Some Issues Limiting Photo (Cata) Lysis Application in Water Pollutant Control - A Critical Review From Chemistry Perspectives

Water Research 174 (2020) 115605
Contents lists available at ScienceDirect
Water Research
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Review
Some issues limiting photo(cata)lysis application in water pollutant

control: A critical review from chemistry perspectives
Lei Wang a, Qi Zhang a, Baiyang Chen a, *, Yinan Bu a, Yi Chen a, Jun Ma b,
Fernando L. Rosario-Ortiz c, Rongshu Zhu a, **
a
Shenzhen Key Laboratory of Organic Pollution Prevention and Control, Harbin Institute of Technology, Shenzhen, 518055, China
b
State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin, 150090, China
c
Department of Civil, Environmental and Architectural Engineering, 428 UCB, University of Colorado, Boulder, CO, 80309, United States
a r t i c l e i n f o a b s t r a c t
Article history: For decades, photolysis and photocatalysis have been touted as promising environment-benign and
Received 22 October 2019 robust technologies to degrade refractory pollutants from water. However, extensive, large-scale engi-
Received in revised form neering applications remain limited now. To facilitate the technology transfer process, earlier reviews
5 February 2020
have advocated to developing more cost-effective and innocuous materials, maximizing efficiency of
Accepted 10 February 2020
Available online 13 February 2020
photon usage, and optimizing photoreactor systems, mostly from material and reactor improvement
perspectives. However, there are also some fundamental yet critical chemistry issues in photo(cata)lysis
processes demanding more in-depth understanding and more careful consideration. Hence, this review
Keywords:
Photolysis
summarizes some of these challenges. Of them, the first and paramount issue is the interference of
Photocatalysis coexisting compounds, including dissolved organic matter, anions, cations, and spiked additives. Sec-
Kinetics ondly, considerable concerns are pointed to the formation of undesirable reaction by-products, such as
Mechanisms halogenated, nitrogenous, and sulfur-containing compounds, which might increase instead of reduce
Radicals toxicity of water if inadequate fluence and catalyst/additive are supplied due to time and cost constraints.
Lastly, a critical issue lies in the uncertainty of current approaches used for identifying and quantifying
radicals, especially when multiple radicals coexist together under changing and interconvertible con-
ditions. The review hence highlights the needs to better understand these fundamental chemistry issues
and meanwhile calls for more delicate design of experiments in future studies to overcome these
barriers.
© 2020 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Interference from coexisting compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Interferences from organics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Interferences from inorganics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. Impacts from additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Formation of undesirable byproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1. Sequential UV-redox processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2. Simultaneous UV-redox processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4. Uncertainty in radicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.1. Uncertain radicals’ transformation and interconversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.2. Uncertain radicals’ determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.3. Limited H2O2 information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (B. Chen), [email protected] (R. Zhu).
https://doi.org/10.1016/j.watres.2020.115605
0043-1354/© 2020 Elsevier Ltd. All rights reserved.
2 L. Wang et al. / Water Research 174 (2020) 115605
5. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Nomenclature and Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1. Introduction pollutant with catalyst, and low sensitivity of photocatalyst at

visible light region. To overcome these barriers, the measures
For several decades, disinfection of pathogens and treatment of proposed include reducing the radicals recombination (e.g., by
aqueous pollutants by ultraviolet (UV)-based technologies have introducing novel catalyst), increasing the contact of pollutant with
been of interests to numerous environmental scientists and engi- catalyst (e.g., combining TiO2 with activated carbon), and extending
neers (Oppenla €nder, 2003). A number of UV-based processes, spectral range of catalysts (e.g., by doping N element). Meanwhile,
including vacuum UV (VUV), UV-ozone (UVeO3), UV-hydrogen some researches highlighted the importance of catalyst recovery
peroxide (UVeH2O2), UV-Fenton (UV-ferrous-H2O2), UV-titanium and photoreactor design (Chong et al., 2010; Ahmad et al., 2016).
(UVeTiO2), UV-persulfate (UVeS2O2 8 ), UV-chlorine (UVeCl2), and Oriented by these strategies, it is expected that numerous studies
UV-sulfite (UVeSO2- 3 ), have been examined in bench, pilot, and full- will be motivated to explore more robust, innocuous, and economic
scale studies (Miklos et al., 2018). Depending on the types of lights materials in the future, mostly from material and reactor
and the availability of additive and/or catalyst, UV-based technol- improvement perspectives.
ogies can general be classified into three groups: 1) light-only However, there are also some fundamental yet critical chemistry
photolysis (e.g., UV, VUV, or sunlight), which does not employ issues commonly encountered in photolysis and photocatalysis
any additive/catalyst to degrade contaminants; 2) photooxidation, processes that demand more thorough understanding and more
which degrades compounds by adding oxidizing additive/catalyst careful considerations, e.g., the complicated effects of pH on system
to produce oxidative species like hydroxyl radical (OH), sulfate performance and the mechanisms responsible for radicals’ forma-
radical (SO4-), and chlorine radical (Cl); and 3) photoreduction, tion and inhibition (Table 1). Therefore, this review intends to
which removes contaminants by UV-induced reductive radicals like summarize some of chemistry challenges currently limiting pho-
hydrated electron (e aq), hydrogen atom (H), and superoxide anion to(cata)lysis applications. Although many of them are difficult to
radical (O2-). solve at current stage, we hope to raise a more in-depth recogni-
Because of the outstanding performance and operating con- tion, avoid some misuses and misinterpretations, and therefore
venience, some UV-based advanced oxidation processes (AOPs) provoke more novel solutions in the future. The general topics of
have been widely accepted in several niche arenas, such as pro- interests are outlined in Fig. 1.
ducing ultrapure water (Lee et al., 2016) and analyzing aqueous
elements (Scheuer et al., 1995; Golimowski and Golimowska, 2. Interference from coexisting compounds
1996; Bendicho et al., 2010) embedded in organic compounds
(e.g., nitrogen, halogen, and sulfur) and coordinated metals (e.g., For any AOP to be used in real water, a common challenge is the
cadmium, arsenic, and nickel). For example, UV-S2O2 8 was often impairment of degradation efficiency by coexisting compounds,
used for analysis of total organic carbon (TOC) (Yoon et al., 2018); such as dissolved organic matter (DOM) and inorganic ions. Such
medium pressure mercury lamp-induced UV (MPUV) was once impairments may either be caused by screening of UV photon,
employed for detection of total nitrogen (TN), total phosphorous undesired competition between UV or radicals with non-targeted
(TP), and TOC (Armstrong and Tibbitts, 1968); MPUV-H2O2 was compound, and/or inhibition of radical formation (Table 1).
applied for measurement of TN (Bronk et al., 2000), TP, and iron Regardless of reason, they could decrease system performance and
(Henriksen, 1970); UV-O3 was used for chemical oxygen demand increase cost, eventually making the efficiency less appealing.
analysis (Yu et al., 2016); and VUV was employed for determina- Hence, a thorough and systematic assessment of the impacts of
tion of TOC and TN (Huber et al., 2011). More recently, some common aqueous components on the photo(cata)lysis efficiency is
studies used VUV as a pretreatment step to assist detection of total necessary. Here below shows some examples of contradictory or
organic halogen (TOX) (Bu et al., 2018; Zhang et al., 2018) and confusing results reported before.
dissolved organic nitrogen (Zhu et al., 2015; Chen et al., 2019),
hence further expanding the horizons of UV technology in
analytical chemistry area. 2.1. Interferences from organics
However, up to date, extensive, large-scale applications of UV-
based technologies on pollution control in engineering waters Usually, the presence of DOM can result in significant inhibition
(e.g., drinking, municipal, industrial, and swimming pool waters) of photochemical processes, either by light screening effect or via
remain limited. The abundance of published paper and tested scavenging of OH generated by photosensitizers. Using atrazine as
compounds apparently do not alien with the scarcity of photo(cata) a practical example, although UV-S2O2 8 was more powerful than
lysis practices. The reason of the gap is largely attributed to low UV-H2O2 in degrading atrazine when it was treated alone, UV-H2O2
light-usage efficiency of materials and reactors, namely unsatisfy- outperformed UV-S2O2 8 when a mixture of compounds (including
ing cost-effectiveness (Pichat, 2015; Ahmad et al., 2016). To facili- atrazine, methyl tert-butyl ether, cis-dichloroethane, 1,4-dioxane
tate the technology transfer process from a technical hype into a and 1,1,1-trichloroethane) were treated together (Antoniou and
real hope, some explanations are provided and some strategic Andersen, 2015). The efficiency discrepancy indicates that the
countermeasures are advocated (Loeb et al., 2018). For example, susceptibility of each compound was subject to influences by other
Pichat (2015) pointed out three barriers related to material’s low coexisting organic compounds. Meanwhile, it illustrates the diffi-
performance, including wasted radicals, insufficient contact of culty in selecting the best system to treat target compound under
different conditions.
L. Wang et al. / Water Research 174 (2020) 115605 3
Table 1
A summary of key radicals and reactions occurring in typical UV-induced processes (k Unit: M1 s1).
VUV UV-TiO2 UV-H2O2
Key reactions H2O þ VUV/e þ

aqþOH þ H /OH þ H TiO2þhn/e-cbþ hþ vb H2O2þhn/2OH (9)
O2þVUV/2O hþvbþH2O/OH þ H
þ
HO2 þ hn/OH (10)
þ
O2þO4O3 hvbþOH /OH H2O2þOH/HO2 þ H2O (11)
O3þOH/HO 2 þ O2 (1) e-cbþ O2/O2- (6) 2OH/H2O2 (4)
O3þHO 2 /HO2þO3 2)
(
2e-cbþ O2þ2Hþ/H2O2 HO2 þ H2O2/O2þOH þ H2O (12)

