Journal of Photochemistry & Photobiology, A: Chemistry: Sciencedirect
Journal of Photochemistry & Photobiology, A: Chemistry: Sciencedirect
Journal of Photochemistry & Photobiology, A: Chemistry: Sciencedirect
Radicals (•OH, Cl•, ClO• and Cl•2− ) concentration profiles in the intensified
degradation of reactive green 12 by UV/chlorine process: Chemical kinetic
analysis using a validated model
Mohamed Larbi Djaballah a, Aouattef Belghit b, Aissa Dehane b, *, Slimane Merouani b,
Oualid Hamdaoui c, Muthapandian Ashokkumar d
a
National Polytechnic School of Constantine, P.O. Box 75, 25000 Constantine, Algeria
b
Laboratory of Environmental Process Engineering, Faculty of Process Engineering, University Salah Boubnider Constantine 3, P.O. Box 72, 25000 Constantine, Algeria
c
Chemical Engineering Department, College of Engineering, King Saud University, P.O. Box 800, 11421 Riyadh, Saudi Arabia
d
The University of Melbourne, School of Chemistry, Parkville, Victoria 3010, Australia
A R T I C L E I N F O A B S T R A C T
Keywords: Understanding the production of reactive species in chlorine photolysis is critical for applying advanced
Advanced oxidation processes (AOPs) oxidation processes (AOPs) in future. This paper developed a chemical kinetic model consisting of 66 chemical
UV/chlorine reactions, including many radicals and non-radical intermediates/products, to elucidate the intensified removal
Reactive green 12 (RG12)
of reactive green 12 (RG12) dye by UV/chlorine AOP. The generated kinetic model fits our experimental data
Kinetic model
Hydroxyl radicals
satisfactorily across a broad range of solution pH and initial chlorine concentration. The simulation process was
accomplished by COPASI® software coupled with the deterministic Nelder-Mead optimization method for
determining some unavailable rate constants, including the reaction of RG12 with OH (k = 1.2 × 1010 M− 1 s− 1),
•
Cl (k = 2.1 × 109 M− 1 s− 1), Cl2− (k = 1.26 × 107 M− 1 s− 1) and ClO (k = 6.12 × 104 M− 1 s− 1). As well, the first-
• • •
order rate constants of chlorine photolysis, HOCl + hv → OH + Cl and OCl− + hv → O − + Cl , were respectively
• • • •
(0.81–6.90) × 10− 3 s− 1 and (0.87–8.29) × 10− 3 s− 1, depending on the solution pH and chlorine dosage. The
radicals concentration (and RG12 degradation rate) increased with the increase of initial chlorine dosage,
whereas a solution pH of 5 is recorded for the best process efficiency (i.e., radicals’ yield and dye destruction
rate). Even though the steady-state concentration of ClO (~10− 8 M) and Cl2− (~10− 11 M) are highest compared
• •
− 12 − 12
to OH (~10 M) and Cl (~10 M), the selectivity analysis results showed that OH radicals contributed
• • •
majorly in the degradation (~85 %) for the different investigated scenarios of pH and initial chlorine concen
tration. The remaining portion (~15 %) is ensured by Cl and ClO nearly equitably. These findings were
• •
attributed to the high reactivity of RG12 toward OH rather than reactive chlorine radicals, as reflected by the
•
1. Introduction and IO3) that can effectively oxidize almost all organic molecules at
•
the selectivity of the different oxidants (with the exception of OH), the tiveness of the destruction of micropollutants [7,8]. Therefore, UV-
•
generation of highly reactive radicals (such as OH, SO4 , Cl , ClO , Cl2− assisted processes like UV/H2O2, UV/S2O2− and UV/chlorine are
• •− • • •
8
* Corresponding author.
E-mail addresses: aissaleon15@gmail.com, aissaleon@yahoo.com (A. Dehane).
https://doi.org/10.1016/j.jphotochem.2023.114557
Received 19 October 2022; Received in revised form 8 January 2023; Accepted 12 January 2023
Available online 16 January 2023
1010-6030/© 2023 Elsevier B.V. All rights reserved.
M.L. Djaballah et al. Journal of Photochemistry & Photobiology, A: Chemistry 439 (2023) 114557
regarded as AOPs for effective water treatment [9]. Since chlorine ab Table 1
sorbs light at longer wavelengths, sunlight treatment applications of Model equations for RG12 degradation in UV/chlorine system.
chlorine photolysis are feasible, whereas H2O2 and persulfate-based N◦ Reaction Rate constant, k Ref.
AOPs can only employ light in the UV-C interval due to restrictions in − 3 − 1
1 HOCl + hv → OH + Cl (0.81–6.9) × 10 s This study
• •
tive species (RCS: ClO , Cl and Cl2− ) that are capable of degrading 5 × 1010 M− 1 s− 1
• • •
12 OCl− + H+ → HOCl [38]
organic water contaminants [11]. The UV/chlorine is of dual role, 13 2 OH → H2O2 5.5 × 109 M− 1 s− 1 [38]
•
micropollutants degradation and water-borne pathogens inactivation 14 H2O2 → H+ + HO−2 1.3 × 10− 1 s− 1 [38]
15 H+ + HO−2 → H2O2 5 × 1010 M− 1 s− 1 [38]
[11,14]. Hypochlorous (HClO) acid has an acid dissociation constant 16 H2O2 + OH → HO2 + H2O
• •
2.7 × 107 M− 1 s− 1 [38]
pKa = 7.5 (see chlorine speciation in Fig. S1 of the SM), which makes the 17 HO−2 + OH → HO2 + OH−
• •
7.5 × 109 M− 1 s− 1 [38]
photochemistry of both species relevant at pH levels that are relevant to 18 HO−2 + OH → H2O + O2−
• •
7.5 × 109 M− 1 s− 1 [5]
the environment [15]. HClO photolysis forms OH and Cl radicals (Re 19 HO2→ H+ + O2− 7 × 105 s− 1 [38]
• • • •
1
conjugate base, in addition to two excited states of oxygen, O( D) and O 23 H2O2 + O2− → OH− + O2 + OH
• •
1.3 × 10− 1 M− 1 s− 1 [38]
(3P) [i.e., OCl− +hν → O(1D) + Cl− and OCl− + hν → O(3P) + Cl− ]. 24 H2O2 + HO2 → H2O + O2 + OH 3 M− 1.s− 1 [38]
• •
However, the formation of O(1D) and O(3P) are less expected than O −
• 25 2H2O2 → 2H2O + O2 2.3 × 10− 2 M− 1 s− 1 [5]
1 26 2HO2 → H2O2 + O2 8.3 × 105 M− 1 s− 1 [54]
•
(3P), i.e., 0.133 and 0.074, against that forming O − at 254 nm irradia
•
28 Cl + H2O → HOCl − + H+ 2.5 × 105 s− 1 [51]
• •
tion wavelength [5]. More reactive chlorine species can be formed 29 HOCl − + H+ → Cl + H2O
• •
2.1 × 1010 M− 1 s− 1 [51]
during chlorine photo-activation. For example, ClO is formed by the 30 HOCl − + Cl– → Cl2− + OH− 1 × 104 M− 1 s− 1 [55]
• • •
Table 1). Compared to OH (non-selective), Cl (more selective than OH) 2.1 × 109 M− 1 s− 1
• • •
34 Cl + Cl2− → Cl2 + Cl− [52]
• •
reacts preferentially with electron-rich substrates [14]. Cl2 is generally 35 Cl2− + H2O2 → H+ + 2Cl− + HO2 1.4 × 105 M− 1 s− 1 [56]
•− • •
less reactive compared to OH and Cl , however, it reacts selectively with 36 Cl2− + HO2 → H+ + 2Cl− + O2 3 × 109 M− 1 s− 1 [57]
• •
• •
main oxidants playing significant role in UV/chlorine system at envi 39 Cl2− + H2O → HClOH + Cl−
• •
1.3 × 103 s− 1 [59]
ronmentally pH values (pH 6–9) [11]. They are characterized by greater 40 HClOH → HOCl − + H+
• •
1 × 108 s− 1 [59]
redox potentials of 2.43 V for Cl , 2.13 V for Cl2− and 1.5–1.8 V for ClO , 41 HClOH → Cl + H2O 1 × 102 s− 1 [17]
• • • • •
water pollutants [17–22,22–28]. These radicals react with organic 44 Cl2− + OH → HOCl + Cl−
• •
1 × 109 M− 1 s− 1 [50]
compounds at rates of ~ 102-106 M− 1 s− 1 for Cl2− , ~ 107-109 M− 1 s− 1 for
•
45 Cl2 + H2O → HOCl + Cl− + H+ 22 s− 1 [60]
8 11 − 1 − 1
ClO and 10 -10 M s for OH and Cl [11,13]. 46 Cl2 + O2− → O2 + Cl2− 1 × 109 M− 1 s− 1 [50]
• • • • •
For the utilization of chlorine photolysis in water treatment, it is 47 Cl2 + HO2 → H+ + O2 + Cl2− 1 × 109 M− 1 s− 1 [61]
• •
tive effects are taken into consideration. For example, the t-butanol 61 H2O → H+ + OH− 1 × 10− 3 s− 1 [38]
impact (i.e., a quencher of OH, Cl , and ClO ) can be compared to that of 62 H+ + OH− → H2O 1 × 1011 M− 1 s− 1 [38]
• • •
bicarbonate (i.e., a quencher of OH, Cl , and Cl−2 ) [29]. As a result, ClO 63 OH + P → OH-Prod. 1.2 × 1010 M− 1 s− 1 This study
• • • • • •
is being cited as a crucial oxidant for the degradation of various organic 64 Cl + P → Cl -Prod. 2.1 × 109 M− 1 s− 1 This study
• •
compounds (e.g., caffeine, naproxen, microcystin-LR and trimethoprim) 66 ClO + P → ClO -Prod.
