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INTRODUCTION

Disinfection:
Disinfection is an important step in ensuring that water is safe to drink. Water systems
add disinfectants to destroy microorganisms that can cause disease in humans. The Surface
Water Treatment Rule requires public water systems to disinfect water obtained from surface
water supplies or groundwater sources under the influence of surface water.
Disinfection kills or inactivates disease-causing organisms in a water supply and must
provide a 99.9 percent inactivation of Giardia lamblia cysts and enteric viruses to protect
health.

The World Health Organisation Drinking Water Guidelines (WHO, 1993) provides an
appropriate context for the subject matter covered: Disinfection is unquestionably the most
important step in the treatment of water for public supply. The destruction of microbiological
pathogens is essential and almost invariably involves the use of reactive agents such as
chlorine, which are not only powerful biocides but also capable of reacting with other water
constituents to form new compounds with potentially long-term health effects.

There are two kinds of disinfection: primary disinfection achieves the desired level of
microorganism kill or inactivation, while secondary disinfection maintains a disinfectant
residual in the finished water that prevents the regrowth of microorganisms.

Primary methods of disinfection are chlorination, chloramines, ozone, and ultraviolet


light. Other disinfection methods include chlorine dioxide, potassium permanganate and
nano-filtration. Since certain forms of chlorine react with organic material naturally present in
many water sources to form harmful chemical byproducts, the U.S. Environmental Protection
Agency has proposed maximum levels for these contaminants.

The disinfection of potable water is almost universally accomplished by the use of


gaseous chlorine or chlorine compounds, because of the limitations of other procedures, for
example ozone, ultraviolet light, chlorine dioxide etc. Chlorine is easy to apply, measure and
control. It persists reasonably well and it is relatively inexpensive.

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Chlorine and Chlorine Residuals:
Chlorine, being a powerful oxidant, is capable of destroying biological molecules. It
is universally used as a disinfectant for drinking water treatment and as a biocide for cooling
water treatment. However, the very oxidizing nature of chlorine involves it in a number of
side reactions with organic and inorganic substances present in water.

Chlorine, when dissolved in natural waters, gives rise to various oxidizing compounds
depending on the reaction of hydrolysis and oxidation of ammonia, which leads to the
production of free chlorine (as hypochlorous acid or its dissociated form) as well as various
chloramines, all of which retain oxidant property. The oxidants also react with organic matter
to produce halogenated organics. Therefore, chemistry of water chlorination is complex and
involves many molecular and ionic species, with often confusing terminology. In literature,
chlorine dissolved in water may be described as free, active, available, combined,
or residualor a combination of the above. A brief explanation of the nomenclature
associated with water chlorination is given below.

Free Chlorine/Free Available Chlorine (FC/FAC)


This refers to the amount of hypochlorous acid present in water in its dissociated or
undissociated form:
Cl2 + H2O HOCl + HCl
HOCl H+ + OCl

In seawater (which contains about 65 mg/L bromide), the following reactions will also take
place:
HOCl + Br HOBr + Cl

Therefore, in seawater chlorination, HOBr (as well as hypobromite ion, OBr) is also
categorized into FC/FAC.

Combined Chlorine/Combined Available Chlorine


Combined chlorine refers to chloramines, which result from the reaction of free chlorine with
ammonia (or other nitrogenous compounds with an N-C link) present in water:

HOCl + NH3 NH2Cl + H2O


NH2Cl + HOCl NHCl2 + H2O

Additionally, the following reactions are also possible in seawater environments:

NH3 + HOBr NH2Br + H2O


NH2Br + HOBr NHBr2 + H2O
2NH2Cl + Br NHBrCl + NH3 + Cl

Chloramines are much less reactive (that is, less effective as biocides) when compared with
bromamines. Combined forms of chlorine are, in general, less efficient biocides than free

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chlorine, but are more persistent than it. Hence, they are very important from the
environmental point of view.

Total Available Chlorine (TAC)


This refers to the sum of the two terms just defined and represents a major part of the biocidal
capacity of the chlorinated water.

Residual Chlorine
This term is analogous to TAC and is often used to represent the oxidisinfectant capacity of
water (consisting of free and combined oxidants). This capacity goes on reducing as a
function of time because of what is known as chlorine decay. The dosed chlorine
continuously engages in a series of reactions with substances present in water, which in due
time will result in complete disappearance of all measurable chlorine.

Figure 1. Typical Break-point Chlorination Curve

Chlorine Demand (CD)


It is defined as the difference between the amount of chlorine added and the useful residual
chlorine that remains at the end of a specified contact time. It refers to the amount of chlorine
lost in side reactions referred to earlier. As the CD of a given sample of water varies with
the chlorine dose applied and the contact time (that is, the interval between chlorine dosing
and chlorine measurement), it is always denoted with reference to the dose and the contact
time.

