Arabian Journal of Chemistry (2020) 13, 5009–5017

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Fe (II)-activated persulfate oxidation effectively

degrades iodoform in water: Influential factors and
kinetics analysis
Zijun Dong a,1, Feng Wang b,1, Xiulan Song c, Miao Zhang c, Chengchun Jiang a,
Feiyun Sun b,*, Mu Li b

a
School of Civil and Environmental Engineering, Shenzhen Polytechnic, Shenzhen 518055, China
b
Harbin Institute of Technology (Shenzhen), Shenzhen 518055, China
c
College of Environment Science and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received 9 October 2019; accepted 28 January 2020

Available online 6 February 2020

KEYWORDS Abstract Iodoform (CHI3) is one of the disinfection by-products (DBPs) that is formed in the
2+
Fe /PS oxidation process; pre-oxidation and disinfection processes of drinking water treatment. In this study, Fe(II)-
Iodoform degradation; activated persulfate oxidation (Fe2+/PS) was employed to degrade iodoform, the effects of initial
Optimal operating condi- reactants concentration, reaction parameters, kinetics model were investigated, and the underlying
tions; mechanisms of CHI3 degradation in Fe2+/PS oxidation process was unveiled. The results showed
Kinetics that the mole ratio Fe2+/PS of 1:5, initial PS concentration of 15 lmmol/L, and pH of 3.0 were
identified as the optimum operating parameters. In addition, a relatively higher temperature could
enhance CHI3 removal and deiodination. The kinetic model has two different reaction steps: a fast
one during the first ten minutes of reaction; then followed by a much slower one. Suppression of the
reaction by TBA and MeOH showed that the combined effects of SO
4  and OH contributed to the
degradation of CHI3, but OH played a dominant role. The degradation pathways and the products
of total liberated iodine species demonstrate that the applicability of the Fe2+/PS oxidation process
for CHI3 degradation. These results indicated that the Fe2+/PS oxidation process is an effective
advanced oxidation process for CHI3 removal in water treatment.
Ó 2020 The Authors. Published by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding author.
E-mail address: sun_fy@hit.edu.cn (F. Sun).
1
These authors contributed equally to this work.
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
1. Introduction
As one of the unregulated iodinated trihalomethanes (I-
THMs), iodoform (CHI3) has been identified as a disinfection
by-product (DBP), and which formed through the reactions
between natural organic matter (NOM) and reactive iodine
species, i.e. hypoiodous acid (HOI) in drinking water treat-
ment process (Bichsel et al., 2000). The highest concentration

https://doi.org/10.1016/j.arabjc.2020.01.023
1878-5352 Ó 2020 The Authors. Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
5010 Z. Dong et al.

of I-THMs was found in drinking water treated with chlo-

Ahmed and Chiron (2014)

ramines. Hansson et al. reported that a change from chlorina-

Pulicharla et al. (2018)

tion to chloramination lead to the formation of 5 lg/L CHI3

Romero et al. (2010)

(I
concentration of 50 lg/L) (Hansson et al., 1987). Krasner

Zhang et al. (2014)

Wang et al. (2019)

Wang et al. (2018)

Wang et al. (2017)

Yang et al. (2018)

Zhou et al. (2013)

Rao et al. (2014)

Xu et al. (2010)
Bu et al. (2016)
et al. observed that the maximum concentration of unregulated
I-THMs around 15 lg/L in drinking water, which is relatively

Reference
lower than the US EPA limitation (< 80 lg/L) (Krasner et al.,
2006). According to literature reports, I-THMs are more cyto-
toxic and genotoxic than their regulated chlorinated and
brominated analogs. Richardson et. al. demonstrated that
the cytotoxicity of CHI3 was 146 times and 60 times higher

About 100%
Degradation
than that of CHCl3 and CHBr3, respectively (Richardson et.

