Need for antimicrobials

Chlorine gas

Risks of using Cl2 gas

Alternatives

Discovered in the year 1774, Chlorine is one of the most useful chemicals in
the treatment of water and waste-water. It is a powerful oxidizing agent which
itself is not flammable but reacts explosively or forms explosive compounds
with other chemicals.
Chlorine is used for:
1. Disinfection
2. Control of Microorganisms
3. Removal of Ammonia
4. Control of taste and odour
5. Colour reduction
6. Destruction of organic matter
7. Hydrogen sulphide oxidation
8. Iron and Manganese oxidation
Chlorine gas is easily available and relatively cheaper than its alternatives.
The residual chlorine that remains in the water can prolong disinfection even
after initial treatment.
When chlorine gas is added to water, it hydrolyzes to hypochlorus acid which
dissociates into hypochlorite ions. The hypochlorite ions reduce the pH of the
water making it more acidic. Since hypochlorus acid is more effective as a
disinfectant than hypochlorite ions, a lower pH is preferred.
Cl2 + H2O HOCl + H+ + OClHowever due to the risks it poses, Chlorine gas nowadays is only used by
large municipal and industrial water purification installations.
Chlorine gas is toxic in nature. Since it is denser than air, it stays close to the
ground when released. When its concentration in air increases to3-5 ppm, it
can be detected by smell, and exposure to 4ppm of Cl 2 gas in air for 1 hour
has serious effects on the respiratory system. An increase in the
concentration of this gas is fatal.
A few of the possible by-products of chlorination are trihalomethanes. They
pose an environmental threat to public drinking water supplies. Some of the
trihalomethanes are extremely volatile. Thus, they easily evaporate which
makes it possible to inhale them. Some THMs are considered carcinogenic.
Chlorine is corrosive and toxic making transportation, storage and handling to
have increased safety measurements.
The residual chlorine is unstable in high concentrations of chlorine
demanding materials, thus requiring higher doses for adequate chlorination.
Chlorination is also ineffective toward some parasitic species when low doses
of Chlorine gas are used.
1. Sodium hypochlorite:
Sodium and Calcium hypochlorite are formed by the reaction of
chlorine with the respective hydroxides. The hypochlorites dissociate in
water to form hypochlorite ion and hypochlorus acid in a manner
similar to chlorination using Cl2 gas. Solutions of sodium hypochlorite
contain some amount of excess caustic which increases the alkalinity
and raises the pH of the water. This can cause hardness scale to form.
Sodium hypochlorite is as effective as chlorine, however it is a
corrosive substance. It disintegrates when it comes in contact with air.
When sodium hypochlorite is used, acetic acid or sulphuric acid are
added to the water. An overdose of the acids can produce poisonous

gases. A low dosage causes the pH levels to remain high which can
irritate the eyes. NaOCl can oxidize pollutants as well as remove
pathogenic microorganisms.
Inhaling NaOCl causes coughing and a sore throat. Swallowing this
compound has effects like a burning sensation, stomach ache,
coughing, vomiting, diarrhea, etc.Sodiumhypochlorite on skin or eyes
causes redness and pain. NaOCl is poisonous for water organisms. It is
very toxic in nature when it comes in contact with ammonium salts.
2. Chloramination
Chloramination is the process of disinfecting using compounds of
chlorines and amines. Monochloramine is preferred over di- & trichloramines, which contribute to an objectionable taste and odour.
Chloramines are weaker oxidizing agents, and therefore a higher
residual will be required for secondary disinfection. These chloramines
remain in the distribution system for a longer time, as the reaction
processes are slower comparatively.
Chloramination cause a reddishdiscoloration when introduced in
unlined cast-iron pipes. Since Chloramines are a product of chlorine
and ammonia, it is necessary to take precautionary steps to avoid
Nitrification:
Nitrification is a bio-chemical process carried out by nitrifying
bacteria under certain conditition.
Over time, as chloramines decomposes, it releases ammonia.
Excess of ammonia in the system speeds up the nitrifying
process. These bacteria, known as nitrosomonas bacteria,
oxidize the ammonia and produce nitrite. Nitrobacter bacteria
convert the nitrite into nitrate. Short term exposure to drinking
water containing nitrite/nitrate levels above the health standard
is causes a problem especially for babies. This is because excess
levels of nitrite/nitrate is related to the capacity of the blood to
carry oxygen. Nitrification also causes depletion of chloramines
in the water. An increase in nitrification causes the pH levels to
reduce and thus can lead to corrosion of pipes made of lead and
copper.

