Water Research 103 (2016) 215e223

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Oxidative degradation of triclosan by potassium permanganate:

Kinetics, degradation products, reaction mechanism, and toxicity
evaluation
Jing Chen, Ruijuan Qu*, Xiaoxue Pan, Zunyao Wang**
State Key Laboratory of Pollution Control and Resources Reuse, School of the Environment, Nanjing University, Jiangsu, Nanjing 210023, PR China

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

Article history: In this study, we systematically investigated the potential applicability of potassium permanganate for
Received 22 February 2016 removal of triclosan (TCS) in water treatment. A series of kinetic experiments were carried out to study
Received in revised form the influence of various factors, including the pH, oxidant doses, temperature, and presence of typical
18 July 2016
anions (Cl
, SO2


4 , NO3 ), humic acid (HA), and fulvic acid (FA) on triclosan removal. The optimal reaction
Accepted 18 July 2016
conditions were: pH ¼ 8.0, [TCS]0:[KMnO4]0 ¼ 1:2.5, and T ¼ 25  C, where 20 mg/L of TCS could be
Available online 20 July 2016
completely degraded in 120 s. However, the rate of TCS (20 mg/L) oxidation by KMnO4
([TCS]0:[KMnO4]0 ¼ 1:2.5) was 1.64  10
3 mg L
1$h
1, lower than that at an initial concentration of
Keywords:
Triclosan
20 mg/L (2.24  103 mg L
1$h
1). A total of eleven products were detected by liquid chromatography-
Permanganate quadrupole-time-of-flight-mass spectrometry (LC-Q-TOF-MS) analysis, including phenol and its de-
Product identification rivatives, benzoquinone, an organic acid, and aldehyde. Two main reaction pathways involving CeO bond
Degradation pathway cleavage (
C(8)eO(7)
) and benzene ring opening (in the less chlorinated benzene ring) were proposed,
Acute toxicity and were further confirmed based on frontier electron density calculations and point charges. Further-
Frontier electron density more, the changes in the toxicity of the reaction solution during TCS oxidation by KMnO4 were evaluated
by using both the luminescent bacteria Photobacterium phosphoreum and the water flea Daphnia magna.
The toxicity of 20 mg/L triclosan to D. magna and P. phosphoreum after 60 min was reduced by 95.2% and
43.0%, respectively. Phenol and 1,4-benzoquinone, the two representative degradation products formed
during permanganate oxidation, would yield low concentrations of DBPs (STHMFP, 20.99e278.97 mg/mg;
SHAAFP, 7.86  10
4
45.77 mg/mg) after chlorination and chloramination. Overall, KMnO4 can be used as
an effective oxidizing agent for TCS removal in water and wastewater treatment.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction Europe (Halden and Paull, 2005; Pintado-Herrera et al., 2014;

Triclosan (5-chloro-2-(2,4-dichlorophenoxy)-phenol, TCS) is a
broad-spectrum antimicrobial and preservative agent that is widely
used in a range of consumer products such as toothpastes, anti-
septic soaps, detergents, cosmetics, plastic kitchenware, socks,
carpets and toys (Bedoux et al., 2012; Reiss et al., 2002; Singer et al.,
2002). The global demand for TCS has continued to increase over
the last thirty years, and about 350 tons are consumed every year in
* Corresponding author. State Key Laboratory of Pollution Control and Resources
Reuse, School of the Environment, Xianlin Campus, Nanjing University, Jiangsu,
Nanjing 210023, PR China.
** Corresponding author.
E-mail addresses: quruijuan0404@nju.edu.cn (R. Qu), wangzy@nju.edu.cn
(Z. Wang).
Young et al., 2008). Given the widespread use, this compound has
been detected in surface water, wastewater, sediment, soil, organ-
isms, and even in human milk (Fu et al., 2016; Toms et al., 2011). The
high octanol water partitioning coefficient of TCS (log Kow ¼ 4.8 at
pH ¼ 7) indicates that it can bioaccumulate in the biota and be
biomagnified along the food chain. Triclosan is highly toxic to
freshwater aquatic species like green algae, the water flea Daphnia
magna, and fish (zebrafish, fathead minnows, bluegill sunfish) (Chen
et al., 2014; Dann and Hontela, 2011). Previous researches have
also shown that TCS may cause bacterial resistance, skin irritation,
endocrine disruption, and even increase the formation of carcino-
genic by-products (Brausch and Rand, 2011; Dayan, 2007; Novo
et al., 2013).
Over the past few decades, various water treatment techniques,
including ozonation, Fenton, photolysis, and permanganate