• •
6.12 × 104 M− 1 s− 1 This study
[17,18,29,30]. Following the quenchers technique, OH was found to be
•
In the presence of NB
the predominant oxidant in the destruction of ibuprofen [25] and 67 NB + OH → Prod
•
3.9 × 109 M− 1 − 1
s [13]
ronidazole [31], while RCS were responsible for the removal of
trimethoprim [30] and benzoic acid [23]. According to Wang et al. [22],
OH and Cl play a substantial role in the elimination of carbamazepine.
• •
2
M.L. Djaballah et al. Journal of Photochemistry & Photobiology, A: Chemistry 439 (2023) 114557
However, the use of the quenchers’ method does not always generate chlorine system was performed using COPASI® kinetic simulation
meaningful outcomes due to the multiple interactions between radicals software. This efficient simulation tool allows determining the concen
and quenchers and the complicated nature of the chlorine photo tration–time profiles of the different species involved in the reaction
activated system, particularly in the presence of multiple organic com scheme of Table 1. This Table 1 regroups 66 chemical reactions
pounds (e.g., target pollutant and probe-compounds). Recently, Bulman including, in addition to the initial constitutes (i.e., HOCl/ClO− , RG12,
et al. [5] used a combination of reactive oxidant quantification with H2O, O2, H+ and OH− ), a number of reactive radicals (Cl , ClO , OH,
• • •
verified probe chemicals and kinetic modeling to study the generation of Cl2− , HO2, O2− , O3− ) and non-radical intermediates/products (O3, ClO−2 ,
• • • •
reactive oxidants during chlorine photolysis as a function of pH (6–10) ClO−3 , H2O2, HO−2 , and Cl2O2).
and irradiation wavelength (254, 311 and 365 nm). Due to their specific
reactivity and photostability at the irradiation wavelengths, nitroben 2.3. Reactive species contribution
zene, benzoate, and cinnamic acid were chosen as the probe chemicals
for the hydroxyl radical, RCS, and ozone, respectively. The experimental The contribution of each reactive species (RS: Cl , ClO , OH, Cl2− ) in
• • • •
route has been accomplished by a kinetic model revealing the most the overall degradation rate of RG12 was calculated based on selectivity
important reaction pathways published in UV/chlorine mechanism. as.
According to the author’s findings, steady-state concentrations of OH
•
and Cl are higher in acidic environments when exposed to either 254 or (rRC− prod )
(1)
•
SRS/CB =
311 nm radiation, whereas O3 is typically at its highest concentration (− rRG12 )
when exposed to 254 nm radiation at high pH. Due to hypochlorite’s
increased molar absorptivity under high-wavelength irradiation, chlo where (− rRG12) is the disappearance rate of RG12 and (rRC-prod) is the
rine loss rate constants rise with pH. The author concluded that kinetic formation rate of the organic product that comes from the direct reac
modeling could be a potent tool for examining the radical photochem tion of each specific reactive species RC with RG12, both evaluated at
ical mechanisms in UV/chlorine process. On the other hand, the opti the initial stage of the reaction.
mum operating conditions for the UV/chlorine process are well
established in the literature. For instance, independent of the chlorine 3. Results and discussion
and pollutant concentrations, the degradation rate decreased with a pH
increase in the range 5–10 (pH 5 is optimal). However, the optimal 3.1. Model verification
concentration of chlorine depends on the irradiation wavelength and the
initial pollutant concentration. All these issues are well documented in Fig. 1 shows the confrontation between the experimental and
different references [5,11,13,32]. The concentration profiles of the simulated (using the model of Table 1) photodegradation profiles of
various free radicals present in the system and their reactivity with the RG12 (C0 = 16.3 µM) in the presence of chlorine (0.5 mM) and either
target pollutant, however, are truly what is missing (this changes with nitrobenzene (NB: 10 mM) or chloride ions (Cl− : 10 mM), as specific
the experimental condition and the nature of the pollutant). Therefore, radical scavengers. As it can be seen in Fig. 1, as time proceeds, the
there is a critical need to concentrate more study on identifying the decay of RG12 is proportionally increased with a rapid kinetic for the
distribution of radicals in the system.
In this study, the free radical oxidation of reactive green 12 (RG12)
azo dye in chlorine photoactivated (254 nm) system was simulated
under different conditions of solution pH (3–11) and initial chlorine
dosage (80–500 µM). A mechanism with 66 chemical reactions
comprising several reactive radicals (Cl , ClO , OH, O − , HO2, O2− , Cl2− )
• • • • • • •
and Cl2O2) has been developed for simulating the experimental degra
dation data of RG12. The simulation process was conducted using the
open source COPASI® software. The model’s overarching goals are: (i)
establishing the concentration profiles and steady-state concentration of
the various reactive species (i.e., OH, Cl , ClO and Cl2− ) formed in the
• • • •
The used reagents and their specifications are provided in Text SM-1
of the Supplementary Material file (SM). Text SM-2 described the
experimental setup and all procedures followed during the degradation
of RG12, i.e., from the solution preparation to runs and RG12 analysis.
2.2. Kinetics model and computational algorithm Fig. 1. Experimental and modeling effect of UV/chlorine oxidation system on
the removal kinetics of RG12 in the absence and presence of nitrobenzene (NB)
Text SM-3 described in detail the kinetics model and the computa and chloride ions (Cl− ) (conditions: C0 = 16.3 µM, [chlorine]0 = 0.5 mM, [NB]0
tional algorithm. The kinetics modeling of RG12 degradation in the UV/ = [Cl− ] = 10 mM, pHi 5, Temp. = 25 ◦ C).