Non-oxidizing Chlorine Byproducts (CBP)


These are byproducts of chlorination that result from the reaction of chlorine with organic
matter present (especially humic substances) in water. Several of these compounds exist, but
the majority of them come under the category organo halogens called trihalomethanes
(THM).

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Chlorination:
The chlorination process in the Drinking Water Distribution System (DWDS) has
been practiced in many countries to encounter the water bone diseases. The primary
objectives of the chlorination process are disinfection, taste and odour control in the system,
preventing the growth of algae and other micro organisms that might interfere with
coagulation and flocculation, keeping filter media free of slime growths and mud balls and
preventing possible built up of anaerobic bacteria in the filter media, destroying hydrogen
sulphide and controlling sulphurous taste and odour in the finished water, removing iron and
manganese, bleaching of organic colour.

It can also be used for flushing pipeline before it is brought into operation after
carrying out repairs etc. However in such case chlorinator is adjusted to apply chlorine or
hypochlorite solution at the rate of 50 ppm. Heavily chlorinated water should be allowed to
stand in the pipeline for at least 30 min. and preferably for 12 hours before being replaced
with potable water.

Disinfecting Action of Chlorine:

Henry rule gives the equilibrium of chlorine in water as:


Cl2 (aq) ------- Cl2 (g) (1)

Since the evaporation of chlorine is minimal, aqueous chlorine is hydrolyzed as below


Cl2 + H2O HOCl + HCl (2)
(Hypochlorous acid)
HOCl H+ + OCl- (3)
(Hypochlorite ions)

Figure 2. Dependence of the ratio HOCl/OCl on pH

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According to the equilibrium of reaction 3, more than 99% of the free chlorine is HOCl at pH
5 and similarly more than 99% is OCl at pH 10. Figure 1 shows this relation graphically. The
HOCl is 80 to 200 times stronger than OCl- in-term of disinfecting the pathogens.

Organic and inorganic reactions

The organic and inorganic compounds can be ammonia, nitrite, nitrate, amino acid, and
suspended solids. When hypochlorous acid reacts with organic compounds, the disinfections
capability of the HOCl becomes weak. The reactions are as follow;

HOCl + NH3 ------------> NH2Cl + H2O pH > 7.5


( Monochloramine)

NH2Cl + HOCl -----------> NHCl2 + H2O pH - 5 to 6.5


( Dichloramine)

NHCl2+ HOCl ------------> NCl3 + H2O pH < 4.4


( Trichloramine)
The chloramines so formed are stable and are found to possess disinfecting properties.
They can also remove odour from water but only to certain extent.

Others reactions are such as:


a) Carbon:
C + 2Cl2 + 2H2O ------------> 4HCl + CO2
b) Cyanide:
For pH 8.5 or more
2Cl2 + 4NaOH + 2NaCN --------> 2NaCNO + 4NaCl + 2H2O
5Cl2 + 10NaOH + 2NaCN --------> 2NaHCO3 + 10NaCl + N2 + 4H2O.
c) Hydrogen Sulphide:
H2S + 4Cl2 + 4H2O -------> H2SO4 + 8HCl
H2S + Cl2 ----------> S + H2O
d) Ferrous:
2Fe(HCO3)2 + Cl2 + Ca(HCO3)2 ---------> 2Fe(OH)3 + CaCl2 + 6CO2
e) Manganese:
MnSO4 + Cl2 + 4NaOH ---------> MnO2 + 2NaCl + Na2SO4 + 2H2O
f) Methane:
CH4 + 4Cl2 -----------> CCl4 + 4HCl

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Disinfection by-products:
DBPs are formed when chlorine reacts with the natural, organic materials found in
water, such as algae and decaying plants. Organic materials can wash into surface water from
surrounding lands, such as farms and wooded areas. Urban runoff also carries organic
material into surface water when it rains. During the warmer months, surface water often
contains a lot of organic material. As a result, DBP levels are generally higher in the summer
and fall than other times of the year.

Apart from the fact that chlorine sometimes imparted a bad taste to drinking water, its
liberal use for disinfection purposes went unquestioned until the 1970s when improving
analytical techniques revealed the production of a variety of disinfection by-products (DPBs).
The DPBs of main concern arising from chemical disinfection of drinking water are listed in
Table. The presence of substances such as trihalomethanes (THMs) in drinking water gives
rise to public health concern because of a possible carcinogenic link. For this reason, there
has been a progressive tightening of drinking water standards in respect of the limit value for
total THM (TTHM) in drinking water.

Chlorine by-products:
1. Free chlorine
2. Trihalomethanes (THMs)
3. Chlorinated acetics acids
4. Halogenated acetonitriles
5. Chloral hydrate (trichloroacetaldehyde)
6. Chlorophenols
7. MX (3-chloro-dichlormethyl-5-hydroxy-2(5H)-furanone)

For countries wishing to control DBP, it may not be necessary to set standards for all
of the DBP for which guideline values have been proposed. The trihalomethanes, of which
chloroform is the major component, are likely to be the main DBP, together with the
chlorinated acetic acids in some instances. In many cases, control of chloroform levels and
where appropriate, trichloroacetic acid will also provide an adequate measure of control over
other chlorination by-products.

