CVL100:Environmental Science(2-0-0)

(Tuesday and Wednesday; Friday slot reserved for extra class)

Chemical Treatment Methods

Lec9: Jan 29th,2022

Prof. Arun Kumar

(arunku@civil.iitd.ac.in)
Objective: To introduce steps for estimating chemical demands for
pathogen removal

1
 Courtesy: Dr. Irene Xagoraraki (MSU, USA)

Disinfection
Disinfectants:
NaOCl
Ca(OCl)2
Cl2 gas
Chloramines
Ozone
UV irradiation

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 Disinfection
• Any process to destroy or prevent the growth of
microbes
• Intended to inactivate the microbes by physical,
chemical or biological processes
• Inactivation is achieved by altering or destroying
essential structures or functions within the microbe
• Inactivation processes include denaturation of:
– proteins (structural proteins, transport proteins,
enzymes)
– nucleic acids (genomic DNA or RNA, mRNA,
tRNA, etc)
– lipids (lipid bilayer membranes, other lipids)
 Factors Influencing Disinfection Efficacy and
Microbial Inactivation - Water Quality
• Particulates: protect microbes from inactivation;
consume disinfectant
• Dissolved organics: protect microbes from inactivation;
consumes or absorbs (for UV radiation) disinfectant; Coat
microbe (deposit on surface)
• pH: influences microbe inactivation by some agents
– free chlorine more effective at low pH where HOCl
predominates
• neutral HOCl species more easily reaches microbe
surface and penetrates)
• negative charged OCl- has a harder time reaching
negatively charged microbe surface
– chlorine dioxide is more effective at high pH
• The Chick’s Law:
Number of pathogens at time t (Nt) for initial N0 pathogens:
Nt=N0 exp (-ktm) [1]
Where k is disinfection constant and depends on pathogen-
disinfectant interaction (unit=1/time unit);
m is interaction constant

• The Watson’s Law (relationship between chemical

concentration and contact time)
Cntp=constant [2]
Here, C is disinfectant concentration (mg/L) and tp is time required to
effect a constant % kill (mg/L)
If n>1 => contact time is more important than dosage and n=1, both
parameters contribute equally.

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 Ct concept
• Ct Concept: Disinfection can be expressed at the product
of disinfectant concentration and contact time
• (always : concentration in mg/L unit and time in minutes
unit)
– Applies best when disinfection kinetics are first order
 Inactivation of Cryptosporidium Oocysts in Water by
Chemical Disinfectants (Ct99=Ct value for 99%
disinfection)
Disinfectant Ct99 (mg-min/L) Reference

Free Chlorine 7,200+ Korich et al., 1990

Monochloramine 7,200+ Korich et al., 1990
Chlorine Dioxide >78 Korich et al., 1990
Mixed oxidants <120 Venczel et al., 1997
Ozone ~3-18 Finch et al., 1994
Korich et al., 1990
Owens et al., 1994

C. parvum oocysts inactivated by low doses of UV radiation: <10 mJoules/cm2

 chlorination
• Free chlorine: HOCl (hypochlorous) acid and OCl-
(hypochlorite ion)
– HOCl at low pH and OCl- at high pH; HOCl more potent
germicide than OCl-
– strong oxidant; relatively stable in water (provides a
disinfectant residual)
• Chloramines: mostly NH2Cl: weak oxidant; provides a
stable residual
• Chlorine dioxide, ClO2,: strong oxidant; unstable (dissolved
gas)

Concerns due to health risks of chemical disinfectants and

their by-products (DBPs), especially free chlorine and its
DBPs
 Free Chlorine
• Considered to be first used in 1905 in London
• Reactions for free chlorine formation:
Cl2 (g) + H2O <=> HOCl + H+ + Cl-
HOCl <=> H+ + OCl-
• Chemical forms of free chlorine: Cl2 (gas), NaOCl
(liquid), or Ca(OCl)2 (solid)
• Has been the “disinfectant of choice”, recommended
maximum residual concentration of free chlorine < 2
mg/L
• Concerns about the toxicity of free chlorine
disinfection by-products (trihalomethanes and other
chlorinated organics)
Effect of pH on Percentages of HOCl and OCl-
 Chlorination
• Reactions in water
• Reactions with ammonia
• Breakpoint reaction