About 50%
al., 2008). In addition, CHI3 could produce bad taste and odor

81.4%

73.4%

100%

100%

100%
100%
problems in drinking water (Hansson et al., 1987). Hansson

76%

78%

99%
73%
and Cancho reported that CHI3 has a lower odor threshold
concentration (0.03–1 lg/L) compared with CHCl3 and CHBr3
(300 and 100 lg/L, respectively) (Hansson and Cancho et al.,

agent dose
Activation

0.125 mM
1000 mM
2001). Therefore, the effective removal of CHI3 from drinking

0.72 mM

1.25 mM
1.0 mM
1.0 mM
4.0 mM

4.0 mM
0.4 mM

4.0 mM

4.0 mM
20 lM
water is highly expected.
However, there are only a few studies investigated the
degradation of CHI3 in drinking water and wastewater treat-
ment processes, and some researchers recognized that CHI3

concentration
could not be effectively degraded by conventional treatment
techniques, such as coagulation, sedimentation, filtration,
Brief summary of the efficient of Fe2+/PS oxidation characteristics for a series of the target pollutant.

500 mM
Oxidant

0.8 mM
4.0 mM
4.0 mM

4.0 mM
0.4 mM
1.0 mM

4.0 mM
2.5 mM
2.5 mM
and ozonation (Amy et al., 1999). Various advanced oxidation

20 lM
2 mM
processes (AOPs), such as Fenton reactions (Li et al., 2012),
UV/H2O2 oxidation (Duan et al., 2016), Fe2+/H2O2 oxidation
(Velo-Gala et al., 2014), and Ferrate oxidation (Wang et al.,
2018) have been identified as effective ways to remove DBPs
Temperature

and trace organics, as well as to eliminate I-THMs from water.

Wang et al. have investigated UV/chlorine advanced oxidation

n. a.
n. a.

n. a.
(°C)

for CHI3 degradation, and the results showed that over 90% 20
20
25
25

25

50
20
25

25
CHI3 could be effectively removed (Wang et al., 2017a,
2018b). A rapid oxidation of iodide and hypoiodous acid with
ferrate in the ferrate/I/HA system was developed by Wang
concentration

et al., and the experiments displayed that ferrate would rapidly

0.025 mM
Pollutant

0.05 mM

0.05 mM

0.09 mM

0.05 mM
oxidize HOI formed in the I
oxidation process, and when 0.1 mM
100 lM

0.5 lM
6.6 lM
20 lM
1 mM
1 mM

humic acids (HA) existed in the solution, no formation of iod-

oform and monoiodoacetic acid (MIAA) was observed in the
oxidation of iodide with ferrate (from 10 mM to 80 mM)
(Wang et al., 2018).
(min)
Time
Reaction conditions

Among the commonly used AOPs oxidants, persulfate (PS)

120
120
240

240

180

240

240
30

10
40

60

60

has superior redox potential to effectively degrade organic pol-

lutants (Neta et al., 1988). By comparison of the effect of dif-
ferent AOPs, PS can be activated to produce SO
4  that
3.0–4.0

4.0–5.0

4.0–5.0

possessing a similar or even higher oxidation potential

n. a.a

n. a.

n. a.

(2.5–3.1 V vs. NHE) and a longer half-life period than OH

pH

3.0

3.0

3.0

3.0

3.5

3.0

(30–40 ls vs 20 ns), SO
4  can transfer long distances to target

contaminants and oxidize them more thoroughly. Addition-
ally, those reactions can take place effectively in aqueous sys-
Domestic wastewater (carbamazepine)

n.a.—information not available.

