Journal of Hazardous Materials 168 (2009) 1290–1295

Contents lists available at ScienceDirect

Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Effects of operating conditions on THMs and HAAs formation during wastewater

chlorination
Ying-Xue Sun, Qian-Yuan Wu, Hong-Ying Hu ∗ , Jie Tian
Environmental Simulation and Pollution Control State Key Joint Laboratory, Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084, China

a r t i c l e i n f o a b s t r a c t

Article history: Disinfection is the last barrier of wastewater reclamation process to protect ecosystem safety and human
Received 14 October 2008 health. However, the chlorination process results in the formation of mutagenic/carcinogenic disinfection
Received in revised form 24 January 2009 by-products (DBPs) deriving from the reaction of the chlorine with organic compounds in wastewater.
Accepted 3 March 2009
The effects of operating conditions (chlorine dose, contact time, reaction temperature and pH value) of
Available online 14 March 2009
chlorination on the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) in biologically
treated wastewater samples were investigated in this study. The results indicated that the total THMs
Keywords:
(TTHM) and total HAAs (THAA) increased exponentially with increasing chlorine dose, but there are
Chlorination
THMs
discrepancies between the formation rates of TTHM and THAA. The THAA reached a peak at contact time of
HAAs 2 h and thereafter decreased with extended time. The formation time of THMs depends on the wastewater
Wastewater reuse content of quick or slow formers. The yields of bromated HAAs (as MBAA, BCAA, and BDCAA) would
Wastewater disinfection decrease markedly after the contact time over 2 h during wastewater chlorination, and were favored in
low pH values of 4 and high pH values of 9 under certain contact time. In addition, the formation of MBAA,
BCAA, BDCAA decreased gradually as reaction temperature increased from 4 to 30 ◦ C in the chlorination of
wastewater containing a certain concentration of bromide. The effects of operating conditions on THMs
and HAAs formation during wastewater chlorination were completely different from those of surface
water disinfection.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction amounts of pathogens and various types of DOM in biologically

Chlorination is widely used in wastewater reclamation pro-
cesses to protect ecosystem safety and human health, due to its
low cost and broad-spectrum inactivation to pathogenic bacteria
[1,2]. But during chlorination of wastewater, chlorine could also
react with dissolved organic matter (DOM) to produce numer-
ous disinfection by-products (DBPs) [3–5]. It is found that many
DBPs have been identified with genotoxic, mutagenic and/or car-
cinogenic activity and considered as toxic risk to human beings
and aquatic organism in water chlorination [6]. Among them, tri-
halomethanes (THMs) and haloacetic acids (HAAs) as two major
groups of DBPs have been regulated in US Stage 2 Disinfectants and
Disinfection Byproducts Rule for drinking water because of the huge
volume of production and of genotoxicity [7].
Researchers have paid more attention to the investigation of
THMs and HAAs formation (including influencing factors, mod-
els and operating conditions, etc.) to control DBPs in the drinking
water chlorination process during the past several decades [8,9].
However, compared with drinking/natural water, there are more
∗ Corresponding author. Tel.: +86 10 62794005; fax: +86 10 62797265.
E-mail address: hyhu@tsinghua.edu.cn (H.-Y. Hu).
treated wastewater [2,10]. In addition, compositions in the precur-
sor of THMs and HAAs of wastewater are distinctly different from
those found in that of typical drinking water [11,12], and the reac-
tions between chlorine and DOM during wastewater chlorination
would be more complex than the reactions during drinking water
disinfection [13]. But related studies on the formation of THMs and
HAAs in wastewater chlorine disinfection processes are very lim-
ited. Rebhun et al. found that high concentrations of THMs and
HAAs were formed during chlorination of effluents, and reduc-
tion of DBPs formation could be achieved by applying treatment
processes producing low-DOC effluents and leaving a small concen-
tration of residual ammonia [4]. Koukouraki and Diamadopoulos
studied the THMs concentrations during chlorination of nitrified
and partially nitrified secondary effluents and tertiary effluent and
proposed exponential models for the THMs formation [5,14]. Mata-
moros et al. studied the THMs occurrence in chlorination of treated
wastewater effluents (i.e. secondary and tertiary from full-scale
wastewater treatment plants) and analyzed the effects of operating
conditions of disinfection (such as UV light exposure, tank storage
and water temperature, etc.) and ammonia nitrogen and bromide
concentrations [15]. Some other researchers studied the effects of
ammonia nitrogen and bromide on the formation of THMs and/or
HAAs, and found that such effects in wastewater chlorination are

