Water Research 124 (2017) 446e453

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A Fe(II)/citrate/UV/PMS process for carbamazepine degradation at a

very low Fe(II)/PMS ratio and neutral pH: The mechanisms
Li Ling a, Dapeng Zhang a, Chihhao Fan b, *, Chii Shang a, c, **
a
Department of Civil and Environmental Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
b
Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei, Taiwan, ROC
c
Hong Kong Branch of Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, The Hong Kong University of
Science and Technology, Clear Water Bay, Kowloon, Hong Kong

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

Article history: A novel Fe(II)/citrate/UV/PMS process for degrading a model micropollutant, carbamazepine (CBZ), at a
Received 17 May 2017 low Fe(II)/PMS ratio and neutral pH has been proposed in this study, and the mechanisms of radical
Received in revised form generation in the system was explored. With a UV dose of 302.4 mJ/cm2, an initial pH of 7, and CBZ, PMS,
24 July 2017
Fe(II) and citrate at initial concentrations of 10, 100, 12 and 26 mM, respectively, the CBZ degradation
Accepted 25 July 2017
Available online 27 July 2017
efficiency reached 71% in 20 min in the Fe(II)/citrate/UV/PMS process, which was 4.7 times higher than
that in either the citrate/UV/PMS or Fe(II)/citrate/PMS process. The enhanced CBZ degradation in the
Fe(II)/citrate/UV/PMS process was mainly attributed to the continuous activation of PMS by the UV-
Keywords:
Photo-fenton-like AOPs
catalyzed regenerated Fe(II) from a Fe(III)-citrate complex, [Fe3O(cit)3H3]2-, which not only maintained
Ferric-citrate complexation Fe(III) soluble at neutral pH, but also increased 6.6 and 2.6 times of its molar absorbance and quantum
Carbamazepine removal yield as compared to those of ionic Fe(III), respectively. In the Fe(II)/citrate/UV/PMS process, the SO
e4
PPCP produced from the fast reaction between PMS and the initially-added Fe(II) contributed 11% of CBZ
UV degradation. The PMS activation by the UV radiation and regenerated Fe(II) contributed additional 14%
Peroxymonosulfate and 46% of CBZ removal, respectively. The low iron and citrate doses and the fast radical generation at
neutral pH make the Fe(II)/citrate/UV/PMS process suitable for degrading recalcitrant organic com-
pounds in potable water.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction rate constants of 108e1010 M1
s1, and oxidizes target organic

Advanced oxidation processes (AOPs) using ozone, hydroxyl
radicals (HO
) and UV radiation have been applied to treating a
variety of recalcitrant contaminants in water and wastewater
(Ikehata et al., 2006; He et al., 2014; Oturan and Aaron, 2014;
Zuorro and Lavecchia, 2014). Recently, sulfate radical (SO
-
4 ) has
been proposed as an alternative to degrade aqueous refractory
organic contaminants, because of its high redox potential
(2.5e3.1 V) compared with those of HO
at acidic (2.4e2.7 V) and
alkaline (1.9e2.0 V) environment (Buxton et al., 1988; Neta et al.,
1988). SO
-
4 reacts with many refractory organic contaminants at
* Corresponding author. Department of Bioenvironmental Systems Engineering,
National Taiwan University, Taipei, Taiwan, ROC.
** Corresponding author. Department of Civil and Environmental Engineering, the
Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong
Kong.
E-mail addresses: chfan@ntu.edu.tw (C. Fan), cechii@ust.hk (C. Shang).
compounds more selectively through electron transfer and
hydrogen abstraction/addition under homogeneous as well as
heterogeneous conditions (Neta et al., 1988; Wols and Hofman-
Caris, 2012; Ghauch et al., 2013, 2015; Ayoub and Ghauch, 2014;
Xiao et al., 2015; Naim and Ghauch, 2016; Oh et al., 2016; Ghauch
et al., 2017).
Although UV has been widely applied to activating perox-
ydisulfate (PDS) and peroxymonosulfate (PMS) for SO
- 4 generation
(Eqs. (1) and (2)) (De Laat et al., 1999; Ou et al., 2008; Yang et al.,
2010; Wols and Hofman-Caris, 2012; Ghauch et al., 2017), both
the UV/PDS and UV/PMS processes are still considered energy- and
chemical-intensive, because the low light absorbance and quantum
yields of PDS and PMS limit the SO
- 4 generation (Goldstein et al.,
2007; Guan et al., 2011; Fang and Shang, 2012). Meanwhile, the
Fenton-related AOPs, including Fe(II)/PDS (Eq. (3)) and Fe(II)/PMS
(Eq. (4)), have a higher radical generation than the UV-based ones
due to their ability to activate the participating oxidants at a faster
rate (Anipsitakis and Dionysiou, 2004). Between the