tems on a wider pH range (2–8) (Fan et al., 2018, Jin et al.,

2018), PS can be activated by ultraviolet (UV) or heat
(Gao et al., 2016), and transition metals, such as Cu2+,
Mn2+, Fe2+, Co2+ and Ag+ (Xu et al., 2008), while Fe2+ is
deemed a less toxic and more affordable agent (Ike et al.,
2018). Accordingly, the Fe2+/PS reaction system with rela-
Sulfamethoxazole

tively low energy (14.8 kcalmol
1) has been widely applied

Chlortetracycline
Acetaminophen

Carbamazepine
Trimethoprim

in disinfection (Wordofa et al., 2017, Ike et al., 2018), dewater-

Bisphenol A
Sulfadiazine

Orange G

ing activated sludge (Zhen et al., 2012), and some refractory

Pollutant

Atrazine
Table 1

Arsenic
Diuron

toxic pollutants (Xu et al., 2010). The efficiency of Fe2+/PS

oxidation characteristics is summarized in Table 1.
a
Fe (II)-activated persulfate oxidation effectively degrades iodoform in water
However, to our knowledge, studies on CHI3 degradation
by the Fe2+/PS oxidation process are rarely reported. In the
present study, Fe2+/PS oxidation was employed to remove
CHI3, and the influence of operational parameters on the
CHI3 treatment efficiency was examined to determine the opti-
mum conditions. CHI3 degradation kinetic model was estab-
lished to depict the reaction mechanisms and further revealed
the CHI3 degradation pathway. The obtained results will be
invaluable for CHI3 degradation and removal from water
and wastewater.
2. Materials and methods
2.1. Chemicals
All chemicals used in this study were analytical grade. Iod-
oform (CHI3, 99%) was purchased from Sigma-Aldrich
(USA), and sodium persulfate (Na2S2O8, 99%) was purchased
from Aladdin (China). Ferrous sulfate heptahydrate (FeSO4-
s_ 7H2O, 99%) and sodium thiosulfate (Na2S2O3, 99%) were
purchased from Xilong Chemical Co., Ltd. Sodium carbonate
anhydrous (Na2CO3) was from Tianjin Mao Tai Chemical
Reagent Factory.
2.2. Experimental set-up
All experiments were conducted in 250 mL (effective volume:
200 mL) glass reactors. Firstly, a CHI3 concentration of
5 mg/L was added to the glass reactors, and then added appro-
priate volumes of ferrous sulfate solution and pure water. The
ferrous sulfate solution was freshly prepared, to avoid being
oxidized. The initial solution pH was adjusted by using
0.1 M H2SO4 and NaOH. A certain volume of sodium persul-
fate was added, and the reaction was conducted in electric heat
thermostat shocks sink at an appropriate temperature. Ali-
quots of 9 mL were withdrawn at selected time intervals
(0 min, 5 min, 10 min, 30 min, and 60 min) and quenched
immediately with 1 mL Na2S2O3 after filtered by a filterable
membrane. Similarly, the experiments were conducted at the
same condition with varied concentrations of SO
 

4 , OH, I ,



IO , and IO3 .
2.3. Analytical procedures
Agilent 7697 Headspace Sampler and Agilent 6890 gas chro-
matography (GC) equipped with an electron capture detector
(ECD) and DB-1MS fused silica capillary column (30 m  0.
25 mm) were used to determinate iodoform. The temperature
program used to separate the analyses was as following proce-
dure: initially column temperature was held at 60 °C for 1 min,
increased at 10 °C/min to 150 °C, maintained for 2 min, and
then increased at 20 °C/min to 250 °C and held for 5 min. Both
of the injector and detector temperature was 260 °C. The tem-
perature of the heating cabinet, sample loop, and transmission
line were 60 °C, 90 °C, 110 °C, respectively. Degradation prod-
ucts (I
, IO
3 ) were detected by ion chromatography (IC,
Thermo Dionex ICS-1500), which was equipped with a con-
ductivity detector, Ionpac AG9-HC guard column
(4  50 mm) and Ionpac AS9-HC analytical column
(4  250 mm). The eluent was 9 mmol/L Na2CO3 and the flow
5011
velocity was 1 mL/min. The column and detector temperature
both were 35 °C. The detection limit was 0.3 lg/L. Samples
were filtered by SPE C18 to remove the coexisted organic mat-
ter and then injected into ion chromatography. IO
was mea-
sured as 4-iodine-2,6-chlorophenesic acid by HPLC equipped
with Symmetry C18 column (4.6 mm  250 mm; 5 lm) and
the conditions were as follows: flow rate 1 mL/min, mobile
phase acetonitrile/water (1‰ acetic acid) 70%: 30%, detection
wavelength 212 mm, sample size 10 lL, and retention 10 min.
The exposure values of sulfate radicals were calculated by
the indicator, atrazine (ATZ). The exposure values of hydroxyl
radicals could be calculated by the indicator, nitrobenzene
(NB). Therefore, free radical exposure can be calculated
according to Eqs. (1) and (2) (Xian et al., 2017).
Z  
NB
ð ½OHdtÞ ¼
ln =kOH;NB ð1Þ
NB NB0
ðOH; NBÞ——Secondary reaction rate constants of hydro-
xyl radical
R and nitrobenzene (M
1∙s
1).
ð ½OHdtÞNB ——The hydroxyl radical exposure value
obtained with nitrobenzene as the indicator (M∙s).
  R
Z
ln ½ATZ
ATZ