0304-3894/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2009.03.013
 Y.-X. Sun et al. / Journal of Hazardous Materials 168 (2009) 1290–1295
not similar with those of water chlorination and even more com-
plicated [11,12,16,17]. To ensure the ecological safety of reclaimed
water for its broad utilization, further studies on THMs and HAAs
formation during wastewater chlorination are needed.
As the operating conditions of disinfection are important aspects
in controlling the formation of DBPs, the purpose of this study was
to investigate the effects of operating conditions on the formation
of THMs and HAAs during chlorination of two kinds of wastewater
effluent obtained from different municipal sewage treatment works
in Beijing, China. The studied operating conditions of chlorination
were chlorine dose, contact time, temperature and pH value.
2. Materials and methods
2.1. Wastewater samples
Wastewater samples were collected from two domestic sewage
treatment works (named as A-STWs and B-STWs, respectively),
in which activated sludge process (AS) and membrane bioreactor
(MBR) were used as the main treatment process, respectively. The
samples (correspondingly named sample A and sample B) were
immediately delivered to the laboratory, then filtered to eliminate
suspended solids and stored at 4 ◦ C to minimize changes in the
constituents.
2.2. Chemicals
HPLC grade methanol, acetone and methyl-tert-butyl ether
(MTBE) were purchased from Sigma–Aldrich. HAAs consist of
monochloroacetic acid (MCAA), monobromoacetic acid (MBAA),
dichloroacetic acid (DCAA), bromochloroacetic acid (BCAA),
trichloroacetic acid (TCAA), dibromoacetic acid (DBAA), bro-
modichloroacetic acid (BDCAA), dibromochloroacetic acid (DBCAA)
and tribromoacetic acid (TBAA). THMs consist of chloroform,
bromodichloromethane, dibromochloromethane and bromoform.
Both HAAs and THMs were analytical grade and obtained from
Supelco and National Institute of Metrology, PR China. Stock solu-
tions of chlorine (3000 mg/L) were prepared by diluting 10%
analytical grade sodium hypochlorite (NaOCl) with ultrapure water
(18.2 M cm) and they were standardized with a DPD/FAS titration
analyzer (HANNA, Italy) before chlorine disinfection [18].
2.3. Chlorine disinfection
A series of experiments were conducted to test the effect of each
of four factors on the formation of THMs and HAAs in chlorina-
tion of treated wastewater. Chlorine disinfection was conducted in
600 mL glass bottles with teflon inner plugs. Each bottle was filled
with about 580 mL wastewater sample. Prior to chlorination, pH
was adjusted to the desired value with 1 M H2 SO4 or 2 M NaOH
solution, and then 12.5 mL of buffer solution (34.0 g/L KH2 PO4 and
35.5 g/L Na2 HPO4 ) were added to keep the pH stable during dis-
infection. The stock chlorine solution was added to the bottles at
required dosage (calculated as available chlorine). The bottles were
sealed and the solutions were well mixed for 30 s at room tem-
perature (14 ± 1 ◦ C). Then the solution was immediately portioned
into 40-mL amber glass vials that were sealed with polypropylene
screw caps and TFE-faced septa. The vials were carefully filled so
Table 1
Water quality characteristic of wastewater samples used in this study.
Sample Sourcea CNH3–N (mg/L) CDOC (mg/L)
A AS 5.4 16.8
B MBR 0.9 7.0
a
AS and MBR show that the samples were collected from activated sludge process and membrane bioreactor, respectively.
1291
that trapping of air bubbles inside was prevented. Then the vials
were incubated at certain conditions until the desired contact times
were fulfilled. Then, residual chlorine was measured according to
the DPD colorimetric method and the quenching agent for depletion
of residual chlorine was added [18]. Other aliquots were quenched
with sodium thiosulfate and extracted with MTBE immediately for
subsequent analysis of other DBPs by GC–ECD.
When the influencing factors of chlorination are to be studied,
an orthogonal matrix experimental design was employed where
chlorine dose, reaction time, temperature and pH was varied one
parameter at a time from the baseline condition: chlorine doses
(5, 15, 25 and 40 mg/L as Cl2 ), reaction times (0.25, 2, 6 and 12 h),
temperatures (4, 13, 20, 25 and 30 ◦ C), pH values (4, 5, 6, 7, 8 and 9).
When the effects of temperature, contact time and pH value were
investigated, the chlorine doses in samples A and B were fixed as
15 mg/L and 12 mg/L, respectively.
2.4. Analytical methods
2.4.1. Water quality measurements
The characteristics of wastewater samples were analyzed
according to the standard methods within 24 h after sampling
[18] and the results are shown in Table 1. Concentration of
ammonia nitrogen (CNH3–N ) was determined by colorimetry by
using the Nesslerizatin method. Concentration of DOC (CDOC ) was
detected with a TOC analyzer (Model: TOC-5000A, Shimadzu,
Japan). Concentration of bromide ion (CBr −) was measured by ion
chromatogram (Model: DX-100, Dionex, USA). UV absorbance at
254 nm (UV254 ) with 10 mm quartz cuvette was measured with a
photospectrometer (Model: UV-2401, Shimadzu, Japan).
2.4.2. THMs and HAAs analyses
THMs concentrations were measured by liquid–liquid extrac-
tion and gas chromatography (DB-5, 30 m × 0.32 mm × 0.25 ␮m,
Agilent 6890N) with an electron capture detector (ECD) based on
the USEPA method 551.1 [19]. THMs were extracted immediately
from the disinfected wastewater with MTBE and then analyzed
with GC–ECD. The GC–ECD operating conditions for THMs were:
detector 290 ◦ C, injector 200 ◦ C, injection volume: 1 ␮L, tempera-
ture program: 35 ◦ C for 5 min, ramped to 75 ◦ C by 10 ◦ C/min, held
for 5 min, then ramped to 100 ◦ C by 10 ◦ C/min, held for 2 min.
HAAs concentrations were measured by liquid–liquid extrac-
tion, derivatization and GC–ECD (Agilent 6890N) based on the
USEPA method 552.3 [20]. HAAs were extracted immediately