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(a) Free Chlorine:
Free chlorine in drinking-water is not particularly toxic to humans. The major source
of exposure to chlorine is drinking-water. Therefore, 100% of the TDI was allocated to
drinking water giving a health-based GV of 5 mg/litre for the sum of hypochlorous acid and
hypochlorite ion. Based on the taste and odour threshold of free chlorine, it is doubtful
however that consumers would tolerate such a high level of chlorine. Most individuals are
able to taste chlorine at concentrations below 5mg/litre, and some at levels as low as 0.3
mg/litre. The health-based guide line for chlorine should not be interpreted as a desirable
level of chlorination.

((b) Trihalomethanes:
The predominant chlorine disinfection by-products are the THMs. Nevertheless, they
account for only about 10% of the total organic halogen compounds formed by water
chlorination.

The U.S. Environmental Protection Agency (EPA) survey shows that THMs are
present in most chlorinated water supplies. Even though they pose a less acute health risk
than do waterborne diseases, THMs are still among the important water quality issues.

THMs are formed by the aqueous chlorination of humic substances, of soluble


compounds secreted from algae and of naturally occurring nitrogenous compounds (Morris,
1982). The most common THM compounds are dibromochloromethane (CHClBr 2),
bromoform (CHBr3), chloroform (CHCl3), and dichlorobromomethane (CHCl2Br). The sum
of these four compounds is referred to as Total Trihalomethanes (TTHMs).

Formation of THMs:
When chlorine is added to water with organic material, such as algae, river weeds and
decaying leaves, THMs are formed. Residual chlorine molecules react with this harmless
organic material to form a group of chlorinated chemical compounds, THMs. They are
tasteless and odourless, but harmful and potentially toxic.

The quantity of byproducts formed is determined by several factors, such as the


amount and type of organic material present in water, temperature, pH, chlorine dosage,
contact time available for chlorine, and bromide concentration in the water. The organic
matter in water mainly consists of a) humic substance, which is the organic portion of soil
that remains after prolonged microbial decomposition formed by the decay of leaves, wood
and other vegetable matter; and b) fulvic acid, which is a water soluble substance of low
molecular weight that is derived from humus.

Levels of THMs present in water


The byproduct concentration is mainly determined by the amount of organic material
in the source water. Water facilities that draw water from surface water (lakes, rivers, and
reservoirs) produce water with higher levels of THMs than facilities with groundwater (wells
and springs) as their source of water. TTHM concentrations range from 0.030 to 0.150

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milligrams per liter (mg/l) in surface water and 0.001 to 0.010 mg/l in groundwater. The
distribution of these four compounds varies with bromide concentration in water.

EPA is currently regulating TTHMs for small communities as part of the Microbial/
Disinfection and Disinfection Byproducts (M/DBP) Rules. Under these rules the allowable
TTHM concentrations are 0.080 mg/l of TTHMs, and there are plans to reduce these limits to
0.040 mg/l by the year 2002.

State drinking water standards developed for the other three THM compounds are 0.6
ppb for bromodichloromethane (BDCM), 60 ppb for (dibromochloromethane) DBCM, and 5
ppb for bromoform. The drinking water standards for the four individual contaminants apply
only if a water source was not intentionally chlorinated. If the well or water body was
chlorinated, the federal MCL for the sum of the four THMs applies.

When bromide is present in drinking-water, it is oxidized to hypobromous acid by


chlorine:
HOCl + Br-- = HOBr + Cl-
(hypobromous acid)
HOBr reacts with natural organic compounds to form brominated halomethanes. Similarly,
the presence of iodide may lead to the formation of mixed chlorobromoiodo-methanes.

Some generalized statements can be made with regard to THMs in chlorinated drinking-
water:
(IARC, 1991; Morris, 1982; Canada, 1993):
Concentration of THMs in drinking-water varies widely and ranges from not
detectable to 1mg/litre or more;
THM levels are higher in chlorinated surface water than in chlorinated groundwater;
Concentrations of THMs tend to increase with increasing temperature, pH and
chlorine dosage;
Concentrations of THMs increase upon storage even after exhaustion of residual
chlorine or after dechlorination. This indicates the formation of intermediates products
leading to the slow production of THMs;
Chloroform is usually the most abundant THM often accounting for greater than
90% of the total THM concentration;
If there is a significant amount of bromide in the raw water, the brominated THMs,
including bromoform, may be dominant;
Formation of THMs can be minimized by avoiding pre-chlorination and by effective
coagulation, sedimentation and filtration to remove organic precursors prior to final
disinfection;
Removal of THMs after their formation is difficult and involves resource-intensive
processes such as activated carbon adsorption or air stripping.

