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The New Generation of Disinfection

Byproducts (DBPs)
Term Paper in Biogeochemistry and Pollutant Dynamics
Master Studies in Environmental Sciences, ETH Zrich
by
Stefan Rieder
Academic Advisor:
T. Hofstetter and U. von Gunten
Zrich, November / Dezember 2007

Abstract
Disinfection of drinking water is an important procedure to maintain the water quality.
There are four common disinfectants; chlorine, chloramine, chlorine dioxide and
ozone. Chlorine is the most used. Water treatment leads with all disinfectants to
different byproducts. Chlorination, chloramination and chlor dioxination of water can
lead to the same DBPs but in different amounts. But there also exist specific DBPs
for each disinfectant. Among of them shows toxic effects of human health. Especially
brominated DBPs can lead to serious health problems, often they induce cancer.
Bromate is one of these toxic DBPs, formed by ozonation of bromide in water. The
reduction of such DBPs is one of the main targets of the DBP research. Therefore it
is important to understand, how the particular DBPs are formed and which conditions
promote their formations. Generally is the formation dependent on the amount and
characteristic of organic matter in the water, the pH, the disinfect time and the
amount of the disinfectant.

1. Introduction
Water resources and its maintain of quality are important issues in human life.
Many human diseases are related to water-borne pathogens, mainly if the drinking
water is affected by wastewater or human or animal excretions. To process water,
people have disinfected drinking water since the end of the 19th century [8]. The
disinfection of fresh water has the main target to destroy microbial and viral
pathogens in order to eliminate waterborne diseases like cholera and typhoid. In
many papers is the disinfection of drinking water described as a major public health
success of the last century [9]. Before it was widespread used, huge numbers of
humans died of cholera, typhoid and other waterborne diseases. The outbreak of
these diseases is extremely decreased. Recent outbreaks, for example of
Escherichia coli-induced gastroenteritis (Walkerton, Ontario, 2000) or cholera (Peru
beginning in 1991), shows the importance of water disinfections [9].
A minor drinking water problem can be the taste and odor from the water.
Chlorine, ozone, chloramine and chlorine dioxine are the most used disinfectants to
minimize the number of the pathogens in water. This compounds are strong oxidants
and convert natural organic matter to disinfection byproducts (DBPs). The first DPB
was described in 1974. Many studies showed negative influence of DBPs to humans
health. Animal studies adverted to a correlation between some DBPs and the
appearance of cancer. Other concerns showed negative reproductive and
developmental effects after the exposure by DBPs [10].
Typical, there exist two sources of raw water for the drinking water production namely
groundwater and surface water. Ground water is usually of better quality as
compared to surface water (microbial). Additionally surface water (water from rivers,
lakes and reservoir) contains higher levels of organic matter and particles.
Therefore, lower disinfectants are necessary by groundwater disinfection than by
surface water disinfection. The higher amounts of disinfectants combined with the
higher amount of organic matter and other compounds in the surface water usually
lead to more DBPs than disinfection of groundwater. In the USA, water treatment
often involves the disinfection of waste water that often leads to higher
concentrations of DBPs, because higher amounts of organic matter are presented
and more disinfectant are necessary. In Switzerland, the waste water first will be
treated in sewage treatment plants (STP). In this treatment, DBPs can be formed by
oxidation of organic compounds by disinfectants. To get drinking water, one
disinfects raw water. Raw water treatment processes including usually coagulation,
flocculation, sedimentation, filtration and disinfection. In this step, DBPs can be
formed too.
The literature describes approximately 600-700 DBPs today which are formed by the
common disinfectants [2].
In this paper I will try to explore how and in which conditions these products were
formed. I will concentrate on the three most used disinfectant, chlorine, chloramines,
and ozone. In a second part, I will elect a special DBP, n-nitrosodimethylamine, and I
will describe this formation in details. Influence factors can be the disinfectant way,
the concentration of the disinfectant, the contact time, the organic compounds in
water (DBP precursors), the treatment and the pH [6].