-
O3þO2 /O3 þ O2 (3) e-cbþ H2O2/OH þ OH HO2 þ O
2 /O2 þ HO2 (13)
O3þOH/HO2þO2 O2- þ Hþ4HO2 pKa ¼ 4.69 HO2 þ OH/O2þ H2O (14)
2OH/H2O2 (4) O2- þ H2O2/O2þOH þ OH (7) O
2 þOH/O2þOH
(
15)
O3þH2O2/HO2þOH þ O2 (5) 2HO2/O2þH2O2 (8) HO2 þOH/HO2 þ OH (16)

References (Lovato et al., 2011; Moussavi and Rezaei, 2017) (Mills and Le Hunte, 1997; Carp et al., 2004) Chuang et al. (2016)
UV/VUV-S2O2-
8 UV-SO2-
3 UV-Cl2
Keyreactions S2O2 n
8 þ h /2SO4
-
SO32- þ hn/SO3- þ e-aq ClO þ hn/2ClþO-
SO4- þ SO4-/S2O2 8 (17) HSO3- þ hn/SO3- þ H HOCl þ hn/ClþOH
SO4- þ S2O2 -
8 /S2O8 þ SO4 (18)
2
e-aqþ H2O/HþOH (23) Cl þ OH/ClOH- (29)
SO4- þ OH4SO2 4 þOH (19) e-aqþ Hþ/H (24) ClOH- þ Hþ / Cl þ H2O (30)
SO4-þOH/HSO
5 /HSO4 þ O2 (20) e-aqþ HSO3-/HþSO3- (25) ClOH-/Cl þ OH (31)

S2O28 þOH/OH þ S2O8 (21)
-
HþOH/e-aqþ H2O (26) Cl þ Cl/Cl2- (32)

S2O28 þ2eaq/2SO4
2-
HþO2/HO2 (27) Cl þ Cl2-/Cl þ Cl2 (33)

SO24 þ eaq/S
2
þ2O2 SO3- þ O2/SO5- Cl þ H2O2/HþþCl þ HO2 (34)
e-aqþ S2O2
8 /SO 2 -
4 þ SO4 (22) SO3- þ SO3- þ H2O/SO32- þ SO42-þ2Hþ (28) Cl þH2O/OHCl þ Hþ (35)
Cl þOH/OHCl (36)
Cl þH2O/Cl(H2O) (37)
Cl þHOCl/OCl þ HþþCl (38)
References Moussavi and Rezaei (2017) Li et al. (2012) (Chuang et al., 2017; Minakata et al., 2017)
k1 ¼ 7 104; k2 ¼ 2.2 109; k3 ¼ 1.6 1012; k4 ¼ 5.5 109; k5 ¼ 1 102; k6 ¼ 2 1010; k7 ¼ 1.3 101; k8 ¼ 8.3 105; k9 ¼ 2.5 105; k10 ¼ 3.3 104; k11 ¼ 2.7 107;
k12 ¼ 3; k13 ¼ 9.7 107; k14 ¼ 6.6 109; k15 ¼ 7 109; k16 ¼ 7.5 109; k17 ¼ 0.16e8.1 108; k18 ¼ 1.5 103e1.2 106; k19 ¼ 1.4e7.3 107; k20 ¼ 1e10 109;
k21 ¼ 1.2e1.4 107; k22 ¼ 1.2 1010; k23 ¼ 1.9 101; k24 ¼ 2.3 1010; k25 ¼ 2.0 107; k26 ¼ 2.2 107; k27 ¼ 1 1010; k28 ¼ 4 108; k29 ¼ 4.3 109; k30 ¼ pKa ¼ 5.3;
k31 ¼ 6.1 109 s1; k32 ¼ 6.5e8.5 109; k33 ¼ 2.1 109; k34 ¼ 2.0 109; k35 ¼ 1.6 105; k36 ¼ 1.8 1010; k37 ¼ 2.5 105; k38 ¼ 2.5 109.
Fig. 1. Some chemistry barriers hindering application of photo(cata)lysis in water discussed in this review.
Earlier studies have reported second-order reaction rate con- and EfOM (Thomas-Smith and Blough, 2001; Glover and Rosario-
stants (k) for a variety of surface water-derived natural organic Ortiz, 2013; Sun et al., 2015; Rosario-Ortiz and Canonica, 2016),
matter (NOM) and wastewater-derived effluent organic matter which are capable of facilitating compound degradations during
(EfOM) reacting with OH, which ranged from 1.39 to irradiation process (Table 2). The coexistence of ROS scavenging
2.18 108 M1 s1 for NOM isolates (Westerhoff et al., 2007) and and generating effects is apparently inconsistent, meaning that the
2.0 to 4.0 108 M1 s1 for EfOM (Keen et al., 2014), attesting that diversity of NOM and EfOM property and quantity may complicate
both NOM and EfOM could inhibit photo(cata)lysis significantly by the treatability of UV processes and therefore make their applica-
acting as OH scavengers for most of target compounds (Zhu et al., tions unpredictable to broad environmental conditions. As for
2007; Wu et al., 2016; Lv et al., 2017). However, there are also photocatalytic process, since photocatalysts are more powerful
studies reporting considerable production of reactive oxygen spe- than NOM/EfOM in generating radicals, it is difficult for NOM/EfOM
cies (ROSs), such as singlet oxygen (1O2), O2-, and H2O2 from NOM to bring additional beneficial effects to the system; therefore, the
4
Table 2
A summary of ε254/185 of typical compounds in water and their k with typical radicals (Unit: M1 s1).
ε254/ε185 (M1cm1) SO4- (2.5e3.1 eV) OH (1.9e2.7 eV) Cl/ClOH (2.4 eV) HO2/O2- (0.33 eV) H (2.3 ~ 2.1 eV) e
aq (2.9 ~ 2.6 eV)
L. Wang et al. / Water Research 174 (2020) 115605

a 7 10 10 8
OH 0.07 /> 3099 1.4e8.3 10 1.2e1.3 10 1.8 10 2.2 10 1.8e2.2 107 NA
Hþ NA/NA NA NA NA/2.1 1010 4.8e7.2 1010 NA 6.3e28 109
CO2-
3 0.04a/> 630 1.0e6.1 106 3.2e4.2 108 5.0 108 <4 102 NA 3.9 105
HCO 3 <0.01/269 1.6e9.1 106 8.5e10 106 2.2e26 108 NA 4.4 104 <1.0 106
Cl 2.3a/3063 2.3e660 106 3.0e4.3 109 6.5e21 109/1.0 105 <1.4 102 <1.0 105 <1.0 106
Br 15/> 11502 3.5 109 1.1e1.9 1010 1.2 1010 NA 1.7e28 106 NA
NO3 3.51/4779 5.0e210 104 NA 0.9e1.1 108 NA 1.4e24 106 8.6e11 109
NO2 13.0/> 3550 8.8e9.8 108 2.5e14 109 4.8e5.2 109 5.0e360 106 7.1e10 108 3.4e6.0 109
2-
SO4 0.1a/146 NA NA 1.5e2.5 108 NA NA <1.0 106

HPO2 4 /H2PO4 0.97a/NA 1.2e16 106 2.0e15 104 NA 3.5 106 <5.0e50 104 1.4e190 105
NHþ 4 /NH3 NA/NA 3.0 105 ~ 1.0 108 4.3e100 106 2.6 108 NA <4.0e67 104 1.5e2.0 106
O2 NA/NA NA 3.6 109 NA NA 1.0e2.1 1010 1.8e2.2 1010
DOM <720/1402 7.8 107 1.39e4.0 108 1.08 108 NA NA NA
Reference(s) (Sauer et al., 2004; Duca et al., (Neta et al., 1988; Criquet and (Buxton et al., 1988; von (Buxton et al., 2000; Fang et al., (Bielski et al., 1985; Buxton Buxton et al. (1988) Buxton et al. (1988)
2017; Birkmann et al., 2018; Leitner, 2009; Yang et al., 2016) Gunten, 2003; Westerhoff et al., 2014; Chuang et al., 2016; et al., 1988)
Serrano Mora and Mohseni, 2007; Keen et al., 2014; Chuang Zhang et al., 2019)
2018) et al., 2016)
a
data measured by authors in the laboratory.