Health Effects of THMs:


1. Absorption and Exposure

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Chloroform may be absorbed into the body through ingestion, inhalation, and through
the skin. The largest source of human exposure to THMs in the U.S. is from the consumption
of chlorinated drinking water. Besides consuming water, other water uses in the home may
contribute significantly to total chloroform exposure both from breathing in chloroform
vaporized into the air and from it passing through the skin during bathing. Swimming in
chlorinated pools will also contribute to the total exposure from the same exposure paths.
One study observed that a greater percentage of chloroform passed through the skin when
bathing water temperatures were increased. Chloroform does not concentrate in plants;
therefore, the contribution from food to total chloroform exposure is small.

2. Short-Term (Acute) Effects


Evidence of chloroform's acute effects on humans has been obtained primarily during
its past use as an inhalation anesthetic. In addition to central nervous system effects,
chloroform anesthesia was associated with cardiac arrhythmias and abnormalities of the liver
and kidneys. Inhalation exposure experiments with animals revealed that high levels are toxic
to the liver and secondarily to the kidneys. Skin contact with undiluted chloroform may cause
a burning sensation, redness and blistering.

Acute effects of exposure to the other THMs are not documented in the literature, but
are expected to be similar to chloroform.

3. Long-Term (Chronic) Effects


Chronic oral exposure of humans to chloroform at high doses results in adverse
effects on the central nervous system, liver, kidneys and heart. Animal studies have shown
decreased body weights in rats and mice given chloroform at high oral doses and an increased
incidence of respiratory disease at higher doses. At still higher doses given orally, liver
abnormalities and decreased size of the reproductive organs were observed in rats. In animal
studies investigating effects of chronic exposure to each of the other THMS, liver toxicity
was observed. Bromodichloromethane (BDCM) also caused kidney toxicity.

4. Carcinogenic (cancer-causing) Effects


Chloroform has been demonstrated by several studies to produce kidney and liver
tumors in rats and mice when given orally. In studies of human populations using chlorinated
drinking water in which chloroform is the predominant THM, small increases in the
incidence of rectal, colon and bladder cancer have been consistently observed, with evidence
strongest for bladder cancer. However, because other possible carcinogens were found in this
water, it is impossible to identify chloroform as the sole carcinogenic agent. Therefore,
chloroform has been classified by the U.S. Environmental Protection Agency (EPA) as a
Group B2 or "probable human carcinogen," based on sufficient animal evidence and
inadequate human evidence of carcinogenicity. Evidence from animal studies now strongly
indicates that chloroform exposure causes cancer only after first producing sustained cell
toxicity. Because a certain threshold level of exposure is necessary to cause cell toxicity,
cancer from chloroform exposure can only occur if that threshold is exceeded.

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Based on the results of animal studies in which bromodichloromethane (BDCM)
exposure increased tumours of the large intestine, kidney, and liver, and bromoform increased
tumours of the large intestine, they are also classified in Group B2. Dibromochloromethane
(DBCM) is classified in "possible human carcinogen," based on limited animal evidence of
an increase in liver tumours.

5. Developmental/Reproductive Effects
Reports in the scientific literature in which chloroform was administered to animals
indicate that chloroform has the potential to cause birth defects, miscarriages, and delays in
fetal development. Results have generally been inconclusive regarding exposure to THMs
and adverse developmental or reproductive effects in humans. However, the results of a
recent study suggest an increased risk of early-term miscarriage from high levels of THMs in
tap water, particularly bromodichloromethane (BDCM).

Then why were THMs not regulated for small communities earlier?
The earlier THM regulations only applied to larger systems (those serving more than
10,000 people). EPA, keeping the following factors in mind, believed that exempting smaller
systems would not negatively affect the health of small community people because:

a) The majority of smaller systems use groundwater as their source;


b) Small systems usually use less detention time and hence less contact time;
c) Lack of required professional expertise to control the THMs and the necessity of
disinfection; and
d) Small systems often use less chlorine.

Systems to reduce THMs:


Drinking water systems can reduce THM formation in several ways.
a) Reduce the organic material before chlorinating the water. Treatment techniques, such as
coagulation, sedimentation, and filtration can remove most of the organic materials.
However, activated carbon can be used to remove greater amounts of organic material than
can be removed by other techniques.

b) Optimize chlorine usage.

c) Change the point of chlorine addition in the treatment series. If the point of chlorine
addition is moved to a location after sedimentation or filtration, THM production can be
reduced as these processes remove parts of the organic matter.

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d) Use alternative disinfection methods. Using a mixture of chlorine and ammonia
(chloramine) reduces THM formation. Chloramine also disinfects, but doesnt form THMs.
Ozone can be used along with chlorine and chloramine. Chlorine dioxide is another
alternative. The combination of disinfectants not only reduces the formation of THMs, but
also maintains the residual concentration in the distribution system. But changing the
disinfectant may alter the whole treatment process and might affect the removal of other
contaminants.

e) Other methods:
These include filtration, aeration, boiling, distillation, commercial home treatment
systems or filters, nanofiltration, activated carbon filtering, or leaving tap water standing in a
pitcher in the fridge overnight.