http://dx.doi.org/10.1016/j.watres.2017.07.066
0043-1354/© 2017 Elsevier Ltd. All rights reserved.
 L. Ling et al. / Water Research 124 (2017) 446e453
aforementioned two processes, the Fe(II)/PMS process has a pro-
duction rate constant of 3.0  104 M1
s1, which is about 1000
times higher than that of the Fe(II)/PDS process (Laat and Gallard,
1999; Rastogi et al., 2009b; De Luca et al., 2017), suggesting that
the Fe(II)/PMS process may be more capable of degrading target
pollutants than the Fe(II)/PDS process. Heterogeneous micrometric
Fe(0) has also shown its reactivity towards PDS (Ghauch et al.,
2013). However, the reactivity was still not comparable to that
between Fe(II) and PMS.
(1)
(2)
The Fe(II)/PMS process was applied for the removal of diuron
and polychlorinated biphenyls (Rastogi et al., 2009b; Tan et al.,
2012), and it was characterized as a 2-stage process, including the
1st-stage reaction between the initially-added Fe(II) and PMS, and
the 2nd-stage reaction between the regenerated Fe(II) and PMS
(Huang et al., 2016). In the 1st stage, the Fe(II) to PMS ratio was the
key factor affecting pollutant degradation. An Fe(II) to PMS ratio of
1:1 has been reported to effectively degrade aqueous organic pol-
lutants (Rastogi et al., 2009b). However, excessive Fe(II) in the
system can act as an in-situ quencher which consumes SO
- 4,
causing the exhaustion of both Fe(II) and PMS (Rastogi et al.,
2009b). Although a decrease in the Fe(II)/PMS ratio improved the
over-consumption problem and generated less iron precipitates, a
low Fe(II)/PMS ratio decelerated the PMS activation and reduced
the SO
-
4 generation (Anipsitakis and Dionysiou, 2004). In the 2nd
stage, activation of PMS by the Fe(II) regenerated from Fe(III) was
the critical reaction responsible for pollutant degradation. In order
to assure the continuous supply of Fe(II), UV radiation was applied
sometimes to facilitate the regeneration of Fe(II) from Fe(III) in the
Fe(II)/PMS process. Few notable examples where UV radiation was
used to trigger the regeneration process include: (1) the study by
Xu and Lu (2000), in which the Fe(II) generation as a by-product in
the UV/Fe(III) process was observed, and (2) the study by Rao et al.
(2016), in which UV radiation was used to facilitate ibuprofen
degradation by Fe(III)/PMS process (Xu and Lu, 2000; Rao et al.,
2016).
In most cases, the Fe(II)/PMS process was required to operate at
pH less than 3.0 to prevent the formation of Fe(III) precipitates,
which retarded the PMS catalytic reaction (Burbano et al., 2005;
Stefansson, 2007). The Fe(III) precipitation at neutral pH can be
avoided by adding ligands, such as ethylenediaminetetraacetic acid
(EDTA), nitrilotriacetic acid (NTA) and citrate, to form soluble
Fe(III)/ligand complex (Hamm et al., 1954; Zhou et al., 2008; De
Luca et al., 2015). The addition of EDTA and NTA might not be a
wise choice in potable water treatment, because their permissible
concentrations levels in potable water are rather limited (i.e., sub-
ppm levels) (WHO, 2003a; WHO, 2003b). Besides, they may react
447
with chlorine to form trichloronitromethane (Hoigne  and Bader,
1988), which is a regulated disinfection by-product (Richardson
et al., 2007). On the contrary, citrate is a food additive with sour
taste thresholds around 120e570 mM (Hoehl et al., 2014), which
suggests the possible formation of Fe(III)-citrate complex up to
285 mM in a potable water treatment process.
After understanding the limitations of Fe(II)/PMS process and
interactions among Fe(II), citrate, UV and PMS, an integrated novel
Fe(II)/citrate/UV/PMS process is expected to degrade refractory
organic contaminants, including pharmaceutical and personal care
products (PPCPs), solving the problems of iron sludge generation,
PMS over-consumption, and operating pH range. Carbamazepine
(CBZ) is selected as a model pharmaceutical in this study, because
(3)
(4)
its reaction rate constants towards and degradation products by
HO
and SO
- 4 have been well studied (Vogna et al., 2004; Ghauch
et al., 2011; Matta et al., 2011; Deng et al., 2013). The main objec-
tive of this study is thus to investigate the Fe(II)/citrate/UV/PMS
integrated process and its application to degrading CBZ at a low
Fe(II)/PMS ratio and neutral pH. The mechanisms of the radical
generation, the degradation kinetics of CBZ, and the roles of PMS,
Fe(II), UV radiation and citrate were confirmed. The concentrations
of HO
and SO
- 4 were calculated by competition kinetics, and the
obtained result was used to determine their respective contribu-
tions to the CBZ degradation.
2. Materials and methods
Chemicals. Double deionized (DDI) water with 18.2 MU-cm
resistivity from Milli-Q water purification system (Millipore, USA)
was used to prepare all the solutions in this study. Carbamazepine,
OXONE® (KHSO3
0.5, KHSO4
0.5K2SO4), ferrous sulfate, hydroxyl-
amine hydrochloride (NH2OH
HCl), phenanthroline and ammo-
nium acetate were purchased from Sigma-Aldrich. Tri-sodium
citrate, potassium iodide and sodium hydrogen carbonate were
purchased from VWR Chemicals. All chemicals were of reagent
grade and used as received without further purification. Sodium
hydroxide (0.2 N) and sulfuric acid solution (0.25 N) were used to
adjust the initial pH.
Experimental setup. The light source was a bench-scale quasi-
collimated beam UV irradiator consisting of four low-pressure Hg
UV lamps (254 nm, TUV G15T8, 15 W, Philips) housed inside a
shuttered box with a collimated tube extending from the bottom. A
250-ml cylindrical glass reactor of 6.5 cm in height and 7.5 cm in
inner diameter was placed under the collimated tube of the irra-
diator. The reactor contains 150 mL solution with constantly rapid
mixing at the bottom at ambient temperature (22 ± 2  C). The
photon flux entering the solution was 0.252 mW/cm2, determined
by the iodide-iodate chemical actinometry (Rahn et al., 2003). The
optical path length of the solution in the reactor at 254 nm was
3.2 cm determined by the photolysis rate of H2O2 (Ling et al., 2016).
The quasi-collimated beam reactor used in this study may not be
448 L. Ling et al. / Water Research 124 (2017) 446e453