3. Ozone
Ozone is a compound consisting of 3 negatively charged oxygen
atoms. Ozone molecules are highly unstable and are powerful oxidants.
Ozone acts on not only organic and inorganic chemicals, but also on
microorganisms such as virus, bacteria and fungi. Ozone does not have
any effect on the taste or pH of the water. However, the following are
its disadvantages along with being a relatively complex system to
operate:
Low dosages may not effectively inactivate some viruses, spores, and
cysts.
Ozone is very reactive and corrosive, thus requiring corrosion-resistant
material, such as stainless steel.
Ozonation is not economical for poor quality (poorly treated)
wastewater.

Ozone is extremely irritating and possibly toxic, so off-gases from the

contactor must be destroyed to prevent worker exposure.
The cost of treatment is relatively high, being both capital- and powerintensive.
There is no measurable residual to indicate the efficacy of ozone
disinfection
4. Chlorine Dioxide
As a disinfectant, chlorine dioxide is effective in relatively low
concentrations.Chlorine dioxide is a small, volatile and very strong
molecule. In diluted, watery solutions chlorine dioxide is a free radical.
At high concentrations it reacts strongly with reducing agents. Chlorine
dioxide is highly soluble in water and stays as a dissolved gas.
Bio film is usually hard to defeat. It forms a protective layer over
pathogenic microorganisms. Most disinfectants cannot reach those
protected pathogens. However, chlorine dioxide removes bio films and
kills pathogenic microorganisms. Chlorine dioxide also prevents bio film
formation, because it remains active in the system for a long time.

Cl2
Good

NaOCl
Good

Ca(OCl)2
Good

Chloroamines
Poor

O3
Very good

ClO2
good

Poor
Poor
YESTHMs
And
HAA5

Poor
Poor
Yes
-THMs
and
HAA5

Poor
Poor
Yes
-THMs
and HAA5

Poor
Poor
Yes,but less
THMs than
Cl2

Good
Fair
Yes,but less
than Cl2

Persistent Residual

Good

Good

Good

Very good

Safety Concerns

High

Low

Medium

Complexity of
Operations/Mainte
nance
Size Applicability

Minimal

Low(fo
r onsite)
Mediu
m
Minima
l

Very good
good
Yes,Bromi
ne
Insig.
Levels
THMs
formed
None
(good for
ww)
Medium

Moderate

Minimal

Moderate

Moderate

All sizes

All
sizes

All sizes

Mediumlarge

Small-medium

Relative Cost
Long Term
Applicability For:
Potable Water
Waste Water

Low
Low(saf
ety
issues)

Low
Mediu
m

Smallmedium(c
ost)
Moderate
Medium

mediu
m

high
Mediummust
have
residual
high

moderate
Medium

medium

Low
Effective only
for residual
purposes
none

Disinfection
Capabilities
Bacteria
Viruses
Cysts
Generation of
Hazardous
Disinfection byproducts

medium

Chlorite/chlorat
e produced
Fair
Medium-high

Low (cost)

MANUFACTURING OF CHLORINE DIOXIDE- GENERATORS

Table 4-1. Commercial Chlorine Dioxide Generators

Generator type
ACID-CHLORITE
(Direct Acid System)
AQUEOUS CHLORINECHLORITE

RECYCLED AQUEOUS
CHLORINE OR "FRENCH
LOOP"
ELECTROCHEMICAL
ACID/PEROXIDE/CHLORI
DE
GASEOUS CHLORINESOLIDS CHLORITE
MATRIX

Main Reactions
4HCl+5NaClO24ClO2+ClO3 Low pH
ClO3- possible
Slow Reaction Rate
Cl2+H2O[HOCl/HCl]
[HOCL/HCl]+ NaClO2ClO2(g)
+H/OCL-+NaOH+ClO3 Low pH
ClO3- possible
Relatively slow
reaction rates
2HOCl+2NaClO22ClO2+Cl2
+2NaOH
Excess Cl2 or HCl needed
due to NaOH formed
NaClO2(aq)ClO2(aq)+ e New technology
2NaClO3 + H2O2+ H2SO4
2ClO2+O2+ NaSO4+ H2O
Cl2(g)+ NaClO2(s)ClO2(g)+
NaCl

Why should ClO2 be used?