Drinking Water Regulations:

The US drinking water standards relating to disinfection are set in USEPA regulations
known as the microbial-disinfection byproduct (M-DBP) rules. The following provisions of
the 1998 M-DBP rules are of relevance in the current context (Brass, 2000):

The TTHM limit was reduced from 100 g/l to 80 ug/l


The limit for the sum of 5 haloacetic acids (HAA5) was set at 60 g/l
Disinfectant residual limits: Chlorine 4 mg/l
Chloramines 4 mg/l
Chlorine dioxide 0.8 mg/l
Cryptosporidium: Goal of zero contamination level; 2-log removal by filtration
required for surface waters.

(c) Haloacetic Acids:

Haloacetic acids (HAAs) are formed when hydrogen atoms in acetic acid (vinegar)
CH3COOH are replaced by atoms from the halogen group.

Haloacetic acids (HAAs) are compounds containing chlorine and/or bromine. HAAs
are formed during some industrial processes and when water supplies are chlorinated or
disinfected.

In water the HAAs are stable with the five most common referred to as HAA5 which
are monochloroacetic acid (MCA) ClCH2COOH, dichloroacetic acid (DCA) Cl2CHCOOH,
trichloroacetic acid (TCA) Cl3CCOOH, monobromoacetic acid (MBA) BrCH2COOH and
dibromoacetic acid (DBA) Br2CHCOOH.

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Haloacetic Acids Get Into Water:
HAAs can be formed by chlorination, ozonation or chloramination of water with
formation promoted by slightly acidic water, high organic matter content and elevated
temperature. Chlorine from the water disinfection process can react with organic matter and
small amounts of bromide present in water to produce various HAAs.

HAAs are formed when drinking water and wastewater are disinfected. HAAs are also
formed during production processes in chemical and pharmaceutical plants. Bleaching wood
pulp at paper mills can result in HAAs.

People could be exposed to HAAs through:


1. Drinking water containing HAAs: Exposure can also occur by eating food prepared
with such water.
2. Touching water containing HAAs, such as while showering.
3. Eye Contact by touching the eyes with water containing HAAs.

Affect on health:

HAAs can destroy tissues of the mucous membranes and upper respiratory tracts.
Breathing HAAs could cause a burning feeling, coughing, wheezing, sore throat, and
shortness of breath. You could also have a headache or nausea. Breathing HAAs can cause
death from severe damage to the throat, lungs and breathing system.

Swallowing HAAs can be fatal because the compounds severely burn the mouth,
throat and stomach. Other harmful effects are sore throat, vomiting or diarrhea.

The levels of HAAs in drinking water are well below levels that would be harmful.
Some people who drink water containing HAAs at higher than normal levels over many years
may have a higher risk of getting cancer.

Skin contact can cause redness, pain and severe burns. Eye contact can cause blurred
vision, redness, pain and severe burns.

Long-term exposure to HAAs causes liver and kidney problems. Persons with lung
disease may experience more harmful effects.

Removal of Haloacetic Acids From Drinking Water:

The most effective way to reduce HAA concentrations is to remove the organic
precursor compounds that result in the HAA formation. Organic matter can be reduced by
conventional treatment (coagulation, sedimentation and filtration).

Activated carbon filters can be used to remove HAAs after formation as can a reverse
osmosis unit, while biofiltration using anthracite, sand or garnet is also effective in HAA
reduction.

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Standard for Haloacetic Acids in Drinking Water:

Health Canada has proposed a maximum acceptable concentration for the total
concentration of the HAA5 compounds of 80 g/L based on an annual average of at least four
samples.

How is HAA poisoning treated?


There is no treatment just for HAA poisoning. Doctors can treat the symptoms.

What should I do if exposed to HAAs?

1. If you breathe HAAs, move to fresh air. If breathing is difficult, give oxygen. Get
medical help right away.
2. If you swallow HAAs, DO NOT THROW UP. Take large quantities of water. Get
medical help right away.
3. If you touch HAAs, flush skin with plenty of water for at least 15 minutes. Remove
clothing and shoes that contacted HAAs. Get medical help. Wash clothing before
wearing again.
4. If you get HAAs in your eyes, flush eyes right away with water for 15 minutes or
more. Lift the lower and upper eyelids from time to time. Get medical help right
away.

What factors limit use or exposure to HAAs?


Using proper safety procedures in workplaces will help limit exposures.

Is there a medical test to show whether Ive been exposed to HAAs?


There is no test that can show exposure to HAAs. A doctor will check for symptoms of
exposure.