http://dx.doi.org/10.1016/j.watres.2016.07.041
0043-1354/© 2016 Elsevier Ltd. All rights reserved.
216 J. Chen et al. / Water Research 103 (2016) 215e223
treatment have been used to degrade TCS (Buth et al., 2009; Suarez
s et al., 2007; Zhang and Huang, 2003). Compared
et al., 2007; Sire
with other oxidizing agents, permanganate possesses the attractive
characteristics of high efficiency, relatively low cost, comparative
stability, and ease of handling. Jiang et al. (2009) investigated the
kinetics of triclosan degradation by permanganate, revealing the
catalytic role of MnO2 formed in situ under slightly acidic condi-
tions. Wu et al. (2012) found that degradation of TCS by perman-
ganate followed pseudo-first order kinetics in a buffered DI water
system at pH 7.0 and 8.6. In a drinking water system treated with
permanganate, 2,4-dichlorophenol was identified as the major
oxidation product of TCS. Unfortunately, to date, very little infor-
mation is available on the transformation products, reaction
mechanism and toxicity changes of TCS during oxidative degrada-
tion by KMnO4, though such knowledge is essential for practical
implementation of the permanganate oxidation technique.
In this study, we systematically investigate the oxidation of TCS
by permanganate. A series of operating parameters influencing the
degradation processes, including the solution pH, temperature, and
the presence of typical inorganic anions, humic, and fulvic acid, are
evaluated to explore the optimum reaction conditions. The degra-
dation products are identified by liquid chromatography-mass
spectrometric analysis, and the reaction pathways are thus pro-
posed. Frontier electron density (FED) calculations and point
charges analysis are also employed to further confirm the identity
of the intermediate products. Changes in the toxicity of triclosan
during the oxidation process are evaluated using the luminescent
bacteria Photobacterium phosphoreum and water flea Daphnia
magna. In addition, the generation of disinfection-by-products from
triclosan degradation products after implementing chlorination
and chloramination in a full-scale treatment plant are discussed
herein.
2. Materials and methods
2.1. Chemicals
Triclosan (purity  99%) was purchased from Aladdin (Shanghai,
China). The HPLC grade methanol and formic acid were supplied by
Merck (Darmstadt, Germany). Other chemicals were of analytical
grade and were used as received. Stock solutions of TCS, KMnO4 and
NaNO2 were prepared with ultrapure water at concentrations of
500 mg/L, 5 g/L, and 30 g/L, respectively, and were all stored in
brown bottles at 4  C in a refrigerator.
2.2. Oxidation procedures
The oxidation reactions were initiated by adding 30 mL of po-
tassium permanganate solution (5 g/L) to centrifuge tubes con-
taining 3 mL of TCS solution (20 mg/L). The mixture solution was
agitated with a vortex stirrer to ensure a uniform reaction. After 10,
30, 60, 90, 120, 180, and 300 s, permanganate was quenched with
30 mL of NaNO2 stock solution (the reason for choosing NaNO2 as
quenching agent is shown in Text S1). All experiments were per-
formed in triplicate. The pH of the solutions was adjusted using HCl
or NaOH (Merck). For product identification, all the sample solu-
tions were concentrated by solid phase extraction (SPE) to elimi-
nate interference from MnO2 precipitation and certain other ions
such as Naþ, MnO



