IDENTIFICATION OF NEW DRINKING WATER DISINFECTION BY-

PRODUCTS FROM OZONE, CHLORINE DIOXIDE, CHLORAMINE,

AND CHLORINE

S. D. RICHARDSON1, A. D. THRUSTON, JR. 1, T. V. CAUGHRAN1,

P. H. CHEN1, T. W. COLLETTE1, K. M. SCHENCK2, B. W. LYKINS, JR. 2,
C. RAV-ACHA3, and V. GLEZER3
1
National Exposure Research Laboratory, U.S. Environmental Protection Agency, 960 College
Station Rd., Athens, GA 30605, USA, 2National Risk Management Research Laboratory, U.S.
Environmental Protection Agency, 26 W. Martin Luther King Dr., Cincinnati, OH 45268, USA,
3
Research Laboratory of Water Quality, Israel Ministry of Health, 69 Ben-Zvi St., Tel-Aviv 61082,
Israel

Abstract. Many drinking water treatment plants are currently using alternative disinfectants to treat
drinking water, with ozone, chlorine dioxide, and chloramine being the most popular. However,
compared to chlorine, which has been much more widely studied, there is little information about the
disinfection by-products (DBPs) that these alternative disinfectants produce. Thus, it is not known
if the DBPs from alternative disinfectants are safer or more hazardous than those formed by chlorine.
To answer this question, we have set out to comprehensively identify DBPs formed by these
alternative disinfectants, as well as by chlorine. The results presented here represent a compilation
of the last 8 years of our research in identifying new DBPs from ozone, chlorine dioxide, chloramine,
and chlorine. We also include results from recent studies of Israel drinking water disinfected with
both chlorine dioxide and chloramine. Over 200 DBPs were identified, many of which have never
been reported. In comparing by-products formed by the different disinfectants, ozone, chlorine
dioxide, and chloramine formed fewer halogenated DBPs than chlorine.

Keywords: chloramine, chlorine, chlorine dioxide, disinfection by-products, drinking water, ozone

1. Introduction

Although chlorine has been used to disinfect drinking water for approximately 100
years, there have been concerns raised over its use due to the formation of some
potentially hazardous by-products. Of the more than 300 disinfection by-products
(DBPs) that have been reported formed from chlorine treatment (Richardson, 1998),
at least four of them--chloroform, bromodichloromethane, bromoform, and MX (3-
chloro-4-(dichloromethyl)-4-oxobutenoic acid)--have been shown to cause cancer
in laboratory animals (Bull and F.C. Kopfler, 1991; Komulainen et al., 1997).
Potential adverse health effects for many of the other reported chlorine DBPs are not
known, as appropriate health effects studies have not been carried out. Because of
these concerns, alternative disinfectants are being explored. Ozone, chlorine
dioxide, and chloramine are popular alternatives, as they are effective against
microorganisms, and do not form appreciable levels of the chlorine-containing

Water, Air, and Soil Pollution 123: 95102, 2000.

2000
c Kluwer Academic Publishers. Printed in the Netherlands.
96

by-products that are of concern. However, compared to chlorine, which has been
much more widely studied, there is little information about the disinfection by-
products (DBPs) that these alternative disinfectants produce. Thus, it is not known
if the DBPs from alternative disinfectants are safer or more hazardous than those
formed by chlorine. To answer this question, we have set out to comprehensively
identify DBPs formed by these alternative disinfectants, as well as by chlorine.
Most of the drinking water samples were taken from locations in the United States;
however, results from recent studies of Israel drinking water, which is disinfected
with both chlorine dioxide and chloramine, are also included. Because Israels
source water (Lake Kinneret - the Sea of Galilee) contains natural levels of bromide
that are among the highest in the world, it offered a unique opportunity to study the
effect of elevated bromide levels on the formation of chlorine dioxide DBPs. DBP
studies typically target a few expected chemicals in the drinking water. Due to
advanced instrumentation available in our laboratory, we were able to carry out more
comprehensive DBP studies, with the ability to identify new DBPs that are not
present in mass spectral library databases. In this paper, we report the successful
identification of many DBPs from the alternative disinfectants and from chlorine,
many of which have not been previously reported.