2. Formation of DBPs by different disinfectants


This paper focuses on three common disinfectants, chlorine, chloramines and ozone.
I exclude chlorine dioxide, a forth often used disinfectant, of this paper because it
forms most the same DBPs like Chlorine. In the last approximately 100 years,
chlorine was the usual disinfectant. Chlorine forms many DBPs; some of these are
carcinogenic (see point 2.1). In this part, Ill describe the most used disinfectants and
their major DBPs. A recently realized US Nationwide DBPs Occurrence Study
ascertained the most priority organic DBPs. They arranged the DBPs in 11 groups.
Table 1 shows a part of the results of this study [2]. The seven shown groups are part
of the discussed or mentioned DBPs in this paper. The most groups in table 1 include
halogenated DBPs. The halogen atom can come from the treated water (for example
bromide) or can bring in by the disinfectant (for example Cl by chlorination).
Table 1. Priority DBPs Selected for Nationwide Occurrence Study
a
Not a DBP but included because it is an important source water contaminant.b DBP not originally
prioritized (identified in drinking water after initial prioritization) but included due to similarity to other
priority compounds.c Not analyzed; not stable in water.d DBP not given a high priority but included for
completeness sake to provide more representation to ozone DBPs for occurrence.
From Krasner et al. 2006: [2]

chloromethane
bromomethane (methyl bromide)a
bromochloromethane
dibromomethane

halomethanes
dichloroiodomethane
bromochloroiodomethane
b
dibromoiodomethane
b
chlorodiiodomethane

chloroacetonitrile
bromoacetonitrile

haloacetonitriles
bromodichloroacetonitrile
dibromochloroacetonitrile

chloropropanone

haloketones
1-bromo-1,1-dichloropropanone

1,1,3,3-tetrabromopropanoneb

1,1,3,3-tetrachloropropanone
1,1,1,3-tetrachloropropanone

1,1,1,3,3-pentachloropropanone
c
hexachloropropanone

haloaldehydes
b
bromochloroacetaldehyde

tribromoacetaldehyde

1,3-dichloropropanone
1,1-dibromopropanone
1,1,3-trichloropropanone

chloroacetaldehyde
dichloroacetaldehyde

chloronitromethaneb
bromonitromethane
b
dichloronitromethane

monochloroacetamide
monobromoacetamideb

bromodiiodomethane
triiodomethane (iodoform)b
carbon tetrachloride
tribromochloromethane

tribromoacetonitrile

halonitromethanes
bromochloronitromethaneb
dibromonitromethane
b
bromodichloronitromethane

dibromochloronitromethaneb
b
tribromonitromethane (bromopicrin)

haloamides
dichloroacetamide
dibromoacetamideb

trichloroacetamide

carbonyls

2-hexenal

5-keto-1-hexanal

cyanoformaldehyde
d

methylethyl ketone

6-hydroxy-2-hexanoned

dimethylglyoxal

2.1. Chlorination
Chlorination is the process of adding chlorine (Cl2) into water:
Cl2 + H2O HOCl + HCl
Salts of hypochlorous acid (mostly NaOCl) are often used in place of Cl2 due to the
lower hazard during handling.
The results of the reaction above are hypochlorous acid (HOCl) and hydrochloric acid
(HCl). Hypochlorous acids react with many organic components and destroy
efficiently many forms of bacteria and viruses. As a result of the chlorine reaction with
organic matter, DBPs will be formed.
Chlorine was the most used disinfectant for drinking water in the last 100 years. In
USA, it is still the main disinfectant. The first observed DBP was formed after raw
water chlorination treatment. This was the start of DBP research. The most efforts
were spent to find out more about the chlorination treatment [6]. More than 300
reported DBPs are formed from chlorination. The two major classes of formed DBPs
are trihalomethanes (THMs) and haloacetic acids (HAAs). These both are the most
observed DBPs after the chlorination of wastewater. A third important class is the
Haloacetonitriles (HANs). At least four of these compounds are carcinogenic
(chloroform, bromodichloromethane, bromoform, MX) [11]. In the follow parts, I'll try
to describe the different chlorinated DBPs briefly, especially their formation and
effects.