kðOH;ATZÞ ½OHdt

 
ð SO4 dtÞ ¼
0
ð2Þ
ATZ kSO
4 ;ATZ
kSO
4
;ATZ ——Secondary reaction constants of sulfate-free
radical and atrazine.
kðOH;ATZÞ ——Secondary reaction constants of hydroxyl
radical and atrazine.
R
ð SO
 4 dtÞATZ ——The sulfate-free radical exposure value
obtained with atrazine as a tracer (M∙s).
2.4. Kinetic model
The kinetic model of the CHI3 degradation in the Fe2+/PS sys-
tem can be expressed as shown in Eq. (3) (Frontistis et al.,
2011).
t d=ðC=C0 Þ
q
¼ q þ dt () ¼ ð3Þ
1
ðC=C0 Þ dt ðq þ dtÞ2
where C and C0 are the substrate concentration at time t and 0,
q and d are two characteristic kinetic constants. The reciprocal
of q corresponds to the initial reaction rate (i.e. at t = 0), while
the reciprocal of q corresponds to the maximum conversion
that can be achieved at the end of the reaction.
3. Results and discussion
3.1. Effects of reactants concentration
3.1.1. PS concentration
The effects of initial PS concentration and Fe2+/PS mole ratio
on CHI3 degradation were studied, as shown in Fig. 1. The
effects of PS concentration on CHI3 degradation was investi-
gated at a pH of 3.0, a temperature of 25 °C and a constant
Fe2+/PS mole ratio of 1:5. Fig. 1(a) showed the concentration
of CHI3 variation under the different initial Na2S2O8 concen-
trations, 2, 4, 6, 8, 10, and 15 lmol/L, all of the reactions
activated by sufficient Fe2+. It can be clearly observed that
an increased PS concentration from 2 to 15 lmol/L leads to
5012
Fig. 1 The effects of initial PS concentration on the CHI3 degradation and ROS production.
a continuous decrease of CHI3 concentration. The CHI3
degradation rate increased rapidly within the first 10 min
and then went smoothly. A higher initial PS concentration
induced a greater removal efficiency of CHI3, and its removal
efficiency reached 83% when the PS concentration was
15 lmol/L, during which IO