3
M.L. Djaballah et al. Journal of Photochemistry & Photobiology, A: Chemistry 439 (2023) 114557
UV/chlorine and UV/chlorine/Cl− systems. Whereas, in the presence of respectively, OH, Cl , Cl2− and ClO were found to be k63 = 1.2 × 1010
• • • •
NB, the decomposition of RG12 is drastically decelerated. Furthermore, M− 1 s− 1, k64 = 2.1 × 109 M− 1 s− 1, k65 = 1.26 × 107 M− 1 s− 1 and k66 =
it is clearly observed (Fig. 1) that the adopted kinetics model perfectly 6.12 × 104 M− 1 s− 1. In fact, azo dyes react with high second-rate con
fitted the experimental degradation profiles either in the absence or in stants with OH, e.g., methyl orange (2 × 1010 M− 1 s− 1 [37]), calmagite
•
the presence of NB or Cl− (less precision for this last case). Besides, it (1.3 × 10 M− 1 s− 1 [37]), acid blue 40 (1.7 × 1010 M− 1 s− 1 [38]), acid
10
should be noted that the hydride process (UV/chlorine) improved the red 265 (1.1 × 1010 M− 1 s− 1 [38]), acid orange 7 (6.0 × 109 M− 1 s− 1
destruction of RG12 by 300 % as compared the sum of the two single [35]) and chlorazol black (1.0 × 109 M− 1 s− 1 [35]). On the other hand,
processes separately (Fig. S2(a) of the SM and its analysis in Text-S3 of measurements revealed that Cl is higher reactive as OH toward organic
• •
9 − 1 − 1
the SM). The experimental pseudo-first-order rate constants (calculated aromatic solutes like benzene (k = 6.0 × 10 M s ), toluene (k = 1.8
using -dC/dt = kC law) of the experimental profiles of Fig. 1 are 0.02 s− 1 × 1010 M− 1 s− 1), chlorobenzene and (k = 1.8 × 1010 M− 1 s− 1) benzoic
for the UV/chlorine system, 0.031 s− 1 for the UV/chlorine/Cl− system acid (k = 1.8 × 1010 M− 1 s− 1); however, a lower value of k = 9.18 × 107
and 0.002 s− 1 for the UV/chlorine/NB system. Those calculated from the M− 1 s− 1 was predicted for acid orange 7 dye [34]. Besides, Cl2− reacts
•
simulated profiles are 0.021, 0.033 and 0.003 s− 1 for successively UV/ with acid orange 7 azo dye at a rate constant of k = 3.65 × 10 M− 1 s− 1
7
chlorine, UV/chlorine/Cl− and UV/chlorine/NB systems. It should be [34]; but other values of 2.5 × 108, 2.8 × 108 and 3.0 × 106 M− 1 s− 1
stressed here that the free radical-oxidation mechanism is the main were reported for phenol, p-hydroxybenzoic acid and p-chlorobenzoic
pathway for the synergism retrieved for RG12 abatement in the UV/ acid, respectively [11]. The rate constants for the reactions of ClO with
•
chlorine photoassisted treatment. This was confirmed experimentally by solutes in water are very scarce. ClO , which has a reduction potential
•
adding NB and chloride a specific radicals scavengers (Fig. S2(a)), and in lower than those of Cl and Cl2− (i.e., E0 = 1.5–1.8 V vs NHE), is a se
• •
another hand, by the simulation data where the adopted model (which is lective radical. It was not found to play a role in the UV/chlorine-
entirely based on free radical oxidation processes) excellently fitted the degradation of several organic pollutants like carbamazepine, geo
dye removal in the three photoassisted systems of Fig. 1. In the UV/ smin, benzothiazole, 2-methylisoborneol and 2-isobutyl-3-methoxypyr
chlorine system, NB reacts with OH only (k = 3.9 × 109 M− 1 s− 1) [13] azine [22,27,39]; however, Kong et al. [24] reported an appreciable
•
whereas Cl− reacts with Cl , OH and Cl2− with rate constants of 8.5 × reactivity of ClO with gemfibrozil and bezafibrate with second-order
• • • •
9 9 9 − 1 − 1
10 , 4.3 × 10 and 2.1 × 10 M s , respectively (Eqs. 7, 9 and 34 of rate constants of 4.2 × 108 and 6.3 × 108 M− 1 s− 1, respectively. Be
Table 1). Based on these rate constants, Cl− is more reactive with Cl , sides lower constants of < 3 × 106 M− 1 s− 1 were measured for the re
•
where the producing product is the dichlorine radical anion (Eq. (34) of action of ClO with formate and benzoate [40].
•
Table 1). Therefore, although Cl− is classified as a radicals-scavenger, it The assessment that has been provided above suggests that the
is also a Cl2− enhancer [33], as it will be confirmed by the simulation computed reaction rate constants of RG12 with OH and chlorine radi
• •
results. The contribution of OH in the global degradation rate of the dye cals are in the best accord with data that has been published in the
•
(as calculated from NB results) is ~90 % based on the experimental literature. Additionally, the predicted rate constants of Reactions (63)–
findings and 86 % based on the simulated profiles [both percentages are (66) of Table 1 indicate that the removal of RG12 is expected to be
calculated from the k values as: (kUV/chlorine− kUV/chlorine/NB)/kUV/chlorine], conducted through its reactions with OH and Cl radicals. However, as it
• •
Fig. 1. The remaining fractions represent the contribution of chlorine is known the importance of the reactive species (RS: OH, Cl , Cl2− , and
• • •
radicals, as it will be specified in the following sections. ClO ) is dependent on both its concentration in the bulk liquid and the
•
19 M− 1 cm− 1 for H2O2 and 47.5 M− 1 cm− 1 for S2O2− 8 [23]). Moreover, are among the main radicals created during the photolysis of chlorine.
the greater value of k2 compared to k1 was also well supported by the Several other reactive species (O2− , O − , HO2, HOCl − ) were created at
• • • •
higher εHOCl (66 M− 1 cm− 1 [36]) compared to εOCl− =59 M− 1 cm− 1 inappreciable quantities against the other radicals (even in the presence
[36]. of NB or Cl− , as in Figs. S3(b) and S4(b)). We can notice from Fig. 2(b)
On the other hand, rate constants of RG12′ s reactions with, that at the steady-state, the OH and Cl radicals reach concentrations of
• •
4
M.L. Djaballah et al. Journal of Photochemistry & Photobiology, A: Chemistry 439 (2023) 114557
Fig. 2. Concentration profiles of the different created species during the aqueous oxidation of RG12 by UV/chlorine system (conditions: C0 = 16.3 µM, [chlorine]0 =
0.5 mM, pHi 5, Temp. = 25 ◦ C).
1.66 × 10− 12 and 9.86 × 10− 13 M ([ OH]ss/[Cl ]ss = 1.7), whereas the confirm the dominant implication of hydroxyl radical in the destructive
• •
huge level of [ClO ]ss = 2.0 × 10− 8 M (i.e., resulting in [ClO ]ss/[Cl ]ss = action of UV/chlorine system toward RG12. Several studies [25,39,42]
• • •
4 4
2.06 × 10 and [ClO ]ss/[ OH]ss = 1.21 × 10 ) is ascribed to the rapid have reported that hydroxyl radicals are the dominant oxidants involved
• •
reaction of the primary created radicals ( OH and Cl ) with chlorine in the degradation of pollutants by the UV/chlorine process. Recently,
• •
(which is in excess at the initial stage of reaction) through Reactions (5), Yang and al. [43] have reported that OH dominated Benzothiazoles
•
(6), (10) and (11) of Table 1. However, the concentration of Cl2− con degradation at neutral and alkalinity conditions, while RCS played a
•
tinues to increase with time up to 230 s ([Cl2− ] = 2.1 × 10− 11 M) and significant role in Benzotriazoles degradation. Although all earlier
•
decreased after that. The Cl2− profile is ascribed to the reaction of Cl experimental studies agreed with the fact that the degradation mecha
• •
with Cl− (Eq. (9), k = 8.5 × 109 M− 1 s− 1). Because Cl− is continually nism of organic pollutants happens through the free radical pathway,
released (as the main product of HOCl photolysis, Fig. 2(a)), it is unlikely there is no unanimity about the main species driving the degradation
that the Cl2− would have the same transitory profile as the other radicals route.
•
in the system.
