Chemical Engineering Journal 347 (2018) 379–397

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Review

Insight into electro-Fenton and photo-Fenton for the degradation of T

antibiotics: Mechanism study and research gaps
⁎
Xiaocheng Liua,c, Yaoyu Zhoua, , Jiachao Zhanga, Lin Luoa, Yuan Yanga, Hongli Huanga,
⁎
Hui Penga, Lin Tangb, Yang Muc,
a
College of Resources and Environment, Hunan Agricultural University, Changsha 410128, China
b
College of Environmental Science and Engineering, Hunan University, Changsha 410082, China
c
Department of Chemistry, University of Science & Technology of China, Hefei 230026, China

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Fundamental and key parameters of

EF and PF process are systematically
reviewed.
• Recent advances in pH, catalyst, elec-
trode, light source, device are in-
vestigated.
• Decay pathway and toxicity evalua-
tion to eliminate antibiotics are dis-
cussed.
• The unfilled gaps and research needs
for the EF, PF, PEF and SPEF are pro-
posed.

A R T I C LE I N FO A B S T R A C T

Keywords: With the development of the degradation of persistent organic pollutants in the wastewater, antibiotics have
Electro-Fenton been considered as emerging pollutants. Their lasting effects on the entire ecosystems directly resulted in ir-
Photo-Fenton reversible damage all over the world. Electro-Fenton, photo-Fenton, photoelectro-Fenton and solar photoelectro-
Antibiotic Fenton processes have been adopted to the elimination of antibiotics for the considerable efficiency. The me-
Mechanism
chanism, advantage, disadvantage, and the impacts of key parameters for each method are discussed based on
Key parameters
the recent works, respectively. The cost aspects of electro-Fenton and photo-Fenton are analyzed for practical
Gaps
application. The degradation pathway as well as the toxicity evaluation of the antibiotics is reviewed. Finally,
research needs and unfilled gaps have been proposed, including blocks from unpredicted impurities, pilot-scale
study for the remediation of polluted water, pretreatment of antibiotic effluent, cognition of high-performance
electrode, and characterization of intermediates. All of them suggested that electro-Fenton and photo-Fenton
could be adopted as an ecological and efficiency ways for the elimination of antibiotics.

1. Introduction antibiotic against bacteria has been hailed as a four-edged sword, which
means resistance to bacterial infection, control of infectious diseases,
Antibiotics, different from other drugs, have not aroused sufficient enhancement of antibiotic resistance and damage of the beneficial
attention for the negligible direct toxicity. Exactly, the effect of bacteria [1]. There is no doubt that the complete reversion of antibiotic

⁎
Corresponding authors.
E-mail addresses: zhouyy@hunau.edu.cn (Y. Zhou), yangmu@ustc.edu.cn (Y. Mu).

https://doi.org/10.1016/j.cej.2018.04.142
Received 17 January 2018; Received in revised form 30 March 2018; Accepted 20 April 2018
Available online 22 April 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