2. Experimental

Ozonated water was collected from three sources: 1) a full-scale ozone treatment
plant in Valdosta, GA, 2) a pilot ozonation plant in Jefferson Parish, LA, and 3)
laboratory-scale ozonations carried out on Suwannee River humic and fulvic acid-
fortified distilled water (5 mg/L), with an ozone dose of 2:1 ozone:dissolved organic
carbon (DOC). Samples were concentrated using XAD resins. Additional
experimental details are similar to those in a previous study (Richardson et al.,
1994). Secondary chlorine and chloramine were applied to some ozone samples
collected from the Jefferson Parish pilot plant, in amounts to achieve residuals of 2
to 3 mg/L. The effect of bromide was studied by adding 1.0 ppm sodium bromide
to the raw water prior to disinfection.
Chlorine dioxide-treated water was collected from a pilot drinking water
treatment plant in Evansville, Indiana, and from two full-scale treatment plants in
Israel. For the samples taken in Evansville, IN, secondary chlorine was applied to
some of the chlorine dioxide treated samples, in amounts to obtain a free chlorine
residual of 2 to 3 mg/L; additional experimental details for these samples can be
found elsewhere (Richardson et al., 1994). For water collected from the two full-
scale plants in Israel, the following treatment conditions applied. At the first plant:
0.75 ppm chlorine dioxide was applied, along with 0.6 ppm of chloramine, which
was generated with 0.8 ppm chlorine and excess ammonia. Residual disinfectant
levels at the time of the sampling were 0.0 ppm free chlorine, 0.0 ppm chlorine
 97

dioxide, and 0.6 ppm chloramine. At the second plant, 0.85 ppm chlorine dioxide
was applied (without additional chloramine treatment). The residual disinfectant
level of chlorine dioxide at the time of the sampling was 0.35 ppm. Samples were
concentrated using XAD resins.
Low and high resolution gas chromatography-electron ionization mass
spectrometry (GC/EI-MS) analyses were performed on a VG 70-SEQ high-
resolution hybrid mass spectrometer, equipped with a Hewlett Packard model 5890A
gas chromatograph and a DB-5 column. Low resolution experiments were carried
out at 1000 resolution; high resolution experiments at 10,000. Chemical ionization
mass spectrometry (CI-MS) experiments were carried out on a Finnigan TSQ 7000
triple quadrupole mass spectrometer using methane gas. LC/MS analyses were
accomplished using a Hewlett Packard 1050 LC coupled to a Fisons Platform
quadrupole mass spectrometer. Electrospray ionization was used with a flow rate
of 0.3 mL/min and a source temperature of 160oC. Samples (50 L) were injected
onto a Supelco Supelcosil C18 LC column (5 m particle size, 150 x 2.1 mm i.d.),
which was eluted using a gradient of 50:50 acetonitrile/water to 98:2
acetonitrile/water over 1 hour. Gas chromatography/infrared spectroscopy (GC/IR)
analyses were performed on a Hewlett Packard Model 5890 Series II GC (with
Restek Rtx-5 column) interfaced to a Hewlett Packard Model 5965B infrared
detector (IRD).

3. Results and Discussion

3.1. OZONE DBPS

To determine the identity of ozone DBPs, we first applied a combination of GC/MS

and GC/IR techniques to the XAD resin extracts of ozonated water samples. The
criteria we used for listing an identified compound as a DBP was its presence in the
treated samples in quantities at least 2 to 3 times greater than in the untreated, raw
water (as judged from comparing chromatographic peak areas). Overall, many
DBPs were identified, several of which have never been reported previously. Table
I lists these by-products. The majority of the ozone by-products identified
contained oxygen as part of their structure, with aldehydes, ketones, carboxylic
acids, aldo-acids, keto-acids, keto-aldehydes, hydroxy-ketones, and cyano-aldehydes
observed. No halogenated by-products were found. Many of the compounds were
not present in any spectral library (NIST or Wiley). For compounds that did not
contain molecular ions (which provide molecular weight information), chemical
ionization mass spectrometry (CI-MS) was used to obtain this information. High
resolution electron ionization mass spectrometry (EI-MS) provided the necessary
empirical formula information for the molecular ion and fragments, and helped to
limit the number of possible structures for each unknown DBP. GC/IR was useful
98