2.1.1. Halomethanes
The structure of halomethanes is based of methane. Halogenes take up the binding
places of hydrogen atoms. For example the structural formula of
Br
bromodichloromethane is showed on the left.
Cl C
H Halomethanes with three haloatomes are called trihalomethanes
(THMs), see in table 1 (column in the middle and on the right).
Cl
Trichloromethane (chloroform; CHCl3), tribromomethane (bromoform;
CHBr3) and triiodomethane (iodoform; CHI3) are the most described
forms of THMs. Especially chlofororm, bromoform and bromodichloromethane are
human hazard. In animal experiments a correlation were found between these three
THMs and the appearance of tumors in target organs (e.g. liver, kidney and bladder)
[12]. Brominated DBPs are often more carcinogenetic than their chlorinated analogs.
Bromide-ions are strong nucleophils and can interact with cellular components,
especially with the DAN.

The origin of chloroform can be illustrated by the interaction between chlorine and
propanone. Propanone (an example for organic matter) will be oxidized into
trichloropropanone if water became chlorinated:
CH3COCH3 + HOCl  CH3COCCl3
In the following reaction, trichloropropanone becomes hydrolyzed, especially at high
pH:
CH3COCCl3 + H2O  CH3COOH + CHCl3
The result of both reactions is chloroform.
An important influence of THM formation is the organic matter in the water.
Hydrophobic organic matter (contains more aromatic compounds, less carboxlic
acids and is probably of higher molecular weight compared to hydrophilic organic
matter) leads to higher precursors concentrations of THMs than hydrophilic
components (contains more carboxylic acids and less aromatic compounds, it is of
lower molecular weight compared to hydrophobic organic matter). Due to this, more
THMs are produced if in the organic matter is more hydrophobic than hydrophilic
matter present [6].
Another factor is the contact time between the waste water and the chlorine. Figure 1
shows the THM4/TOC ratio (TOC = total organic carbon) depending on the contact
time. This graphic descend from a observation by Liang and Singer [6]. Under THM4
they collect the sum of the four observed THMs (trichloromethane,
bromodichloromethane, chlorodibromomethane, tribromomethane). All experiments
were conducted from five water utilities. The water sources were in Tolt, Manatee,
Groton, E.St.Louis and Indianapolis.

Fig.1: Formation of THM4 (sum of four diffrent THMs) in


raw water depends of chlorine contact time by pH = 8 for
five difftent water samples.
From Ligan and Singer 2002: [6]

In figure 1 we can see, that in the first 10 hours the THMs formation is much faster
than in the following hours. Chlorinated raw water from Tolt shows the highest
THM4/TOC ratio, chlorinated raw water from E. St. Louis and Indianapolis the lowest.
How mentions above, THM formation increases with higher amounts of hydrophobic
components. Organic matter in Told water shows the highest percentage of
hydrophobic fraction (see chapter 3.1.2) and the highest ratio of THM4/TOC.
The pH value has an effect of the formation of THMs too. The formation of THMs
increases due to a increasing pH from 6 to 8 [6]. Richardson et al. observed that in
warmer water, more THMs were produced than in colder [13].
Bromoform and bromodichloromethane can only appear, if bromide has been
presented in the disinfected water. The highest concentrations of bromide in water
can we find in seawater. Normally, the amount of salt in water reflects the value of
bromide. In water by arid region (higher evaporations rates than rainfall) we find the
highest concentrations of bromide excluded seawater. A second important point for
building brominated trihalomethanes is the concentration of dissolved organic carbon
in water. Normally, a high concentration of brominated trihalomethanes is observed
at low dissolved organic carbon concentrations.