Fig. 2. An example of interconversions of radicals and reactive species during UV-S2O2 2
8 process in the presence of Cl , NO3 , CO3 , and DOM (copyright for Guan et al. (2018)).

Fig. 3. An example of interconversions of radicals and reactive species during UV-H2O2, UV-S2O2
8 , or UV-Cl2 processes in the presence of Cl , Br , and HCO3 (copyright from Li et al.
(2017)).
role of NOM/EfOM is usually inhibitive and less desirable for radicals and inorganic species. For example, anions like bicarbonate
practical applications. (HCO 2
3 ), carbonate (CO3 ), chloride (Cl ), and bromide (Br ) can
Compared to OH (1.9e2.7 eV), SO- 4 (2.5e3.1 eV) has compa- scavenge OH while anions like HCO 3 , Cl
, sulfate (SO2
4 ), and
rable or even stronger oxidizing capability than OH (1.9e2.7 eV) phosphate (PO3 4 ) can quench both holes and electrons (Liao et al.,
whereas less scavenging effect by DOM (7.8 107 M1 s1) than 2001; Chong et al., 2010). Their OH quenching ability can generally
OH (2.8 108 M1 s1) (Yang et al., 2016), hence justifying the be ranked as hydroxide (OH) z Br z nitrite
development of SO- 4 -relevant techniques for degrading trace (NO 2
2 ) > Cl > CO3 > HCO3 under identical concentration levels
organic contaminants. Overall, when multiple contaminants based on their k values (Table 2). Meanwhile, Fig. 2 shows the in-
coexist in a water with DOM, the choice of UV-H2O2 or UV-S2O2 8 is fluences of Cl, NO 2 -
3 , and CO3 on the SO4 , indicating that con-
likely determined not only by their own reaction rates with radicals version and inhibition of radicals may occur during the process
but also by the relative impacts of DOM on the radicals and their because of the different reactivities of target compounds, radicals,
influences on each other. and anions (Guan et al., 2018). Using 1,4-dioxane, carbamazepine,
phenol, 17b-estradiol, aniline, and sulfamethoxazole as examples,
2.2. Interferences from inorganics although the orders of treatability were ordered as UV-S2O2 8
(which yielded both SO4- and OH) > UV-H2O2 (which generated
Inorganic components are another pool of compounds known to OH) > UV-Cl2 (which produced Cl and CO2-) in simulated

be reactive with radicals generated in photochemical processes. effluent water, UV-S2O2 8 was more likely interfered by pH, Cl , and

Table 2 summarizes some k values for the reactions between typical HCO3 than other processes (Fig. 3). However, the rates of reactions
between anions and radicals indicate that SO4- should be theo- OH (kOH ¼ 0.25e1.4 1010 M1 s1) and considerable UV ab-
retically scavenged by HCO
3 , Cl , and OH more slowly than OH sorptivity at 254 nm (ε254 ¼ 13.0 M1 cm1, Table 2), meaning that
(Table 2), meaning that UV-H2O2 is expected to be more sensitive the presence of NO 2 is more likely to inhibit rather than facilitate

than UV-S2O2 8 in the presence of pH, Cl , and HCO3 . Such differ- OH formation to degrade target pollutant (Fig. 2). In contrast,
ences between theoretical estimations and experimental results although the FOH of nitrate (NO
3 ) is similar to NO2 , being 1.3e9.0%
thus make UV-based technologies more difficult to be practiced at 254e300 nm wavelengths, the ε254 of NO3 (3.5 M1 cm1,
under conditions simulative of reused wastewater. Table 2) was much lower than that of NO 2 and its reaction rate with
For anions with different reactivities, their relative concentra- OH was almost negligible (kOH < 1 105 M1 s1). Hence,
tions are expected to play important roles too (Yuan et al., 2011; although NO
3 yields similar amount of OH as NO2 , NO3 screens

Guan et al., 2018). For example, a water containing 1 mM Cl in less photons and consumes less OH than NO 2 , eventually making
acidic condition (kOH is 3.0 109 M1 s1) is supposed to be more more OH available for pollutant control than NO 2 . Even so, a re-
inhibitory to OH than a water with 10 mM HCO 3 in neutral con- view once stated that neither NO
2 nor NO3 could generate as much
dition (kOH ¼ 1.0 107 M1 s1) for degradation of target pollutant OH as H2O2 (FOH ~ 100%) (Mack and Bolton, 1999) and therefore
(Figs. 2 and 3). However, most of earlier studies simply compared their potentials in generating OH should not be overstated.
them at identical levels and seldom mentioned about their con- Meanwhile, although nitrite is considerably more photoactive than
centration effects. nitrate, nitrate is usually more concentrated than nitrite in solution,
In addition, only a few studies have examined the influences of thus compensating it low reactivity.
cations on photo(cata)lysis. For example, potassium has much Notably, there are numerous exceptions and unpredictable re-
higher light absorptivity (841 M1 cm1) at 185 nm (ε185) than that sults documented in previous UV-based processes. For example, the
of sodium (<0.01 M1 cm1) (Duca et al., 2017), meaning that presence of Cl might eventually enhance instead of inhibit the
special care should be taken toward potassium when it is used on removal of target pollutant (Yuan et al., 2011), because the pollutant
VUV process. In terms of other cations, there was a general census preferred to react with specific radical (e.g., Cl) formed by OH in
reached from earlier photocatalysis studies that cupric, ferrous, and acidic solution (reactions 29, 30, and 32 in Table 1). In another
aluminum ions at certain levels can reduce mineralization rates example, the inhibitory effects of Cl and HCO 3 on OH were shown
whereas calcium, magnesium, and zinc ions impose little changes to be minor even at very high concentration levels (250 mM) (Liao
(Chong et al., 2010). In order to make it convenient for future et al., 2001), which apparently disagree with earlier theoretical
studies, a list of ε185 and ε254 values are summarized in Table 2. A derivations. The lack of inhibition effect from HCO 3 might due to the
study evidenced that metal cations could react with reactive spe- formation of carbonate radical (CO3-) from reaction between OH
cies generated from photolysis of DOM (Wan et al., 2019). Generally, and HCO 3 . Although the reactivity of OH is much higher than that of
the paramagnetic metal cations (trivalent chromium, magnesium, CO3-, the steady-state concentration of CO3- is likely higher than
ferrous, and cupric ions) exhibited stronger inhibition for reactive that of OH, thus compensating for its lower reactivity (Sa nchez-Polo
species such as triplet excited state DOM (3DOM*), 1O2, and OH et al., 2013). Moreover, CO3- might be more selective to DOM,
than other cations (e.g., calcium, magnesium, aluminum, and zinc thereby suffering less than OH from the scavenging effect and ul-
ions) (Wan et al., 2019). timately enhancing the degradation (Wu and Linden, 2010; Liu et al.,
Of all anions, special attention should be paid to NO x species 2016b). Interestingly, earlier studies have demonstrated formation of
because of their double-edge effects. On the one hand, UV irradi- not only oxidative radicals (e.g., Cl, SO4-, and OH) (Herrmann,
ation of NO 2 is able to yield OH with the quantum yield of OH 2007) but also reductive radicals (e.g., e aq) from UV/VUV irradia-
(FOH) as 1.5e8.0% at 254e350 nm wavelengths (Mack and Bolton, tion of the same anions (Sauer et al., 2004). These contrasting effects
1999). On the other hand, NO 2 features strong scavenging ability on require further clarification too in the future.