tolerant variants is impossible, causing by the most notorious obstacle Hydroxyl radicals play a vital role in EF/PF/PEF process, oxidizing
of antibiotic resistance [2]. Meanwhile, forefront researchers also pay most organics into CO2, H2O and inorganic ions via dehydrogenating or
attention to antibiotic resistance genes (ARG), leading an unpredicted hydroxylating reaction for the high standard reduction potential (E0
future of environmental organisms [3]. The abuse of antibiotics even (%OH/H2O) = 2.80 V/standard hydrogen electrode (SHE)) [29]. Mean-
increases the concentration reaching a specific level that would while, the Fe2+ is the representative of Fenton process, whereas the
strengthen bacterial transcription [4]. Therefore, the worldwide oc- Fenton-like process could be carried out with diverse metal ions (e.g.,
currence of the antibiotics suggested the urgency to figure out several Cu2+) for the decomposition of H2O2 [18].
effective and economical methods.
Fe2+ + H2 O2 →Fe3+ + OH− + %
OH (1)
Fenton process is commonly used in water treatment processes
[5,6]. The photo-Fenton (PF), electro-Fenton (EF), photoelectro-Fenton The photolysis of H2O2 plays a vital role in the PF process to break
(PEF) and solar photoelectro-Fenton (SPEF) are highly superior to the the OeO bond for the production of %OH (Eq. (2)), leading the proce-
conventional treatments without altering the structure of antibiotics dure of propagation (Eqs. (3–5)), and termination (Eqs. (6–8)) [32].
[7–9]. Indeed, recent sound investigation on the electrode and light
source would accelerate the development of antibiotics degradation by H2 O2 + hv →2 OH (2)
EF and PF, respectively. In addition to the comprehensive study on the %
OH + H2 O2 →H2 O + HO2 %
(3)
wavelength of artificial light source for PF [10], the sunlight also uti-
% %
lized to the antibiotic decay by compound parabolic collector (CPC) HO2 + H2 O2 → OH + H2 O + O2 (4)
[11], and NETmix@ photoreactor [12]. Several strategies for mod- % − % −
OH + HO2 →HO2 + OH (5)
ification of the cathode have shown great superiority [13–15], whereas
Ti4O7 was proposed as a convincing alternative to the classic high 2HO2 %→H2 O2 + O2 (6)
performance electrode in the EF degradation [16,17]. %
OH + HO2 %→H2 O + O2 (7)
Actually, the forms of energy input are not the only difference, and
%
there is always a misunderstanding that the improve methods about the 2 OH →H2 O2 (8)
pH and catalyst are interchangeable between the EF and PF processes. 3+ %
The continuous Fe2+ in the PF process is mainly determined by the The presence of Fe blocks the continuous generation of OH in
photo activity of the Fe(OH)2+, and it could be improved by organic the classical Fenton process, leading a slow decomposition of H2O2 and
ligand for the generation of the [Fe3+(RCO2)]2+ [18]. Meanwhile, the unpleasant generation of hydroperoxyl radical (HO2%) (Eq. (9)).
introduction of organic matter would change the solubility of Fe [19], Therefore, the introduction of the photo current in PF process has
indicating a modified method for the neutral PF process [20]. Never- certainly improved by photo-reduction of Fe3+ according to the (Eqs.
theless, the methods for the wide range pH and natural pH are ac- (10) and (11)), whereas the limited rate for the regeneration of Fe2+
complished by the generation of the O2%– [21], and hydrolysis of cat- significantly hinder the Fenton process. Interestingly, the reduction of
alyst [22]. Besides, the participation of the carbon materials for the Fe3+ and production of %OH could accomplished at the same time in the
synthesis of the catalyst could improve the adsorption capacity, further PF process (Eq. (12)) [33]. Moreover, some Fe(III)–carboxylate com-
enhancing both of the EF [23], and PF catalytic efficiency [24]. plexes generated from the coordination of Fe3+ and organic inter-
Moreover, the pilot plant study for the antibiotic removal is regarded as mediates have a considerable adsorption in the UV–vis region for the
a key parameter in the section of PEF and SPEF. reduction of Fe3+ (Eq. (13)), named ligand-to-metal charge transfer
Furthermore, the degradation pathways in the PF, EF, PEF and SPEF (LMCT) [8]. The zero-valent iron (ZVI) could also be the source of Fe2+
process are suitable to provide an impressive cognition of the structure in the PF process for the photo-oxidation of Fe0 (Eq. (14)), accompanied
of antibiotics. Each detection instrument as well as the concise reaction with series reaction with H2O2 and O2 [34].
of the complete pathway for PF, EF, PEF and SPEF is reviewed, and the Fe3+ + H2 O2 →Fe2+ + HO2 %+ H+ (9)
characteristics of specific investigation are refined. The eco-toxicity
%
[25], luminescence assay [17,26], and antimicrobial activity (AA) Fe 2+
+ H2 O2 →Fe(OH) 2+
+ OH (10)
[27,28] for the treated antibiotic solution are discussed. Interestingly, 2+ 2+ %
Fe(OH) + hν→Fe + OH (11)
the intermediates of the antibiotics after the EF and PF process might
3+ 2+ + %
improve the original toxicity. Fe + H2 O + hν→Fe +H + OH (12)
To our knowledge, several excellent reviews have been published %
[Fe 3+
(RCO2 )] 2+
+ hv →Fe 2+
+ CO2 + R (13)
previously focusing on the EF process [29,30], PF process [18], and
antibiotic removal [31]. However, there is no paper summarized data Fe0 + hv → Fe2 + + 2e− ( < 400 nm) (14)
on the performance of EF and PF process for the degradation of anti-
biotics. In this paper, we present a critical review in this topic (Fig. 1), Additional H2O2 is easy to break down wastefully, increasing the
comparing the fundamental and key parameter of the recent research cost of the Fenton and PF processes. Nevertheless, the cathode of EF
on the antibiotic decay by EF, PF and PEF/SPEF process, respectively. process carried out the generation of in-situ H2O2 (Eq. (15)), considered
The essences of the degradation pathway and toxicity evaluation are as an important evaluation indicator for the current efficiency. Inter-
figured out, and the analysis of the cost aspects in related field and estingly, the accumulation of H2O2 in the EF system is limited for the
unfilled research gaps in this field are presented. reduction at the cathode surface (Eq. (16)) and the H2O2 disproportion
at the bulk solution (Eq. (17)) [9]. The competition of evolution of H2
2. The fundamental of EF and PF process (Eq. (18)) would enhance if the current density is excess. Compared to
the PF process, the reduction of Fe3+ is more direct and fast though Eq.
2.1. The mechanism of EF and PF process (19) on the cathode, causing no obvious obstruction to the EF process.
O2 + 2H+ + 2e− → H2 O2 (15)
EF and PF processes always compare with each other in wastewater
treatment based on the separation and degradation of organic and in- H2 O2 + 2H+ + 2e− → 2H2 O (16)
organic pollutants according to different mechanisms. The Fenton re-
action is the fundamental reaction for the generation of homogeneous 2H2 O2 → O2 + 2H2 O (17)
hydroxyl radicals (%OH) though Eq. (1), and the strategies for the im-
provement of efficiency are mainly in accordance with each parameter. 2H+ + 2e− → H2 (18)