for determining the functional group. When available, standards were purchased
to confirm difficult identifications and to determine a particular isomer precisely,
when spectra were not conclusive. Because it is believed that many of the
unidentified DBPs from ozone are located in the polar fraction, which cannot be
easily extracted from water, we also applied two derivatization procedures coupled
with either GC/MS or liquid chromatography/mass spectrometry (LC/MS). The
first derivatization procedure involved the use of pentafluorobenzylhydroxylamine
(PFBHA), which reacts with small, polar aldehydes and ketones to form nonpolar
oximes that can be easily extracted into an organic solvent and analyzed by GC/MS
(Glaze and Weinberg, 1993). The second derivatization procedure involved the
use of 2,4-dinitrophenylhydrazine (DNPH) (Grosjean and Grosjean, 1995),
followed by LC/MS analysis, and has not been applied previously for the
identification of DBPs. DNPH also reacts with the carbonyl group of aldehydes and
ketones, but, unlike PFBHA, it permits the analysis of highly polar compounds
(with multiple polar substituents). Using these approaches, we were able to
successfully identify some polar aldehydes and ketones that were DBPs of ozone.

TABLE I
Ozone DBPs Identified
DBPs

Aldehydes: formaldehyde, acetaldehyde, propanal, butanal, 2-methyl propenal, pentanal,

3-methyl butanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal,
benzaldehyde, 2-methoxy-4-hydroxy-benzaldehyde, cyanoformaldehyde

Ketones: acetone, 2-butanone, 3-methyl-2-butanone, 2-pentanone, 3-hexanone, 2-hexanone,

3-methyl cyclopentanone, C7-ketone (2 isomers), 6-methyl-5-hepten-2-one,
6-hydroxy-2-hexanone

Di-carbonyls: glyoxal, 2-ketopropanal (methylglyoxal), 2,3-butanedione (dimethylglyoxal),

isomer of 2,3-butanedione, C5-dicarbonyl, 5-keto-hexanal

Carboxylic acids: 2-methyl propanoic acid, butanoic acid, 3-methyl butanoic acid, pentanoic
acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic
acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic
acid, heptadecanoic acid, octadecanoic acid, phenylacetic acid, benzoic acid, ethanedioic acid,
propanedioic acid, butanedioic acid, 2-ethyl-3-methyl maleic acid, tert-butyl maleic acid,
pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid,
decanedioic acid, undecanedioic acid, tridecanedioic acid, phthalic acid, isophthalic acid,
terephthalic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid,
1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid,
1,2,3,5-benzenetetracarboxylic acid

Keto-acids: 3-keto-butanoic acid, 3-methyl-2-keto-butanoic acid, 9-keto-nonanoic acid

Nitriles: benzeneacetonitrile, heptanenitrile

NOTE: Underlined DBPs were confirmed by the analysis of authentic standards; other DBPs listed
are tentative identifications.
 99

3.2. OZONE-CHLORINE AND OZONE-CHLORAMINE DBPS

When chlorine or chloramine was used as a secondary disinfectant (after treatment

with ozone), a greater variety of chlorinated and brominated DBPs was found (Table
II). All of these compounds were also found in samples treated with chlorine or
chloramine only. A few DBPs, however, were formed at higher levels in the ozone-
chlorine and ozone-chloramine samples, indicating that the combination of ozone
and chlorine or chloramine is important in their formation. In comparing by-
products formed by secondary treatment of chlorine or chloramine, chloramine
appeared to form the same types of halogenated DBPs as chlorine, but they were
generally fewer in number and lower in concentration.