Fig. 4. A summary of schemes for radicals’ formation, transformation, and interconversion in six typical photo(cata)lysis processes: a) UV/VUV, b) UV-H2O2, c) UV-S2O2
8 /HSO5 , d)
UV-Cl2, e) UV-TiO2 (Nosaka and Nosaka, 2017), and f) UV-SO2- 3 (pKa values are obtained from Stanbury (2010)).
Fig. 5. Effects of pH on the redox potentials (eV) of typical reactive oxygen species and catalysts (copyrights from Nosaka and Nosaka (2017) and Pichat (2015)).
2.3. Impacts from additives practice. In theory, the rate constant of reaction between H2O2 and
OH is rapid (2.7 107 M1s1) (Zhang et al., 2020), meaning that
Solution pH and the type and dose of additives are often an excessive amount of H2O2 could scavenge OH in the meantime
important operational factors affecting chemical reactions. of producing it, and therefore be detrimental to the overall degra-
Although it is usually difficult to control and adjust pH for treating dation performance (Goldstein et al., 2007).
large amount of water in real practice, people investigated it often In addition, one single compound may trigger formation of
for sake of better understanding. In one exemplary study, re- multiple radicals with different properties (Fig. 4). For example
searchers compared the treatabilities of UV-monochloramine formic acid (FM), it can yield either strong oxidative radical OH
(NH2Cl) and UV-Cl2 for abatement of several wastewater-derived upon irradiation by UV (Wang and Bai, 2016) or strong reductive
compounds (i.e., benzoate, carbamazepine, and 1, 4-dioxane) radical CO2- upon exposure to UV-S2O2 8 (Gu et al., 2017c).
(Chuang et al., 2017); although the results showed that UV-Cl2 Although the formation of reductive species might somehow be
performed better than UV-NH2Cl at ambient condition, the later explained by hydrogen (H) atom abstraction of formate from
was ultimately favored because its performance was independent organic radicals (i.e., HCOO þ R / CO2- þ RH), it is hard to
of pH whereas the performance of UV-Cl2 decreased markedly from understand why adding a strong oxidant S2O2 8 into a UV system
pH of 5.5e8.3. The decreased efficiency in UV-Cl2 at elevated pH would facilitate formation of reductive species like CO2-.
was largely attributed to a conversion of Cl into OH, which was In brief summary, earlier studies mostly demonstrated the
not favored for the selected compounds (Chuang et al., 2017). promising sides of proposed photo(cata)lysis technologies but
Another study reported similar phenomenon, in which Cl formed seldom examined the harmful effects of coexisting compounds on
by UV-Cl2 was more powerful than OH formed by UV-H2O2 at pH the performance of selected systems. While many individual
of 7.0e8.0 but became less capable than OH at pH of 6.0 (Yin et al., studies have pioneering demonstrated the diversity and robustness
2018), confirming that the relative robustness of Cl and OH are of many photo(cata)lysis systems, a bigger and whole picture
highly reliant upon solution pH (Fig. 4d). Although some com- should be made to cover not only promising but also unsatisfying
pounds could actually become easier to oxidize at higher pH (e.g., sides. In the future it would be necessary to apply a list of inter-
phenols / phenolates) (Babuponnusami and Muthukumar, 2012), fering compounds in water to verify the photo(cata)lysis ability in
the general decreasing trend of redox potentials for ROSs with more realistic conditions. Particularly, we agree with an earlier
elevating pH certainly accompany with decreasing photo- proposal (von Gunten, 2018) that it is important to compare
degradation ability (Fig. 5). emerging technologies with established benchmark technologies
Besides the types of additive, the dosing amount and dosing (e.g., ozone and UV-H2O2) in terms of energy demands, economics,
mode of additive also add up complexity of reactor operation. For and the possibilities of integration into existing water treatment
example, although UV-Cl2 was shown to be more efficient than UV- systems. In theory, it is also crucial to have an in-depth investiga-
H2O2 in degrading nitrobenzene at oxidant levels of 0.05e0.06 mM, tion of the interfering mechanisms imposed by different types of
the trend reversed when the oxidants were dosed at 0.15 mM level compounds.
(Watts et al., 2007). In another study, a small amount of H2O2 was
added intermittently for multiple times instead of dosing a large 3. Formation of undesirable byproducts
amount of H2O2 once at the beginning to enable more efficient
oxidation of ammonia by OH (Wang et al., 2017a). Compared to In addition to degradation efficiency issues, another major
dosing once, such operation may add difficulty to implement it in barrier hindering the acceptance of UV-driven technologies is their
Table 3
Typical studies regarding formation of DBPs during UV processes.
Target DBP(s) Light type and additive DBPs precursor Key findings Reference
Scenario 1. UV irradiation followed by redox

dichloroacetic acid, UV (2.26 mW cm2)-H2O2 Resorcinol, serine, leucine HAAs FPs decreased in resorcinol Sakai et al. (2013)
trichloroacetic acid (1 mM) treatment, increased slightly for serine,
and greatly increased for leucine;
THMs, HAAs, aldehydes, MPUV-TiO2 (0.1 g L1)-H2O2 NOM While total DBPs FPs dropped and Liu et al. (2008)
ketones (1 mM) specific THM FP reduced from 56 to
10 mg mg1, the specific HAAs FP
remained relatively unchanged after
photocatalytic oxidation
THMs, HAAs UV, MPUV-H2O2 Real river water Both TTHM and HAAs increased in both Metz et al. (2011)
UV or MPUV and regardless of
conventional or post-GAC treatments
THMs MPUV (450 W)eH2O2 NOM fractions THM FP in general decreased with time Lin and Wang (2011)
(100 mg L1) but increased with insufficient
irradiation; UV-H2O2 transformed
higher MW hydrophobic compounds to
smaller hydrophilic ones
THMs, HAAs, NDMA MPUV (450 W), UV 6 dissolved organic nitrogen Sufficient oxidation resulted in better Chen et al. (2011)
(40 mW cm2)-H2O2 (0.33 or compounds reduction of DBPs FPs. However,
3.26 mM) insufficient contact time and oxidant
doses led to a rise of DBPFPs in the early
stages of reactions. DBPs FPs showed
different trends for different precursors,
lights, and contact time.
THMs, HAAs, aldehydes MPUV, UV, pulsed UV Synthetic water containing For doses < 1000 mJ cm2, UV Liu et al. (2002)
carboxylic acids NOM and alginic acid irradiation did not affect THM and HAAs
formation in subsequent chlorination
processes; however, higher UV doses
resulted in lower THMs and HAAs. UV
irradiation resulted in formation of
aldehydes and carboxylic acids at UV
doses above 500 mJ cm2.
iodate, I-THM UV NOM UV transformed iodate into iodide and Tian et al. (2017)
hypoiodous acid that subsequently
reacted with NOM to form I-THMs
THMs, HAAs, HANs MPUV Swimming pool water Chlorine consumption increased, HAAs Cheema et al. (2017)
concentrations decreased, but THMs
and HANs increased with post-UV
chlorination.
Volatile compounds MPUV, UV (60 mJ cm2) swimming pool water Both MPUV and UV decreased most Zare Afifi and Blatchley (2016)
volatile DBPs formed in indoor
swimming pool; MPUV was more
efficient than UV.
THM, HAN, HKs, Natural solar Reclaimed water Solar significantly decreased the FPs of Wu et al. (2016)
trichloronitromethane, HANs, trichloronitromethane, and HKs
trichloroacetaldehyde but little for those of THMs and
trichloroacetaldehyde; the products of
tryptophan had lower chloroform,
trichloroacetaldehyde and DCAN FPs
than tryptophan.
Cytotoxicity, AOX Natural solar Reclaimed water Solar reduced cytotoxicity and AOX Lv et al. (2017)
significantly; chlorine residuals in
reclaimed water tended to increase the
cytotoxicity; compounds with
MW < 1 kDa were major contributors of
cytotoxicity and TOX in chlorinated
reclaimed water.
Scenario 2. Simultaneous UV irradiation and redox
Various DBPs UV (19.5e585 mJ cm2)-Cl2 (0 Tyrosine For UV-Cl2, stable C-DBPs increased but Chu et al. (2012)
e2.5 mM) DCAN, dichloroacetamide, 4-
chlorophenol decreased with a rising
UV dose.
TOX MPUV (0.37 mW cm2)-Cl2 NOM, model compound Compared to chlorination, UV-Cl2 Zhao et al. (2011)
(0.28 mM) produced less TOX for phenol, little
change for maleic acid and NOM, but
more TOX for nitrobenzene and benzoic
acid. Br altered TOX speciation but not
ultimate quantity.
THM, HAA, AOX, CH, UV (1.80 mW cm2)-Cl2 NOMs from IHSS Compared to dark chlorination, UV-Cl2 Wang et al. (2017d)
cytotoxicity (50 mg L1) increased the formation and FPs of
HAAs and CH, but not for THMs; AOX
and cytotoxicity became higher too.
Degradations of chromophores and
fluorophores were more efficient than
dissolved organic carbon.
Table 3 (continued )
Target DBP(s) Light type and additive DBPs precursor Key findings Reference
AOX 300 W MPUV - NaOCl (10 g L1) Phenol (100 mg L1) AOX was produced during the phenol Zeng et al. (2009)
degradation process; increasing pH or
oxygen decreased the formation of
AOX.
Brominated HAAs UV (1.80 mW cm2)-Cl2 NOM, dihydroxybenzoic acid UV-S2O28 yielded brominated HAAs but Wang et al. (2017d)
(50 mg L1) or PDS not UV-H2O2 although oxidization of