In the presence of NB, the [ OH]ss decreases to 3.33 × 10− 14 M 3.4. Analysis of the initial chlorine dosage effect
•
decreased to 1.4 × 10− 8 M (instead of 2.03××10− 8 M without NB) due In Fig. 3, the simulated RG12-concentration profiles are compared
to the decrease of the rate of Reaction (5), i.e., OH + HOCl → ClO +H2O, with the experimental profiles at different initial chlorine concentra
• •
due to the efficient quench of OH by NB. In contrast, the [ OH]ss tions (from 0.08 to 0.5 mM) under conditions of solution pH and tem
• •
− 12
increased from 1.67 × 10 M for the UV/chlorine system to 2.13 × perature of 5 and 25 ◦ C, respectively. It can be seen that the
10− 12 M for the UV/chlorine/Cl− (1.28-fold increase); however, that of experimental and simulation results agree with the fact that the degra
Cl decreased from 9.86 × 10− 13 M to 5.33 × 10− 13 M (1.78-fold dation rate of RG12 goes up with increasing the initial chlorine con
•
decrease) when passing from UV/chlorine to UV/chlorine/Cl− (Fig. 2(b) centration, with a fort concordance between the experimental and the
and S4(b)). This is ascribed to the rapid quench of Cl with Cl− (Eq. (9) of modeling profiles. The same increasing degradation trend was obtained
•
9 − 1 − 1
Table 1, k = 8.5 × 10 M s ), which effectively accelerates the initial in several experimental studies for several contaminants [19,22,44].
yield of Cl2− from 1.1 × 10− 12 M for the UV/chlorine system to 7.25 × However, optimum chlorine dosage was reported in some cases [23,25];
•
10− 10 M for the UV/chlorine/Cl− (650-fold increase), as calculated from the case which was not reached in our study may be due to the lower
Fig. 2(b) and S4(b). However, ClO seems to be unaffected by the initial upper chlorine limit used (0.5 mM). The initial removal rate of the dye
•
presence of chloride ([ClO ]ss ~ 2 × 10− 12 M (Fig. 2(b) and S4(b)). increased from 0.0545 µM s− 1 for [chlorine]0 = 0.08 mM to 0.0858,
•
From Fig. 2(c), it is noted that the concentration profiles of OH-prod, 0.191 and 0.359 µM s− 1 for [chlorine]0 = 0.2, 0.4 and 0.5 mM,
•
Cl -prod, ClO -prod, and Cl2 -prod increase with time and then take a
•−
respectively. The complete elimination of RG12 was obtained for 0.5
• •
plateau. Which we interest from these profiles is the initial stage, as after mM of chlorine after 300 min of irradiation, against 97% for 0.6 mM,
a long irradiation time, by-products becoming competitors for radicals 94% for 0.4 mM, 76% for 0.2 mM and 68% for 0.08 mM (at 300 min).
consumption (the Table 1-based reaction model did not consider this In Fig. 4(a), chorine depletion and chloride (main product) formation
scenario). At the initial stage of reaction (for up to t1/2 [41]), the re kinetics are shown under the best fittings conditions of Fig. 3. The rate of
actions of the target dye (RG12) with radicals dominate (by-products both substances increased with chlorine dosage increase, explaining the
levels is too low), thus allowing an effective evaluation of the radical RG12-degradation comportment retrieved in Fig. 3. In fact, higher
contribution in the RG12 degradation using Eq. (1). This equation pro chlorine depletion could ensure higher yield of radicals generation (and
vided percentages of 85.6%, 8.9%, 5.4% and 0% for the contributions of huge rate of Cl− release as well, Eq. (10)) as it will be demonstrated.
OH, Cl , ClO and Cl2− in the overall degradation rate of RG12 in the According to Fig. 4(a), chlorine depletes with increasing initial rates of
• • • •
chlorine-photoassisted process. With adding NB, the OH contribution 9.10 × 10− 8, 2.85 × 10− 7, 1.13 × 10− 6 and 2.62 × 10− 6 M s− 1, whereas
•
decreased to 12% against 61.8% for Cl and 25.9% for ClO , as calculated those of Cl− going as 2.46 × 10− 8, 1.65 × 10− 7, 6.80 × 10− 7 and 1.61 ×
• •
from Fig. S3(c) using Eq. (1). However, for the UV/chlorine/Cl− system, 10− 6 M s− 1 as the initial chlorine dosage increased from 0.08 mM to 0.2,
the radical contributions are 69% for OH, 3% for Cl and ClO and 25% 0.4 and 0.5 mM, respectively. Therefore, the yield of chloride formation
• • •
for the Cl2− , as calculated from Fig. S4(c) using Eq. (1). These results from chlorine depletion is about 61%.
•
5
M.L. Djaballah et al. Journal of Photochemistry & Photobiology, A: Chemistry 439 (2023) 114557
created from Reactions (5) and (10) can degrade chlorine with higher
rate constants (i.e. k5 = 2 × 109 M− 1 s− 1 for OH and k10 = 3 × 109 M− 1
•
initial chlorine concentration. At 5 s, the OH radicals reached maximum various [chlorine]0, and (b) overall rate constant for chlorine decay upon UV/
•
centrations than those of OH and Cl radicals with values of 2.03 × 10− 8, proportionally with the rise of chlorine concentration [chlorine]0
• •
1.3 × 10− 8, 5.69 × 10− 9 and 2.92 × 10− 9 M for, respectively, 0.5, 0.4, (Fig. S5 of the SM). The formation rate of Prod- OH is superior to that of
•
0.2 and 0.08 mM of chlorine (Fig. 5(d)). On the other hand, it can be other products. This is owing to the fact that the rate constant of RG12′ s
observed that the evolution of Cl2− radicals concentration is relatively reaction with OH (k63# = 1.2 × 1010 M− 1 s− 1) is greater than that of the
• •
different; it follows a progressive augmentation and sometimes (e.g. the reaction of RG12 with other radicals, i.e., Cl (k64 = 2.1 × 109 M− 1 s− 1),
•
case of 500 mM of chorine) attained an optimum at 250 s (Fig. 5(c)). Cl2− (k65 = 1.26 × 107 M− 1 s− 1) and ClO (k66 = 6.12 × 104 M− 1 s− 1), as
• •
Nevertheless, the maximum concentration of all radicals is reached for a shown in Table 1. Based on these last findings (Fig. S5 of the SM), the
concentration of 0.5 mM chlorine. contribution of each of the radicals in the overall degradation rate of the
Meanwhile, the concentration of the reaction products Prod- OH,
•
dye can be calculated using Eq. (1) (Fig. 6). As shown in Fig. 6, the
6
M.L. Djaballah et al. Journal of Photochemistry & Photobiology, A: Chemistry 439 (2023) 114557
of 7–9 % for Cl and 5–7 % for ClO . However, Cl2− has shown a null
• • •
contribution.
As a conclusion of this section, the increase of chlorine dosage in
creases its activation via direct photolysis and oxidation with radicals
(Fig. 4(a)), which increases the concentrations of reactive radicals
(Fig. 5(a)–(d)), thereby enhancing the degradation of the pollutant
substrate (RG12) in the solution (Fig. 3). Therefore, the numerical
analysis has provided an excellent quantitative and qualitative
comprehension of the chlorine dosage effect on the micro-mechanisms
responsible for the destruction of micropollutants by the photo-
activated chlorine, with specifying the contribution of all reactive spe
cies created in the process (Fig. 6).