4 , NO2 , and Cl .
2.3. Analytical methods
The concentration of TCS was quantified by using a HPLC system
(Agilent 1100) equipped with a C18 column (Agilent Zorbax 300SB)
with UV detection. The analysis was conducted using a mobile
phase comprising methanol (80%) and water (20%), a flow rate of
1.0 mL/min, an injection volume of 10 mL, and a detection wave-
length of 230 nm.
Identification of the TCS degradation products was performed
using the SPE-LC-MS method. At various reaction times, the solu-
tion was concentrated by using a solid phase extraction (SPE)
workstation using CNWBOND LC-C18 SPE cartridges
(2.CA0955.0001, 1 g, 6 mL). The procedure was slightly modified
from previous approaches (Loos et al., 2010; Ji et al., 2013). After
activation with 5 mL methanol and 5 mL ultrapure water, each
column was loaded with 3 mL of sample, washed with 5 mL ul-
trapure water, and then dried under vacuum. After eluting with
3 mL methanol, the degradation products in the extracts were
subjected to LC-MS analysis. A similar SPE method was employed to
enable LC determination of TCS in the kinetics experiment per-
formed at a low initial concentration (20 mg/L), where the samples
were concentrated 200-fold.
LC-MS analysis was conducted using a high resolution hybrid
quadrupole time-of-flight mass spectrometer (Triple TOF 5600, AB
Sciex, Foster City, CA) equipped with an electrospray ion source. A
5 mL sample was injected into the source using an Agilent 1260
infinity high performance liquid chromatography (HPLC) system.
Chromatographic separation was performed on a Thermo BDS
Hypersil C18 column (2.1 mm  100 mm, particle size: 2.4 mm;
Thermo Fisher Scientific, Waltham, MA) maintained at 30  C, and
the mobile phase consisting of 0.3% formic acid in water (A) and
methanol (B) was eluted at a flow rate of 200 mL/min. The linear
gradient was decreased from 90% A (2 min) to 10% A in 1 min,
maintained for 23 min, then returned to the starting condition in
1 min, followed by an 8 min equilibration. Mass spectra (m/z
70e1000) were recorded in negative ion mode by using an elec-
trospray ion (ESI) source with the following ion source parameters:
ion source gas 1,
55 psi; ion source gas 2,
55 psi; curtain gas,
35
psi; temperature, 550  C; ionspray voltage floating,
4500 V;
declustering potential, -80 V; collision energy,
10 V. Nitrogen gas
was used throughout. Following the MS analysis, the individual
parent ions of the possible transformation products of TCS were
manually selected for MS/MS analysis. A sweeping collision energy
setting of
30 ± 10 V was applied for collision-induced dissociation.
The high-resolution LC-MS data were acquired with Analyst TF
software (Version 1.6, AB Sciex) and processed using PeakView
software (Version 1.2, AB Sciex).
2.4. Toxicity assay
Changes in the toxicity of the triclosan solution during KMnO4
oxidation were assessed by using the luminescent bacteria
P. phosphoreum and water flea D. magna. The lyophilized lumines-
cent bacteria P. phosphoreum was supplied by the Institute of Soil
Science, Chinese Academy of Sciences (Nanjing, China). The
D. magna was purchased from the Research Center from Eco-
Environmental Sciences, Chinese Academy of Sciences (Wuhan,
China). For the toxicity texts, the reaction solutions were centri-
fuged and filtered to remove the insoluble product MnO2. The
bioluminescence test was carried out by following the ISO standard
method. After activation and incubation, the bacteria were exposed
to the reaction solutions for 15 min at 25  C, and the biolumines-
cence was measured on a Tecan Infinite 200® PRO multimode
microplate reader (Tecan, Switzerland). After 15 min exposure to
the reaction solutions at pH 8.0 and 25  C, the luminescence in-
tensity was measured; the result is expressed as the inhibition
percentage versus the black control. Six replicate tests were per-
formed for all bioluminescence experiments. The toxicity of NaNO2
to P. phosphoreum was considered negligible since the concentra-
tion used in this study is much smaller than the non-lethal
 J. Chen et al. / Water Research 103 (2016) 215e223
concentration (1.1 g/L). Acute toxicity testing with D. magna was
conducted in accordance with the OECD guideline. Seven daphnia
neonates (<24 h) were exposed to 20 mL of sample in a 50 mL
beaker, which was held at 20 ± 2  C in an illuminating incubator
with a 14 h: 10 h light: dark photoperiod. D. magna was not fed
during the experimental period. After 24 h exposure, the number of
dead organisms (dead number) was recorded and the inhibition
rate was calculated for each sample. All sample tests and control
experiments for D. magna were performed in triplicate. A reagent
control with the same concentration of NaNO2 was also assessed to
eliminate the possible influence of NaNO2.
2.5. Chlorination and chloramination
The trihalomethane formation potential (THMFP) and haloacetic
acids formation potential (HAAFP) measurements were performed
according to Standard Method 5710B. Monochloramine stock so-
lution was prepared by reference to the method of Chen and Young
(2008). The chlorine dosage for each water sample was determined
such that the final residual concentration of chlorine in the sample
after 5 days of incubation at 25  C was 3e5 mg/L. Samples were
adjusted to a pH of 7.0 ± 0.2 using H2SO4 and NaOH. The neutralized
solution was then buffered with a phosphate solution prior to in-
cubation in amber bottles at 25  C for five days. At the end of the
incubation period, the samples were dechlorinated using sodium
sulfite (Na2SO3). The chlorinated samples were extracted with
methyl-tert butyl ether (MTBE) to analyze four kinds of tri-
halomethanes (THMs), i.e. Chloroform (TCM), bromodichloro-
methane (BCDM), dibromochloromethane (DBCM), and
bromoform (TBM) using a modified EPA method 551.1. Five species
of haloacetic acids (HAAs), i.e. monochloroacetic acid (MCAA),
dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), mono-
bromoacetic acid (MBAA), and dibromoacetic acid (DBAA), were
analyzed in accordance with EPA method 552.2. MTBE was used as
the sole extracting solvent. The concentrations of THMs and HAAs
were measured using a gas chromatograph (Agilent 6890A) with an
electron capture detector (ECD).
3. Results and discussion
3.1. Kinetic study
3.1.1. Effect of initial solution pH
The pH of the aqueous solution may greatly influence the
oxidative degradation of TCS by potassium permanganate, due to
changes in the existing species of TCS (pKa ¼ 8.1) (Kim et al., 2013)
and the oxidation-reduction potential (E0) of KMnO4 (Yan and
Schwartz, 1999). The following reactions proceed under the
stated conditions, under acidic conditions: MnO
þ
4 þ 8H þ 5e #
e
2þ
Mn þ 4H2O, E0 ¼ 1.51 V; under neutral or slightly alkaline con-
ditions: MnO
e