3 could be detected. IO3 is one
stable sink of iodine species in the drinking water treatment
process because it is proven to be non-toxic and it can be con-
verted to I
by glutathione quickly (Zhen et al., 2016). As
shown in Fig. 1(b), the amount of IO
3 generated has a positive
correlation with an initial concentration of PS. When the ini-
tial dosage of PS reach to 15 lmol/L, the amount of IO
3 could
reach to 0.5 lmol/L with the decreasing of CHI3 concentration
in the bulk solution, indicating there was the occurrence of
deiodination reaction.
CHI3 was believed to be degraded by the oxidative free rad-
icals SO
4 s_ and s_ OH generated in the Fe
2+
/PS oxidation sys-
tem. Fig. 1(c, d) showed the exposure values of SO
4 s_ and
s_ OH during oxidation, and it was obvious that SO
4 s_ generated
in the Fe2+/PS system was increased with the increasing of PS
concentration, and the highest SO
4 s_ reach to about 2.4 lmol/
L. However, as the concentration of PS raised, the number of
hydroxyl groups insignificantly changed. Due to the Fe2+/PS
oxidation mainly attributed to the combined effects of SO
4 s_
and s_ OH (Shang et al., 2019), the persulfate oxidation was
more beneficial and cost-effective in enhancing CHI3 degrada-
tion, owing to the lower requirement for pH adjustment (Zhen
et al., 2012). Generally, SO
4 s_ was thought to be the primary
ROS during the oxidation of PS, and an increasing PS concen-
tration produced more SO
4 s_ , thus improved the oxidation
Z. Dong et al.
capacity of the reaction system and enhanced CHI3 removal
efficiency.
3.1.2. Fe2+/PS mole ratio
CHI3 degradation efficiency was also affected by the Fe2+/PS
mole ratio. Under the condition of a temperature of 25 °C, pH
of 3.0, and an initial PS dosage of 4 lmol/L, the effect of Fe2+/
PS mole ratio on CHI3 degradation was studied by changing
Fe2+ dosage from 0.1 to 5.0 mmol/L, which corresponded to
n(Fe2+)/n(PS) of 1:20, 1:10, 1:5, 1:2, 1:1 and 2:1. The varia-
tions of CHI3 degradation efficiency and the IO
3 concentra-
tion with the reaction were shown in Fig. 2. It can be
observed from Fig. 2(a) that CHI3 removal efficiency increased
rapidly with increasing mole ratio of Fe2+/PS from 1:20 to 1:5,
and then reached to the maximum once the n(Fe2+)/n(PS)
increased to 1:5. After the continuous increase of n(Fe2+)/n
(PS) to 2:1, CHI3 removal efficiency began to decrease. As
shown in Fig. 2(b), a similar profile of IO
3 generated with
the change of n(Fe2+)/n(PS) could be found. As the generated
IO
3 increased firstly with the increasing of mole ratio from
1:20 to 1:5, and then began to decrease with the increasing
of mole ratio from 1:5 to 2:1. This result displayed that either
an insufficient or an excessive Fe2+ in the bulk solution was
unfavorable for CHI3 degradation and deiodination when
the PS dosage was fixed.
The effective exposure values of SO
4 s_ and s_ OH in the reac-
tion showed in Fig. 2(c, d). When the Fe2+/PS ratio increased
from 1:20 to 1:5, the produced SO
4 s_ and s_ OH were promoted
significantly. Afterward, a further increase of n(Fe2+)/n(PS)
above 1:5 resulted in a decreasing trend in SO
4 s_ and s_ OH
Fe (II)-activated persulfate oxidation effectively degrades iodoform in water 5013

Fig. 2 The effects of Fe2+/PS mole ratio on the CHI3 degradation and ROS production.

concentration. It was observed that the change of SO
4 s_ was
coincident with CHI3 degradation efficiency under varied n
(Fe2+)/n(PS). The Fe2+ dosage in an appropriate range
around 1:5 could increase SO
4 s_ generated from Fe
2+
/PS sys-
tem, which could eventually enhance its oxidizing capability
and CHI3 degradation efficiency. However, once the Fe2+
dosage increased to above 1:5, the excessive Fe2+ would react
with SO


4  (Eq. (4)), while the SO4  in a high concentration
could also self-quenched via Eq. (5) (Rodriguez et al., 2014)
20% when the initial pH reached to 11. This negative correla-
tion between CHI3 degradation efficiency and initial pH ran-
ged from 3 to 11 may be attributed to an increased pH
resulted in an obviously decreased IO
3 generation (Fig. 3
(b)), leading to a rather low deiodination capability.
Fig. 3 (c, d) demonstrated that an acid condition was pos-
itive to SO