Technical information for HAAs:


CAS Number:
1. Monochloroacetic Acid 79-11-8
2. Dichloroacetic Acid 79-43-6
3. Trichloroacetic Acid 76-03-9
4. Bromoacetic Acid 79-08-3
5. Dibromoacetic Acid 631-64-1
Chemical Formula:
1. Monochloroacetic Acid CH2ClCOOH
2. Dichloroacetic Acid C2H2Cl2O2
3. Trichloroacetic Acid CCl3COOH
4. Bromoacetic Acid C2H3BrO2
5. Dibromoacetic Acid C2H2Br2O2
Carcinogenicity (EPA): Possible carcinogens.

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MCL (Drinking Water): The MCL for HAAs is 0.06 mg/L
OSHA Standards: There are no OSHA standards for any of the HAAs.
NIOSH Standards: 1 ppm (7 mg/m3) time weighted average for a 10 hour day, 40 hour week.

(d) Halogenated acetonitriles:


1. Dichloroacetonitrile,
2. Dibromoacetonitrile,
3. Bromochloroacetonitrile
4. Trichloroacetonitrile.

Halogenated acetonitriles are produced during water chlorination or chloramination


from naturally occurring substances, including algae, fulvic acid and proteinaceous material.
In general, increasing temperature and/or decreasing pH have been associated with increasing
concentrations of halogenated acetonitriles. Ambient bromide levels appear to influence, to
some degree, the speciation of halogenated acetonitrile compounds. Dichloroacetonitrile is by
far the most predominant halogenated acetonitrile species detected in drinking-water.

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Chemical Fact sheet

Toxicological review:

IARC has concluded that dichloro-, dibromo-, bromochloro- and trichloroacetonitrile are not
classifiable as to their carcinogenicity in humans. Dichloroacetonitrile and
bromochloroacetonitrile have been shown to be mutagenic in bacterial assays, whereas results
for dibromoacetonitrile and trichloroacetonitrile were negative. All four of these halogenated
acetonitriles induced sister chromatid exchange and DNA strand breaks and adducts in
mammalian cells in vitro but were negative in the mouse micronucleus test.

The majority of reproductive and developmental toxicity studies of the halogenated


acetonitriles were conducted using tricaprylin as a vehicle for gavage administration of the
compound under study. As tricaprylin was subsequently demonstrated to be a developmental
toxicant that potentiated the effects of trichloroacetonitrile and, presumably, other
halogenated acetonitriles, results reported for developmental studies using tricaprylin as the
gavage vehicle are likely to overestimate the developmental toxicity of these halogenated
acetonitriles.

1. Dichloroacetonitrile:
Dichloroacetonitrile induced decreases in body weight and increases in relative liver
weight in short-term studies. Although developmental toxicity has been demonstrated, the
studies used tricaprylin as the vehicle for gavage administration.

2. Dibromoacetonitrile:
Dibromoacetonitrile is currently under test for chronic toxicity in mice and rats. None
of the available reproductive or developmental studies were adequate to use in the
quantitative doseresponse assessment. The data gap may be particularly relevant since
cyanide, a metabolite of dibromoacetonitrile, induces male reproductive system toxicity, and
due to uncertainty regarding the significance of the testes effects observed in the 14-day
National Toxicology Program (NTP) rat study.

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3. Bromochloroacetonitrile:
Available data are insufficient to serve as a basis for derivation of a guideline value
for bromochloroacetonitrile.

4. Trichloroacetonitrile:
Available data are also insufficient to serve as a basis for derivation of a guideline
value for trichloroacetonitrile. The previous provisional guideline value of 1mg/litre was
based on a developmental toxicity study in which trichloroacetonitrile was administered by
gavage in tricaprylin vehicle, and a recent re-evaluation judged this study to be unreliable in
light of the finding in a more recent study that tricaprylin potentiates the developmental and
teratogenic effects of halogenated acetonitriles and alters the spectrum of malformations in
the fetuses of treated dams.

Standards:

The 1958, 1963 and 1971 WHO International Standards for Drinking-water and the
first edition of the Guidelines for Drinking-water Quality, published in 1984, did not refer to
halogenated acetonitriles. The 1993 Guidelines established provisional healthbased guideline
values of 0.09 mg/litre for dichloroacetonitrile, 0.1mg/litre for dibromoacetonitrile and 0.001
mg/litre for trichloroacetonitrile. The guideline values were designated as provisional because
of the limitations of the databases (i.e., lack of longterm toxicity and carcinogenicity
bioassays). Available data were insufficient to serve as a basis for derivation of a guideline
value for bromochloroacetonitrile.
(e) Chlorophenols :

Chlorophenols are present in drinking-water as a result of the chlorination of phenols


during disinfection, as by-products of the reaction of hypochlorite with phenolic acids, as
biocides or as degradation products of phenoxy herbicides.

Chlorination increased the concentrations of 2-CP (maximum 65 ng/litre), 2,4-DCP


(72 ng/litre), and 2,4,6-TCP (719 ng/litre).