Br was evident. Bromine radical could
be immediately reduced back to Br by
H2O2.
THMs, HAAs, HANs, HKs, AOX, MPUV-Cl2 or H2O2 River and lake waters UV-Cl2 yielded more instantaneous Wang et al. (2015)
etc. (10 mg L1) DBPs than Cl2 alone or UV-H2O2 with
1 min contact time, but similar DBPs FPs
to UV-H2O2. One key issue for UV-Cl2
was the formation of chlorate.
Various DBPs UV-H2O2 & UV-TiO2 Micropollutants Toxic and assimilable products were Wang et al. (2018)
observed in >80% of UV-AOPs of organic
pollutants; products may be generated
by hydroxylation, dealkylation,
decarboxylation, and deamination;
concentrations and risks of parent and
daughter compounds are both
important.
Bromate, Br-polymers UV-S2O2
8 & UV-H2O2 2,4-bromophenol Bromate was detected in UV-S2O2 8 but Luo et al. (2018)
not in UV-H2O2; Br-polymeric products
were formed in both processes via
electrophilic addition and coupling
reactions.
potential formation of undesirable compounds (von Gunten, 2018). In terms of DBPs formation trends, earlier results vary greatly
Since most of UV processes cannot completely mineralize con- among studies depending on many operational and environmental
taminants, mostly due to energy and cost constraints, their pho- factors. For example, while one study reported less formation of
togenerated intermediates and end-products inevitably arouse DBPs with the use of UV pretreatment (Zare Afifi and Blatchley,
concerns (Zare Afifi and Blatchley, 2016), especially when the 2016), another study documented elevated DBPs formation with
process is followed by other treatment processes. In this review, we the same type of UV lamp (Cheema et al., 2017). Meanwhile,
present some examples of studies (Table 3) to help support the although UV-H2O2 pretreatment decreased the HAAs formation
opinions as shown below rather than summarize all evidences re- potentials (FPs) of resorcinol in following chlorination process, it
ported before, because many of them are already reviewed in two increased the HAAs FPs slightly for serine and dramatically for
recent articles (Ike et al., 2019a, 2019b). According to the applica- leucine (Sakai et al., 2013), an indicator of the importance of pre-
tion modes of photolysis and redox practices, we classify earlier cursor type. For a fixed precursor, the effects of UV on DBPs FPs
studies into two categories: one uses UV process as a pretreatment might govern the species of formed DBPs. In one exemplary study,
approach prior to redox process (e.g., chlorination or chloramina- pretreatment of NOM via MPUV-TiO2-H2O2 had led to lower THMs
tion), namely sequential UV-redox process; and the other uses UV FPs but remained unchanged for HAAs FPs (Liu et al., 2008). In
and redox compound (e.g., disinfectant, sulfite) together and another pilot-scale study, both THMs and HAAs FPs were promoted
simultaneously, namely, simultaneous UV-redox process. with the use of UV-H2O2 pretreatment (Metz et al., 2011), serving as
an excellent evidence of the negative sides of poor-managed UV
3.1. Sequential UV-redox processes pretreatment.
The abovementioned inconsistencies are likely caused by vari-
For all UV processes, the common side-effect of UV irradiation is ations of organic type, quantity, and water characteristics on the
formation of relatively smaller molecular weight (MW) compounds DBP formation. On the one hand, UV-based methods could trans-
like ketones, aldehydes, and carboxylic acids, which can serve as form high MW hydrophobic compounds into small MW hydro-
precursors of halogenated disinfection byproducts (DBPs) in philic and assimilable compounds (Liu et al., 2002, 2008), thus
ensuing chlor(am)ination processes. The types of lights evaluated raising the concerns of biological safety of distribution system and
before include UV, MPUV, pulsed UV, VUV, and sunlight while the formation of secondary byproducts. On the other hand, insufficient
additives examined already focus on the uses of H2O2 and TiO2. The contact time and additive application could result in minor
precursors tested before cover from model compounds like resor- reduction (Liu et al., 2002) or even elevated formation of DBPs
cinol to typical NOM isolates (purchased from International Humic (Chen et al., 2011). Therefore, a challenge for future study is perhaps
Substances Society) and sometimes even real water samples. The to determine the threshold or boundary separating sufficiency and
types of DBPs studied mostly aim to regulated species such as tri- insufficiency of light and additive dosage.
halomethanes (THMs) and haloacetic acids (HAAs) but relatively
less to emerging DBPs like nitrosodimethylamine and hal- 3.2. Simultaneous UV-redox processes
oacetonitriles (HANs) (Table 3). In general, the amount of DBPs and
corresponding toxicities of water increased at low UV dosage Within this category, UV-Cl2 process is a special concern
conditions (i.e., early reaction period) but decreased with further although it is an attractive approach for treating numerous
increases of UV dose, meaning that there is a possibility of exac- micropollutants recently (Fang et al., 2014) due to its operational
erbating water quality along the reaction, especially in conditions simplicity and comparable treatability as UV-H2O2 (Wang et al.,
with insufficient UV dosage. 2015). The reason mainly comes from its potential formation of
with lower biological activity from the parent compound. A good

photo(cata)lysis technology should avoid the latter two directions
but improve the first way in the future.
In addition, there are some controversies about the formation
and transformation of halogenated species in similar types of
photochemical processes. For example, while some studies re-
ported decomposition of organic halogen compounds in seawater
into halides upon sunlight irradiation (Wong and Cheng, 2001; Liu
et al., 2017), other studies had documented formation of iodinated
organic compounds in seawater via sunlight-driven halogenation
of DOM (Me ndez-Díaz et al., 2014) or even polymerization of un-
saturated organic contaminants (Legrini et al., 1993). These results
hence trigger debates about whether the rate of decomposition is
dominant over that of DBP formation during irradiation process,
and if no, how to avoid it.
In brief summary, there are many inconsistent and incompa-
rable data reported from existing studies, which underscores the
importance of developing a series of protocols for studying the
toxicity of photo(cata)lysis processes. In authors’ opinion, since
formation and transformation of redox byproducts always coexist,
people should provide a more general view of the pollutants’
treatment process, instead of just reporting the degradation levels
at a fixed time, to allow better evaluation of the benefits and risks of
all UV technologies in the future.
4. Uncertainty in radicals
Radicals are usually characterized as short-lived, highly reactive

compounds with extremely low steady-state concentrations in
water (e.g., 10 1012e10 1016 M). Up to date, marvelous ad-
vances have been made in understanding the formation and
occurrence of radicals in UV irradiated waters. For example, it is
already known that pulse radiolysis and laser photolysis of water in
Fig. 6. Potential changes of cytotoxicity, absorbable organic halogen (AOX), micro- the presence of nitrous oxide (N2O) can yield relatively pure OH;
pollutant (MP), transformation products (TPs), bromate, assimilable or biodegradable flash laser photolysis of S2O2 -
8 can produce SO4 ; UV photolysis of
(AOC/BDOC) in UV-Cl2 processes (copyrights from von Gunten (2018) and Wang et al. -
(2017d)). Case 1: lower biological activity than parent compound (lower red curve);
FM can yield CO2 radicals; UV irradiation of methanol can create
cases 2 and 3: higher toxicity or high biological activity than parent compounds (upper methanol radical (Gara et al., 2007); UV photolysis of alcohols (like
red curves). (For interpretation of the references to color in this figure legend, the ethanol, 2-propanol) or ketones (like acetone, benzophenone) in
reader is referred to the Web version of this article.) DO-rich and alkaline solutions could generate O2- (Gara et al.,
2007); and UV photolysis of phenol or p-benzoquinone in
oxygen-free solution could generate e aq (Gu et al., 2017a, 2017b). Of
toxic, assimilable, and sensory-unpleasant products by Cl (Wang
all radicals, OH is the most commonly-used oxidative radical and
et al., 2018) (Fig. 6). For example, when UV254 was used to reduce
eaq is the most known reductive radical.
iodate into iodide, hypoiodous acid was likely formed and then
Of all OH sensitizers (or precursors), the FOH at 254 nm UV
reacted with NOM to form iodinated DBPs (Tian et al., 2017). In
generally follow the order: DOM (0.00048) < NO 2 (0.083) < NO3