7
M.L. Djaballah et al. Journal of Photochemistry & Photobiology, A: Chemistry 439 (2023) 114557
the pH variation in the range of pH 5–11; however, pH 3 seems to be pH 5. Moreover, according to the rate constants of Reactions 5 (k5 = 2 ×
relatively lower efficient than pH 5 in term of degradation rate partic 109 M− 1 s− 1), 6 (k6 = 8.8 × 109 M− 1 s− 1), 10 (k10 = 3 × 109 M− 1 s− 1) and
ularly at advanced stages of reaction. As a result, the degradation of 11 (k11 = 8.3 × 109 M− 1 s− 1) in Table 1, it is clearly observed that the
RG12 with the UV/Chlorine process is more efficient in mildly acidic deactivation (consumption) of OH and Cl radicals is highly accelerated
• •
conditions (pH ~ 5). After 2 min, removal of 84%, 87.12%, 81.85%, in the presence of OCl compared to HOCl species [23]. Consequently,
−
81.26% and 55.61% were achieved for solution pH of 3, 5, 7, 9 and 11, the increase of solution pH increases the consumption of hydroxyl and
respectively. The passage from HOCl to OCl− with pH change between 3 chlorine radicals, which is reflected by the decrease in RG12 degrada
and 11 may be the key reason controlling the influence of pH (see Fig. S1 tion (Fig. 7). As a result, the degradation of RG12 with the UV/Chlorine
of the SM). Between pH 3 and 6, the HClO form is dominant while hy process is more efficient in mildly acidic conditions (pH ~ 5). The same
pochlorite (OCl− ) overweighed for pH superior to 8.5. At pH 7, chlorine tendency has been reported previously by several authors for different
is a mixture of both forms (77%/23% for the HOCl/ OCl− mixture). pollutants [19,25,31,45,46]. In addition, Feng et al. [47] and Jin et al.
The above degradation findings were supported by the radicals [47] have reported that in an acidic environment where HOCl is
concentration profiles (Fig. 8(a)–(d)) simulated under the best data dominant in the speciation of free chlorine, higher yields OH radicals
•
fitting of Fig. 7. It is found that the concentration of OH, Cl and Cl2− are generated through the UV/chlorine oxidation process.
• • •
goes down with the increase of solution pH, with maximum values for a In Fig. S6(a)–(d) of the SM, the predicted concentration profiles of
pH of 5 (Fig. 8(a)–(d)). Different behavior is observed for ClO radicals organic products (obtained from the direct reactions of OH and chlorine
• •
where a maximal concentration is obtained for pH 9 (Fig. 8(d)). At 5 s of radicals with RG12) are plotted for various initial solution pH (3, 5, 7, 9
reaction, the OH-steady concentration is 1.5 × 10− 12, 1.67 × 10− 12, and 11) for the same conditions in Fig. 8. It can be observed that the
•
respectively (Fig. 8(a)). For Cl radicals at 5 s, relatively lower molar increase of solution pH, with maximum values at pH 5. However, a
•
concentrations are obtained: 8.8 × 10− 13, 9.86 × 10− 13, 7.50 × 10− 13, different trend was observed for the evolution of Prod-ClO (Fig. S6(d)),
•
4.71 × 10− 13 and 5.35 × 10− 14 M for solution pH of 3, 5, 7, 9 and 11, where the production rate is proportional to the pH value. It can be
respectively (Fig. 8(b)). In contrast, higher concentrations are recorded noted that at the beginning of the process, the concentrations (Prod- OH,
•
for ClO radicals for the same range of solution pH: 1.78 × 10− 8, 1.87 × Prod-Cl and Prod-Cl2 and Prod-ClO ) increase very quickly, then, con
• • • •
10− 8, 1.76 × 10− 8, 2.23 × 10− 8 and 1.70 × 10− 8 M (Fig. 8(d)). There stant values are reached. It is also observed that the production rate of
fore, it is expected that the production of OH and Cl radicals is pro Prod- OH is relatively higher than that of Prod-Cl with concentrations of
• • • •
− 5 − 6
moted through the photoactivation of HOCl more than OCl− at solution the order of 10 and 10 M, respectively. This is owing to the fact that
the rate constant of the reaction of RG12 with OH (k65 = 1.2 × 1010 M− 1
•
s ) is higher than that of the reaction of RG12 with Cl (k66 = 2.1 × 109
− 1 •
− 1 − 1
M s ). In addition, the concentration of OH is higher than that of Cl ,
• •
Prod-Cl .
•
Fig. 8. Concentration profiles of OH and chlorine radicals for various initial Fig. 9. Effect of initial solution pH on the contribution of OH and chlorine
• •
solution pH (conditions: C0 = 16.3 µM, [chlorine]0 = 0.5 mM, pHi 3–11, Temp. radicals in the overall degradation rate of RG12 (conditions: C0 = 16.3 µM,
= 25 ◦ C). [chlorine]0 = 0.08–0.5 mM, pHi 5, Temp. = 25 ◦ C).
8
M.L. Djaballah et al. Journal of Photochemistry & Photobiology, A: Chemistry 439 (2023) 114557
whereas a low contribution is observed for Cl and ClO radicals against deduced that our modeling results are very acceptable. For example, at
• •
negligible participation for the case of Cl2− radicals. A similar tendency pH 9, our rate constant (7 × 10− 3 s− 1) is 1.75-times greater than that
•
is obtained by Fang et al. [39], where it has been found that the obtained experimentally by Bulman et al. (4 × 10− 3 s− 1); however, that
degradation of some selected taste and odor compounds is mainly due to obtained by Li et al. (12 × 10− 3 s− 1) is 3-folds greater than Bulman’s rate
the contribution of OH radicals with a relatively lower participation of constant. In addition, it should be indicated that the same variation
•
the reactive chlorine species (Cl , Cl2− and ClO ) in pH range from 6 to 8. tendency is observed in our results as well as in Bulman’s findings (in
• • •
However, the contribution of Cl was 7–9% for pH 3–9 and only 1.5% at crease in pH 6–9 and then goes down for pH 9–10).
•
instead of acidic ones. Modeling the oxidation kinetics of RG12 dye in UV/chlorine AOP
Finally, in Fig. 10(a) and (b), the rate constants of chlorine disap allowed a better understanding of the contribution of the different
pearance (a) and the steady-molar concentration of hydroxyl radicals (b) reactive species ( OH and chlorine radicals) in the overall degradation
•
are shown as functions of solution pH (for irradiation at 254 nm), from process, in addition to the determination of several key reaction rate
different works (including our results). The experimental data reported constants like those of direct chlorine photolysis and RG12 oxidation
in these figures are those of Bulman et al. [5], and all other data were with free radicals. Accordingly, the kinetics modeling clarified quanti
predicted theoretically. As it is shown in Fig. 10(b), a little agreement is tatively the link between the operating conditions (i.e., pH and chlorine
observed between our results and those of Bulman et al. [5], Chuang dosage), the free radical concentrations and the measured degradation
et al. [15], Guo et al. [17], Li et al. [48], and Sun et al. [10] for the rate kinetics. Thanks to the validated kinetics model, the second order-rate
constants of chlorine decay (overall rate). However, a satisfying agree constants of RG12 reaction with OH, Cl , Cl2− and ClO were 1.2 ×
• • • •
10 9 7 4 − 1 − 1
ment is observed between the experimental results of Chuang et al. [15] 10 , 2.1 × 10 , 1.26 × 10 and 6.12 × 10 M s , respectively.