4 þ 2H2O þ 3e # MnO2 þ 4OH , E0 ¼ 0.58 V; under
alkaline conditions, MnO
e 2

4 þ e # MnO4 , E0 ¼ 0.56 V. In this
study, the solution pH was varied from 2.0 to 10.0 to evaluate the
effect of the pH on the TCS degradation efficiency. As shown in
Fig. 1A, the removal of TCS is highly dependent on the solution pH.
Under acidic conditions (pH ¼ 2.0e4.0), the oxidation efficiency
decreased with increasing pH. The lowest degradation was
observed at pH ¼ 4.0, where 22% TCS remained after 5 min of
oxidation. In contrast, the oxidation efficiency increased rapidly
with an increase of the pH from 4.0 to 8.0, and TCS was almost
completely degraded in 120 s at pH ¼ 8.0. With a further increase of
the pH to 10.0, the removal rate decreased to some degree. For the
studied pH range, the degradation rate was relatively high at
pH ¼ 2.0, which is attributed to the high oxidation-reduction po-
tential of KMnO4 (Dash et al., 2009); although the oxidizing ability
217
of MnO
4 decreased as compared to that in acidic medium, the re-
action rate obtained at pH ¼ 8.0 was still very high. At this pH point,
the percentage of ionic TCS was almost identical to that of the
molecular species. The strong electron-donating ability of the
deprotonated hydroxyl groups makes TCS easily oxidized by MnO
4
(Jiang et al., 2009; Qiao et al., 2014; Waldemer and Tratnyek, 2006).
Consequently, the degradation kinetics of TCS at different pH can
result from a combination of the effects of the pH on TCS speciation
and the oxidizing properties of MnO
4 . Because the highest removal
efficiency was achieved at pH 8.0, all subsequent experiments were
performed at this pH.
3.1.2. Effect of oxidant doses
It is well known that the oxidant dose dramatically influences
the degradation of organic substances (Abdelraheem et al., 2015;
Wacławek et al., 2016). In order to achieve an efficient degrada-
tion rate at low cost, the oxidation of triclosan by permanganate
was evaluated for initial KMnO4 concentrations of ranging from
10 mg/L (TCS:KMnO4 ¼ 1:0.5) to 150 mg/L (TCS:KMnO4 ¼ 1:7.5).
Fig. 1B shows that the removal efficiency increased with an
increasing amount of permanganate. After 300 s, triclosan was
degraded by 42.5%, 82.3%, and nearly 100% at the TCS:KMnO4 ratios
of 1:0.5, 1:1.5, and 1:2.5, respectively. When the TCS:KMnO4 ratio
changed from 1:2.5 to 1:7.5, the influence of permanganate on the
removal efficiency was not so obvious, and nearly complete
removal was achieved at 120 s for the three oxidant dosages. From
the economic perspective, the ratio of 1:2.5 was considered as the
most suitable KMnO4 dosage for triclosan removal.
3.1.3. Effect of temperature
The degradation of TCS was evaluated at various temperatures
in the range of 15e35  C to examine the influence of temperature.
As shown in Fig. 1C, the rate of triclosan degradation by perman-
ganate increased with increasing temperature. Specifically, the
remaining triclosan after 10 s decreased from 57.5% to 19.4%, when
the reaction temperature increased from 15  C to 35  C. The
temperature-dependence is not unexpected as the well-established
Arrhenius law suggests that the number of activated reactant
molecules will increase at a higher temperature. On the whole, the
removal of triclosan was fast at the three temperatures, with
degradation ratios of 94.4e100.0% in 90 s. To avoid energy con-
sumption associated with heating, 25  C was selected as the best
reaction temperature.
3.1.4. Effect of the typical anions and humic acid
Since industrial wastewaters and raw waters are complex sys-
tems, the influence of many inorganic ions and organic species
should be examined for treatment of real TCS-containing water
with permanganate. In this study, the typical anions (Cl
, SO2
4 ,
NO
3 ), humic acid (HA), and fluvic acid (FA) exerted a slight effect on
the degradation of triclosan (Fig. S1). The fast reaction between TCS
and KMnO4 (nearly 100% removal in 90 s) may account for the
insignificant influence of the investigated water components.
3.1.5. Kinetic study in a low initial concentration
To get a better understanding of the oxidation efficiency of tri-
closan in realistic environmental conditions, the tests were per-
formed at a relatively low initial concentration (20 mg/L) with
different dosages of the oxidizing agent. The concentration varia-
tion of TCS at five different ratios of TCS:KMnO4 (1:2.5, 1:5, 1:10,
1:50, and 1:100) was shown in Fig. 1D. The result at low initial
concentration (20 mg/L) showed that the degradation of TCS at a
ratio of TCS:KMnO4 ¼ 1:2.5 was in accordance of the pseudo-first-
order reaction kinetics. That is, the reaction rate is proportional to
the substrate concentration. The rate of TCS (20 mg/L) oxidation by
218 J. Chen et al. / Water Research 103 (2016) 215e223

1.0 pH = 2 1.0 [TCS]0:[KMnO4]0 = 1:0.5

pH = 3 [TCS]0:[KMnO4]0 = 1:1.5
0.8 pH = 4
pH = 5
0.8 [TCS]0:[KMnO4]0 = 1:2.5
pH = 6

C/C0
0.6 pH = 7 0.6
pH = 8 [TCS]0:[KMnO4]0 = 1:5

C/C0
pH = 9 [TCS]0:[KMnO4]0 = 1:7.5
0.4 pH = 10 0.4

0.2 0.2

0.0 0.0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Time (s) Time (s)
1.0 1.0 [TCS]0:[KMnO4]0 = 1:2.5
15
25 [TCS]0:[KMnO4]0 = 1:5
0.8 35 0.8 [TCS]0:[KMnO4]0 = 1:10
[TCS]0:[KMnO4]0 = 1:50
0.6 0.6

C/C0
[TCS]0:[KMnO4]0 = 1:100
C/C0

0.4 0.4

0.2 0.2

0.0 0.0
0 50 100 150 200 250 300 0 10 20 30 40 50
Time (s) Time (h)