applicable in real practice due to the low light utilization efficiency

comparing to UV immersed lamps, but it provides a more
uniformly-distributed UV irradiation and thus is more suitable for
our mechanism study (Fang et al., 2013; Ling et al., 2016).
The degradation kinetics of CBZ in the Fe(II)/citrate/UV/PMS
process was investigated by sequentially spiking a predetermined
concentration of CBZ, PMS and citrate in 150 mL DDI water. After
the pH adjustment, the solution was spiked with a given dose of
Fe(II) and immediately subjected to UV radiation. The concentra-
tions of CBZ, PMS, citrate and Fe(II) employed in the present study
were adopted from our previous publication in optimizing the
Fe(II)/citrate/UV/PMS process using a response surface methodol-
ogy (Ling et al., 2017). An aliquot of 1 mL sample was taken at
predetermined time intervals (1, 5, 10, 15 and 20 min for the 20-min
reaction and 1, 5, 15, 30 and 60 s for the 60-sec reaction), quenched
with 40 mL methanol followed by CBZ concentration determination
using a high performance liquid chromatograph (HPLC). In parallel
tests, exposures of CBZ to UV/PMS, Fe(II)/PMS, Fe(II)/UV/PMS, cit-
rate/PMS, citrate/UV, Fe(II)/citrate/PMS, and citrate/UV/PMS were
conducted using the similar approach.
The steady-state concentrations of the major oxidants in the
Fe(II)/citrate/UV/PMS process were determined by a competition
kinetic method with the addition of probe compounds (i.e., benzoic
acid (BA) and nitrobenzene (NB)). Because BA reacts with both HO