and those of our work (Fig. 10(a)), especially in the pH range from 7 to Moreover, the specific reaction rate constants of HOCl and OCl−
10. On the other hand, in Fig. 10(b), an inversely proportional variation photolysis (k1# and k2#) were determined for different pH and diverse
is observed between the OH-steady concentration and the solution pH, chlorine dosages. Their values are in the range (0.81–6.9) × 10− 3 s− 1 for
•
where according to Chuang’s group [15], an intense decrease in hy k1, and (0.867–8.29) × 10− 3 s− 1 for k2. It was also found that among the
droxyl radicals concentration is observed proportionally with the in various formed reactive species, OH played an important role in the
•
crease of solution pH up to 10. Furthermore, Fig. 10(b) shows that in the RG12 degradation, with a contribution of ~ 85%, under various con
pH range from 5 to 8, a good agreement is obtained between the ditions of pH (3–11), initial chlorine concentration (0.08–0.6 mM) and
experimental work of Guo et al. [17] and our theoretical and experi for an initial dye concentration of 16.32 µM. The contribution of Cl , Cl2−
• •
mental findings for the variation of hydroxyl radicals concentration. and ClO is marginal compared to OH. This theoretical evidence has
• •
Above this pH value (from 8 to 10), all the obtained results (for [ OH]) in been confirmed experimentally using nitrobenzene as a specific and
•
Fig. 10(b) are in good accordance. selective scavenger for OH radical. Accordingly, the numerical model
•
It should be noted that due to the different operating conditions was able to predict the intensifying effect of chloride ions (Cl− ) in the
(nature of pollutant, chlorine concentration, water matrices…) and UV/chlorine process and confirmed the conversion of the main radicals
theoretical predicting models [Fig. 10(a)], the observed discrepancies responsible for RG12 degradation, from OH predominately (85%)
•
are logical and satisfying because as it can be seen in Fig. 10(a), our without Cl− to OH (69%) and Cl2− (24%) in the presence of 10 mM of
• •
findings are in very good concordance especially with those of Bulman Cl− .
et al. (pH 8–9), Chuang et al. and Guo et al. (pH 5–7). However, a little In conclusion, even though it was validated using only the RG12
agreement is retrived between our results and those obtained by Li et al. degradation profile, the model is very accurate because it is framed by
and Sun et al.; whereas, even in this case, our results are very acceptable. various severe conditions that can be summarized in the following
In another hand, referencing all the theoretical results to the experi points:
mental findings of Bulman et al. (red circles) in Fig. 10(a), it can clearly
Fig. 10. Overall rate constants of chlorine disappearance (a) and hydroxyl radical concentration (steady) vs pH for various works. The experimental data are those of
Bulman et al. [5], and all other data were predicted theoretically by Bulman et al. [5], Chuang et al. [15], Guo et al. [17], Li et al. [48].and Sun et al. [10].
9
M.L. Djaballah et al. Journal of Photochemistry & Photobiology, A: Chemistry 439 (2023) 114557
• All predicted rate constants (i.e., of chlorine photolysis or RG12 re [2] S.D. Richardson, T.A. Ternes, Water Analysis: Emerging Contaminants and Current
Issues, Anal. Chem. 90 (2018) 398–428, https://doi.org/10.1021/acs.
action with free radicals) should be supported by literature data,
analchem.7b04577.
• The predicted rate constants excellently fit the RG12 degradation [3] D.J. Fairbairn, W.A. Arnold, B.L. Barber, E.F. Kaufenberg, W.C. Koskinen, P.
(improvement) in the presence of chloride ions (Fig. 1), J. Novak, P.J. Rice, D.L. Swackhamer, Contaminants of Emerging Concern: Mass
• The predicted rate constants excellently fit the RG12 degradation Balance and Comparison of Wastewater Effluent and Upstream Sources in a Mixed-
Use Watershed, Environ. Sci. Technol. 50 (2016) 36–45, https://doi.org/10.1021/
(inhibition) in the presence of nitrobenzene (Fig. 1), acs.est.5b03109.
[4] S. Merouani, O. Hamdaoui, Sonochemical treatment of textile wastewater, in: M.P.
Nevertheless, using additional experimental data (for example, Inamuddin, A. Asiri (Eds.), Water Pollut. Remediat. Photocatal., Springer-Nature
Switzerland, 2021. https://doi.org/10.1007/978-3-030-54723-3_5.
concentration profiles of chlorine and RG12-degradation intermediates) [5] D.M. Bulman, S.P. Mezyk, C.K. Remucal, The Impact of pH and Irradiation
to estimate the unknown rate constant can strengthen the quality of our Wavelength on the Production of Reactive Oxidants during Chlorine Photolysis,
constructed model and make it more reliable. Despite this, the current Environ. Sci. Technol. 53 (2019) 4450–4459, https://doi.org/10.1021/acs.
est.8b07225.
model has consistently shown good RG12 degradation profile trends [6] P. Neta, R.E. Huie, A.B. Ross, A.B.R.P. Neta, R.E. Huie, Rate constants for reactions
across a range of experimental conditions. Additionally, it was able to of inorganic radicals in aqueous solution, J. Phys. Chem. Ref. Data. 17 (1988)
explain the influence of pH and chlorine concentration based on how 1027–1284, https://doi.org/0047-2689/88/031027-258/$21.00.
[7] M.I. Stefan, Advanced oxidation processes for water treatment: Fundamentals and
they affected the radicals concentration. applications, IWA Publishing, London, UK, 2017.
[8] G. Boczkaj, A. Fernandes, Wastewater treatment by means of advanced oxidation
processes at basic pH conditions: A review, Chem. Eng. J. 320 (2017) 608–633,
Funding
https://doi.org/10.1016/j.cej.2017.03.084.
[9] M. Antonopoulou, E. Evgenidou, D. Lambropoulou, I. Konstantinou, A review on
This study was funded by The Ministry of Higher Education and advanced oxidation processes for the removal of taste and odor compounds from
Scientific Research of Algeria (project No. A16N01UN250320220002) aqueous media, Water Res. 53 (2014) 215–234, https://doi.org/10.1016/j.
watres.2014.01.028.
and the General Directorate of Scientific Research and Technological [10] P. Sun, W.-N.-N. Lee, R. Zhang, C.-H.-H. Huang, Degradation of DEET and caffeine
Development (GD-SRTD). under UV/Chlorine and simulated sunlight/Chlorine conditions, Environ. Sci.
Technol. 50 (2016) 13265–13273, https://doi.org/10.1021/acs.est.6b02287.
[11] J. De Laat, M. Stefan, UV/chlorine process, in: M.I. Stefan (Ed.), Adv. Oxid.
CRediT authorship contribution statement Process. Water Treat. Fundam. Appl., IWA Publishing, London, UK, 2017: pp.
383–428.
[12] R. Yin, Z. Zhong, L. Ling, C. Shang, The fate of dichloroacetonitrile in UV/Cl2 and
Mohamed Larbi Djaballah: Investigation, Visualization, Valida UV/H2O2 processes: Implications on potable water reuse, Environ. Sci. Water Res.
tion, Software, Data curation, Conceptualization. Aouattef Belghit: Technol. 4 (2018) 1295–1302, https://doi.org/10.1039/c8ew00195b.
Data curation, Investigation, Methodology. Aissa Dehane: Writing – [13] C.K. Remucal, D. Manley, Emerging investigators series: The efficacy of chlorine
photolysis as an advanced oxidation process for drinking water treatment, Environ.
review & editing, Investigation, Formal analysis, Data curation. Sli Sci. Water Res. Technol. 2 (2016) 565–579, https://doi.org/10.1039/c6ew00029k.
mane Merouani: Writing – review & editing, Writing – original draft, [14] H. Dong, Z. Qiang, J. Hu, J. Qu, Degradation of chloramphenicol by UV/chlorine
Validation, Supervision, Project administration, Investigation, Formal treatment: Kinetics, mechanism and enhanced formation of halonitromethanes,
Water Res. 121 (2017) 178–185, https://doi.org/10.1016/j.watres.2017.05.030.
analysis, Data curation, Conceptualization. Oualid Hamdaoui: Formal
[15] Y.-H.-H. Chuang, S. Chen, C.J. Chinn, W.A. Mitch, Comparing the UV/
analysis, Project administration, Supervision, Visualization. Mutha monochloramine and UV/Free Chlorine advanced oxidation processes (AOPs) to
pandian Ashokkumar: Visualization, Investigation, Formal analysis, the UV/Hydrogen Peroxide AOP under scenarios relevant to potable reuse,
Environ. Sci. Technol. 51 (2017) 13859–13868, https://doi.org/10.1021/acs.
Data curation.
est.7b03570.
[16] M.J. Watts, K.G. Linden, Chlorine photolysis and subsequent OH radical production
during UV treatment of chlorinated water, Water Res. 41 (2007) 2871–2878,
Declaration of Competing Interest https://doi.org/10.1016/j.watres.2007.03.032.