TABLE II
Halogenated Ozone-Chlorine and Ozone-Chloramine DBPs Identified
Halogenated DBPs

Halo-alkanes/alkenes: chloroform, bromoform, bromodichloromethane, dibromochloromethane,

dichloroiodomethane, bromochloroiodomethane, dibromoiodomethane, tribromochloromethane,
1,2-dibromo-1-chloroethane, 2,3-dichlorobutane, hexachlorocyclopentadiene
Haloaldehydes: chloroacetaldehyde, trichloroacetaldehyde (chloral hydrate),
dichloroacetaldehyde, bromodichloroacetaldehyde, 2-chloro-2-methyl propanal,
2-bromo-2-methyl propanal
Haloketones:1,1-dichloropropanone,1,3-dichloropropanone,1-bromo-1-chloropropanone,
1,1-dibromopropanone,1,1,1-trichloropropanone, 1,1,3-trichloropropanone,
1-bromo-1,1-dichloropropanone,1,1,3-tribromopropanone,1,1,3,3-tetrachloropropanone,
1,1,1,3-tetrachloropropanone,1,1-dibromo-3,3-dichloropropanone,1,3-dibromo-1,3-dichloropropa
none, 1,1,3-tribromo-3-chloropropanone, 1,1,3,3-tetrabromopropanone,
1,1,1,3,3-pentachloropropanone, 1,1,1-trichloro-2-butanone
Halo-dicarbonyls: 2,2,4-trichloro-1,3-cyclopentenedione
Haloacids: chloroacetic acid, bromoacetic acid, dichloroacetic acid, trichloroacetic acid,
bromochloroacetic acid, dibromoacetic acid, 2-chloropropanoic acid, 2,2-dichloropropanoic acid,
2-chloro-3-methyl maleic acid
Haloacetonitriles: dichloroacetonitrile, bromochloroacetonitrile, dibromoacetonitrile,
bromodichloroacetonitrile, dibromochloroacetonitrile
Haloalcohols: 2-bromoethanol, 3-chloro-2-butanol
Halo-nitro-methanes: dibromonitromethane, trichloronitromethane (chloropicrin),
tribromonitromethane (bromopicrin)

Other halogenated DBPs: chloromethyl benzene, bromoxylene, 2-chlorobenzothiazole,

2-bromobenzothiazole, 2,2,2-trichloroacetamide, methane sulfonyl chloride, dichloromethyl
methyl sulfone
NOTE: Underlined DBPs were confirmed by the analysis of authentic standards; other DBPs listed
are tentative identifications. Haloaldehydes are likely present in hydrated form (as for chloral
hydrate).
100

3.3. DBPS FORMED WITH ELEVATED BROMIDE LEVELS

When elevated levels of bromide (1.0 ppm) were added to the water prior to
ozonation, only one brominated by-product--dibromoacetonitrile--was found. Many
more by-products were identified when secondary chlorine or chloramine was
applied after ozonation. When comparing low-bromide water to water with elevated
bromide, a tremendous shift in speciation was observed for samples treated with
secondary chlorine or chloramine. In the absence of elevated bromide levels,
chlorinated species dominate (e.g., chloroform, trichloroacetaldehyde,
tetrachloropropanone, dichloroacetonitrile, trichloronitromethane); with elevated
bromide levels, these shift to brominated species (e.g., bromoform,
tribromoacetaldehyde, tetrabromopropanone, dibromoacetonitrile,
tribromonitromethane). Additional details will be available elsewhere (Richardson
et al., in press).