2.1.2. Haloacetic acids


The based forms of haloacetic acids are carboxylic acids in which
halogen atoms can take the place of hydrogen atoms in acetic acid. The
Cl
formula of acetic acid is CH3COOH. For example dichloroacetic acid is
OH
H
shown on the left.
There exist 9 common HAAs which we can arrange in 3 different groups of haloacetic
acids. The amount of halogen atoms which replaced the hydrogen atoms at the alpha
position, define the 3 groups  monohaloacetic-, dihaloacetic-, trihaloacetic acids
(see table 1). Some HAAs shows toxic effects. Exposure of some HAAs showed
mutagenic effects or leaded to tumors. Therefore, the US Environmental Protection
Agency (USEPA) and the WHO published guidelines for some HAAs in drinking
water [12].
Chlorinated and brominated acetic acids are produced in chlorinated water as often
or a bit fewer as those of trihalomethanes [12].
Same by the formation of THMs, hydrophobic organic matter in water leads to higher
concentration of HAAs than by hydrophilic components. This is shown in Figure 2 for
pH 6 [6]. The HAA9 formations from the hydrophobic fractions were in all cases
higher than the corresponding HAA9 formation from the hydrophilic fractions. SUVA
(Specific ultraviolet absorbance) is an indicator of natural organic material and a good
predictor of aromatic carbon content in water. SUVA is calculated by the water
samples ultraviolet absorption at a wavelength of 254 nm, times 100, divided by the
sample concentration of dissolved organic carbon. As mentioned above, it exist a
strong correlation between the SUVA value and the aromatic carbon content of
natural organic matter in raw water. The SUVA value of the raw water increases as
the percentage of hydrophobic carbon fraction (in raw water) increases [6].
O

Cl
C

Fig.2: Building of HAAs in five different clorinated water during


72 hours by pH = 6.
From Ligan and Singer 2002: [6]

In figure 2, the corresponding SUVA values are the numbers above the bars. In all
cases, higher SUVA values correlate with higher HAA9/TOC ratios than the samples
with the lower SUVA values. The one SUVA value from treated water from Told is
more than two times higher than the other. The value of HAA9/TOC is in this water
sample almost two times higher than in the waters with the lower SUVA values.
The different HAA9/TOC values by chlorination of water from the five source regions,
correlate with the values of THM4/TOC (see chapter 2.1.1). Water from Tolt has the
highest HAA9/TOC value. The THM4/TOC ratio is in this water higher then in the four
other waters. Treated raw water from Groton has the second highest value of
THM4/TOC and HAA9/TOC (see figures 1, 2).
Another effect to the formation of HAAs has the pH value. Does the pH in water
increased from 6 to 8, a very little effect to the formation of monohaloacetic acids and
dihaloacetic acids was observed. It seems that the pH in this range has only a
significant effect for the formation of trihaloacetic acids. Decrease the pH from 8 to 6,
the amount of trihaloacetic acids increase significantly [6].
On other observation was that more HAAs were formed in warmer months than in
colder [13].
Brominated haloacetic acids have been observed by chlorination of water with
elevated bromide concentrations. By chlorination of seawater the most common
produced HAAs are dichloroacetic acid, bromodichloroacetic acid and dibromoacetic
acid.