from disinfected wastewater with MTBE, derivatized with acidic
methanol and then analyzed with GC–ECD. The GC–ECD operating
conditions for HAAs were: detector 300 ◦ C, injector 170 ◦ C, injec-
tion volume: 1 ␮L, temperature program: 35 ◦ C for 5 min, ramped to
75 ◦ C by 5 ◦ C/min, held for 5 min, then ramped to 135 ◦ C by 5 ◦ C/min,
held for 2 min. Each sample was analyzed twice, and the average of
the measurements was calculated.
3. Results and discussion
3.1. Effect of chlorine dose on THMs and HAAs formation
Fig. 1 presents the effect of chlorine dose on the concentra-
tion of THMs and HAAs per mmol DOC for wastewater samples
CBr − (mg/L) UV254 (Abs/cm) SUVA (L/mg m) pH
0.18 0.152 0.899 7.3
0.05 0.137 1.971 7.8
1292 Y.-X. Sun et al. / Journal of Hazardous Materials 168 (2009) 1290–1295
Fig. 1. The formation of THMs and HAAs as a function of chlorine dose and the
breakpoint chlorination curves in chlorination of wastewater samples A (left bar)
and B (right bar) (temperature = 14 ± 1 ◦ C, contact time = 0.5 h, pH 7.0).
A and B after 30 min chlorination. CHCl3 , CHCl2 Br and CHClBr2
were observed for both samples in the experimental scope and
raised gradually with increasing available chlorine concentration
(as shown in Fig. 1(a)). Among the three, CHCl3 was the domi-
nant species and occupied over 71% of the total THMs concentration
(TTHM), represented by the total height of the stacked bars, in the
chlorination of both wastewater samples. However, the concentra-
tion of THM species and TTHM formed in sample B were higher than
those of in sample A during chlorination, which can be explained by
the different SUVA value (the specific UV absorbance, UV254 /DOC)
in different wastewater samples. The SUVA value in sample B
(1.971 L/m mg) was higher than that of sample A (0.899 L/m mg),
which indicated the higher aromatic contents of precursors in the
sample B, and the formation of THMs in sample B was therefore at
a higher level.
Fig. 1(b) illustrates the formation of HAA speciation per mmol
DOC as a function of chlorine dose for samples A and B. The total
HAAs concentration (THAA) increased distinctly with increasing
chlorine dose in chlorination of both wastewater samples. DCAA
occupied greater fractions of THAA in chlorination of both wastew-
ater samples and increased with increasing chlorine doses. This
result indicated that the formation of dihalogenated HAAs may pro-
ceed through a substitution reaction with further free chlorine from
monohalogenated HAAs, which formed quickly at initial chlorina-
tion in wastewater chlorination. Then the dihalogenated HAAs as
intermediates can either be hydrolyzed or further halogenated to
form the trihalogenated HAAs in wastewater chlorination as men-
tioned in ref. [21].
It is interesting to found that the formation of MCAA, DCAA,
MBAA, BCAA, and BDCAA are the main species in the process
of sample A, which increased gradually with increasing chlo-
rine dose from 5 to 40 mg/L. Whereas, the formation of MCAA,
DCAA, TCAA, BCAA and MBAA are the main species in the process
of sample B, which increased gradually with increasing chlorine
dose from 5 to 25 mg/L. The HAA species in order of sample B
was MCAA > DCAA > BCAA > TCAA > MBAA when the initial addi-
tion of chlorine was lower than 25 mg/L, while the order became
DCAA > MBAA > TCAA > MCAA > BCAA when the initial addition of
chlorine was 40 mg/L. This phenomenon presented that the yields
of BCAA and MCAA decreased with the chlorine addition from 25
up to 40 mg/L, and were converted to the yields of MBAA, DCAA
and TCAA with substitution reaction when the chlorine dose in the
higher level. The results showed that BCAA was easy to form in the
chlorination of wastewater with even low bromide ion (0.63 ␮M in
sample B) under limited contact time of 30 min, and may convert
to bromated HAAs as MBAA with higher chlorine levels.
Furthermore, the concentration of THAA, represented by the
total height of the stacked bars, in sample B was higher than that
of sample A with chlorine dose from 5 to 25 mg/L, which became
lower than that of sample A when the chlorine dose was 40 mg/L.
This phenomenon may be caused by the coexistence of ammo-
nia, bromide and chlorine in the solution. The breakpoint curves
are varied among the samples from different sources as shown in
Fig. 1(c). Chlorine dose to achieve 30 min breakpoint chlorination of
the wastewater samples of A and B were found to be 3.5 and 25 mg/L,
respectively. Therefore, the dominating form of chlorine residuals
in sample A with ammonia concentration of 5.4 mg-N/L was chlo-
ramine when the chlorine addition was lower than 25 mg/L, and
was monochloramine with the chlorine addition from 5 to 25 mg/L.
The form of chlorine residuals in sample B with ammonia concen-
tration of 0.9 mg-N/L was free chlorine with chlorine addition from
5 to 40 mg/L [22].
As a result, the lower concentration of THMs and HAAs in chlori-
nation of sample A with the chlorine addition from 5 to 25 mg/L may
be caused by the form of chlorine residuals and its lower SUVA value
compared with that of sample B. The SUVA values in the different
wastewater samples were the dominating influence on the forma-
tion of THMs. However, the containing of bromide ion in wastewater
samples made the reaction system more complex in wastewater
chlorination for the formation of hypochlorous acid, bromate, and
brominated organic DBPs [23]. The forms of chlorine residuals in
both samples were free chlorine at chlorine addition of 40 mg/L,
where Br− /DOC may affect dominantly the formation of HAAs. The
bromo HAAs occupied 45% of THAA in sample A with Br− /DOC value
of 1.61 ␮mol/mmol, while the bromo HAAs occupied 24% of THAA in
sample B with Br- /DOC value of 1.08 ␮mol/mmol. Moreover, the for-
mation of bromated HAAs might be affected by the characteristic of
 Y.-X. Sun et al. / Journal of Hazardous Materials 168 (2009) 1290–1295 1293