3.4. CHLORINE DIOXIDE DBPS

Evansville, Indiana, drinking water. Chlorine dioxide treatment, by itself, produced

several DBPs that have not been reported previously (Richardson et al., 1994).
Table III lists these by-products. Most of the DBPs contained oxygen in their
structures: ketones, carboxylic acids, and maleic acids. Only two of the by-products
were chlorinated, and no halomethanes were observed. When chlorine was used as
the secondary disinfectant (after treatment with chlorine dioxide), a greater number
and variety of chlorinated and brominated DBPs were found.

TABLE III
Chlorine Dioxide Disinfection By-products Identified in Evansville, Indiana Drinking Water

DBPs

Chlorine-containing compounds:1,1,3,3-tetrachloropropanone, (1-chloroethyl)dimethylbenzene

Carboxylic acids: butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, 2-ethylhexanoic
acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, tridecanoic acid, tetradecanoic
acid, hexadecanoic acid, 2-tert-butylmaleic acid, 2-ethyl-3-methylmaleic acid, benzoic acid

Ketones:2,3,4-trimethylcyclopent-2-en-1-one,2,6,6-trimethyl-2-cyclohexene-1,4-dione

Aromatic compounds: 3-ethyl styrene, 2-ethyl styrene, ethylbenzaldehyde, naphthalene,

2-methylnaphthalene, 1-methylnaphthalene

Esters: hexanedioic acid, dioctyl ester

 101

3.4.1. Israel drinking water

Figure 1 shows the chlorine dioxide and chlorine dioxide-chloramine DBPs that
were identified in the high-bromide Israel drinking waters. Evident from these
structures is the high degree of bromine incorporation into the DBP structures.
Precise isomers of the brominated aromatic DBPs are not known at this time, and
in most cases, multiple isomers were evident. As most of these isomers would be
expected to give similar, if not identical mass spectra, standards will be required to
give precise isomer assignments. However, for these brominated aromatic
compounds, it is known from high resolution EI-MS and CI-MS information that the
empirical formula assignments for these compounds are correct. An interesting
finding from this study is the presence of 1,1,3,3-tetrabromopropanone, which is the
brominated analog of 1,1,3,3-tetrachloropropanone--a DBP found in the Evansville,
IN, chlorine dioxide study.

ClO2 ClO2 + NH2Cl

2-Hexanone Methyl glyoxal Br
Cl
1,1,1-Tribromopropanone Br
Bromopropanone
CH3 CH3 Br CH3
1,1,3,3-Tetrabromopropanone CH3 CH2 CH2 Cl

CH3
CH2 Br OH

Br CH2 Br
CH3 CH3
CH3

Br CH3
Br CH3 CH3
CH3 CH3

Br Br CH3 CH3 Br OH
OH
CH3 CH3 Br Cl

Br Br Br CH3

Br Br
OCH3 OCH3 Br OH

CH3
OCH3 Br CH3

Fig. 1. Chlorine Dioxide and Chlorine Dioxide-Chloramine Disinfection By-products Identified in

Israel Drinking Water
NOTE: Structures in boxes were observed in both samples treated with chlorine dioxide only and
for samples treated with chlorine dioxide and chloramine. Precise isomers are not known for the
brominated aromatic structures (an example structure is given in each case).
102

4. Conclusions

In comparing the different disinfectants studied, chlorine formed the largest number
of halogenated by-products. Chloramine produced the same types of halogenated
by-products as chlorine, but they were fewer in number and lower in concentration
than for chlorine. Ozone produced no halogenated by-products, except for
dibromoacetonitrile, which was formed in the presence of elevated bromide levels.
In the absence of elevated bromide levels, chlorine dioxide produced relatively few
DBPs, with only two halogenated DBPs observed. When elevated bromide levels
were present, as in the case of the Israel drinking water, a host of brominated
compounds was observed, including 1,1,3,3-tetrabromopropanone, which is the
brominated analog of 1,1,3,3-tetrachloropropanone--a DBP found with chlorine
dioxide treatment in the absence of elevated bromide. Non-halogenated DBPs were
quite similar for all of the different disinfectants studied (e.g., carboxylic acids,
aldehydes, etc.).

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