4  production, as more SO4  could be generated
with the decreasing of pH from 7 to 3. In contrast, under an
alkaline condition, less SO
4  was generated, while more OH


to induce insufficient SO
4  in the bulk. This negative consump- might be produced that could slightly increase the solution
tion of SO
4  limited the oxidation ability of the reaction sys- pH. The reasons may be that in alkaline conditions, persulfate
tem, leading to a low CHI3 degradation efficiency. was easily decomposed to generate SO

4 , which generated OH
–
by reacting with OH in solution (Rodriguez et al., 2014), as
Fe2þ þ SO

4  ! Fe
3þ
þ SO2

4 K ¼ 4:6  109 mol L
1 ð4Þ
shown in Eq. (6). Since the oxidation-reduction potential of

OH was lower than SO
4 , the oxidizing ability of the system
SO


4  þSO4  ! S2 O8
2

K ¼ 8:9  108 mol L
1 ð5Þ
would be dropped off, and decreased CHI3 removal efficiency.
In addition, SO2
4 existed in the reaction system could also
3.2. Effects of operation condition parameters on CHI3 consume OH by reacting with it and weaken the oxidizing
degradation ability of the system.
SO


4  þOH ! OH þ SO4
2

ð6Þ

3.2.1. Initial solution pH

The effects of initial pH on CHI3 degradation were investi-
gated under a pH of 3, 5, 7, 9 and 11, with a PS dosage of
2 lmol/L, n(Fe2+)/n(PS) of 1:5 and an ambient temperature
of 25 °C. As presented in Fig. 3(a), when the initial pH was
kept at 3.0, more than 52% CHI3 could be degraded. How-
3.2.2. Temperature
The effects of the temperature of 25, 30, 35, 40 and 45 °C on
CHI3 removal rate were studied with a PS dosage of 2 lmol/
L, n(Fe2+)/n(PS) of 1:5 and a pH of 3.0. The CHI3 removal
rate and IO
3 variation was shown in Fig. 4. It was found that

ever, with the increasing of initial pH, the CHI3 degradation CHI3 degradation efficiency increased remarkably with the
efficiency began to decrease continuously, to even as low as temperature increased from 25 °C to 45 °C at the beginning
5014 Z. Dong et al.

Fig. 3 The effects of the initial pH on the CHI3 degradation and ROS production.

Fig. 4 The effects of operating temperature on the CHI3 degradation and ROS production.
Fe (II)-activated persulfate oxidation effectively degrades iodoform in water 5015

of 10 min reaction. More than 70% of CHI3 could be removed
at a temperature above 45 °C. Similarly, IO
3 generation
increased with elevated temperature (Fig. 2(b)) in the Fe2+/
PS process. The reaction was an endothermic reaction between
Fe2+ and PS (Shang et al., 2019), therefore, a high tempera-
ture can enhance PS reaction to produce more SO
4  in this
process, and lead to a remarkable degradation efficiency and
a high degree of deiodination directly.
Fig. 4(c, d) showed more SO
4  could be produced at a high
temperature, but there was no obvious impact on OH. This
was due to the fact that thermal could also activate PS to pro-
duce SO


4 , and more SO4  were generated with the increased
temperature (Han et al., 2015). In addition, owing to that the
reaction was an endothermic reaction, an increased tempera-
(i.e. at excessive ratios) (Frontistis et al., 2011; Chan and
Chu, 2003).
A scavenging experiment was conducted to examine the
role of radicals in CHI3 degradation by using methanol that
has significant inhibitory effects on both SO