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 Monochloramine…
Monochloramine formation:
• HOCl + NH3 <=> NH2Cl + H2O
• Stable at pH 7 - 9, moderate oxidation potential
• Generation
– initial free chlorine residual, followed by ammonia
addition to produce monochloramine
• greater initial disinfection efficacy due to free
chlorine
 Reaction of Ammonia with Chlorine:
Breakpoint Chlorination
• Presence of ammonia in water or wastewater and the addition of free
chlorine results in an available chlorine curve with a “hump”
Free chlorine present
Combined
Cl2
present

Chlorine added, mg/L

• At chlorine doses between the hump and the dip, chloramines are
being oxidatively destroyed and nitrogen is lost (between pH 6.5-8.5).
 Breakpoint Reaction for Chlorine

Monochloramine,
organochloramines

Dichloramine,
nitrogen trichloride,
Cl2:N < 5:1 mass basis and
organochloramines

Ref: Metcalf & Eddy, Inc., Wastewater Engineering, Treatment and Disposal. McGraw-Hill, New York.
 Total and combined chlorine
• Total chlorine = free chlorine + combined
chlorine
• Combined chlorine = inorganic
chloramines (monochloramine,
dichloramine, nitrogen trichloride) +
organic chloramines
 Example: Chlorine Demand?

• For a 1-h contact time, chlorine dose to achieve a combined

residual of 0.4 mg/L is 0.6 mg/L. Determine the daily amount
of NaOCl to be applied to treat a wastewater to produce 0.4
mg/L combined residual and 0.5 mg/L free residual
(flow=24000 m3/day)

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 Example: Chlorine Demand: Solution
• NaOCl Na+ + OCl-
– Molecular weight of NaOCl=75.5 g/mole
– As 1 mole of Cl2 gives 1 mole of OCl- (reversible reaction)
– So 1 mole of OCl- also produces 1 mole of Cl2 in water
during use of NaOCl.
• Amount of NaOCl added to meet the required
demand of 0.6 mg/L chlorine
– =(24000 m3/day)(0.6mg chlorine gas/L)(74.5 mg
NaOCl/71 mg Cl2)(1000L/m3)(1kg/106mg)=15.1 kg/day

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 Example: Chlorine Demand: Solution

• Amount of NaOCl added to meet the required

demand of 0.5 mg/L free chlorine (i.e., total
required = 1.6 mg/L)
– =(24000 m3/day)(1.6mg chlorine gas/L)(74.5 mg
NaOCl/71 mg Cl2)(1000L/m3)(1kg/106mg)=40.3 kg/day

Say NaOCl is 80% pure.

So, NaOCl required =40.3kg/day /(0.80)

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 A big picture overview

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 A big picture overview

Singh, D. and Kumar, A. (2015)

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 Big-picture
Emerging Water Contaminants (EWCs)
1. Pharmaceuticals, Endocrine-disrupting chemicals(ex:
triclosan; Bisphenol-A)

2. Nanoparticles (nanosilver, nanoparticles: TiO2, CuO,

Carbon nanotubes)

3. Micro-plastics Some of these are

not regulated
4. Viruses and bacterial pathogens

5. Bioaerosols
Snyder et al. (2007); Kumar and Xagoraraki (2010a); Boone
and Gerba (2007)

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 Big- Picture Overview

Adapted from the Singh, D. and Kumar, A. Understanding effect of interaction of nanoparticles
January
with 28,uptake
roots on 2022 in plants” Environmental Nanotechnology (Book Chapter - (in press)* 22
 Pieces

Singh and Kumar (2014)

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 EWCs: Why to worry now?
1. Occurrence (although low concentration)

2. Toxic nature (long-term toxicity unknown)

3. Long-term implications unknowns

4. How to go about? Additional costs? Additional benefits?

Cost-benefit? Can we afford?

Solution:
Environmental solutions with the help of all areas

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 Perspectives
• More information on parameters are
required.
• Site-specific characterization are required.
• Detailed monitoring and performance
assessment of water treatment plants are
required.
• Prof. B.J. Alappat will take classes from
Feb 1st (tuesday).
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