were 0.21 ␮mol/mmolDOC and occupied 41.2% of THAA of sample A.

The concentration of bromo HAAs in sample A increased 3.4 times
and occupied 62.8% of THAA when the chlorinated contact time
was extended from 0.25 to 2 h. Then the concentration of bromo
HAAs in sample A sharply decreased to 0.12 ␮mol/mmolDOC at
contact time of 6 h and kept constant thereafter. Therefore the con-
centration of THAA reached a peak after 2 h then decreased with
extended time for sample A in chlorination. However, the formation
of HAA speciation was independent of contact time in chlorination
of sample B. The discrepancy between THMs and HAAs formation
in chlorination of the same sample may be caused by differences
of their each formation mechanisms. The formation mechanism
of THMs is relatively simple, while for HAAs formation there are
a number of speed limit steps [25]. The concept of quick formers
and slow formers may not directly infer the formation of HAAs in
chlorination of wastewater from different sources. The influences
of the characteristics of different wastewater quality are worthy
of attention. In presence of bromide in wastewater samples, the
chlorination system became further complicated by HOBr, which
once formed reacts with ammonia and organic matter in a simi-
lar manner to chlorine producing corresponding bromamines and
brominated organic compounds [26]. The concentration of HAAs
decreased finally because some species as BDCAA, DBCAA, and
TBAA formed would decompose at neutral pH value [27].