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X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Fig. 1. Trends in the number of publications on the topic of “Fenton and antibiotic”, “electro Fenton and antibiotic” and “photo Fenton and antibiotic” (data obtained
from Web of Science on November 11, 2017).

% −
Fe3 + + e− → Fe2 + (19) OH + SO42 →OH− + SO4%− (30)
The hydrogen peroxide is not the only way to produce hydroxyl SO4%− +e −
→SO42 − (31)
radicals, for the EF process, electrode material (M) used to the oxidation
of water has a vital effect on the generation of heterogeneous hydroxyl
radical (M(%OH)) though Eq. (20). Generally, the higher current would
increase the amount of M(%OH), whereas the extra electricity would 2.2. The advantage and disadvantage of EF and PF process
lead unexpected evolution of O2 on the anode (Eqs. (21) and (22)). The
H2O2 would also be oxidized into HO2% considered as a weak oxidant As the representative of advanced oxidation processes (AOPs), the
(Eq. (23)), and finally convert into O2 on the anode (Eq. (24)) [35]. investigation on operational parameters of EF and PF processes have
Although, the Fe anode has been once adopted to the EF process due to been discussed in some excellent reviews, respectively [8,18,29,30].
the oxidation of Fe provides the Fe2+ via Eq. (25), which has been Nevertheless, the key parameters for the degradation of antibiotics in
abandoned for the severe anodic corrosion [36]. the recent researches have shown different trends for EF and PF pro-
cesses. For instance, the nanoscale zero-valent iron (nZVI) presents a
%
M + H2 O →M( OH) + H+ + e− (20) pH-responsive characteristic in the Fenton process as if it could be
2H2 O→ O2 + 4H+ + 4e− (21) simply used to PF and EF processes [38]. Actually, the nZVI is suitable
for the heterogeneous PF process according to the Eq. (14) while the
investigation on performance of nZVI in the EF process is valueless
%
2M( OH) →2M + O2 + 2H+ + 2e− (22) [39].
% − EF and PF processes seem to be the extension of Fenton process, but
H2 O2 →HO2 + H +
+e (23)
there is a huge difference between them in terms of the main me-
% −
HO2 →O2 + H +
+e (24) chanism and key parameters. The typical PF process would occur in the
simultaneous presence of Fe, hv and H2O2, showing a higher efficiency
Fe → Fe2 + + 2e− (25)
than Fenton process and lower energy consumption than EF process
In addition, the conductivity of solution for the EF process is ne- [18]. Most of the high performance catalysts for Fenton process are
cessary, and the Na2SO4 is the most common electrolyte due to the low available for PF process, and the excess salt conductivity is not neces-
activity of SO42−. However, the effect of electrolyte could not always sary for the reaction of photo current. Moreover, the semiconductor in
been ignored, and the presence of Cl− would introduce the Cl2 and the photocatalysis is usually adopted to produce active electron-hole
HClO to the EF process (Eqs. (26) and (27)) [37]. There are several pairs, accelerating the oxidation, reduction and radical reaction [40].
unexpected reactions between the %OH and Cl− (Eqs. (28) and (29)), Although the hv for the most of PF process usually need extra energy
whereas the high concentration of SO42− also contribute to the con- input, the energy loss in the treated solution is negligible as compared
sumption of hydroxyl radicals (Eqs. (30) and (31)) [30]. to EF process.
As a matter of fact, the capacity of PF process is still limited even if
2Cl− → 2e− + Cl2 (26)
the hv promotes photo-reduction of Fe2+ and direct photolysis of H2O2.
Cl2 + H2 O→ H+ + Cl−+HClO (27) The optimal dosage of H2O2 is significantly determined by the con-
centration of pollutant, and the total organic carbon (TOC) removal is
not satisfied for PF process without efficient semiconductor [12].
%
OH + Cl− →% OHCl− (28) Moreover, the instability of the H2O2 increases the difficulty to control
% − the H2O2/Fe2+ molar ratio, blocked by unexpected reaction in the ty-
OHCl +H +
→Cl +
H2 O (29)
pical Fenton process [8]. The alleged initial concentration of H2O2 in