Fig. 1. Degradation kinetics of triclosan by permanganate. (A) Effect of pH. Experimental conditions: [TCS]0 ¼ 20 mg/L, [TCS]0:[KMnO4]0 ¼ 1:2.5, T ¼ 25  C. (B) Effect of oxidant
doses. Experimental conditions: [TCS]0 ¼ 20 mg/L, pH ¼ 8.0, T ¼ 25  C. (C) Effect of temperature. Experimental conditions: [TCS]0 ¼ 20 mg/L, pH ¼ 8.0, [TCS]0:[KMnO4]0 ¼ 1:2.5. (D)
Removal of TCS at a low initial concentration. Experimental conditions: [TCS]0 ¼ 20 mg/L, pH ¼ 8.0, T ¼ 25  C.

KMnO4 ([TCS]0:[KMnO4]0 ¼ 1:2.5) was 1.64  10
3 mg L
1$h
1,
compared with that at an initial concentration of 20 mg/L
(2.24  103 mg L
1$h
1). Thus, permanganate effectiveness for TCS
degradation is lower at a low initial TCS concentration that is only
one in a thousand of high initial concentration. However, the
elimination rate also increased with increasing oxidant dosage. The
remaining TCS after 48 h was 30% and 20% at the respective
TCS:KMnO4 ratios of 1:2.5 and 1:5, whereas complete removal was
observed in 12 h, 4 h, and 30 min at the ratios of 1:10, 1:50 and
1:100, respectively. Thus, a typical dosage of 2 mg/L KMnO4
([TCS]0:[KMnO4]0 ¼ 1:100) was required for efficient removal of
TCS at the mg/L level in water and wastewater treatment (Liu et al.,
2009). This can be used as a cost-effective technique for reducing
the operational fee to less than 4.56  10
3 US dollars per ton. In
addition, the removal of TCS in real wastewater at mg/L levels was
also investigated. Select physico-chemical properties of the test
wastewater are presented in Table S1. As illustrated in Fig. S2, no
obvious difference in the decomposition of TCS was observed for
ultrapure water versus real waste water, implying that the waste-
water components exerted no influence on the TCS oxidation.
Similar phenomena were also observed in the presence of some
typical ions and dissolved organic matter (DOM; see Fig. S1).
3.2. Exploration of reaction mechanism
3.2.1. Identification of oxidation products
The products of triclosan oxidation by permanganate were
detected by LC-Q-TOF-MS analysis. The total ion current (TIC)
chromatograms of TCS solution before and after oxidation are
shown in Fig. 2. From the reaction sample at 0 min, we can see that
the peak of TCS appears at near 17.2 min. This substrate peak
gradually disappeared with progress of the oxidation reaction, and
a total of eleven new peaks were observed with evident changes in
the relative intensity at different reaction times. Notably, the six
products with precursor ions at m/z 330.94, 274.96, 272.98, 230.96,
204.95 and 148.95 were observed for the first time. Typical frag-
ment losses like CO, CO2, COeCO, COeCO2 and CO2eCO2 were
observed from the MS/MS analysis, implying the presence of
carbonyl, carboxylic, and aldehyde groups in the degradation
products.
P2, P4: The chromatographic peak with a retention time of
12.13 min comprised an ion cluster with m/z 274.96/276.96/278.96,
indicating that this compound (P2) contained two Cl atoms. In the
product ion spectra (Fig. 3B), the fragment ion peaks with m/z
230.96 and 186.95 indicate sequential losses of CO2 from the parent
ion (274.96), which provides direct evidence of the presence of two
carboxyl groups in P2. Notably, loss of C2H2 from the species with
m/z 186.95 generates a fragment ion peak at m/z 160.95, which is
consistent with the parent ion of P6 (C6H3Cl2O, M-H). Furthermore,
the fragment ion at m/z 124.98 results from cleavage of the CeCl
bond in the m/z 160.95 species. Hence, it can be assumed that
oxidation takes place in the hydroxyl-containing benzene ring.
At 12.13 min, an ion cluster with m/z 230.96/232.96/234.96 was
detected, having a chlorine isotope ratio of 100.0%/63.9%/10.2%,
suggesting the presence of two Cl atoms in the compound P4. As
shown in Fig. 3C, the fragment ions at m/z 202.96, 174.97, 160.95 and
124.98 correspond to the loss of CO, CO, CH2 and Cl, respectively.
Thus, P4 was identified as C9H6Cl2O3, the structure of which is
shown in Fig. 3C.
The presence of two Cl atoms in the molecules of P1, P3, P8, and
P9 was also confirmed by the chlorine isotopic distribution. The
fragmentation spectra of these compounds are similar to that of P2
and P4 (Fig. S3). Likewise, the fragment peaks at m/z 160.95 and
124.96 implied the occurrence of the 2,4-DCP unit in the structures.
 J. Chen et al. / Water Research 103 (2016) 215e223 219

Fig. 2. Total ion current (TIC) chromatograms of the oxidized samples at different reaction time.

Fig. 3. Product ion spectrum of TCS (A), P2 (B) and P4 (C) obtained by HPLC-TOF-MS/MS and proposed fragmentation pathway.