Compound CAS no. Molecular formula


2-Chlorophenol 95-57-8 ClC6H4OH
2,4-Dichlorophenol 120-83-2 Cl2C6H3OH
2,4,6-Trichlorophenol 88-06-2 Cl3C6H2OH

A total of 19 possible chlorinated phenols exist, but only 2-chlorophenol (2-CP), 2,4-
dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) will be evaluated here, as
these are the most likely to occur in drinking-water as possible by-products of disinfection.

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Major uses:

2-CP is used as a precursor in the production of higher chlorophenols and dyestuffs,


and as a preservative.
2,4-DCP is used as a mothproofing agent, germicide and antiseptic, and in the
production of the pesticide.
2,4-D. 2,4,6-TCP is used in the production of 2,3,4,6-tetrachlorophenol and
pentachlorophenol, and as a germicide, glue and wood preservative.

Effects on Laboratory Animals:


1. 2-Chlorophenol:
Long-term exposure:
Immunological (e.g. humoral and cell-mediated immunity, macrophage
function) and haematological (e.g. red and white blood cell count, haematocrit,
haemoglobin) effects were assessed in groups of 1220 weanling female Sprague-
Dawley rats exposed to 0, 5, 50, or 500 mg of 2-CP per litre in drinking-water (0, 0.5,
5, or 50 mg/kg of body weight per day) in a reproductive study. Females were
exposed from 3 weeks of age until breeding at 90 days, and throughout gestation to
parturition. No treatment-related differences were found.

Treatment was continued during breeding, gestation, and weaning. Parameters


evaluated included percentage conception, litter size, birth weight, number of
stillbirths, weanling weight, and haematology in weanling rats. A treatment-related
increase in conception rate, an increase in the number of stillbirths, and a decrease in
the size of the litters were observed at the highest dose.

In a 24-month experiment, female Sprague-Dawley rats (1222 per dose) were


given 2-CP in drinking-water at 0, 5, 50, or 500 mg/litre (0, 0.5, 5, or 50 mg/kg of

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body weight per day) for 10 weeks, then bred. Ethylurea and nitrite, precursors of the
transplacental carcinogen nitrosoethylurea (NEU), were administered to females on
days 1421 of pregnancy.

The effects on tumour incidence and latency were most evident in male
progeny that received 2- CP with NEU, both pre- and postnatally. The lowest level of
2-CP appeared to exert the greatest effect.

The scientists suggested that 2-CP is a co- carcinogen.

2. 2,4-Dichlorophenol:

Long-term exposure:
Investigations of the effects of long-term exposure to 2,4-D have been
designed primarily to test its carcinogenic properties.

3. 2,4,6-Trichlorophenol:
Acute exposure:
2,4,6-TCP was mixed with corn oil and administered daily by gavage to
Sprague Dawley rats (10 per sex per dose) for 90 consecutive days at 0, 80, 240, or
720 mg/kg of body weight per day. At 240 mg/kg of body weight per day, liver weight
increased in males and adrenal gland weight increased in females. At the highest dose,
treatment-related effects included salivation, increased weights of the kidneys, liver,
adrenal glands, and testes, and an increase in serum albumin, total protein, and serum
alanine aminotransferase, as well as a decrease in urinary pH.

Long-term exposure:
Dose-related decreases in mean body weights were seen in male and female
mice. There was no statistically significant dose-related trend in mortality in either
sex. There was no effect on mitotic crossing-over or mitotic gene conversion.

4. 2,4,6-Trichlorophenol:
2,4,6-TCP has been reported to induce lymphomas and leukemias in male rats
and hepatic tumours in male and female mice. IARC has concluded that 2,4,6-TCP is
possibly carcinogenic to humans.

The hepatic tumours found in this study were not used for risk estimation,
because of the possible role of contaminants in their induction.

The lowest reported taste threshold for 2,4,6-TCP is 2 g/litre. If water


containing this chlorophenol is free from taste, it is unlikely to present an undue risk
to health.

(f) 2-chloro-5-oxo-3-hexene diacyl chloride (COHC):

MX was widely considered as one of the most important disinfection by-products


(DPBs) and as the strong carcinogen in the chlorinated drinking water.

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MX was produced only in the chlorinated substituted aromatic aldehydes and amino
acids, while a possible new compound (COHC) was found in some substituted aromatic
aldehydes, chlorinated substituted aromatic acids and phenols. Through the analysis of the
peaks presented in mass spectrum, the composition and structure of the new compound are
proposed as 2-chloro-5-oxo-3-hexene diacyl chloride (COHC) which could cause
interference in the detection of MX.

It is widely accepted that dissolved humic substance (HS) in raw water is the primary
precursor of DBPs of chlorinated drinking water including MX. Due to the complexity of the
structure of HS, model compounds were selected as surrogates of HSs to study the formation
of MX upon chlorination.