381
X. Liu et al.
previous study must take the actual parameters of wastewater into
consideration, hindering the practical degradation of antibiotics from
unstable source.
The EF and PEF processes are both electrochemical advanced oxi-
dation processes (EAOPs), known for the considerable efficiency for
almost all of the antibiotics. The TOC and dissolved organic carbon
(DOC) are common indicators for the assessment of mineralization
degree for the EF and PEF process, which are more convincing in terms
of the elimination of toxicity [26]. For instance, the problem caused by
initial concentration of antibiotics shows slightly influence to the mi-
neralization, and even the extremely higher concentration could be
easily settled by prolonging the treated time [41,42]. The concentration
of in-situ H2O2 in the EF process is much lower than the dosage in the PF
process, continuously generating on the cathode to produce %OH. The
regeneration of Fe2+ maintain a suitable ratio of Fe2+/Fe3+ by directly
electron reduction of Fe3+ (Eq. (25)). In addition, the heterogeneous M
(%OH) on the anode is also a vital part of the anode oxidation during the
electrocatalysis, especially for the BDD and Pt anode [43].
Nevertheless, the large energy loss in the treated solution caused a
serious waste, let alone negative impact of excess salt to the aquatic
organisms in freshwater. The electric current contributes to different
key parameters of EF process, and the heterogeneous catalyst in Fenton
process and PF processes could not simply introduced without suitable
characteristics. Although the carbon based heterogeneous catalysts are
universally applicable to promote the contact of active substances with
large surface for EF [23], and PF processes [24]. Moreover, the in-
troduction of electric current caused an extremely serious corrosion for
both of electrode and catalyst if the electrocatalytic system is vulner-
able [36]. Hence, there should be separated discussions on the key
parameters blocked the total degradation process of antibiotics, espe-
cially for the distinguish function of the catalysis in every aspects.
3. Treatment methods and key parameters
3.1. The degradation of antibiotic by PF process
3.1.1. pH
The pH significantly affects the oxidation state and solubility of the
Fe in the PF process, and the coordination of natural organic matter
(NOM) could moderate the extreme condition [19]. The weakly ionized
H2O2 would bring about H+ causing decomposition of H2O2 into O2
and H2O at basic condition [44].
The structure of oxacillin (OXA) seems to have vulnerable moiety
due to the efficient degradation process at pH of 5.6 [45], and the effect
of additives is not obvious [46]. Meanwhile, the introduction of powder
activated carbon supported magnetite nanoparticles (Fe3O4@C) as the
heterogeneous catalyst for the degradation of tetracycline (TC) could
not change the optimum pH with the assessment of the response surface
method (RSM) [24]. Iron citrate could slightly improve the pH of the PF
treatment of ciprofloxacin (CIP) and fluoxetine (FLU) after the anae-
robic treatment to 4.5 for the influence of the ligands [47]. Interest-
ingly, the ethylenediamine-N,N’-disuccinic acid (EDDS) has been suc-
cessfully adopted to moderate the pH of PF process, reducing the cost of
previous acidification and secondary treatment [48]. Moreover, the
oxalate has accomplished the modification of PF treatment of levo-
floxacin (LEV) at mild pH [20]. Obviously, most value of pH for the
degradation of antibiotics is at acidic range achieving the best perfor-
mance in the PF process as illustrated in Table 1, the modification
methods with organic matter is seem to moderate the mild pH of PF
process.
3.1.2. Iron source and heterogeneous catalyst
Many people would mistake PF process for conventional photo-
catalysis with semiconductor, indeed, the function of light in the main
PF process is to maintain the concentration of Fe2+ from the additional
iron source as Eqs. (11–13) [45]. The most common and convenient
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Chemical Engineering Journal 347 (2018) 379–397