4  and OH, and
by using TBA that has a strong inhibitory effect on OH and
a weak constraint on SO
4 (Wordofa et al., 2017). As shown
in Fig. 5(a), more than 53% CHI3 could be degraded without
any radical scavenger. When there was a coexistence of metha-
nol or TBA with a ratio of 500:1 and 2000:1 (methanol/TBA),
the CHI3 degradation efficiency decreased to 23% and 48%,
20% and 33%, respectively. It was evidenced that CHI3 degra-
dation in the Fe2+/PS oxidation process was mainly attributed
to the combined function of SO

4  and OH. Generally, SO4 

ture could also accelerate the reaction that leads to an was thought to be the primary ROS during the oxidation of
enhanced degradation affection and high deiodination rate PS. Nevertheless, the contribution of SO
4  to CHI3 degrada-
(Frontistis, 2018). The coupling of thermal treatment with tion could not be overestimated, as there were a series of reac-
the Fe2+/PS process enhanced the oxidation ability and tions listed as Eqs. (7)–(17) (Wang et al., 2017a, 2017b).
improved CHI3 removal efficiency.

Fe2þ þ S2 O2

8 ! SO4  þFeðIIIÞ þ SO4
2

K < 30 M
1 s
1
3.3. Degradation kinetics and paths analysis ð7Þ

SO

4  þH2 O ! OH þ SO4 þ H
2
þ
K < 3  103 M
1 s
1 ð8Þ
CHI3 degradation in the present work likely has two different
reaction steps: a fast degradation rate during the first 10 min
reaction, followed by a much slower rate. Fitting of the data SO


4  þOH ! OH þ SO4
2

K ¼ ð6:5  1:0Þ  107 M
1 s
1
is excellent, the respective kinetic constants and the coefficients ð9Þ
of regression (r2) were presented in Table 2. Increased n(Fe2+)/



n(PS) mole ratio would increased the initial rate, and the max- 8 þ OH ! SO4  þHSO4 þ 1=2O2
S2 O2
K ¼ 1:2  107 M
1 s
1
imum conversion rate was achieved at the n(Fe2+)/n(PS) mole ð10Þ
ratio of 1:5. The removal rate of CHI3 also affected by acidity
and alkalinity of the solution. Under an acid condition, CHI3 SO


4  þ  OH ! HSO4 þ 1=2O2 K ¼ 1:0  1010 M
1 s
1
has a higher removal efficiency, which was similar to the Fen-
ð11Þ
ton process that depends on the ions forms in solution. As the
temperature increased, the activity of the Fe2+/PS oxidation

8 þ SO4  ! S2 O8 þ SO4
S2 O2
2
2

K ¼ 6:1  105 M
1 s
1 ð12Þ
process gradually elevated, and the relative concentration of
PS, iron and initial CHI3 concentration influenced the degra-
SO


4  þSO4  ! S2 O8
2

K ¼ 4:0  108 M
1 s
1 ð13Þ
dation efficiency. As a matter of fact, the PS to CHI3 concen-
tration ratio at a constant catalyst concentration is a critical
þ
8 þ 2H2 O ! 2SO4 þ HO2 þ 3H
S2 O2
ð14Þ
2

parameter to keep that the reaction would not be limited by
the number of hydroxyl radicals generated (i.e. at very low

þ
8 þ 2H2 O ! 3SO4 þ SO4  þO2  þ4H
2S2 O2
ð15Þ
2

ratios) or it was not hindered by auto-scavenging reactions

Table 2 Kinetic modeling of CHI3 degradation by Fe2+/PS oxidation.

Run n (Fe2+)/n (PS) pH T(°C) q
1 (min
1) d
1 (%) r2 (%)
1 1:20 3.0 25 0.09 37 98.6
2 1:10 0.15 47 98.3
3 1:5 0.15 52 98.7
4 1:2 0.11 37 98.6
5 1:1 0.08 33 99.8
6 2:1 0.06 14 99.5
7 1:5 3.0 25 0.16 52 98.6
8 5.0 0.15 47 99.5
9 7.0 0.15 37 99.6
10 9.0 0.06 25 99.6
11 11 0.05 16 99.3
12 1:5 3.0 25 0.15 52 98.6
13 30 0.16 53 99.0
14 35 0.17 55 97.6
15 40 0.26 59 96.1
16 45 0.27 68 93.8
5016 Z. Dong et al.