3.3. Effect of temperature on THMs and HAAs formation

Fig. 3 illustrates the formation of THMs and HAAs as a func-

tion of reaction temperature in wastewater chlorination. Generally,

Fig. 2. The formation of THMs and HAAs as a function of contact time in chlorination
of wastewater samples A (left bar) and B (right bar) (temperature = 14 ± 1 ◦ C, pH 7.0).

precursors in wastewater samples with bromide ion in chlorination

process [24].

3.2. Effect of contact time on THMs and HAAs formation

Fig. 2 shows the formation of THMs and HAAs in wastewater

chlorination as a function of contact time. As shown in Fig. 2(a),
CHCl3 was also the dominant species during the chlorination of both
wastewater samples. It is found that more than 96% of THMs formed
in the first 0.25 h during the chlorination of sample A, and the con-
centration of TTHM showed no evidence of change in the next 12 h.
However in the chlorination of sample B, the formation of THMs
increased with increasing contact time until 6 h and thereafter
decreased slightly. The discrepancy between the two wastewater
samples concerning the formation of THMs may be explained by
the concept of quick formers and slow formers. As noted in ref.
[16], wastewater contains diverse organic materials, and some of
these organics are simple and very reactive with +1-valent halo-
gens to form THMs (referred to as “fast formers”), while others
(referred to as “slow formers”) are presumably complex molecules
and reluctant to react with +1-valent halogens. Furthermore the rel-
ative yields of “fast formers” and “slow formers” are influenced by
the wastewater treatment scheme employed. For instance, sample
A was expected to contain a higher fraction of the “fast formers” to
form THMs than that of sample B, since those simple-in-structure
“fast formers” were expected to be easily biodegradable.
Fig. 2(b) illustrates the formation of HAAs with the change of
contact time during wastewater chlorination for both samples.
Fig. 3. The formation of THM and HAA species as a function of reaction tempera-
Bromo HAAs as MBAA, BCAA, DBAA, BDCAA and DBCAA were ture in chlorination of wastewater samples A (left bar) and B (right bar) (contact
formed at the initial contact time of 0.25 h and the concentrations time = 0.5 h, pH 7.0).
1294 Y.-X. Sun et al. / Journal of Hazardous Materials 168 (2009) 1290–1295