iron source of the PF process is FeSO4·7H2O particularly for the
homogenous catalysis, and it could certainly combine with semi-
conductor catalyst for the environmental remediation [40].
Bansal et al. fabricated the support materials for the TiO2 by mixing
the clay beads with foundry sand (FS)/fly-ash (FA), and the synergistic
effect of the photocatalysis and PF process for the degradation of ce-
phalexin (CEX) was investigated over composite beads (FS/FA/TiO2)
[49]. As seen in Fig. 2a, the iron leaching from support for the PF and
immobilized TiO2 on the support for the photocatalysis accomplished
the dual process with synergistic effect. Lima et al. carried out the
heterogeneous PF degradation of three types of antibiotics with the
Fe2O3–TiO2 film which fabricated with sol–gel synthesized Fe2O3 as
well as commercial Fe2O3, TiO2 and Fe2O3–TiO2 composites [12]. The
TiO2 and Fe2O3 were adopted as the electron charge carrier conductor
and hole charge carrier conductor for the heterogeneous PF, respec-
tively, and the Fe leaching was observed in the solution contributed to
the homogeneous process (Fig. 2b).
Besides, the introduction of carbon materials for the synthesis of
heterogeneous catalyst also improves the homogeneous PF process for
the adsorption of antibiotics. Kakavandi et al. adopted the co-pre-
cipitation method to prepare the Fe3O4@C, and the degradation of TC
was combined with the adsorption procedure improving the stability,
activity and recyclability [24]. Meanwhile, multiwalled carbon nano-
tubes (MWCNT) could decorate with the Fe3O4 for the degradation of
norfloxacin (NOR), and Shi et al. confirmed the enhancement of the
MWCNT by transmission electron microscope (TEM), X-ray diffraction
(XRD) and Fourier transform infrared (FT-IR) [50]. In summary, the
recent investigation on iron catalyst for antibiotic decay by PF process
tends to improve the recyclability and activity using decoration and
immobilization methods, and the TiO2 and carbon based materials have
shown convincing performance.
3.1.3. Initial H2O2 concentration
The H2O2 is the main source of %OH in the PF process (Eqs. (1) and
(2)), but the instability of the H2O2 certainly disturbs the control of
accurate concentration. There is no obvious regular pattern for the in-
itial H2O2 concentration to the various systems according to the
Table 1. Nevertheless, the investigation on H2O2/Fe2+ molar ratio is
interesting with the analysis of data and mechanism. The best molar
ratio of H2O2/Fe2+ for the PF process is limited [51], mainly blocked by
the recombination of %OH (Eq. (8)), the scavenger of H2O2 (Eq. (3)),
direct oxidation of Fe2+ by %OH (Eq. (32)). Moreover, the combination
of activated sludge (AS) process and sequencing batch reactor (SBR)
under 12 h the hydraulic retention times (HRTs) increase the optimal
H2O2/Fe2+ molar ratio of the PF process [52].
%
OH + Fe2+ →Fe3+ + OH− (32)
Interestingly, the additional H2O2 is not necessary for the photo-
degradation of antibiotics, and some heterogeneous catalyst would
accomplish the Fenton like process attributed to the generation of O2%–
with in-situ generation of H2O2 (Eq. (33)). Huang et al. proposed an
interfacial reaction of the Fe3O4 and oxalate under UV irradiation for
the degradation of NOR [53]. As illustrated in Fig. 3a, the complex of
Fe3O4 and oxalate enhance the utilization of optical energy, generating
the O2%– for the in-situ generation of H2O2 without excess radical re-
action. The C3N4@MnFe2O4-graphene nanocomposites have adopt to
the antibiotic degradation under visible light [54], and the capture of
photo-excited electrons on the semiconductor moiety by O2 is the
source of O2%– (Fig. 3b). Although the initial concentration of H2O2
plays a vital role during the PF process, the development of novel
catalyst for in-situ H2O2 seems to be more valuable to overcome the
negative impact of one-off adding mode.
O2%− + 2H+ →H2 O2 (33)
X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Table 1
The key parameters of the PF process for degradation of antibiotics.
Antibiotics pH Initial H2O2 concentration Iron source (catalyst) Light source Ref.