and SO
-4 , while NB only reacts with HO
. The NB degradation ki-
netics can be used to calculate the steady state concentration of
HO
, while the BA degradation kinetics can then be used to
calculate the steady state concentration of SO
- 4 (Yang et al., 2014).
The experimental procedures were similar to those of the degra-
dation kinetics of CBZ, except for the addition of the probe com-
pounds. All the experiments were conducted in duplicates.
Analytical methods. Concentrations of CBZ were determined by
a reverse phase HPLC (VP series, Shimadzu) equipped with a Wa-
ters symmetry C18 column (4.6 mm  150 mm, 5 mM particle size;
Waters) and a UV detector using 286 nm wavelength. The flow rate
was 1 mL/min and the mobile phase was a mixture of DDI water Fig. 1. Degradation of CBZ in the UV/PMS, Fe(II)/PMS and Fe(II)/UV/PMS processes (a)
and acetonitrile (20/80, v/v %). Concentrations of BA and NB were without and (b) with citrate at CBZ, PMS, Fe(II) and citrate initial concentrations of 10,
100, 12 and 26 mM, respectively, at a UV intensity of 0.252 mW/cm2 and an initial
measured by the HPLC with UV detection at 227 nm and 262 nm,
pH ¼ 7.0 ± 0.1.
respectively (Fang et al., 2013; Xiang et al., 2016). An eluent of water
(pH 3, adjusted by phosphoric acid) and methanol (55:45, v/v %)
and DDI water and acetonitrile (50/50, v/v %) were used to separate process (Fig. 1a) followed 1st order kinetics and had a degradation
BA and NB at a flow rate of 0.8 mL/min, respectively. PMS con- rate of 1.33  104 s1. With the addition of 26 mM citrate, the CBZ
centrations were determined via the UV spectrophotometric degradation rate remained unchanged (Fig. 1b). The no apparent
method with potassium iodide (Liang et al., 2008). Concentrations variation in CBZ degradation rate in the citrate/UV/PMS process,
of dissolved Fe(II) and total dissolved iron (Fe(II) and Fe(III)) were compared to that in the UV/PMS process, indicates that neither
measured by the 1,10-phenanthroline method after filtering sam- citrate can compete with CBZ for SO
- 4 or HO
nor it can produce
ples with 0.22 mm filters (Minisart®, hydrophilic) (Tamura et al., more reactive oxidation species (ROS) under UV radiation. In
1974). This method has a dissolved Fe(II) and total dissolved iron addition, the reaction rate constant between citrate and SO
- 4 was
(Fe(II) and Fe(III)) detection limit of 0.5 mM. The concentration of 2  107 M1
s1 (Xiao et al., 2015), which was 2 orders of magni-
dissolved Fe(III) is calculated by subtraction of the Fe(II) concen- tude lower than those of CBZ and many other recalcitrant organic
tration from the total dissolved Fe concentration. pollutants towards the resulting radicals, suggesting that citrate
was stable in the Fe(II)/citrate/UV/PMS process.
3. Results and discussion As shown in Fig. 1, the CBZ degradation at 1 min in both the
Fe(II)/citrate/PMS and Fe(II)/PMS processes were comparable
3.1. Enhanced CBZ degradation in the Fe(II)/citrate/UV/PMS process (about 13%). In both processes, the applied Fe(II) of 12 mM remained
soluble at pH 7 since the concentration of Fe(II) was much lower
Fig. 1 shows the degradation of CBZ in the UV/PMS, Fe(II)/PMS than its solubility under the experimental condition (Eq. (5))
and Fe(II)/UV/PMS processes (a) without and (b) with citrate at CBZ, (Sawyer et al., 2003):
PMS, Fe(II) and citrate initial concentrations of 10, 100, 12 and
26 mM, respectively, at a UV intensity of 0.252 mW/cm2 and an FeðIIÞ þ 2OH 4FeðOHÞ2 Ksp;FeðIIÞ ¼ 5:0  1015 (5)
initial pH of 7.0 ± 0.1. It should be emphasized that the Fe(II) dose
applied in the present study is about an order of magnitude lower However, in the Fe(II)/citrate/PMS system, only 3% (0.36 mM) of
than that in the Fe(II)-activated persulfate processes mostly- the dissolved Fe(II) formed Fe(II)-citrate complexes as calculated
reported in the literature (Anipsitakis and Dionysiou, 2004; using Eqs. (6) and (7), while 97% (11.64 mM) of the dissolved Fe(II)
Rastogi et al., 2009a, 2009b). The CBZ degradation by the UV/PMS remained in its ionic form:
 L. Ling et al. / Water Research 124 (2017) 446e453 449

FeðIIÞ þ citrate4FeðIIÞ  citrate KFeðIIÞcitrate ¼ 1:2  103

(6)

½FeðIIÞ  citrate
ð½FeðIIÞ  ½FeðIIÞ  citrateÞð½citrate  ½FeðIIÞ  citrateÞ
¼ KFeðIIÞcitrate (7)