MX was not detected in the chlorinated aromatic acid and phenol solutions of which
some compounds such as phenol, o-hydroxyphenol, 3,4-dimethoxyl-benzoic acid, and p-
hydroxybenzoic acid were believed to be precursors of MX. Only substituted aromatic
aldehydes and some amino acids were able to produce MX upon chlorination.

MX were formed by chlorinating phenols and substituted aromatic acids


which are devoid of aldehydes. Because no standard of COHC was available, it was
impossible to quantify it.

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SUMMARY
Disinfection:
Disinfection of all waters supplied for drinking is recommended by WHO to protect
public health.
Main disinfectants evaluated in the Guidelines are: free chlorine, chloramines,
chlorine dioxide and ozone.
Overall ozone is the most effective disinfectant, although chlorine is also effective
and efficient.
All disinfectants have advantages and disadvantages and all produce by-products.

Chlorine and its byproducts:


Chlorine is most common disinfectant
When chlorine is added to water it forms hypochlorous acid, hydrogen ion and a
chlorine ion.
Because of greater efficiency, disinfection with chlorine is done at pH less than 8
and a free chlorine concentration of greater than 0.5 mg/l
The use of chlorine leads to the formation of halogenated byproducts, including the
THMs.
Precursors to THMs are natural humic and fulvic acids and algal material.
Numerous other by-products may be formed.
Impurities in gaseous and liquid chlorine of relevance to the nature of by-products
are carbon tetrachloride and bromide.
Very difficult to estimate exposure to halogenated organic compounds in drinking
water.
May not need to set standards for all by-products it is better to concentrate on the
major groups (e.g. THMs).
Microbiological quality of water should never be compromised by concerns about
disinfection by-products.

Chlorine:

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Free chlorine in drinking-water is not particularly toxic and health-based GV is 5
mg/l.
Very unlikely consumers would accept such levels of chlorine as taste is noted as
low as 0.3 mg/l.
Do not use GV as desirable level of chlorination.

Trihalomethanes:
These are principal by-products of chlorination, but only form 10per cent of total
organic compounds in drinking-water.
THMs more likely to occur in chlorinated surface water than groundwater
THM concentrations vary widely; increasing with increasing temperature, pH,
chlorine dosage and on storage after exhaustion of free chlorine or dechlorination.
Chloroform is most common THM (usually >90% of total THMs).
When bromine present, brominated THMs likely to be dominant
THM formation can be minimised by avoiding prechlorination and by optimising
treatment.
THM removal is expensive and difficult.

Chloramine:
Chloramines formed by reaction of chlorine and ammonia or organic amines.
Can get mono-, di- and trichloramines depending on pH and temperature
Chloramine by-products similar to free chlorine, with exception of cyanogens
chloride.
Monochloramine about 2000 to 100, 000 times less effective than free chlorine for
inactivation of E.coli and rotaviruses.

Chlorine dioxide:
Chlorine dioxide made at point of use because of its explosive hazard.
Chlorine dioxide does not form THMs or chloramines.
Main by-products are chlorite, chlorate and chloride.
Chlorine dioxide more effective than free chlorine in inactivation of Giardia cysts
but less effective against E.coli and rotaviruses.
No GV for chlorine dioxide in water as it rapidly disassociates.

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CONCLUSIONS
Disinfection is important to assure a safe drinking-water supply.
Limited information is available concerning health risk from disinfection by-
products.
Disinfection by-product formation may be reduced if treatment process are
optimised and prechlorination is avoided.
Inadequate evidence exists concerning the carcinogenicity of chlorinated drinking
water.
More information is available concerning chlorine because it has been studied in
more detail and this should not penalise the use of chlorine.
As microbiological quality is of paramount importance, disinfection should not be
compromised.

REFERENCES

1. WATER ENCYCLOPEDIA (DOMESTIC, MUNICIPAL AND INDUSTRIAL


WATER SUPPLY AND WASTE DISPOSAL).

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Published by John Wiley & Sons, Inc., Hoboken, New Jersey.

2. MANUAL ON OPERATION & MAINTENANCE OF WATER SUPPLY SCHEME.


3. PHAC-Position-Paper-Safe-Drinking-Water_2
4. www.sciencedirect.com/science/article/chlorination
5. www.who.int/water-sanitation-health/dwq/chemicals/chloralhydratesumstatement.pdf
6. www.publichealth.wa.gov.au/cproot/trihalomethanes.pdf
7. www.nesc.wvu.edu/ndwc/articles/QandA/OTsp99-Q-A.pdf
8. www.caslab.com/EPA-methods/PDF/552-2.pdf
9. www.water-research.net/trihalomethanes.htm
10. www.saskh2o.ca/PDF-watercommittee/haloaceticAcids.pdf
11. www.chem.agilent.com/Library/apllications/gcm61_chlorophenols_Saturn.pdf
12. www.pjoes.com/pdf
13. www.gfredlee.com/wswq/kinetics chlorinationleemorris.pdf

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