Amoxicillin 3.0 15–40 mM FeSO4·7H2O UV lamp (365 nm) [51]

Ampicillin
Cloxacillin
Amoxicillin Cloxacillin 3.0 17.97–53.9 mM FeSO4·7H2O UV lamp (365 nm) [52]
Oxacillin 5.6 1000 μM FeSO4·7H2O UV lamp (less than 387 nm) [45]
Tetracycline 3 ± 0.2 3 mM Fe3O4@C UV-C lamp (PHILIPS) [24]
Ciprofloxacin 4.5 100 μM Iron citrate Black-light lamp (365 and 410 nm) [47]
Fluoxetine
Oxacillin 5.6 1000 μM FeSO4·7H2O Philips lamp (TL-D Actinic BL) [46]
Ciprofloxacin 3.0 4.2 mM FeSO4·7H2O Philips lamp (365 nm) [28]
Cephalexin 3.5 4.41 mM FeSO4·7H2O/ TiO2 immobilized clay beads Philips UV tubes (365 nm) [49]
Sulfamethoxazole 2.8 0.59–2.94 mM FeSO4·7H2O Compound parabolic collector [11]
Erythromycin
Clarithromycin
Ciprofloxacin 2.8 2.5 mM FeSO4·7H2O/Fe2O3–TiO2 composites NETmix@ photoreactor [12]
Sulfamethoxazole
Trimethoprim
Norfloxacin 3.0 98 mM Fe3O4-multiwalled carbon nanotubes Solar simulator xenon lamp [50]
Penicillins 3.0 10 mM FeSO4·7H2O Philips black lamps (365 nm) [91]
Tinidazole 2.0/6.8 100–1500 μM FeSO4·7H2O UVC and Solar [92]
Levofloxacin 3.0–6.0 147–588 μM FeSO4·7H2O UV lamp (280–400 nm) [20]