In these two processes, Fe(II) was the dominant species that

activates PMS (Eq. (4)) at the low Fe(II)/PMS ratio. In the Fe(II)/PMS
process, Fe(III), resulting from the reaction between Fe(II) and PMS,
formed hydroxide precipitates at pH 7 as the concentration of
Fe(III) was much higher than its solubility (Eq. (8)) (Sawyer et al.,
2003):

FeðIIIÞ þ 3OH 4FeðOHÞ3 Ksp;FeðIIIÞ ¼ 6:0  1036 (8)

The precipitated Fe(III) triggers the activation of PMS for radical

production and in turns caters to additional 11% CBZ degradation in
the Fe(II)/PMS process (Rastogi et al., 2009a). In the Fe(II)/citrate/
PMS process, most of the Fe(III) was in the soluble form of Fe(III)-
complex as calculated using Eqs. (9) and (10):

FeðIIIÞ þ citrate4FeðIIIÞ  citrate KFeðIIIÞcitrate ¼ 7:0  1011

(9)

½FeðIIIÞ  citrate
ð½FeðIIIÞ  ½FeðIIIÞ  citrateÞð½citrate  ½FeðIIIÞ  citrateÞ
¼ KFeðIIIÞcitrate (10)

Interestingly, no further CBZ degradation was observed in the

Fe(II)/citrate/PMS process after the first minute, indicating that the
Fe(III)-citrate complex was incapable of activating PMS to produce
ROS.
In Fig. 1, the citrate/PMS and citrate/UV processes showed no
CBZ degradation, while the Fe(II)/citrate/UV/PMS process exhibited
the highest CBZ removal efficiency (71%), which is about 5.0, 5.0,
2.6, 5.0 and 2.6 times higher than those by the UV/PMS, citrate/UV/
PMS, Fe(II)/PMS, Fe(II)/citrate/PMS and Fe(II)/UV/PMS processes,
respectively. The Fe(II)/citrate/UV/PMS process also has a much
higher PMS decomposition (86 mM) compared to those of the cit-
rate/PMS (0 mM), citrate/UV/PMS (4 mM) and Fe(II)/citrate/PMS
(16 mM) processes (Figure S1). These results imply that there is a
synergistic enhancement in CBZ degradation by the Fe(II)/citrate/
UV/PMS process, whose removing capability is above the overall
performance estimated by the superposition principle considering
its subordinate processes. The reaction stoichiometric efficiency (%
RSE), being the number of CBZ molecule degraded divided by the
number of PMS molecule consumed, in the Fe(II)/citrate/UV/PMS
process reached 4.2%, which was at a similar level to that reported
by Ghauch et al. (2013).
3.2. MechanismseFe(II) regeneration from Fe(III)
Fig. 2a shows the mass balance of total aqueous Fe(II) and Fe(III)
(in both ionic and complex forms) in the Fe(II)/citrate/PMS and
Fe(II)/citrate/UV/PMS processes. In these two cases, the total dis-
solved Fe concentration remained around 12 mM during the 20 min
reaction, implying no Fe precipitation in the systems containing
citrate. In the Fe(II)/citrate/PMS process, only 0.19 mM of Fe(II) ion
was detected at 20 min after the reaction was initiated. In the Fe(II)/
citrate/UV/PMS process, UV radiation increased the Fe(II) concen-
tration gradually to 1.58 mM at 20 min. As discussed previously, the
Fe(III) complexed with citrate cannot be reduced to Fe(II) by PMS.
Fig. 2. (a) Regeneration of Fe(II) in the Fe(II)/citrate/UV/PMS and Fe(II)/citrate/PMS
processes; and (b) Total dissolved Fe in the Fe(II)/citrate/UV/PMS process. Conditions:
UV intensity ¼ 0.252 mW/cm2, [Fe(II)]0 ¼ 12 mM, [PMS]0 ¼ 100 mM, [citrate]0 ¼ 26 mM
and initial pH ¼ 7.0 ± 0.1.
Therefore, the excess of Fe(II) observed in the Fe(II)/citrate/UV/PMS
process (8 times higher) was attributed to the Fe(II) regeneration
driven by UV radiation.
Fig. 2b compares the total dissolved Fe concentration in the
Fe(II)/UV/PMS and Fe(II)/citrate/UV/PMS processes at pH 7. The
total dissolved Fe concentration in the Fe(II)/UV/PMS process was
around 0.5 mM, while it remained completely soluble at 12 mM in
the Fe(II)/citrate/UV/PMS process after 20 min. Apparently, citrate
prevented Fe(III) from precipitating by forming soluble Fe(III)-
citrate complex under the reaction conditions examined (Eqs. (9)
and (10)).
The impact of citrate and UV radiation on the regeneration of
Fe(II) from Fe(III) was further investigated with experiments having
the initial Fe(III) concentration of 12 mM under UV radiation at pH 3
(in the presence and absence of citrate) and pH 7 (in the presence of
citrate). As shown in Fig. 3, the photolytic regeneration of Fe(II)
from Fe(III) under these three conditions follows pseudo-first-order
reaction kinetics, but their reaction rates varies significantly. At pH
3, dissolved ionic Fe(III) and Fe(III)-citrate complex have the com-
parable photolysis rates of 2  104 and 3  104 s1 as calculated
450 L. Ling et al. / Water Research 124 (2017) 446e453
Fig. 3. Regeneration of Fe(II) under UV radiation. Conditions: UV
intensity ¼ 0.252 mW/cm2, [Fe(III)]0 ¼ 12 mM, [citrate]0 ¼ 26 mM and initial