Chlorine dioxide is highly effective against bacteria and a more effective

virucide than chlorine. Studies show that ClO 2 is a more rapid disinfectant
than chlorine as it destroys a relatively greater quantity of bacteria in short
contact times.
o

Biofilms:
According to a research paper by LeChevallier in 1990, despite there
being free residual chlorine as high as 15 mg/l, there was a recurrence
of coliform bacteria. This occurrence was attributed to the presence of
bacterial bio-films. Bio films are produced by many bacteria. These
bacteria attach to the surface of the water a produce a polymeric by-

product that helps to protect them from hostile environments. Bio-film

causes many problems in water systems such as restricting water flow,
nitrification, corrosion, etc. It also provides a refuge for pathogenic
bacteria which cause many diseases. Chlorine is not effective in
removing this bio-film.Chlorine does not penetrate the bio-film well. On
the other hand the hypochlorite ion has been found to be so reactive,
that it is removed by reaction before it can penetrate the biofilm.
It is found that weaker oxidants provide for a better control of biofilm
as the weaker oxidants are less reactive to the biofilm constituents. It
was proved in the year 1988 that sessile bacteria (attached to the
surface), are 150-3000 times more resistant to chlorine as compared
to 10-100 times more resistant to chloramines. However, chloramines
did not completely remove the biofilm.
Chlorine dioxide, whereas, has proven to be a better choice for highly
contaminated systems. It controls and completely removes the biofilm. If the system is nutrient rich, then it is necessary to use Chlorine
dioxide in place of chlorine and chloramines.
Legionella
The Joint Commission on Accreditation of Healthcare Organizations
advised all hospitals in the US to control Legionella through continuous
feed of oxidants including ClO2. The Association of Water Technologies
encouraged the use of ClO2 since it did not cause corrosion problems
like halogen biocides.
Virus
Ozone treatment is highly effective against viruses in a relatively clean
system. Chlorine and chlorine dioxide in this case have a relatively
equal effect. For highly contaminated systems, it is found that ozone is
less effective, and chlorine dioxide has a far better effect on viruses.
ClO2 is a cost effective method for controlling the growth of algae.
When algae are killed suddenly, they produce methyl isoborneol and
geosmin. These are odorous compounds and are highly resistant to
chlorine.Chloramination requires a stronger primary disinfectant for it
to work suitably against algae. Also there is a problem of nitrification
occurring in cases where chloramination is used.

Example of ClO2

Regulations

Chlorine dioxide was first used in municipal drinking water treatment in

1944, to control taste and odor at the Niagara Falls, NY water treatment
plant. Chlorine dioxide was found to be superior to chlorine for destroying
phenols, algae, sulfides, iron and manganese contaminants

Group

Substance

Formu
la

Health
based
guideli
ne by

the
WHO
Disinfecta
nts

Chloramines

NHnCl(
3-n)
,
where
n = 0,
1 or 2

3 mg/l

Chlorine

Cl2

5 mg/l

Chlorine dioxide

ClO2

No
guideli
ne

EPA(ENVIRNOMENTL PROTECTION AGENCY)

Typical dosages of chlorine dioxide used as a disinfectant in drinking
water treatment range from 0.07 to 2.0 mg/L. For plants using chlorine
dioxide, median concentrations of chlorite and chlorate were found to
be 0.24 and 0.20 mg/L, respectively in an EPA survey (USEPA, 1998),
the standard is 1.0 mg/L.
An issue for chlorine dioxide is the formation of by-products chlorate
and chlorite. Health Canadas maximum acceptable concentration
(MAC) for chlorite in drinking water is 1 mg/L. The MAC for chlorate in
drinking water is 1 mg/L. What
HEALTH CANADA
chlorine dioxide as primary disinfectant should not exceed a maximum
feed dose of 1.2 mg/L without approval from the WSA. The Maximum
Residual Disinfectant Level (MRDL) is 0.8 mg/l chlorine dioxide in water
within the distribution system

AGENCY

1.)NATIONA
L
EPA

DESCRIPTI
ON
Maximum
contamina
nt level
Chlorite
Maximum
contamina
nt level
goal
Chlorite

INFORMATI
ON
1 mg/L

.8 mg/L

0.8 mg/L

REFERENCE
EPA 2002e
40CFR141.6
4(a)

EPA 2002f
40CFR141.5
3

EPA 2002g
40CFR141.6
5(a)

Maximum
residual
disinfectant
level
0.8 mg/L

EPA 2002h
40CFR141.5
4

Maximum
residual
disinfectant
level goal
2).STATE
Maine

Drinking
water
guideline

60 g/L
7g/L

HSDB 2002

Chlorine
dioxide
Chlorite
HSDB = Hazardous Substances Data Bank;EPA = Environmental
Protection Agency.
USEPA,1994
GERMANY
SWITZERLAND

Reference:
o
o
o
o
o
o

Chlorine dioxide (mg/l)

.8
.05-.02
.05

www.gewater.com
www.lenntech.com
www.safewater.org
http://www.bouldercounty.org/doc/publichealth/ozonedisinfection.pdf
www.epa.gov
http://nepis.epa.gov/Exe/ZyNET.exe/9101AV5S.txt?
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Practical Chlorine Dioxide Vol. 1 & 2

o
o

http://www.epa.gov/ogwdw/mdbp/pdf/alter/chapt_4.pdf