2.1.3. Haloacetonitriles
Haloacetonitriles (HANs) are toxic, small nitrogenous water
disinfection byproducts and does most exist with two halogen
N substitutions [1]. For example dichloroacetonitrile is shown on the
C
Cl C
left. After chlorination, HANs are usually formed at about an order of
H
magnitude lower concentration than THMs and HAAs [12]. The
formation of HANs has been observed; when in chlorinated water
nitrogen containing organic material was present.
Cl

I could not find somewhere information about factors which influencing the formation
of HANs. I assume that the formation of HANs is not well researched.
Muellner analyzed seven HANs due to their acute genotoxycity and chronic
cytotoxicity in animal experiments with Chinese hamsters [1]. The seven HANs were
iodoacetonitrile (IAN), bromoacetonitrile (BAN), dibromoacetonitrile (DBAN),
bromochloroacetonitrile (BCAN), chloroacetonitrile (CAN), dichloroacetonitrile
(DCAN) and trichloroacetonitrile (TCAN). The result was that DCAN, BCAN, CAN
and TCAN are mutagenic in Salmonella typhimurium. HANs directly induced sister
chromatid exchanges in the ovary cells of the inspected animals. But the toxicity of
this effect was not the same for each of HANs. The rank order was DBNA > BCNA >
TCAN > DCAN > CAN [1].
The results of the experiments are shown in figure 3 + 4. The figure 3 shows the
chronic cytotoxic effect of the seven observed HANs by Chinese hamsters ovary cells
(CHO) due to their concentration. Measured was the reduction in observed cell
density after 72 hours (~ 3 cell divisions) exposure. All seven HANs were cytotoxic.
Iodoacetonitrile, dibromoacetonitrile and bromoacetonitrile show by already low
concentration strong effects to the cell density. A 50% reduction of the cell density
was observed after exposure with these HAAs by a concentration of ~ 5 M. By the
same exposition concentration with chloroacetonitrile, dichloracetonitrile and
tricloracetonitrile, no effect was observed. The level of genomic DNA damage was
measured with Single cell gel electrophoreses (SCGE). This result is shown in figure
4. Iodoacetonitrile and dibromoacetonitrile shows by already low concentrations
strong effects to the cell genomic DNA damage. By a concentration of ~ 50 M of
these two HAAs, more than 60% of the CHO cells show damages. By the same
exposition concentration with bromochloroacetonitrile, chloroacetonitrile,
dichloracetonitrile and tricloracetonitrile, no effect was observed.

Fig. 3: CHO chronic cytotoxity concentration for seven HANs


From Mueller et al. 2007: [1]

Fig. 4: SCGE genotoxicity concentration, response curves for seven


HANs. This figure shows the level of DNA damage in electrophoresed
nuclei.
From Mueller et al. 2007: [1]

If there bromide or iodite was inside the chlorinated water, there could produced iodoand bromohaloacetonitriles.

2.1.4. Halophenols
OH
Br

Br

Halophenols are produced during chloronisation of phenol in water.


Similar to THMs, there exists chlorine-, bromine- and iodinesubstitueted phenols.
In natural water with bromide inside, brominated phenols is the common
species. For example it is shown on the left 2, 4-bromophenol.
Iodophenols are only to find in very low concentrations in chlorinated
drinking water.

2.2. Chloramines
If ammonia is added to chlorine, chloramines (for example monochloramine: NH2Cl)
were formed [12]:
NH3 + HOCl  NH2Cl + H2O
In this reaction, the nucleophile NH3 attacks the hyperchlorus acid (HOCl; formed by
adding chlorine into water, see chapter 3.1).
DBPs which are formed during chloramination often contain nitrogen.
Another important fact is that in chloraminated water the concentration of formed
THMs and HAAs is much lower than in chlorinated water.
Chloramines are a weaker and more stable water disinfectant than chlorine.
Chloramination of water forms the same DBPs which are producing during
chlorination of water. But there are some more like cyanogens halides. The molecule
9

of hydrogen cyanide (HCN) has one hydrogen atom and is mostly produced in a
reaction with ammonia, oxygen and methane. If a halogen atom replaces this
hydrogen atom, cyanogen halides were formed. On the left is shown
Cl C
N cyanogen chloride for example. Cyanogen halides are highly toxic
compounds. For the formation of cyanogen halides it is important, that ammonia is
present in the water. Thats the reason, why cyanogen halides are commonly
detected in chloraminated drinking water.

