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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.
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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.
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.
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.
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.
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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.
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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.
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;
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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.
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.
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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.
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.
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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.
Acute effects of exposure to the other THMs are not documented in the literature, but
are expected to be similar to chloroform.
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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:
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.
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):
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.
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.
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.
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.
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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.
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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.
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 :
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:
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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.
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.
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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.
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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:
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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
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Published by John Wiley & Sons, Inc., Hoboken, New Jersey.
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