addition, bromide and iodide may be oxidized directly by OH to
(0.094) < H2O2 (1.0) < peracetic acid (1.2) (Lester et al., 2013; Cai
bromate/iodate and bromine/iodine, and then the latter enable
et al., 2017). The quantum yields of singlet oxygen (F1O2) from
formation of brominated and iodinated DBPs (von Gunten, 2003).
DOM photolysis (Suwannee River humic acid and Suwannee River
For this reason, UV-H2O2 was preferred over UV-S2O2 8 for samples
fulvic acid) ranged from 1.4% to 3.2%, which are higher than the
containing Br, because SO4- was more powerful than OH in
F1O2 from H2O2 photolysis (0.11%e0.14%) (Lester et al., 2013). The
transforming Br into bromate and bromine and therefore form
quantum yield of SO4- (F-SO4) from peroxymonosulfate (PMS, 0.12)
more brominated byproducts (Wang et al., 2017b). Notably, UV
was usually lower than that from peroxodisulfate (PDS, 1.4 at
technologies may also lead to formation of nitrogenous DBPs
248 nm by Herrmann (2007) or 0.52 at 254 nm (by Gligorovski et al.
(Wang et al., 2015; Cheema et al., 2017), which are usually more
(2015)), making the latter more favored in practice. The quantum
toxic than carbonaceous DBPs. Moreover, sulfur-containing com-
yield of Cl (FCl) from hypochloric acid (HOCl, 0.25) was higher
pounds were observed in a UV-based advanced reduction process
than that from chloroacetone (0.17) at 248 nm (Herrmann, 2007).
(ARP) (Li et al., 2014), meaning that not only AOP but also ARP can
As for DOM radicals, the maximum fluorescence quantum yield of
generate undesirable compounds. Such compounds with unknown
sunlit DOM decreased with additions of Cl and Br, meaning that
toxicities surely deserve more consideration in the future.
these halides can quench singlet excited state DOM (1DOM*)
In addition, photo(cata)lysis may alter the biological activity in
(Glover and Rosario-Ortiz, 2013); in the meantime, the concentra-
three ways (Fig. 6b): 1) loss of biological activity derived from the
tion of 3DOM* was increased, suggesting a conversion of 1DOM*
parent compound; 2) formation of highly bioactive compounds
into 3DOM* (Glover and Rosario-Ortiz, 2013). However, there are
from target compounds with lowly biological activity; and 3)
also some uncertainties, confusions, or even controversial findings
generation of potentially regulated and/or highly toxic compounds
from earlier studies. Here below shows some examples.
Table 4
A summary of ε254/185 and rate constants for reactions between radicals and typical scavenging or probing compounds.
ε254/ε185 (M1 cm1) SO4- (2.5e3.1 eV) OH (1.9e2.7 eV) Cl/ClOH (2.4 eV) HO2/O2- (0.33 eV) H (2.3~-2.1 eV) e
aq (2.9~-2.6 eV)
1
O2 (0.65 eV)
9 9 9 9 10
OH NA 9.5e10 10 4.0e6.2 10 NA 6e10 10 7.0e70 10 2.8e3.1 10 NA
L. Wang et al. / Water Research 174 (2020) 115605