2.2.1. N-nitrosodimethylamine
Nitrosamines are a class of compounds which are carcinogenic, mutagenic and
teratogenic [3]. N-nitrosodimethylamine (NDMA) is an organic compound and a
member of nitrosamines. Since NDMA was observed after chloramination in several
water agencies, recently NDMA research had became a very important area. NDMA
is one of the most potent detected carcinogen DBPs today but it is not regulated in
the USA for drinking water yet [3]. The production of NDMA showed a strong pH
dependence [10]. Because NDMAs are one of the strongest carcinogens and it does
not exists a limitation of their concentration in drinking water, I will have a detailed
view on this DBP in chapter 3.

2.3. Ozone
Ozonation is a powerful oxidizing treatment of water. It kills many forms of bacterias
and parasites which are resistant to conventional disinfectants (chlorination,
chloramination). Ozonation minimizes the formation of haloorganic DBPs like THMs
and HAAs. Ozone reacts very specific. One assume that ozone reacts most with
double bonds, activated aromatic systems and non-protonated amines [14]. Are high
concentrations of bromide (Br-) in water (problematic range about 50-100g/L) the
most problematic formation of a disinfection byproduct is bromate (BrO3-). The
structure formula of bromate is drawn on the left. Bromate is fixed as a
O
Class 2B carcinogen by the International Agency for Research on Cancer
Br
O(IARC); it means that bromat is possibly carcinogens for humans. In animal
O
experiments realized with rats, exposure with potassium bromate leaded to
renal cancer, mesotheliomas and thyroid follicular cell tumors. The United States and
the EU determinate the legal limit of bromate in drinking water at 10 g/L [12].
Brominated nitromethane are extremely cytotoxic and genotoxic in mammalian cells
[12]. Von Gunten propose two different possible ways to form bromate [4]. The first
one includes an oxidation of bromide by ozone (figure 5), the second one is a
reaction with ozone and OH radicals (figure 6). Both processes includes up to six
oxidation states of bromide. In water, both reactions run simultaneously.
To the reaction with ozone (figure 5): This reaction starts with an oxidation of bromide
(Br-) by ozone. An oxygen atom binds to bromide and produce hypobromite (OBr-).
Ozone oxidize OBr- to BrO2- and following BrO2- to BrO3- (bromate).
The free Br- ion at the start of the reaction can form by ozonation too. Ozone oxidizes
NH2Br, as a product Br- is formed.
To the reaction with ozone and OH radicals (figure 6): OH radicals (OH*) transfer Brto Br radicals (Br*). Br* decay to HOBr/OBr- or can be oxidized by ozone to BrO
10

radicals (BrO*). BrO* decay to BrO2-. The next step is an oxidation with ozone to
bromate. HOBr/OBr- undergoes two oxidation with bromate as product or will be
transferred with OH* to BrO*.

Fig.5: Bromate formation by ozone


From U. von Gunten 2003: [4]

Fig.6: Bromate formation by ozone and OH radicals


From U. von Gunten 2003: [4]

The dose of ozone has a significant effect of the formation of bromate. At a dose
above 3.1 mg/L, Wert observed a linear relationship between bromat formation and
ozone doses [7]. He showed that in Figure 7. The bromate concentration increases
approximately about 8 g/l if the ozone dose increases about 1 mg/L.