The most probable molecular formula of P1, P3, P8, and P9 are
proposed as C12H5Cl3O3, C11H8Cl2O4, C12H6Cl2O7 and C7H4Cl2O3,
respectively.
P5eP7, P10, P11: Compound P6 was eluted at 14.43 min. An ion
isotopic cluster was observed at m/z 160.96/162.96/164.96 in the
spectrum, suggesting that two chlorines are present in the product.
The fragments at m/z 124.98, 89.00, and 61.00 confirm the occur-
rence of Cl, Cl, and CO, respectively (Fig. S3). The product was
identified as 2,4-dichlorophenol (2,4-DCP), which has two isomers
(2,6-DCP, 3,5-DCP) with chromatographic retention times of 12.13
and 15.00, respectively. 2,4-DCP has been detected as a trans-
formation product of triclosan in many studies involving oxidative
treatment via manganese oxides (Zhang and Huang, 2003), ferrate,
and ozonation (Chen et al., 2012; Yang et al., 2011), and also in
aqueous photochemical experiments (Latch et al., 2005). Kim et al.
(2011) also observed this compound in the biodegradation of
triclosan. A large amount of the three isomers was detected in the
present study, while the product P5 was produced in a low con-
centration. Based on the fragment ions at m/z 284.93, 248.95,
194.96, 184.98, 160.95 and 124.98, we speculate that P7 (m/z
320.92) may be a 2,4-dichlorophenol adduct, plausibly derived
from the coupling of two 2,4-dichlorophenol molecules (Fig. S3).
Similarly, P11 is assumed to be generated from the coupling of 2,4-
dichlorophenol and TCS.
3.2.2. Elucidation of oxidation pathways
Many studies have suggested different oxidation pathways for
triclosan based on various treatment techniques. During the free-
chlorine-mediated oxidation process, triclosan can undergo ether
cleavage resulting in the production of 2,4-dichlorophenol, or can
be chlorinated to produce one of two chlorophenoxyphenol in-
termediates: 5,6-dichloro-2-(2,4-dichlorophenoxy)phenol and 4,5-
220 J. Chen et al. / Water Research 103 (2016) 215e223

dichloro-2-(2,4-dichlorophenoxy)phenol. Chen et al. (2012) re-
ported that the hydroxylation reaction took place in the less chlo-
rinated benzene ring when TCS was subjected to ozonation. Yang
et al. (2011) proposed some reaction pathways for the oxidation
of triclosan by Fe(VI), involving scission of the ester bond, bond-
breaking of the ether linkage, coupling reaction, phenoxy radical
addition reaction, and phenol ring opening reaction. Based on these
previous research findings and the identified degradation products,
two main reaction pathways are proposed herein for the degra-
dation of TCS by permanganate (Fig. 4).
KMnO4 is inclined to attack the hydroxyl and the para-position
in the less chlorinated phenol moiety, yielding 2-chloro-5-(2,4-
dichlodichlorophenoxy)-[1,4] benzoquinone (P1) via two-electron
transfer. Meanwhile, some ring-opening products are generated,
including 2-(2,4-dichlorophenoxy)maleic acid (P2), (E)-2-(2,4-
dichlorophenoxy)-4-formylbut-2-enoic acid (P3) and 2-(2,4-
dichlorophenoxy)malonaldehyde (P4). Subsequently, (E)-3-(2,4-
dichlorophenoxy)-2,5-dioxohex-3-enedioic acid (P8) was gener-
ated as the ring opening product of P1, while 2,4-dichlorophenyl
hydrogen carbonate (P9) was produced from P2, P3, and P4
through the decarbonylation and decarboxylation reaction.
Another possible reactive site is the ether bond, the cleavage of
which results in the formation of 2,4-dichlorophenol (P6) and 3-
chlorophenol (P5). This reaction pathway was also observed in
the oxidation of TCS by free chlorine, ferrate, O3 or MnO2 (Chen
et al., 2012; Rule et al., 2005; Yang et al., 2011; Zhang and Huang,
2003). Thus, 2,4-dichlorophenol can be further transformed to 2-
(2,4-dichlorophenoxy)-4,6-dichlorophenol (P7) and 2,6-bis(2,4-
dichlorophenoxy)-3-chlorophenol (P11) by coupling with residual
triclosan or another 2,4-dichlorophenol. Furthermore, 2-
chloromaleic acid (P10) was produced from P6 by ring opening.
In brief, the reaction pathways for TCS oxidation by perman-
ganate mainly include cleavage of the ether bond (
C(8)eO(7)
)
and benzene ring-opening (in the less chlorinated benzene ring).
3.2.3. Studies of frontier electron densities (FEDs)
Frontier electron densities theory has been widely used for
evaluating the oxidative degradation behaviors of organic sub-
stances (Dai et al., 2015; Li et al., 2016). According to the frontier
orbital theory, atoms with a larger 2FED2HOMO are probable attack
points for electron extraction. In addition, the oxidation reaction is
more likely to occur at the site with more negative point charges
(Han et al., 2013).
To support our conclusion that the degradation of triclosan by
permanganate is initiated by ether bond oxidation and the ring
opening reaction, molecular orbital calculations were carried out
for the triclosan molecule using the Gaussian 09 program. The
Mulliken atomic charges, the 2FED2HOMO values, and the isosurface
of the highest occupied molecular orbital (HOMO) are displayed in
Fig. 5a
5d. As shown in Fig. 5a, the oxygen in the hydroxyl (O(16))
group had the most negative Mulliken atomic charge, followed by
the oxygen in the ether bond. Thus, the two oxygen atoms would be
easily oxidized. The highest 2FED2HOMO value in the TCS molecule
was also found to be localized at the oxygen in the hydroxyl, second
to which is the C(8) atom, followed by C(10), C(12), and O(7)
(Fig. 5b). These results indicated that the oxygen in the hydroxyl
group was the most vulnerable site for oxidation, and that cleavage
of the ether bond (
C(8)eO(7)
) was reasonable. Moreover, the
C(10) and C(12) atoms are also likely to be oxidized. Consistent with
the 2FED2HOMO calculation results, the HOMO isosurface in Fig. 5c
and d also shows that the orbital is mainly distributed over the
oxygen in the hydroxyl, then at the C(8), C(10), C(12), and O(7)
atoms. These calculations collectively suggest that oxygen in the
hydroxyl group was the most possible site of the oxidation reaction,
but positions around the C(8), C(10), C(12), and O(7) atoms are also
susceptible. Thus, the formation of the intermediate P6 (m/
z ¼ 160.95) shown in Fig. 4 can be ascribed to cleavage of the ether
bond (Pathway I). Moreover, the benzoquinone product P4 (m/
z ¼ 300.93) and the benzene ring opening products P2 (m/
z ¼ 274.96) and P3 (m/z ¼ 272.98) were generated by attack on the