-
eaq NA NA 2.8e3.1 1010 5 1010 1.3 1010 2.4e3.4 1010 5.0e7.0 109 NA
SO4- NA 1.6e8.1 108 9.5e10 109 NA 3.5 109 1.0 1010 NA NA
H NA 1.0 1010 7.0e70 109 2 1010/~1 105 1e2 1010 7.8e12 109 2.4e3.4 1010 NA
HO2/O2- NA 3.5 109 6e10 109 NA 8.3e20 105 1e2 1010 NA/1.3 1010 NA
Cl/ClOH NA NA NA 8.8e210 108 NA <1 105 NA NA
H2O2 18.6/341 1.2 107 2.7e5 107 NA 1.6 101 9 107e1.2 1010 9.5e12 109 NA
TBA <0.1/NA 4.0e9.1 105 4.2e4.8 108 3.0e32 108 NA 1.7 105 <4.0 105 NA
Benzoic acid 763/NA 1.2 109 1.8e5.9 109 1.0 108 NA 9.2e10 108 7.1e16 109 NA
p-CBA 2420/NA 3.6 108 5.0e5.9 109 NA NA 1.1 109 NA NA
Monochloroacetic acid 1.35/NA 4.5 106 4.3 107 NA NA 6.5e7.2 103 8.9e69 108 NA
Methanol <0.1/6.3 5.1e250 105 7.5e12 108 1.3e57 109 NA 2.4e2.6 106 <1 104 NA
Nitrobenzene 5560/NA <10 106 2.0e39 108 NA NA 1.0e2.3 109 2.5e4.2 1010 NA
Azide NA 2.4e3 109 1.2e1.4 1010 NA NA 1.9e29 109 <1.5 106 3.2e5 108
N2O NA NA NA NA NA 2.1 106 8.0e9.6 109 NA
Furfuryl alcohol 19.5/NA NA 1.5 1010 NA NA NA NA 1.2e1.4 108
Reference(s) (Wols and Hofman- (Maruthamuthu et al., (Buxton et al., 1988; (Fang et al., 2014; Hou Bielski et al. (1985) (Maruthamuthu et al., Li et al. (2012) Rosario-Ortiz
Caris, 2012; Lester 1995; Criquet and Maruthamuthu et al., et al., 2018) 1995; Li et al., 2012; and
et al., 2013; Guo et al., Leitner, 2009; Xiao 1995; Chuang et al., Chuang et al., 2016) Canonica
2018) et al., 2015) 2016) (2016)
NA: not available. NIST is the additional source of above data besides references.
11
4.1. Uncertain radicals’ transformation and interconversion methods such as chromatography, spectrophotometry, and elec-
trochemical sensor. Instead, many researchers used a series of in-
While most of earlier studies focused on formation of radicals, direct methods to detect radicals by checking either degradation or
much less attention has been paid to the importance of radicals’ formation of specific compound(s). However, users should be
transformations and interconversion. For example, although UV- aware of the limitations, assumptions, and application scopes of
irradiated peroxymonosulfate generated more OH and SO4- these methods prior to uses. Accordingly, this review prepares a
with increasing pH (Guan et al., 2011), both radicals were subjective table (Table 5) showing the advantages, disadvantages, and key
to reaction with OH (kinetics are shown in Table 2 and Fig. 4c), considerations of each method.
eventually leading to lower treatability in alkaline solution. That Of all methods, electron spin resonance (ESR), electron para-
means, the ultimate treatability of a UV process is actually deter- magnetic resonance (EPR), or laser-induced fluorescence (LIF) are
mined by both radicals’ formation and transformation. To allow a the most commonly-used measures to identify radicals. However,
comprehensive view of the potential transformations of radicals, due to the high equipment cost, operational complication, and
Fig. 3 shows the possibilities of interconversions of radicals and inability of accurately quantifying radicals, their uses are often
reactive species during UV-H2O2, UV-S2O2 8 , or UV-Cl2 processes in supplemented by other radical detection tools. Even though ESR/
the presence of Cl, Br, and HCO 3 , while Table 1, Table 2, and EPR/LIF techniques can prove the presence of specific radicals, it
Table 4 put together a list of reactions and reaction k values for alone cannot justify or confirm if the identified radical plays a
some radicals in the presence of a variety of aqueous components. dominant role in degrading the pollutant in selected process,
The higher the k value is, the more radical is likely transformed. especially in a process where multiple radicals are present simul-
In addition, radicals’ self-termination reactions are often taneously. In addition, ESR/EPR is likely interfered too. For instance,
ignored. For example, the k of OH self-recombination was the technique has failed in providing clear evidence of the relative
>4.0 109 M1 s1 and the k of reaction between OH and SO4- importance of OH vs. ferryl in a Fenton reaction, because the re-
was >1.0 109 M1 s1 (Table 4); both are quicker than reactions action of OH with a probe (intended for ESR/EPR or high perfor-
between OH and DOM. Although in nature [DOM] is greater than mance liquid chromatography analysis) gives exactly the same
[OH] so that people do not need to concern about OH recombi- radical intermediate as an one-electron abstraction process initi-
nation, the radical termination process is sometimes very impor- ated by water and deprotonation (Fontmorin et al., 2016).
tant when radicals are produced either abundantly (e.g., UV-H2O2) The first alternative used for identifying and quantifying radicals
or in a limited space where radicals’ recombination occurs faster is the use of probe compounds (PCs, such as p-CBA for OH, furfuryl
than radicals’ diffusion into solution, such as sonolysis (Hu et al., alcohol for 1O2, tetranitromethane for O- 2 , and monochloroacetic
2008) and TiO2 photocatalysis (Hou et al.). In addition, it was re- acid for e aq) (Rosario-Ortiz and Canonica, 2016), which can be
ported that the OH used for degrading p-chlorobenzoic acid (p- defined as molecules that can selectively react with specific target
CBA, a typical probe compound), was about three orders of radical(s). By monitoring the concentration changes of PCs or its
magnitude lower than that used for OH recombination during the reaction product(s), the steady-state concentrations of radicals can
VUV photolysis (Zhang et al., 2020), meaning that a considerable be derived from their known k values. An ideal probe should be
amount of radicals had been wasted in the self-termination pro- easy to measure, stable in selected environment, and selective to-
cesses. That means, although the steady-state concentrations of ward individual radical species. However, this is often difficult to
radicals are usually order of magnitude lower than those of target achieve when a non-selective reactant, such as OH, is also present.
compounds, the amount of radicals used for contaminant degra- In such condition, it is necessary to spike OH scavenging com-
dation or self-termination may not necessarily be that low. If the pound simultaneously to suppress the interfering radical. Further-
wasted radicals are fully utilized, they can probably significantly more, in order not to interfere with existing reactions between
promote the contaminant degradation reactions. radicals and target compounds, a key prerequisite of the use of PC is
In terms of reaction pathways, it is recognized that both O2- to not overdosing PC. However, probably for measurement conve-
and HO2 recombination can lead to formation of H2O2 (Gonzalez nience purpose, this was not well followed by earlier studies. In
et al., 2004; Zhang et al., 2020) at different rates, as shown below: addition, PC is required to not decompose readily under selected
UV wavelength while most of compounds used before are UV-
2HO2 / H2O2 þ O2 k1 ¼ 2 106 M1 s1 Reaction 1 absorbing (Table 4) and vulnerable to VUV direct photolysis.
Because of so, the influence of direct photolysis may become non-
2O-
2 þ 2H2O / H2O2 þ O2 þ 2OH k2 ¼ 3 10
1
M1 s1Reaction 2 negligible and consequently only the kinetics gap can be attribut-
able to radical’s contribution. In order to minimize bias, researchers
O-
2 þ HO2 þ H2O / H2O2 þ O2 þ 2OH k3 ¼ 6 10
12pH
M1 may develop an optimal PC dose with minimal direct photolysis
1
s Reaction 3 influence. Notably, it is extremely difficult to gain mechanistic in-
sights by using probe molecules in TiO2 photocatalysis study.
Because the pKa of HO2 is 4.8 and it deprotonates in neutral Although trapped OH is likely less reactive than free OH and
solution, O-
2 is expected to be the dominant species for H2O2 for- meantime trapped hole is more powerful than OH, their relative
mation in ambient water conditions (Cooper and Zika, 1983). roles are difficult to differentiate when they coexist. Since water is
However, its reaction rate constant was extremely low easy to form hydroxylated compounds by electron-transfer process,
(k1 ¼ 3 101 M1 s1) (Gonzalez et al., 2004), somehow disputing it is not always possible/convenient to translate those techniques
the possibility. Thus, the fate, transformation, and interconversion that work well in surface water photochemistry into photocatalysis
of radicals in AOPs and ARPs really require more elucidation. processes. For instance, the typical 3DOM* probes for surface waters
work only because [3DOM*] [ [OH], whereas in AOPs the probes
4.2. Uncertain radicals’ determination would behave as almost OH scavengers.
The second but more common alternative approach for
Identifying and quantifying radicals in water is necessary to help detecting radicals is the use of scavenging compounds (SCs, or
understand photo(cata)lysis processes (Rosario-Ortiz and Canonica, quenchers, such as tert-butanol (TBA) for OH, sodium azide for
2016). Due to their short lives and extremely low levels, the con- 1
O2, superoxide dismutase for O-
2 , and N2O for eaq), which are
centrations of radicals cannot be analyzed by conventional defined as compounds capable of inhibiting reactions between
Table 5
A comparison of various radical determination methods.
Methods Advantages Disadvantages Notes for practice
ESR/EPR/LIF Classic, commonly accepted, Expensive equipment and Better be accompanied by other
direct. consumables, complicate in supplementary methods.
operation, superposition of
spectra from various radicals,
qualitative but not quantitative.
Scavenger or quencher (SC) Easy to operate, no extra Easy to underdose, subject to Check dosing sufficiency; verify
analytical burden, easy to interferences from direct potential interfering product or
understand, quantitative photolysis and coexisting secondary reactant.
radical, may produce unknown
product and/or secondary
radicals, and trigger radicals’
interconversion.
Probe compound (PC) Qualitative and quantitative, Easy to overdose, subject to Ensure not overdosing, add SC if
easy to follow. influence of direct photolysis necessary, choose compound
and non-selective radicals, hard insensitive to UV and easy to
to measure, extra analytical measure, check the presence
load, nonexclusive. and roles of other radicals.
Fingerprint product Specific to radical(s). Too low concentration to Enhance analytical ability;
analyze, indistinguishable for better be accompanied by other
similar radicals, may degrade measures.
with time.
Model simulation Easy to implement, high error Incomplete reaction Justify and check multiple
tolerance, quantitative. information, possible random pathways and intermediates by
choice, weak assumption or experiments.
basis.
H2O2 appearance Easily indicate presence of OH Hard to measure, interferable Check background H2O2 and
and/or O2-. by coexisting compounds, other H2O2 formation
reliant on dissolved oxygen, pathways.
degrade over time, useless for
other radicals.
radical(s) and target compounds. This approach assumes that by However, there are some problems for the use of methanol. One of
inhibiting the roles of specific radicals responsible for reaction the key issues is that irradiation of methanol by UV254 was able to
(specifically, by monitoring the kinetics changes before and after trigger formation of secondary radicals or reactive species, such as
addition of SC), people can conclude that such degradation pro- methanol radical (Gara et al., 2007), which may interfere with the
cess is completely or partially attributed to the suppressed radi- determination of OH. Another issue in using methanol is that not
cals. This approach is very easy to implement because it does not all OH, actually probably just a small portion of OH, reacted with