Fig. 7: Bromate formation depends of the ozone dose during bench scale
(BS) and bench-top pilot plant (BTPP) experiments.
From Wert, E.C., et al. 2007: [7]

As shown in figure 7 is the EU and US legal limit for bromate in drinking water (10g/L)
to high above an ozone dose of approximately 4.3 mg/L.
The formation of bromate is strong pH depended. By same ozone exposure, bromate
formation is much higher by pH 8 than by pH 6. Von Gunten propose that the best
11

strategy to minimize bromate concentration in water is to lowering the pH [4]. Another


influence to bromate formation is the presence of ammonia in water. Von Gunten
showed that the formation of bromate is much lower by addition of 200 g/L ammonia
(approximately a factor two after eight minutes) than by addition of <10 g/L
ammonia by constant ozone exposure.
Wert et al detected, that more aldehydes and carboxylic acids were produced by
higher ozone concentration than by lower. A second observation was, that under
same conditions much more carboxylic acids were produced than aldehydes
(approximately about a factor four) [7].
Carboxyl, aldehydes and ketones compounds could produce by ozonation of raw
water (see table 1).
Aldehydes can be formed by an additional reaction on double bounds of organic
matter:
R1R2C=CR3R4 + O3  R1COOH + R1COR2 + R3COR4
Brominated trihalomethanes, phenols, acetic acids, cyanogenes halides,
nitromethanes and acetonitriles are other possible products [12].

3. N-nitrosodimethylamine (NDMA)
CH3

3.1 General Informations

CH3

The formula of N-nitrosodimethylamine (NDMA) is C2H6N2O. Above, the structure of


NDMA is drawn. NDMA was used to produce rocket fuels. After high concentrations
of NDMA were found in air, soil and water samples, which were took near rocket fuel
factories, the production of NDMA was stopped. An other use of NDMA was in soil to
control nematodes or inhibit the nitrification [15]. NDMA is a yellow liquid which has
no typical odor. When NDMA was released into air, itll decompose into minutes by
sunlight. If NDMA is present in water, sunlight or biological processes can destroy it.
But NDMA is not only a commercial used chemical. NDMA can be formed in
chlorinated and chloraminated water as a disinfection by-product.
NDMA shows a strong tendency to harm the liver of humans and animals. Animals
which are exposed to air, water ore food with high NDMA concentration during a
short time (days until few weeks) get liver diseases but not cancer. Are animals
exposed to a low concentration of NDMA during long periods, liver and lunge cancer
occurs often.
In July 1999, the US Environmental Protection Agency (EPA) integrated risk
information service (IRIS) recommends the levels of NDMA in lakes and streams and
drinking water. They advise that the levels of NDMA should not be higher than
0.00069 ppb (0.69 ng/L). This value should prevent humans from negative health
effects by eating fish ore drinking contaminated water. The IRIS database provides
for the same level of risk for chloroform, a trihalomethane, a value of 6 g/L.

12

3.2 Formation
The formation of NDMA can be a reaction between monochloramine and an organic
nitrogen compound. When ammonia (NH3) was presented in the treated raw water,
monochloramine (NH2Cl) can formed directly during chlorination [16].
Mitch and Sedlak [5] described that nitrosamines can be produced by nitrosation of
secondary amines by nitrite. To explain the kinetics of NDMA formation, they showed
the following reactions:
HNO2
NO2- + H+
K1 = 10-3.37
2HNO2
N2O3 + H2O
K2 = 10-6.70
+
+
(CH3)2NH + H K3 = 10-10.72
(CH3)2NH2
N2O3 + (CH3)2NH  (CH3)2NNO + HNO2

(1)
(2)
(3)
(4)

The maximum NDMA formation rate is near a pH = 3.4.


Under waste water treatment conditions, the formation of NDMA with this mechanism
is very slow. Mitch and Sedlak propose, that 100 M nitrite (NO2-) and 100 M
dimethylamine (DMA; (CH3)2NH) would form less than 10-21 g/L NDMA in 24 h at pH 7
[5].
An alternative mechanism of formation NDMA during water treatment involves the
formation and oxidation of unsymmetrical dimethylhydrazine (UDMH) after
chlorination. UDMH occurs during a reaction of monochloramine and dimethylamine
at pH values greater than 10 [5], see figure 8.