the formation of TTHM remained constant with increasing reaction

temperature in chlorination of both wastewater samples. The yields
of THAA in chlorination of sample A decreased sharply with increas-
ing reaction temperature from 4 to 13 ◦ C and thereafter decreased
gradually. However, the formation of THAA in chlorination of sam-
ple B was not sensitive to temperature change.
Seen from Fig. 3(b), the higher THAA in chlorination of sam-
ple A at 4 ◦ C was attributable to the higher production of MCAA,
MBAA, DCAA, BCAA and BDCAA. The formation of bromo HAAs
(the sum of MBAA, BCAA, BDCAA and DBCAA) in sample A was
1.04 ␮mol/mmolDOC and occupied 68% of the THAA at 4 ◦ C, while
the formation of bromo HAAs decreased to 0.7 ␮mol/mmolDOC and
occupied 57% of the THAA at 13 ◦ C. Especially, the formation of
MBAA, BCAA and BDCAA decreased about 40%, 27% and 19%, respec-
tively when the reaction temperature rose from 4 to 13 ◦ C. However,
the formation of MCAA, DCAA, BCAA and TCAA were the major pro-
duction in chlorination of sample B, in which the yields of chloro
HAAs (the sum of MCAA, DCAA and TCAA) occupied 77–82% with
reaction temperature ranged from 4 to 30 ◦ C. The results showed
that the formation of chloro HAAs might be more stable than that of
the bromo HAAs with increasing reaction temperature in wastew-
ater chlorination.
The formation trends of the bromo HAAs as a function of reaction
temperature may be explained with the chemical thermodynam-
ics of the by-product decomposition reactions. The decomposition
reactions are often hydrolysis reaction, and increasing temperature
will accelerate the hydrolysis reactions because these reactions are
endothermic [25]. THMs are much more stable than HAAs especially
the trihaloacetic acids [27,28]. As a result the changes of THMs con-
centration were different from HAAs with increasing temperature.
However, the resultant phenomena of this study do not agree with
the statements concerning chlorination of drinking water [29]. Dur-
ing chlorination of drinking water, formation of the THMs and HAAs
increases with increasing temperature, and there is an Arrhenius Fig. 4. The formation of THM and HAA species as a function of pH value in chlori-
dependency between temperature and the rate constant of forma- nation of wastewater samples A (left bar) and B (right bar) (temperature = 14 ± 1 ◦ C,
contact time = 0.5 h).
tion [29]. The discrepancy between the statements of the references
and the phenomena of this study may be caused by the differences
of the reactant. when pH value is at 7 [22]. However, the form of chlorine resid-
uals changed to dichloramine when the chlorination system is at
3.4. Effect of pH on THMs and HAAs formation lower pH value of 4. The formation of MBAA in chloramination of
sample B with bromide ion occupied 48% of the THAA at lower pH
Fig. 4(a) shows the effect of solution pH on THM species forma- value of 4, which decreased directly with increasing pH value to 7
tion during chlorination of both the wastewater samples. The major and thereafter increased. The results showed that the formation of
species of THMs formed during chlorination was CHCl3 , followed MBAA, BCAA and BDCAA was favored in low pH values of 4 and high
by CHCl2 Br and CHClBr2 . CHCl3 was substantially higher at pH val- pH values of 9.
ues of 6 for sample A and 7 for sample B than at other pH value in The above phenomena do not agree with the statements con-
the studied scope. The formation of TTHM (represented by the total cerning chlorination of drinking water [30,31]. Chen et al. found
height of the stacked bars) detected at near neutral condition was that the TTHM concentration increased with increasing pH value in
two times more than that of pH value at 4. Meanwhile, the effect of the range of 5–10, but the THAA concentration slightly decreases
solution pH on HAAs formation was different from that of THMs. with increasing pH value [31]. Uyak et al. considered the pH depen-
Fig. 4(b) presents the effect of solution pH on HAA species for- dent on speciation and reactivity of chlorine. Therefore the chlorine
mation during chlorination of both the wastewater samples. It was demand was lower in alkaline solutions than in acidic, yet increased
showed that the formation of THAA in chlorination of sample A was CHCl3 formation occurred in alkaline solutions in water chlorina-