[17] K. Guo, Z. Wu, C. Shang, B. Yao, S. Hou, X. Yang, W. Song, J. Fang, Radical
Chemistry and Structural Relationships of PPCP Degradation by UV/Chlorine
The authors declare that they have no known competing financial Treatment in Simulated Drinking Water, Environ. Sci. Technol. 51 (2017)
interests or personal relationships that could have appeared to influence 10431–10439, https://doi.org/10.1021/acs.est.7b02059.
[18] Z. Wu, K. Guo, J. Fang, X.X. Yang, H. Xiao, S. Hou, X. Kong, C. Shang, X.X. Yang,
the work reported in this paper. F. Meng, L. Chen, Factors affecting the roles of reactive species in the degradation
of micropollutants by the UV/chlorine process, Water Res. 126 (2017) 351–360,
Data availability https://doi.org/10.1016/j.watres.2017.09.028.
[19] Z. Guo, Y. Lin, B. Xu, H. Huang, T. Zhang, F. Tian, N. Gao, Degradation of
chlortoluron during UV irradiation and UV / chlorine processes and formation of
Data will be made available on request. disinfection by-products in sequential chlorination, Chem. Eng. J. 283 (2016)
412–419, https://doi.org/10.1016/j.cej.2015.07.074.
[20] W. Wang, X. Zhang, Q. Wu, Y. Du, H. Hu, Degradation of natural organic matter by
Acknowledgements UV / chlorine oxidation: Molecular decomposition , formation of oxidation
byproducts and cytotoxicity, 124 (2017) 251–258. https://doi.org/10.1016/j.
watres.2017.07.029.
This study was supported by The Ministry of Higher Education and
[21] A.-Q. Wang, Y.-L. Lin, B. Xu, C.-Y. Hu, S.-J. Xia, T.-Y. Zhang, W.-H. Chu, N.-Y. Gao,
Scientific Research of Algeria (project No. A16N01UN250320220002) Kinetics and modeling of iodoform degradation during UV / chlorine advanced
and the General Directorate of Scientific Research and Technological oxidation process, Chem. Eng. J. 323 (2017) 312–319.
Development (GD-SRTD). [22] W.L. Wang, Q.Y. Wu, N. Huang, T. Wang, H.Y. Hu, Synergistic effect between UV
and chlorine (UV/chlorine) on the degradation of carbamazepine: Influence factors
and radical species, Water Res. 98 (2016) 190–198, https://doi.org/10.1016/j.
Appendix A. Supplementary data watres.2016.04.015.
[23] J. Fang, Y. Fu, C. Shang, The roles of reactive species in micropollutant degradation
in the UV/free chlorine system, Environ. Sci. Technol. 48 (2014) 1859–1868,
Supplementary data to this article can be found online at https://doi. https://doi.org/10.1021/es4036094.
org/10.1016/j.jphotochem.2023.114557. [24] X. Kong, Z. Wu, Z. Ren, K. Guo, S. Hou, Z. Hua, X. Li, J. Fang, Degradation of lipid
regulators by the UV/chlorine process: Radical mechanisms, chlorine oxide radical
(ClO•)-mediated transformation pathways and toxicity changes, Water Res. 137
References (2018) 242–250, https://doi.org/10.1016/j.watres.2018.03.004.
[25] Y. Xiang, J. Fang, C. Shang, Kinetics and pathways of ibuprofen degradation by the
UV/chlorine advanced oxidation process, Water Res. 90 (2016) 301–308, https://
[1] J.R. Masoner, D.W. Kolpin, E.T. Furlong, I.M. Cozzarelli, J.L. Gray, Landfill
doi.org/10.1016/j.watres.2015.11.069.
leachate as a mirror of today’s disposable society: Pharmaceuticals and other
[26] K. Guo, Z. Wu, J. Fang, UV-based advanced oxidation process for the treatment of
contaminants of emerging concern in final leachate from landfills in the
pharmaceuticals and personal care products, in: Arturo J. Hernández-Maldonado,
conterminous United States, Environ. Toxicol. Chem. 35 (2016) 906–918, https://
doi.org/10.1002/etc.3219.
10
M.L. Djaballah et al. Journal of Photochemistry & Photobiology, A: Chemistry 439 (2023) 114557
Lee Blaney (Eds.), Contam. Emerg. Concern Water Wastewater, Elsevier Inc., 2020: Efficiency, mechanism and toxicity evaluation, Sci. Total Environ. 760 (2021),
pp. 367–408. https://doi.org/10.1016/B978-0-12-813561-7.00010-9. 144304, https://doi.org/10.1016/j.scitotenv.2020.144304.
[27] W.L. Wang, Q.Y. Wu, Z.M. Li, Y. Lu, Y. Du, T. Wang, N. Huang, H.Y. Hu, Light- [44] M.J. Watts, E.J. Rosenfeldt, K.G. Linden, Comparative OH radical oxidation using
emitting diodes as an emerging UV source for UV/chlorine oxidation: UV-Cl2 and UV-H 2O2 processes, J. Water Supply Res. Technol. - AQUA. 56 (2007)
Carbamazepine degradation and toxicity changes, Chem. Eng. J. 310 (2017) 469–477, https://doi.org/10.2166/aqua.2007.028.
148–156, https://doi.org/10.1016/j.cej.2016.10.097. [45] P.T. Biyela, R. Hodon, A. Brown, A. Alum, M. Abbaszadegan, B.E. Rittmann, Low-
[28] J. Deng, G. Wu, S. Yuan, X. Zhan, W. Wang, Z.H. Hu, Ciprofloxacin degradation in pressure UV/Cl2 for advanced oxidation of taste and odor, J. Am. Water Works
UV/chlorine advanced oxidation process: Influencing factors, mechanisms and Assoc. 104 (2012) 49–50, https://doi.org/10.5942/jawwa.2012.104.0006.
degradation pathways, J. Photochem. Photobiol. A Chem. 371 (2019) 151–158, [46] S.-W. Nam, Y. Yoon, D.-J. Choi, K.-D. Zoh, Degradation characteristics of
https://doi.org/10.1016/j.jphotochem.2018.10.043. metoprolol during UV/chlorination reaction and a factorial design optimization,
[29] M. Pan, Z. Wu, C. Tang, K. Guo, Y. Cao, J. Fang, Comparative study of naproxen J. Hazard. Mater. 285 (2015) 453–463, https://doi.org/10.1016/j.
degradation by the UV/chlorine and the UV/H2O2 advanced oxidation processes, jhazmat.2014.11.052.
Environ. Sci. Water Res. Technol. 4 (2018) 1219–1230, https://doi.org/10.1039/ [47] Y. Feng, D.W. Smith, J.R. Bolton, Photolysis of aqueous free chlorine species (HOCl
c8ew00105g. and OCl–) with 254 nm ultraviolet light, J. Environ. Eng. Sci. 6 (2007) 277–284,
[30] Z. Wu, J. Fang, Y. Xiang, C. Shang, X. Li, F. Meng, X. Yang, Roles of reactive https://doi.org/10.1139/s06-052.
chlorine species in trimethoprim degradation in the UV/chlorine process: Kinetics [48] W. Li, T. Jain, K. Ishida, H. Liu, A mechanistic understanding of the degradation of
and transformation pathways, Water Res. 104 (2016) 272–282, https://doi.org/ trace organic contaminants by UV/hydrogen peroxide, UV/persulfate and UV/free
10.1016/j.watres.2016.08.011. chlorine for water reuse, Environ. Sci. Water Res. Technol. 3 (2017) 128–138,
[31] L. Qin, Y.L. Lin, B. Xu, C.Y. Hu, F.X. Tian, T.Y. Zhang, W.Q. Zhu, H. Huang, N. https://doi.org/10.1039/c6ew00242k.
Y. Gao, Kinetic models and pathways of ronidazole degradation by chlorination, [49] S. Zhou, W. Zhang, J. Sun, S. Zhu, K. Li, X. Meng, J. Luo, Z. Shi, D. Zhou, J.