Fig. 8: From Mitch proposed reaction schema for UDMH


formation
From Mitch and Sedlak 2002: [5]

13

Fig. 9: From Mitch proposed reaction schema for NDMH


formation
From Mitch and Sedlak 2002: [5]

Figure 9 shows the formation of different products, produced by transformations of


UDMH at presence of an oxidant (NH2Cl) by moderate pH values. One of these
products is NDMA (figure 9, on the right), produced for small percentage of all
products (less than 5%) [5].
In realized experiments, Mitch and Sedlak found, that the maximum rate of NDMA
formation exists, if in the experiments monochloramine were added to dimethylamine
(DMA; C2H7N). The same result observed Choi and Valentine [3]. They observed the
NDMA formation by adding different components into deionized water including 1 mM
bicarbonate by pH = 7. The results are shown in figure 10. By only adding 0.1 mM
monochloramine or 0.1 mM DMA, no NDMA was found in water. If they added 0.1
mM Nitrite and 0.1 mM monochloramine into the water, no NDMA was formed too.
No significant NDMA amount was formed by adding of HOCl to a solution of DMA,
probably because of the absence of free ammonia .But if they putted 0.1 mM
dimethylamine and 0.1 mM nitrite into the water; small amounts of NDMA were
formed. Approximately six times (~ 12 g/L) higher was the NDMA production by
adding 0.1 mM dimethylamie and 0.1 mM monochloramine. Without DMA, in no
cases were NDMA found.

14

Fig. 10: Formation after 24 h of NDMA as a function of


different added components with each time at 0.1mM.
From Junghoon Choi 2001: [3]

3.3. Factors influencing the formation of NDMA


Choi and Valentine could see a strong, more or less linear, NDMA formation
dependence of the reactions time (for adding DMA and NH2Cl). Mitch / Sedlak and
Choi / Valentine could see dependence for the NDMA formation and the
monochloramine concentration in water. By an analysis of NDMA concentrations by
different monochloramine concentrations, Kim and Clevenger found a increase of
NDMA due higher monochloramine values [16]. By a monochloramine concentration
of 0.05 mM, a NDMA concentration of 1.5 g/L was detected. By a monochloramine
concentration of 5 mM, the NDMA concentration increased to a value of 18 g/L
(constant conditions: pH=8, DMA= 0.01 mM).
In the experiments from Mitch and Sedlak, strong pH dependence due the formation
of NDMA was observed. The maximum pH for NDMA production rate is near pH 3.4.
This value is not relevant for drinking water treatment plants. Mitch and Sedlak found
strong pH dependence too, near a neutral value. They quantified the NDMA
formation rate under laboratory conditions. In the experiment, they added 1 mM
NaOCl, 1 mM dimethylamine and 1 mM ammonia into water and varied the pH. The
maximum detected formation rate was between 7 and 8. As shown in figure 10 the
maximum NDMA formation exists if in water dimethylamine and monochloramine
react together. This reaction shows a dramatically pH dependence. Does this two
components reacts together for 80 minutes at pH = 11.6 prior to adjusting 10 minutes
before the pH was chanced to a value of 6.8, a approximately 30 times higher NDMA
formation was observed than by a constant pH from 6.8 or 11.6 during 80 minutes
(see Mitch and Sedlak, table 1, experiment 3 [5]).

15

4. Outlook
Approximately 600-700 DBPs are noted today. But there may be more DBPs. To
identify these products it is a main experience for future observations. How I have
seen, it is very difficult to find out, on which way the particular DBPs are formed and
which factors influencing their formations. By the known DBPs, the toxic effects are
often not enough evaluated (especially the chronic effects). The most toxicology
studies are only realized with one DBP. Observations of toxic effects of combinations
of DBPs are missing. To know, which DBP lead to which problems is an important
area of research. Are the influence factors of the determined problematic DBPs
evaluated, better water treatment systems can become designed with the goal to
minimize the DBP formation thus to minimize human health problems.

16

References
1.
2.
3.
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5.
6.
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8.
9.
10.
11.
12.
13.
14.
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