OH OH
Cl OH
Pathway II Cl
+ P6 O Cl
Breaking
coulping reaction

Cl
Cl
Cl
P5 P6 P7 Cl
126.99/128.99 160.95/162.95 320.92/322.91/324.91/326.91/328.90
Cl OH /164.95
O
Cl Cl
OH
Cl Cl
TCS C O +TCS Cl O OH
286.95/288.95/290.94/292.95
Cl C O O Cl

Pathway I P10 OH P11 Cl

148.95/150.95 446.90/448.90/450.90/452.89/454.89/456.89

Cl OH Cl OH Cl
Cl O H
O C O C O O C
O O O
H
O C O HC
Cl C Cl C Cl O
Cl Cl P3 H2
P1 P2 OH P4
O
300.93/302.93/304.93/306.93 274.96/276.96/278.96 272.98/274.98/276.98 230.96/232.96/234.96

Cl O Cl
O O OH
COOH C
COOH O
Cl Cl
O P9
P8
330.94/332.94/334.93 204.95/206.95/208.94

Fig. 4. Proposed degradation pathways of triclosan by KMnO4 oxidation.

 J. Chen et al. / Water Research 103 (2016) 215e223 221

Fig. 5. Mulliken atomic charges, computed FED and highest occupied molecular orbital (HOMO) shown as isosurfaces of TCS calculated by Gaussian 09 program at the B3LYP/6-
311G** level: (a) Mulliken atomic charges of TCS, (b) 2FED2HOMO data of each atom, (c) isodensity surfaces of HOMO with an isovalue of 0.05, (d) isodensity surfaces of HOMO with
an isovalue of 0.08. The arrows imply positions for electron extraction.

O(16), C(10), and C(16) atoms (Pathway II).
3.3. Toxicity studies
To assess the potential risks of the intermediates on aquatic
ecosystems, changes in the toxicity of the reaction solutions were
evaluated by using two aquatic model test species P. phosphoreum
and D. magna. Since P. phosphoreum was completely inhibited
within the first 1 min, 2-fold, 4-fold and 8-fold dilution were
applied for the reaction samples to evaluate the true toxicity vari-
ation trend.
As shown in Fig. 6, the toxicity of the reaction solution to
D. magna followed a generally decreasing trend. One hundred
percent immobilization was observed for the raw solution, while
the immobilization ratio decreased to 33.3%, 14.3% and 4.8% after
10 s, 3 min and 60 min of reaction, respectively. For P. phosphoreum,
the toxicity trend was similar to that of D. magna, exhibiting a rapid
decrease at the initial reaction stage followed by a slight change.
The initial TCS solution exerted high toxicity with 100% lumines-
cence inhibition even at 2-fold dilution, and an inhibition ratio of
53.4% at 8-fold dilution. After 10 s, the inhibition rate was 99.3%,
70.9%, 43.3%, and 20.9% for initial sample, 2-fold, 4-fold, and 8-fold
dilution samples, respectively. As the reaction time increased to
3 min, the inhibition ratio decreased to 57.1%, 13.9%, 9.0% and 1.0%,
respectively, suggesting that at a low concentration, the in-
termediates do not reduce the activity of P. phosphoreum. Notably,
the toxicity of TCS (initial concentration ¼ 20 mg/L) to D. magna and
P. phosphoreum after 60 min was reduced by 95.2% and 43.0%,
respectively. In addition, the reaction solution has no inhibitory
effect on D. magna at an initial TCS concentration of 5000 ng/L or
0.5 mg/L. For P. phosphoreum, TCS reaction solution at an initial
concentration of 2 mg/L showed no toxicity after 60 min.