the lowest when pH value is at 7 than those of in acidic or alkaline tion [32]. However, the influence of pH on HAA formation is more
conditions, while the yields of THAA in chlorination of sample B complicated because the rate of formation and hydrolysis varies
kept stable with changing of pH value. This discrepancy between for each individual species. Nikolaou found that MCAA and DCAA
the samples from different sources may be explained by the differ- were favored from high pH values in drinking water chlorination,
ent characteristics of wastewater quality. Compared with sample A, but the opposite was true for TCAA and MBAA, and the optimum
sample B contained lower concentration of ammonia and bromide pH values of BDCAA were 6 and 7, respectively [30]. The concentra-
(seen from Table 1), and the major form of chlorine residuals were tion of active species formed by hydrolysis of hypochlorite changes
free chlorine in chlorination under the experimental scope. There- with different pH values. As such, the precursors contributing to
fore, the dominating formation as MCAA, DCAA, BCAA and TCAA in the MCAA, MBAA and DCAA formation in wastewater are likely to
chlorination of sample B may be independent of the change of pH be different from those in most kinds of water samples. It is obvious
values. that the reactions between chlorine and DOM during chlorination
As mentioned in Section 3.1, the chlorination process in sample of wastewater would be more complex than the reactions during
A with bromide ion might be considered as monochloramination drinking water disinfection. Therefore, controlling pH may be an
 Y.-X. Sun et al. / Journal of Hazardous Materials 168 (2009) 1290–1295
effective way to reduce the formation of disinfection by-products
for wastewater disinfection.
4. Conclusions
(1) Increasing chlorine dose will lead to an increase in reaction
extent, therefore causing an increase of HAAs and THMs for-
mation. The SUVA values in different wastewater samples may
be the dominating influence factors on the formation of THMs
in chlorination.
(2) The discrepancy between wastewater samples concerning for-
mation of THMs as a function of contact time may be depended
on the wastewater content of quick or slow formers. However,
the concept of quick and slow formers may not directly infer the
formation of HAAs in chlorination of wastewater from different
sources.
(3) The formation of THMs was not sensitive to temperature
change. However, the formation of bromo HAAs as MBAA,
BCAA, BDCAA and DBCAA decreased gradually with increasing
of reaction temperature from 4 to 30 ◦ C in the chlorination of
wastewater containing bromide.
(4) The formation of MBAA, BCAA and DBCAA in chlorination of
wastewater samples was favored in low pH values of 4 and high
pH values of 9. The most amounts of THMs and the least amount
of HAAs were detected at near neutral condition generally. In
other words, these two groups of compounds responded to pH
variations almost conversely.
Acknowledgments
This study was supported by the research grant of the
National Science Fund for Distinguished Young Scholars of China
(no.50825801) and the National High-tech R&D Program of China
(863 program, no.2008AA062502).
References
[1] J.Y. Chu, J.N. Chen, C. Wang, P. Fu, Wastewater reuse potential analysis:
implications for China’s water resources management, Water Res. 38 (2004)
2746–2756.
[2] USEPA, Guidelines for water reuse, EPA-A/625/R-92/004, USEPA, Center for
Environmental Research Information, Cincinnati, Ohio, 1992.
[3] S. Stefanie, H.H. Hermann, Generation of halogenated organic compounds in
municipal waste water, Water Sci. Technol. 37 (1998) 303–309.
[4] M. Rebhun, L.H. Grossman, J. Manka, Formation of disinfection by products
during chlorination of secondary effluent and renovated water, Water Environ.
Res. 69 (1997) 1154–1162.
[5] E. Koukouraki, E. Diamadopoulos, THM formation during chlorination of treated
municipal wastewater, Water Sci. Technol.: Water Supply 2 (2002) 235–242.
[6] R. Sadiq, M.J. Rodriguez, Fuzzy synthetic evaluation of disinfection by-products-
a risk-based indexing system, J. Environ. Manage. 73 (2004) 1–13.
[7] USEPA, National primary drinking water regulations: stage 2 disinfectants and
disinfection byproducts rule: final rule, Fed. Regist. 71 (2) (2006).
[8] R. Sadiq, M.J. Rodriguez, Disinfection by-products (DBPs) in drinking water and