pH ¼ 7.0 ± 0.1 or 3.0 ± 0.1.
Fe(III): C initial pH 7 with citrate A initial pH 3 with citrate
: initial pH 3 without citrate ✕ total Fe
Fe(II) B initial pH 7 with citrate ◊ initial pH 3 with citrate
D initial pH 3 without citrate
from Fig. 3, respectively. At pH 7, Fe(III)-citrate complex is in the
form of [Fe3O(cit)3H3]2- with a higher photolysis rate of 1.32  103
s1 (Silva et al., 2009), which is 6.6 and 4.4 times faster than those
of Fe(III) ions and the Fe(III)-citrate complex at pH 3, respectively.
The enhanced photolysis of [Fe3O(cit)3H3]2- might result from its
higher molar absorbance and quantum yield (4233.3 M1cm1,
1.082, respectively), compared to those of ionic Fe(III)
(1500 M1cm1, 0.412, respectively) and the Fe(III)-citrate complex
at pH 3 (2241.7 M1cm1, 0.427, respectively). Therefore, the
addition of citrate at pH 7 not only prevents the precipitation of
Fe(III), but also enhances the molar absorbance/quantum yield of
Fe(III) by forming [Fe3O(cit)3H3]2-, leading to the increase in the
Fe(II) photolytic regeneration. Using the photolysis rate constant of
[Fe3O(cit)3H3]2- at pH 7, 19 mM Fe(III) was estimated being reduced
to Fe(II) in 20 min, suggesting that the added citrate of 26 mM was
repetitively-used about 1.5 times, which increased the CBZ removal
substantially. It is noteworthy that the enhanced CBZ degradation
and PMS decomposition in the Fe(II)/citrate/UV/PMS process was
attributable to the enhanced regeneration of Fe(II) from Fe(III), and
the regenerated Fe(II) activated PMS decomposition at the low
Fe(II) concentration in neutral environment.
3.3. Mechanismseradical involvement
Fig. 4 shows the CBZ degradation in the Fe(II)/citrate/UV/PMS
process at 1, 5, 15, 30, 60, 300, 600, 900 and 1200 s. The CBZ
degradation may be classified into two stages based on their
degradation kinetics (see Scheme 1). The first stage is the rapid
destruction of CBZ (i.e., the reaction occurs within 1 s), and the
second stage is the steady degradation of CBZ from 1 to 1200 s. The
most important step in the first stage is the formation of SO
-
4 driven
by Fe(II) as shown in Eq. (4) (Brandt and Van Eldik, 1995; Rastogi
et al., 2009b), which is fast enough to out-compete both the UV/
PMS process (Eq. (2)) and the reaction between the regenerated
Fe(II) and PMS. With the initial Fe(II)/PMS ratio of 1:8.3, PMS was
considered relatively abundant, and its consumption in such a
Fig. 4. CBZ degradation in the Fe(II)/citrate/UV/PMS process. Conditions: UV
intensity ¼ 0.252 mW/cm2, [CBZ]0 ¼ 10 mM, [Fe(II)]0 ¼ 12 mM [PMS]0 ¼ 100 mM,
[citrate]0 ¼ 26 mM and initial pH ¼ 7.0 ± 0.1.
process might be assumed insignificant. Thus, by setting at a con-
stant PMS concentration of 100 mM in the calculation, the reaction
kinetic of Fe(II) may be calculated using Eq. (11),
d½FeðIIÞ  
¼ kFeðIIÞ;HSO5 ½FeðIIÞ HSO
5 (11)
dt
As estimated, 95% of Fe(II) (11.4 mM) should be oxidized within
1 s (detailed calculation shown in Text S1), suggesting that the
radical generation reaction triggered by the initially-added Fe(II) in
the first stage terminates within 1 s. The calculated result was
found consistent with the experimental observation as shown in
Fig. 4.
In the second stage, the complex formed between Fe(III) and
citrate (i.e., [Fe3O(cit)3H3]2-) regenerates Fe(II) under UV radiation
(Eq. (12)) (Ou et al., 2008):
(12)
followed by an immediate reaction with PMS to produce SO
- 4 . The
reaction between the photo-regenerated Fe(II) and PMS contrib-
utes 46% of the CBZ degradation. In addition, the UV/PMS process
producing SO
- 4 and HO
contributes another 14% of the CBZ
degradation (Wu et al., 2014). The overall CBZ degradation in the
second stage is about 60% and it follows pseudo-first-order kinetics
with a rate constant of 5.19  104 s1. Therefore, the CBZ degra-
dation resulting from various mechanistic contributions in the
Fe(II)/citrate/UV/PMS process exhibits the following order: the re-
action between the photo-regenerated Fe(II) and PMS in the 2nd
stage > the reaction of the UV activated PMS in the 2nd stage > the
reaction between the initially-added Fe(II) and PMS in the 1st stage.
The concentrations of SO
e 4 and HO
in the second stage were
determined by competition kinetics using BA and NB as the probe
compounds. Based on experimental data demonstrated in Fig. 5,
the pseudo-first-order reaction rate constants of BA ðkapp;BA Þ, NB
ðkapp;NB Þ and CBZ ðkapp:CBZ Þ in the second stage are calculated to be
2.93  104 s1, 1.09  104 s1 and 5.19  104 s1, respectively.
The steady-state concentrations of SO
e
4
( ) and
 L. Ling et al. / Water Research 124 (2017) 446e453 451