120 100
A P. phosphoreum B D. magna (24h)
Initial TCS concentration 20 mg/L Initial TCS concentration 20 mg/L
100 P. phosphoreum1/2 D. magna (24h)
P. phosphoreum1/4 80 Initial TCS concentration 0.5 mg/L
Inhibition Rate (%)

80 P. phosphoreum1/8 D. magna (24h)

Inhibition Rate (%)

P. phosphoreum Initial TCS concentration 5000 ng/L

Initial TCS concentration 2 mg/L 60
60

40 40

20 20

0
0
0 0.17 0.5 1 1.5 2 3 5 10 30 60 0 0.17 0.5 1 1.5 2 3 5 10 30 60
Processing Time (min) Processing Time (min)

Fig. 6. Inhibition rate of reaction solutions to P. phosphoreum and D. magna during TCS oxidation by KMnO4. Experimental conditions: pH ¼ 8.0, [TCS]0:[KMnO4]0 ¼ 1:2.5.
222 J. Chen et al. / Water Research 103 (2016) 215e223
It is reported that the aquatic toxicity of chlorinated compounds
depends on the number of aromatic rings and chlorine groups (Del
Castillo et al., 2012). Levy et al. (1999) further pointed out that the
antibacterial activity of TCS was mainly correlated with the
hydroxyl-containing benzene ring. As discussed above, degradation
of TCS by KMnO4 includes cleavage of the ether bond and benzene
ring-opening. This oxidative transformation of triclosan would
reduce the toxicity of the reaction solutions, leading to a relatively
low ecological risk. Thus, KMnO4 is an environmentally friendly
oxidant that can be widely used in water and wastewater
treatment.
3.4. Chlorination and chloramination
In full-scale treatment plants, permanganate treatment is al-
ways used in combination with chlorination and chloramination
(Rodríguez et al., 2007; Chen and Yeh, 2005; Guan et al., 2010).
Phenol and 1,4-benzoquinone are the two major kinds of degra-
dation products formed during oxidation of TCS by permanganate.
Thus, chlorination and chloramination is performed with phenol
and benzoquinone to detect the possible formation of disinfection-
by-products (DBPs).
In the present study, phenol and 1,4-benzoquinone were
completely removed after chlorination and chloramination (anal-
ysis method in Text S2), while the THM and HAA species detected
included four species of THMs and monochloroacetic acid. Thus,
safety evaluation is necessary when phenol and benzoquinone are
present in source water as micropollutants, since they can act as
precursors to generate THMs and HAAs. The specific yields of THMs
and HAAs (expressed as mg/mg C) are shown in Fig. 7 AeD (see
Table S2 for specific values). Results indicate that chlorination and
chloramination of phenol and 1,4-benzoquinone would yield low
concentrations of DBPs (STHMFP, 20.99e278.97 mg/mg; SHAAFP,
7.86  10
4
45.77 mg/mg). As the precursors of DBPs, 1,4-
Fig. 7. The formation potential of THMs and HAAs in subsequent treatment of chlorination and chloramination.
benzoquinone produced THMs easier than phenol during chlori-
nation and chloramination processes, while a contrary tendency
occurred in the formation of HAAs. In addition, compared with
chlorination, chloramination decreased the formation of THMs and
HAAs greatly; the concentrations of the THMs (phenol and 1,4-
benzoquinone) formed during chloramination were only 7.9 and
26.75% of those formed during chlorination, and the concentrations
of HAAs were 0.003 and 0.18% of those formed during chlorination.
This is consistent with previous results (Cowman and Singer, 1995;
Lu et al., 2009).
4. Conclusions
Potassium permanganate treatment is demonstrated to be
effective for the removal of TCS in water. Under the optimum re-
action conditions of pH ¼ 8.0, [TCS]0:[KMnO4]0 ¼ 1:2.5 and
T ¼ 25  C, TCS at a concentration of 20 mg/L can be completely
degraded in 120 s. However, a high KMnO4 dosage is required for
the efficient removal of TCS at mg/L levels in water and wastewater
treatment.
Mass spectrometry analysis reveals the formation of 11 prod-
ucts, including phenol, derivatives of phenol, benzoquinone,
organic acids and aldehydes. Six products with precursor ion at m/z
330.94, 274.96, 272.98, 230.96, 204.95 and 148.95 were reported for
the first time. Two main reaction pathways involving CeO bond
cleavage and benzene ring opening were proposed, which was
further confirmed by frontier electron density calculations and
point charge analysis. Toxicity tests with P. phosphoreum and
D. magna reveal that the treatment by permanganate reduces the
toxicity of solutions containing triclosan, leading to relatively low
ecological risk. Chlorination and chloramination experiments
indicate that chlorination and chloramination of phenol and 1,4-
benzoquinone would yield low concentrations of DBPs (STHMFP,
20.99e278.97 mg/mg; SHAAFP, 7.86  10
4
45.77 mg/mg). Based on
 J. Chen et al. / Water Research 103 (2016) 215e223 223

these findings, we suggest that KMnO4 oxidation can be used as an 2011. Triclosan susceptibility and co-metabolismea comparison for three aer-
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