23
Bromine (Br2) -1.07
Chlorine dioxide (ClO2) -0.95
Monochloramine (NH2Cl) -0.75
Dichloramine (NHCl2) -0.74 3
 Chlorine remains the most popular, why?

Potent germicide
 High oxidation potential
 Residual in distribution system

Chloramine can do the same but is a less powerful oxidant

Taste and odor control
 Oxidation of NOM and removal of compounds causing taste
and odor problems

Biological growth control
 Growth of algae and bacteria in storage reservoirs and water
supply systems

Chemical control
 Iron and manganese removal
 Oxidation of SOCs

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Problems with chlorine!

Hazardous material
 Difficulty in transportation, handling and storage

Pungent compound
 Disagreeable taste and odor
 Dermal and eye irritation

Microbial resistance to chlorine
 More effective against bacteria rather than spores, cysts and
viral particles

Disinfection by-products (DBPs) formation
 Potential health hazard

Carcinogenic, mutagenic, teratogenic compounds are
formed

Non-carcinogenic effects – little information or discussion
in literature

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Disinfection by-products
(DBPs) formation

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DBPs and their history
 First DBP (chloroform – CHCl3) was discovered by Rook 1974
 USEPA national survey found trihalomethanes (THMs) in all
chlorinated drinking waters 1976
 National Cancer Institute published results linking chloroform
with cancers in laboratory animals 1976
 Regulation of THMs to a maximum contaminant level of 100
micro-g/L 1979
 Promulgation of Disinfectants/ DBP rule in the US 1998

Four THMs to 80 micro-g/L

 Guidelines and regulations by WHO and EU followed…

 Today, more than 500 DBPs are known

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 DBP Formation
Natural Organic Matter (TOC) + chlorine (or other disinfectant) +
bromine + iodine = DBPs

Chlorine
 Trihalomethanes (THMs)
 Haloacetic acids (HAAs)
 Haloacetonitriles (HANs)
 Cyanogen chloride, MX (most toxic)

Chloramines
 THMs, HAAs,…….to a lesser extent
 More iodinated and brominated compounds than chlorinated
compounds

These are more toxic

Chlorine dioxide
 Chlorite, THMs, HAAs,…….(as above)

Ozone
 Bromate; Aldoketoacids; Aldehydes

UV radiation: ?? 8
 Health effects
of any contaminant

Genotoxic Cytotoxic

Cell damage

Natural die-off Mutagenic

Tumorigenic Teratogenic

Benign – Malignant Reproductive defects –

removable (carcinogenic) miscarriages, infertility

Developmental defects (affects embryo or fetus) –

low birth weight, mental or physical defects
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 DBP Formation

 Inorganic:chlorate, chlorite, bromate

 Organic: due to reaction with natural organic matter
(NOM)

THMs and HAAs, HANs, MX and its analogs…….

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Richardson SD (2003) Disinfection by-products and other emerging contaminants in
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drinking water. Trends in Analytical Chem., 22(10): 666-683
 DBPs and
regulations (US,
WHO and EU)

Richardson SD (2003) Disinfection by-products and other emerging contaminants in drinking water.
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Trends in Analytical Chem., 22(10): 666-683
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IS10500, 2012
Microbial versus chemical risks

Microbial DBPs
RISK

Regulatory
regime

Disinfection level

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Controlling DBP formation

Reduce chlorine requirements
 Pretreatment for removal of turbidity, and TOC

Reduce precursor concentrations before chlorination

Treatment of water before chlorination to remove
 TOC, bromine, ……..