Scheme 1. Proposed two-stage mechanism of CBZ degradation in the Fe(II)/citrate/UV/PMS process.

respectively, and these calculated concentrations are used to model

pseudo-first-order reaction rate constant of CBZ ðk*app;CBZ Þ in the
second stage using Eq. (15):

(15)

As a result, ðk*app;CBZ Þ is calculated to be 4.78  104 s1, which is

within the stipulated range (less than 7%) compared to that obtained
using data presented in Fig. 5, indicating the adequacy of the calcu-
lated and . In the second stage of Fe(II)/citrate/UV/
PMS process, 80% of the total radical species is SO
e
4 , and the
remaining 20% is HO
. The CBZ degradation in the second stage is
attributed almost equally to both SO
e
4 and HO
, because

is only ¼ of . Since SO
-

4 and HO
are the major ROS in the

Fig. 5. Degradation of NB, BA and CBZ in the Fe(II)/citrate/UV/PMS process. Conditions: process, the degradation products of CBZ in the Fe(II)/citrate/UV/PMS
UV intensity ¼ 0.252 mW/cm2, [BA]0 ¼ 1 mM, [NB]0 ¼ 1 mM, [CBZ]0 ¼ 10 mM, process should be similar to those studies of SO
-4 - and HO
- based
[Fe(II)]0 ¼ 12 mM, [PMS]0 ¼ 100 mM, [citrate]0 ¼ 26 mM and initial pH ¼ 7.0 ± 0.1. AOPs reported by Ghauch et al. (2011) and Deng et al. (2013).