UV irradiation and UV/chlorine processes, Water Res. 65 (2014) 271–281, https:// C. Crittenden, Oxidation mechanisms of the UV/Free chlorine process: Kinetic
doi.org/10.1016/j.watres.2014.07.041. modeling and quantitative structure activity relationships, Environ. Sci. Technol.
[32] K. Guo, Z. Wu, C. Chen, J. Fang, UV/Chlorine Process: An Efficient Advanced 53 (2019) 4335–4345, https://doi.org/10.1021/acs.est.8b06896.
Oxidation Process with Multiple Radicals and Functions in Water Treatment, Acc. [50] B.M. Matthew, C. Anastasio, A chemical probe technique for the determination of
Chem. Res. 55 (2022) 286–297, https://doi.org/10.1021/acs.accounts.1c00269. reactive halogen species in aqueous solution: Part 2 - Chloride solutions and mixed
[33] F.Z. Meghlaoui, S. Merouani, O. Hamdaoui, M. Bouhelassa, M. Ashokkumar, Rapid bromide/chloride solutions, Atmos. Chem. Phys. 6 (2006) 2439–2451, https://doi.
catalytic degradation of refractory textile dyes in Fe (II)/chlorine system at near org/10.5194/acp-6-2439-2006.
neutral pH: Radical mechanism involving chlorine radical anion (Cl⋅-2 )-mediated [51] G.G. Jayson, B.J. Parsons, A.J. Swallow, Some simple, highly reactive, inorganic
transformation pathways and impact of environmental matrices, Sep. Purif. chlorine derivatives in aqueous solution. Their formation using pulses of radiation
Technol. 227 (2019), 115685, https://doi.org/10.1016/j.seppur.2019.115685. and their role in the mechanism of the Fricke dosimeter, J. Chem. Soc., Faraday
[34] R. Yuan, S.N. Ramjaun, Z. Wang, J. Liu, Concentration profiles of chlorine radicals Trans. 1 69 (0) (1973) 1597.
and their significances in •OH-induced dye degradation: Kinetic modeling and [52] X.-Y. Yu, J.R. Barker, Hydrogen peroxide photolysis in acidic aqueous solutions
reaction pathways, Chem. Eng. J. 209 (2012) 38–45, https://doi.org/10.1016/j. containing chloride Ions. I. Chemical mechanism, J. Phys. Chem. A. 107 (2003)
cej.2012.07.127. 1313–1324, https://doi.org/10.1021/jp0266648.
[35] R. Yuan, Z. Wang, Y. Hu, B. Wang, S. Gao, Probing the radical chemistry in UV/ [53] U.K. Klaning, T. Wolff, Laser flash photolysis of HCIO, CIO, HBrO, and BrO− in
persulfate-based saline wastewater treatment: Kinetics modeling and byproducts aqueous solution. Reactions of Cl− and Br− atoms, Berichte Der
identification, Chemosphere 109 (2014) 106–112, https://doi.org/10.1016/j. Bunsengesellschaft/Physical Chem, Chem. Phys. 89 (1985) 243–245, https://doi.
chemosphere.2014.03.007. org/10.1002/bbpc.19850890309.
[36] L.H. Chia, X. Tang, L.K. Weavers, Kinetics and mechanism of photoactivated [54] B.H.J. Bielski, D.E. Cabelli, R.L. Arudi, A.B. Ross, Reactivity of HO2/O2- radicals in
periodate reaction with 4-chlorophenol in acidic solution, Environ. Sci. Technol. 38 aqueous solution, J. Phys. Chem. Ref. Data. 14 (4) (1985) 1041–1100.
(2004) 6875–6880, https://doi.org/10.1021/es049155n. [55] A.E. Grigor’ev, I.E. Makarov, A.K. Pikaev, Formation of Cl−2 in the bulk of solution
[37] S. Padmaja, S.A. Madison, Hydroxyl radical-induced oxidation of azo dyes : a pulse during radiolysis of concentrated aqueous solutions of chlorides, Khimiya Vysok
radiolysis study, J. Phys. Org. Chem. 226 (1999) 221–226. Ehnergij 21 (1987) 123–126.
[38] G.V. Buxton, C.L. Greenstock, W.P. Helman, A.B. Ross, Critical review of rate [56] K. Hasegawa, P. Neta, Rate constants and mechanisms of reaction of chloride (Cl-2)
constants for reactions of hydrated Electrons, hydrogen atoms and hydroxyl radicals, J. Phys. Chem. 82 (1978) 854–857, https://doi.org/10.1021/
radicals (•OH/O-) in aqueous solution, J. Phys. Chem. Ref. Data. 17 (1988) j100497a003.
515–886, https://doi.org/0047-2689/88/020513-374$20.00. [57] A.V. Gogolev, I.E. Makarov, A.K. Pikaev, Pulse radiolysis of strong hydrochloric
[39] J. Fang, J. Liu, C. Shang, C. Fan, Degradation investigation of selected taste and acid, Khimiya Vysok. Ehnergij. 18 (1984) 496–501.
odor compounds by a UV/chlorine advanced oxidation process, Int. J. Environ. [58] T.P. Zhestkova, A.K. Pikaev, Destruction rate of Cl−2 anion-radicals during pulse
Res. Public Health 15 (2018) 284, https://doi.org/10.3390/ijerph15020284. radiolysis of concentrated aqueous lithium chloride solutions, Russ. Chem. Bull. 23
[40] Z.B. Alfassi, R.E. Huie, S. Mosseri, P. Neta, Kinetics of one-electron oxidation by the (4) (1974) 877–878.
ClO radical, Int. J. Radiat. Appl. Instrumentation. Part C, Radiat. Phys. Chem. 32 [59] W.J. McElroy, A laser photolysis study of the reaction of sulfate(1-) with chloride
(1988) 85–88, https://doi.org/10.1016/1359-0197(88)90018-5. and the subsequent decay of chlorine(1-) in aqueous solution, J. Phys. Chem. 94
[41] M.L. Djaballah, S. Merouani, H. Bendjama, O. Hamdaoui, Development of a free (1990) 2435–2441, https://doi.org/10.1021/j100369a044.
radical-based kinetics model for the oxidative degradation of chlorazol black in [60] T.X. Wang, D.W. Margerum, Kinetics of reversible chlorine hydrolysis:
aqueous solution using periodate photoactivated process, J. Photochem. Photobiol. Temperature dependence and general-acid/base-assisted mechanisms, Inorg.
A Chem. 408 (2020), 113102. Chem. 33 (1994) 1050–1055, https://doi.org/10.1021/ic00084a014.
[42] J. Sun, D. Kong, E. Aghdam, J. Fang, Q. Wu, J. Liu, Y. Du, X. Yang, C. Shang, The [61] E. Bjergbakke, S. Navaratnam, B.J. Parsons, A.J. Swallow, Reaction between
influence of the UV/chlorine advanced oxidation of natural organic matter for hydroperoxo radicals and chlorine in aqueous solution, J. Am. Chem. Soc. 103
micropollutant degradation on the formation of DBPs and toxicity during post- (1981) 5926–5928, https://doi.org/10.1021/ja00409a059.
chlorination, Chem. Eng. J. 373 (2019) 870–879, https://doi.org/10.1016/j. [62] Z. Zuo, Y. Katsumura, K. Ueda, K. Ishigure, Reactions between some inorganic
cej.2019.05.096. radicals and oxychlorides studied by pulse radiolysis and laser photolysis, J. Chem.
[43] T. Yang, J. Mai, S. Wu, C. Liu, L. Tang, Z. Mo, M. Zhang, L. Guo, M. Liu, J. Ma, UV/ Soc., Faraday Trans, Faraday Trans. 93 (1997) 1885–1891, https://doi.org/
chlorine process for degradation of benzothiazole and benzotriazole in water: 10.1039/A700256D.
11