Coagulation and clarification
 Optimized in general for turbidity removal
 Can be optimized for turbidity and TOC removal

Ozonation and biofiltration
 Enhanced removal of TOC

Adsorption
 TOC removal

Membrane processes
 TOC removal
 No pre-chlorination, only post-chlorination

Can use ozonation, with or without biofiltration

Use alternative disinfectants (chloramines, ozone, UV)

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 Is there a better alternative to chlorine? Other
halogenated compounds

Chloramines: specific ratio of Cl:NH3 required for formation
 Weaker than chlorine as disinfectant but durable residual

Unlikely to remove virus and Giardia effectively (Krasner et
al 2006)
 Fewer chlorinated DBPs, higher brominated and iodinated DBPs

Latter are often more toxic than chlorinated DBPs (Krasner
et al 2006)
 Penetrates biofilms to a greater extent

weaker oxidizing agent, slower reaction rates

 Difficulty in handling ammonia

Toxicity of ammonia to fish, and in kidney dialysis

Chlorine dioxide
 Formed by reaction of sodium chlorite and elemental chlorine
 Formation of DBPs like chlorite and chlorate, THMs and HAAs
(Chang et al 2000)
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 Is there a better alternative to chlorine? Other
non-halogenated compounds

Ozone
 Most powerful disinfectant, but no disinfectant residual
 Can lead to greater bacterial regrowth problems

Biofiltration as a treatment process prior to final disinfection can
solve that problem
 Reduces formation of THMs and HAAs during post-chlorination

High iodinated THM levels (Krasner et al 2006)
 DBPs formed include bromate, a potent carcinogen and other
brominated organic compounds

UV light
 No residual
 Disinfection efficiency hard to quantify and compare
 Not adequate against virus, spores and cysts, adequate against
bacteria
 DBP formation: generally none, formaldehyde detected;
chlorate, bromate??
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Chlorine application

Elemental chlorine (chlorine gas)

 Cl2 + H2O → HOCl + HCl

Hypochlorite solution (bleach)
 NaOCl + H2O → HOCl + HCl + Na+ + OH-

Dry Ca hypochlorite (powder form)
 Ca(OCl)2 + H2O → HOCl + HCl + Ca2+ + 2OH-

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Chlorine chemistry: reactions in water

Addition of chlorine to water, results in formation of hypochlorous

[HOCl] and hydrochloric acids [HCl]:
 Cl2 + H2O → HOCl + HCl pK = 3.39

Depending on the pH, hypochlorous acid partly dissociates to
hydrogen and hypochlorite ions:
 HOCl → H+ + OCl- pK = 7.57

The hypochlorite ion then most often degrades to a mixture of
chloride and chlorate ions:
 3 OCl- → 2 Cl- + ClO3-

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Effect of pH and temperature on chlorine speciation

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Breakpoint chlorination

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 Example of inactivation assays or disinfection
experiments
dN
= − kN
dt
N
ln = − kt
N0
− kt
N = N 0e
Harriette Chick’s law of
disinfection (1908)

Inactivation rate k is a
f(species, disinfectant conc,
temperature, pH)
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TFC-8ed
Chick-Watson model (1908)
dN
= − kN
dt
k = k 'C n
N n
ln = − k 'C t
N 0

For all n,
N/N0 vs. Ct for a given value of C
is a straight line (Curve B)

Design and process efficiency is

based on C*T (assuming n =1)

Assumptions:
C and n are constants

Najm (2006) 24
 Effect of temperature and species type on their survival

a) 20 s at 110 deg C
Arrhenius’ Law
b) 10 min at 110 deg C
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Brock-10ed for the same log reduction
 Effect of pH and temperature on chlorine inactivation of Giardia
cysts and virus
Effect of pH and temperature on 2 log removal of Effect of pH and temperature on 4 log removal of
Giardia cysts with Free chlorine = 1 mg/L virus by free chlorine = 1 mg/L

350 100
pH 6 90
300 pH = 6-9
pH 7
C*T values, mg-min/L

80
250 pH = 10
pH 8 70

C*T values
200 pH 9 60
50
150
40
100 30

50 20
10
0 0
1 5 10 20 25 0.5 5 10 20 25
Temp., deg C Temperature, deg C

 Better disinfection at lower pH and higher temperature

 Implies HOCl is more powerful than OCl-
 Temperature effect is as expected based on Arrhenius’ law
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Based on data in QMZ (2000)
C vs. t for free chlorine disinfection

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Hammer and Hammer, 2008
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Hammer and Hammer, 2008
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