predictive models for their occurrence: a review, Sci. Total Environ. 321 (2004)
21–46.
1295
[9] R.M. Clark, Predicting the formation of chlorinated and brominated by-
products, J. Environ. Eng. -ASCE 127 (2001) 493–501.
[10] D.J. Barker, D.C. Stuckey, A review of soluble microbial products (SMP) in
wastewater treatment systems, Water Res. 33 (1999) 3063–3082.
[11] X. Yang, C. Shang, J.C. Huang, DBP formation in breakpoint chlorination of
wastewater, Water Res. 39 (2005) 4755–4767.
[12] L.S. Wang, H.Y. Hu, C. Wang, Effect of ammonia nitrogen and dissolved organic
matter fractions on the genotoxicity of wastewater effluent during chlorine
disinfection, Environ. Sci. Technol. 41 (2007) 160–165.
[13] H.Y. Hu, L.S. Wang, D.B. Wei, Technical challenge and resolution for wastewater
disinfection, World Sci. Technol. Res. Dev. 27 (2005) 35–41.
[14] E. Koukouraki, E. Diamadopoulos, Modelling the formation of THM (tri-
halomethanes) during chlorination of treated municipal wastewater, Water Sci.
Technol.: Water Supply 3 (2003) 277–284.
[15] V. Matamoros, R. Mujeriego, J.M. Bayona, Trihalomethane occurrence in chlo-
rinated reclaimed water at full-scale wastewater treatment plants in NE Spain,
Water Res. 41 (2007) 3337–3344.
[16] Y.N. Qi, C. Shang, I.M.C. Lo, Formation of haloacetic acids during monochloram-
ination, Water Res. 38 (2004) 2375–2383.
[17] S. Xue, Q.L. Zhao, L.L. Wei, T. Jia, Effect of bromide ion on isolated fractions of
dissolved organic matter in secondary effluent during chlorination, J. Hazard.
Mater. 157 (2008) 25–33.
[18] APHA, AWWA, WEF, Standard Methods for the Examination of Water and
Wastewater, 20th ed., APHA/AWWA/WEF, Washington, DC, 1998.
[19] D.J. Munch, A.L. Cohen, Determination of chlorination disinfection by-products,
chlorinated solvents, and halogenated pesticide/herbicides in drinking water by
liquid–liquid extraction and gas chromatography with electron capture detec-
tion, Revision 1.0, 1999, USEPA.
[20] M.M. Domino, B.V. Pepich, D.J. Munch, P.S. Fair, Y. Xie, Determination of
haloacetic acids and dalapon in drinking water by liquid–liquid microextrac-
tion, derivatization, and gas chromatography with electron capture detection,
Revision 1.0, 2003, USEPA.
[21] G.A. Cowman, P.C. Singer, Effect of bromide ion on haloacetic acid speciation
resulting from chlorination and chloramination of aquatic humic substances,
Environ. Sci. Technol. 30 (1996) 16–24.
[22] Q. Zhimin, D.A. Craig, Determination of monochloramine formation rate con-
stants with stopped-flow spectrophotometry, Environ. Sci. Technol. 38 (2004)
1435–1444.
[23] X. Yang, C. Shang, Chlorination byproduct formation in the presence of humic
acid, model nitrogenous organic compounds, ammonia, and bromide, Environ.
Sci. Technol. 38 (2004) 4995–5001.
[24] G.H. Hua, D.A. Reckhow, Characterization of disinfection byproduct precursors
based on hydrophobicity and molecular size, Environ. Sci. Technol. 41 (2007)
3309–3315.
[25] D.A. Reckhow, P.C. Singer, Water Chlorination: Chemistry, Environmental
Impact and Health Effects, Lewis Publishers, Chelsea, MI, 1985.
[26] T.V. Luong, C.J. Peters, R. Perry, Influence of bromide and ammonia upon the
formation of trihalomethanes under water-treatment conditions, Environ. Sci.
Technol. 16 (1982) 473–479.
[27] X.R. Zhang, R.A. Minear, Decomposition of trihaloacetic acids and formation
of the corresponding trihalomethanes in drinking water, Water Res. 36 (2002)
3665–3673.
[28] A.D. Nikolaou, T.D. Lekkas, S.K. Golfinopoulos, Kinetics of the formation and
decomposition of chlorination by-products in surface waters, Chem. Eng. J. 100
(2004) 139–148.
[29] C.J. Peters, R.J. Young, R. Perry, Factors influencing the formation of halo-
forms in the chlorination of humic materials, Environ. Sci. Technol. 14 (1980)
1391–1395.
[30] A.D. Nikolaou, S.K. Golfinopoulos, G.B. Arhonditsis, V. Kolovoyiannis, T.D.
Lekkas, Modeling the formation of chlorination by-products in river waters
with different quality, Chemosphere 55 (2004) 409–420.
[31] P.P. Chen, J.Y. Zhang, J.Y. Jin, Study on the effect and formation of tri-
halomethanes and haloacetic ethyl acid in drinking waters, Environ. Chem. 24
(2005) 434–437.
[32] V. Uyak, K. Ozdemir, I. TorozSolution, Multiple linear regression modeling of
disinfection by-products formation in Istanbul drinking water reservoirs, Sci.
Total Environ. 378 (2007) 269–280.