(a) MeOH (b) CHI3

50 TBA 14 IO3-
12 I-
CHI3 removal rate (%) HOI+I2

Concentration(μM)
40
10

30 8

6
20
4
10
2

0
no inhibitors 500/1 2000/1 0 10 20 30 40 50 60
Time (min)

Fig. 5 CHI3 degradation in Fe2+/PS oxidation process: (a) The effects of different inhibitors; (b) the degradation products examination.

þ
8 þ HO2 ! SO4 þ SO4  þO2  þH
2S2 O2

2




8 þ O2  ! SO4 þ SO4  þO2
S2 O2
2

2+
The degradation products of CHI3 by Fe /PS process
were analyzed, and the concentration changes of iodine species
(I, IO

3 and HOI) with reaction time were illustrated. As shown
in Fig. 5(b), the concentration of CHI3 kept a decreasing trend
from the beginning to 30 min. While, the concentration of I

increased rapidly within the first 30 min and then reached a
plateau between 30 and 60 min, and it contributed 52.2% lib-
erated iodine species. Within the first 20 min, HOI and I2 con-
centration increased to 3.8 lM and then kept relatively steady
gradually to 4.2 lM at 30 min. At the end of the reaction, IO
3
was detected and took a small proportion (< 1%) of total lib-
erated iodine species. Taurog et al. studied the conversion of
iodate in vivo, which proved that iodine species could quickly
convert to I
by glutathione. Thus, iodine species were com-
mon stable sink in the drinking water treatment process,
because it has nontoxic. However, compared with the heat-
activated persulfate oxidation process, I
is presumed to trans-
form to IO


3 ultimately in the presence of excessive SO4 .
Meanwhile, in a UV process for CHI3 degradation, there
was no IO
3 observed (Xiao et al., 2014), and less of 2% total
iodine species was found in terms of IO
3 during UV/H2O2
process (Xiao et al., 2015). Compared with heat-activated per-
sulfate oxidation, UV, UV/H2O2, and UV/chlorination pro-
cesses, Fe2+/PS oxidation is a promising AOP technology
for the CHI3 removal from water.
4. Conclusion
Fe2+/PS oxidation process is examined to be an efficient treat-
ment technique for CHI3 degradation, and over 83% CHI3
was removed in 60 min. The mole ratio Fe2+/PS of 1:5, PS
concentration of 15 lmmol/L, and an initial pH of 3.0 was ver-
ified to be the optimum operating condition parameters. The
reaction temperature displayed a positive correlation with
CHI3 removal and deiodination efficiency when the tempera-
tures ranging from 25 °C to 45 °C. Suppression of the reaction
by TBA and MeOH showed that the combined effects of SO
4
and OH contributed to the degradation of CHI3, while OH
ð16Þ
played a dominant role. The kinetic model, pathways and
the products of total liberated iodine species demonstrate the
ð17Þ applicability of the Fe2+/PS oxidation system for CHI3 degra-
dation and provides a new insight for DBPs degradation and
removal in an aqueous environment.
Acknowledgment
This research was supported by the Grant Project Supported by
Guangdong Natural Science Foundation No. 2017A030313285
from the Shenzhen Science and Technology Funding Project
[grant number JCYJ20160406162038258], Program of Interna-
tional S&T Cooperation [grant number 2016YFE0123400];
National Natural Science Foundation of China [grant numbers
51678183, 51408149]; Shenzhen Science and Technology Project
[grant numbers JSGG2017041401900541]. The authors appreci-
ate the thoughtful and constructive comments from the anony-
mous reviewers.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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