4. Conclusions
HO
( ) can be further exemplified using Eqs. (13) and (14):
A novel Fe(II)/citrate/UV/PMS process, capable of removing a
(13) model micropollutant at a low Fe(II)/PMS ratio (1:8.3) and neutral
starting pH, is proposed and evaluated in this study. The CBZ
(14) removal efficiency by the proposed process were 5.0, 5.0, 2.6, 5.0
and 2.6 times higher than those by the UV/PMS, citrate/UV/PMS,
where , 2, 3, 4 and 5 Fe(II)/PMS, Fe(II)/citrate/PMS and Fe(II)/UV/PMS processes,
respectively. The mechanism of the Fe(II)/citrate/UV/PMS process
are reaction rate constants between SO
e
and BA
4 showed that the reactions between initially-added Fe(II) and PMS
(1.2  109 M1
s1), HO
and BA (5.9  10 M
s ), HO
and NB
9 1 1
(the first stage), between regenerated Fe(II) and PMS (the second
(1.8  1010 M1
s1), SO
e 9 1 1
4 and CBZ (1.92  10 M
s ), and HO
stage), and between UV radiation and PMS (the second stage)
9 1 1
and CBZ (8.8  10 M
s ), respectively (Neta et al., 1988; Vogna contributed 11%, 46% and 14% to the CBZ degradation, respectively.
et al., 2004; Matta et al., 2011). The The reaction between the regenerated Fe(II) and PMS contributed
and the most to the enhanced CBZ removal in the Fe(II)/citrate/UV/PMS
13 14
process. The contributions of SO
e
4 and HO
to the degradation of
are calculated to be 2.21  10 M and 6.1  10 M, other recalcitrant organic compounds in the Fe(II)/citrate/UV/PMS
452 L. Ling et al. / Water Research 124 (2017) 446e453
process could be different depending on the reaction rate constants
between the two radicals and organic compounds. In addition, the
molar ratio between S2O2 8 and CBZ is around 20, which is 3-time
lower than those processes with high mineralization levels
(~90%) reported in the literature (Monteagudo et al., 2015; Dura n
et al., 2016). However, the concentrations of CBZ in potable water
are in ng/L to mg/L level (Mohapatra et al., 2014), suggesting that the
Fe(II)/citrate/UV/PMS process may reach a high mineralization level
in real water.
The Fe(II)/citrate/UV/PMS process has the potential to be applied
to the treatment of aqueous PPCPs including CBZ in potable water
treatment plants, wherein groundwater or surface water is used as
the source water. For application to groundwater purification, the
Fe(II) concentration naturally present in groundwater usually
ranges from 0.5 to 10 mg/L (9e179 mM) (WHO, 2003c). It can play an
active role in the Fe(II)/citrate/UV/PMS process and has great po-
tential in the treatment. For the treatment of surface water, addi-
tion of Fe(II) in the very low quantities will ensure the compliance
of regulated iron threshold of potable water even in the presence of
the major ambient iron species (i.e., Fe(III), 0.7 ppm or 12.5 mM) in
rivers and lakes (WHO, 2003c). In fact, the ambient Fe(III) will also
increase the PPCP degradation through the enhanced Fe(II) regen-
eration. Parallel studies conducted have also shown that the CBZ
degradation using this process will not be affected by the presence
of NHþ 
4 (up to 5.0 ppm) and Cl (up to 300 ppm), and is reduced by
about 13%, 34% and 28% in the presence of Br (up to 5.0 ppm),
alkalinity (up to 180 ppm), and NOM (up to 1.0 ppm), respectively
(Ling et al., 2017). The low impacts of aqueous constituents on the
PPCP degradation in the Fe(II)/citrate/UV/PMS process further
demonstrate its application potential to potable water treatment.
Another major advantage of the Fe(II)/citrate/UV/PMS process is
the efficient utilization of PMS as compared with those in the Fe(II)/
citrate/PMS and UV/citrate/PMS processes, as only ~10% of PMS
remains unused in the Fe(II)/citrate/UV/PMS process (with a %RSE
of 4.2%), while ~84% and ~96% of PMS remains unused in the Fe(II)/
citrate/PMS and UV/citrate/PMS processes, respectively. The resid-
ual PMS needs to be removed by the addition of chemical re-
ductants (such as sulfite) to reduce PMS to sulfate (Olmez-Hanci
et al., 2014), which increases the overall operational cost. Besides,
the Fe(II)/citrate/UV/PMS process inputs additional sulfate of no
more than 20.16 ppm (including sulfate from PMS decomposition
and from additional sulfite as the oxidant quencher to remove the
remaining ~10% of PMS) in the treated water, and this concentra-
tion is far less than the sulfate taste threshold of 250 ppm (WHO,
2004), while the citrate concentration (26 mM) used in this pro-
cess will not contribute to any issues related to the taste of the
potable water. In addition, the low citrate concentration (26 mM)
used in this study shall not cause any detectable problem in THM
and HAA formation (Fan and Sokorai, 2015).
Acknowledgements
We gratefully acknowledged Dr. Alok D. Bokare at the Hong
Kong University of Science and Technology for his advice on pho-
toactivity of Fe-citrate complex. This work was supported by the
Hong Kong Research Grants Council under grant number 618312.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.watres.2017.07.066.
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