add any extra analytical loads to existing process, therefore it is methanol to generate formaldehyde (Lester et al., 2013), thus
commonly applied in literature. Under the principles, the reaction making it unreliable to obtain the steady state concentration of
between SC and radicals should be strong enough to exert sig- OH. Moreover, the k of reaction between methanol and OH is
nificant reduction of existing pollutant degradation kinetics. similar to that between methanol and Cl, meaning that it is unable
Therefore, this approach usually requires dosing an excessive to distinguish these two radicals produced simultaneously in UV-
amount of SC. However, not all studies have checked if the amount Cl2 process (Gara et al., 2007). So, its use as either probe or scav-
of scavenger is sufficient or confirmed whether additional or less enger requires careful considerations.
scavenger dosage would further inhibit or facilitate the reaction More importantly, since multiple radicals are likely present
kinetics. For example, of 56 reviewed HAAs photolysis studies together (Fig. 4), a common problem for using PCs and SCs is the
(Wang et al., 2019), only one study had applied two levels of TBA lack of consideration of radicals’ rapid interconversions (Table 1).
to verify complete quenching of OH (Wang et al., 2017c). Mean- For instance, during the UV-TiO2 process, addition of formic acid (a
while, because of the abundance of SC, it should be noted that SC typical scavenger for OH) was capable of converting OH into
is likely to produce other types of reactant (e.g., radicals) or CO2-, thereby dehalogenating trichloroacetic acid more rapidly
products (e.g., FA, FM) that can either facilitate or hinder existing than OH, rather than inhibiting the kinetics (Liu et al., 2016a).
reaction. In addition, some scavengers are able to scavenge/ Because the presence and role of coexisting radicals are often not
quench various types of radicals. For instance, the well-known 1O2 disproven at the same time of other radicals’ confirmation, the
quencher N 3 is also a very effective OH scavenger (Gutie rrez quantity and role of seemingly important radical(s) measured by
et al., 1991). Therefore, the interpretation of experimental data PCs or SCs are likely actually a result of rapid transition of other
might not always be straightforward, and compounding effect radicals. In an exemplary study, the importance of selecting
should be carefully checked (Glover and Rosario-Ortiz, 2013; appropriate scavengers for radical determination was highlighted
Marchisio et al., 2015). (Han et al., 2017). The effects of 20 commonly-used scavengers for
Noteworthy, the use of methanol for OH quantification falls in quantifying five types of radicals were systematically evaluated
between PCs and SCs. Because it does not absorb UV254, people under varying pH conditions in terms of their light absorbance,
often spike methanol in excess just like the use of a SC and then complexation, analytical easiness, and potential anti-interfering
quantify OH via its reaction products (i.e., FA) just like the use of a characteristics (Han et al., 2017). Only 9 scavengers were finally
PC (Lester et al., 2013; Cawley et al., 2015). In addition, because of its chosen as suitable scavengers, while the uses of inappropriate
low absorptivity at VUV185, methanol was often used as an acti- scavengers would lead to severe overestimations of radicals (Han
nometer for quantification of VUV fluence (Zoschke et al., 2014). et al., 2017).
Sometimes, the calculated concentrations of specific radicals addition, since the MDL of H2O2 could be further lowered by
appeared inconsistent among methods. When a DOM was irradi- enlarging injection volume, the method can be used to detect trace
ated by UV254, the steady state OH concentration can be estimated levels of H2O2 in natural water (Cooper and Zika, 1983), serving as a
by multiple methods, which have reached 1.6 1015 M by using p- tool to understand the power of nature in transforming anthro-
CBA as a PC (Kp-CBAþOH ¼ 5.8 109 M1 s1), 9.9 1016 M by using pogenic pollutants. Fundamental questions like where H2O2 comes
TBA as a SC, and 4.0 1018 M by deriving the rate of formaldehyde from in the nature and whether photolysis of H2O2 is an important
formation from methanol (KmethanolþOH ¼ 9.7 108 M1 s1) OH source in surface water are still hot topics of interests
(Lester et al., 2013). These huge data gaps among methods appar- currently.
ently suggest equivalent knowledge gaps in our understandings of
these processes. 5. Concluding remarks
In summary, the uses of ESR/EPR/LIF, PCs, and SCs for the
identification and quantification of radicals need more thoughtful Photodegradation of contaminants in water by UV-based tech-
considerations, cautions, and in-depth understandings from a ho- nologies has been a hot topic of researches for many decades.
listic view. Since many radicals are likely produced upon irradia- Despite of huge advances, there are still many material, reactor, and
tion, their reactions with specific dosed PC and/or SC should be chemistry issues limiting extensive, large-scale, practical applica-
thoroughly and carefully evaluated. In the future, a good strategy tions of photo(cata)lysis processes. While acknowledging the
for verifying the presence or role of certain radical species, to au- importance of material and photoreactors, this review have sum-
thors’ opinion, is to apply at least two abovementioned approaches marized three key barriers from a chemistry perspective, including
as described in Table 5 to supplement each other. Special efforts the interferences of aqueous components on system performance,
should be done to detect at least one of fingerprint products to the formation of undesirable redox products, and the uncertainty of
verify not only the presence but also the real impact of specific radicals’ identification and quantification.
radical(s). E.g., an appearance of a hydroxylated compound with a To overcome these barriers, this study proposes to: 1) examine
hydroxyl group (-OH) is clearly indicative of the presence of OH the applicability of photo(cata)lysis on real samples and compare
while a substitution of chlorine atom with hydrogen into a com- the performances of emerging and conventional technologies un-
pound is a characteristic symbol of Cl. der identical conditions; 2) evaluate the benefits and risks of future
photo(cata)lysis technologies from a dynamic panorama, rather
4.3. Limited H2O2 information than snapshots, of toxicity changes along the process, and explore
solutions for controlling the formation of undesirable products; and
Compared to other reactive oxygen species, H2O2 is relatively 3) verify the presence and role of dominant radicals responsible for
more stable yet not well studied. By far we know, the roles of H2O2 pollutant removal by multiple radical determination methods,
in the environment are double-sided. On the one hand, H2O2 is an especially paying attention to the radicals’ transformation and
important source of OH in the nature (Cooper and Zika, 1983); so it interconversion, and enhance the understanding of H2O2 formation
is sometimes called as “detergent of the environment”. On the and transformation in different UV processes.
other hand, because H2O2 is a product of OH self-termination Besides ideas, this review prepares some schemes to demon-
process, an advent of H2O2 in water can indicate the presence of strate radicals’ formation and transformation pathways (Fig. 4) and
OH and/or O2- in a photochemical process (Diesen and Jonsson, some tables (Table 2 & Table 4) to display the rate constant values
2014). More importantly, earlier study demonstrated that H2O2 is for the reactions between typical radicals and aqueous compo-
not only widespread in ocean and atmosphere but also in ground nents. These information can not only help explain photo(cata)lysis
water (Yuan et al., 2017), suggesting that a cascade of biogeo- phenomena but also help choose suitable SC and PC in various
chemical processes might exert significant impacts on the metal/ scenarios for future study.
nutrient cycling processes. However, not many studies have
recorded its concentrations in UV-based processes, even for studies Declaration of competing interest
intentionally spiking H2O2 (such as Fenton and UV-H2O2).
One key barrier for relatively limited H2O2 measurement in The authors declare that they have no known competing
water is probably its unreliable detection methods, which mostly financial interests or personal relationships that could have
rely on color or fluorescence changes caused by reactions between appeared to influence the work reported in this paper.
H2O2 and certain reactants (Song et al., 2017). Because coexisting
oxidants (e.g., oxygen), reductants (e.g., DOM), and colored com- Acknowledgements
pounds (e.g., ferric) in real water can interfere with the measure-
ment of H2O2 (Li et al., 2012), the accuracy and precision of H2O2 We appreciate the financial supports from the Shenzhen Science
analysis are undermined. To reduce interferences, earlier re- and Technology Innovation Committee (JCYJ20180306171820685)
searchers often applied air-stripping to eliminate coexisting oxi- and the National Natural Science Foundation of China (51978194),
dants (e.g., O3) (Wang et al., 2009) before H2O2 measurement, or as well as assistance from coworkers in the laboratory including Fei
obtained H2O2 by subtracting O3 content from total oxidant con- Yang, Yuanxi Huang, etc. In addition, Lei Wang was partially sup-
centration (Lovato et al., 2011). Apparently, these techniques are ported by Shanghai Tongji Gao Tingyao Environmental Science &
laborious and highly variable. Technology Development Foundation (STGEF).
Recently, one literature report proposed a facile and reaction-
free method for H2O2 measurement by using ion chromatography Nomenclature and Abbreviations
(IC) column to separate H2O2 from other aqueous components,
followed by detection of H2O2 via a UV detector at 210 nm (Song AOP advanced oxidation process
et al., 2017). Because the method is theoretically non-interferable ARP advanced reduction process
by coexisting compounds and is low in MDL (3.0 mg L1), it might Br¡ bromide
help better understand the formation and transformation of H2O2 Cl¡ chloride
in UV-driven processes, and furthermore, through which the roles Cl chlorine radical
and formation pathways of many radicals may also be elucidated. In Cl2 free chlorine
CO2 carboxyl radical FCl quantum yield of chlorine radical

CO23 carbonate FSO4- quantum yield of sulfate radical
CO3 carbonate radical
DBP disinfection by-product
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Some Issues Limiting Photo (Cata) Lysis Application in Water Pollutant Control - A Critical Review From Chemistry Perspectives

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Water Research 174 (2020) 115605

Contents lists available at ScienceDirect

Some issues limiting photo(cata)lysis application in water pollutant

1. Introduction pollutant with catalyst, and low sensitivity of photocatalyst at

VUV UV-TiO2 UV-H2O2

Key reactions H2O þ VUV/e þ

L. Wang et al. / Water Research 174 (2020) 115605

Scenario 1. UV irradiation followed by redox

with lower biological activity from the parent compound. A good

Radicals are usually characterized as short-lived, highly reactive

L. Wang et al. / Water Research 174 (2020) 115605

Methods Advantages Disadvantages Notes for practice

CO2 carboxyl radical FCl quantum yield of chlorine radical

Fontmorin, J., Castillo, R.B., Tang, W., Sillanp€ a€

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