3.1.4. Light source
The light source of the irradiation procedure of antibiotic waste-
water for the PF process is usually carried out by UV lamp at the wa-
velength of 365–410 nm (Table. 1), which might be benefit to the Eqs.
(11–13). The photo-current from the UV lamp requires external elec-
trical energy although the solar could not reach a satisfied miner-
alization [55]. The solar PF process has a negligible cost for the input of
energy, and the available UV light in the natural light is limited. The
solar disinfection with in-situ PF process has been applied for the su-
periority bacterial inactivation, whereas the investigation on the anti-
biotic decomposition under visible light requires the assistance of
equipment [56]. Romero et al. compared the simulated sunlight, pilot
plant with sunlight, CPC, black blue lamps (λ = 365 nm) and UVC
(λ = 254 nm) for the PF process, and the CPC pilot plant shows a lower
energy consumption and higher efficiency than the powerful artificial
solarbox (SB) [10].
Karaolia et al. employ the CPC and membrane bioreactor (MBR) to
improve the solar PF degradation of erythromycin (ERY), sulfa-
methoxazole (SMX), and clarithromycin (CLA) [11]. In the latest re-
search, the light source for the degradation of antibiotics was generated
from novel static mixer photoreactor (called NETmix® photoreactors),
giving a comparison of CPC for the solar PF process [12]. Generally, the
PF process carried out a complete mineralization of antibiotic waste-
water after the MBR pretreatment for the pilot-scale study (Fig. 4a).
Meanwhile, the PF process largely improves the low ratio of BOD5/COD
(biodegradability) as a convincing pretreatment, while the SBR is not
effective for the antibiotic wastewater for the low biodegradability
(Fig. 4b). Sincerely, the UV light provides direct available light with
continuous energy consumption for PF process, whereas the photo-
reactor and CPC show a potential pilot-scale study for the mineraliza-
tion of antibiotic at μg L−1 and ng L−1 level.
3.2. The degradation of antibiotic by EF process
3.2.1. pH
The pH is also essential for the solubility and oxidation state of iron
ion as PF procedure [9], whereas the Fe(III)-carboxylate complexes are
not suitable for the EF process due to a natural photoactivity instead of
electrocatalytic activity (Eq. (13)). As a convincing alternative (Fig. S1),
the sodium tetrapolyphosphate (Na6TPP) has been adopted to improve
the one-electron oxygen reduction processes in the EF process (Eq. (34))
[15], showing highly efficient at a pH range of 4.0–10.2. Moreover, the
acidic condition is vital for the oxygen reduction reaction (ORR) on the
cathode (Eq. (15)), and the major EF process shows the highest mi-
neralization capacity at the pH value of 3.0 (Table. 2).
O2 + e− →O2%− (34)
Nevertheless, several EF systems could function at natural pH, and
some practical strategies have been proposed to widen the pH of the EF
process. Li et al. combined the microbial fuel cell (MFC) and MBR
technology to degrade the TC by FeOOH/TiO2 granular activated
carbon (FeOOH/TiO2/GAC) [57]. The electrical energy supply for the
continuous equipment is provided by the MFC system, and the deem-
phasis on the pH value might be caused by both of the weak current
density for the ORR (Eq. (15)) and the introduction of heterogeneous
FeOOH/TiO2/GAC (Fig. 5a). Meanwhile, Barhoumi et al. firstly in-
troduce the chalcopyrite (CuFeS2) to the heterogeneous EF process for
the degradation of TC [22], and the cooperation of the Fe2+ and Cu2+
for the generation of %OH was also investigated (Fig. 5b). Fig. 5c shows
an interesting time-course of pH value for the different dosage of
chalcopyrite, and the decrease of the pH value accompanied with the
increase of CuFeS2 could be explained by Eq. (35).
CuFeS2 + 16Fe3 + + 8H2 O→ Cu2 + + 17Fe2 + + 2SO24− + 16H+ (35)
Thus, the pH adjustment for the EF process with chalcopyrite seems
to be unnecessary, which is still an important step for the pyrite EF
process [26,41]. Furthermore, the synergistic effect of Fe and Cu is also
interested in the fabrication of the cathode to enhance the electron
transfer on the surface for a wider pH (Fig. S2). Zhao et al. prepared the
iron–copper–carbon (FeCuC) aerogel by embedding the Fe-Cu nano-
particles into 3D carbon matrix, proposing a surface-based reaction
mechanism for the pH range from 3.0 to 9.0 [15]. Jiang et al. reported a
Fe-Mn binary oxide (FMBO) modified electrode that could remain
considerable efficiency at the pH range from 3.0 to 10.0 [58]. In the
recent research, the main strategies to avoid the pre-acidification and
secondary adjustment during the EF process can be concluded as the
introduction of one-electron oxygen reduction process, surface-based
reaction mechanism, and the synergy of bimetallic catalyst.
3.2.2. Iron source and catalyst
The FeSO4·7H2O is a cheap and convenient source for the homo-
geneous EF process, and the reduction of Fe3+ on the cathode guar-
antee the stability for a long time (Eq. (19)). The optimum pH at 3.0 for
homogeneous EF will largely increase processing costs for the

383
X. Liu et al.
Fig. 2. Schematic illustration of combination of photocatalysis and PF process for the degradation of antibiotics: (a) TiO2 immobilized clay beads, reprinted with
permission from ref [49]. Copyright 2017 Elsevier. (b) Fe2O3–TiO2 film, reprinted with permission from ref [12]. Copyright 2016 Elsevier.
neutralization of excess acid with a secondary processing, and the re-
maining iron ion would cause an additional pollution to the effluent
[29]. Thus, the solidification for the recycle procedure and adaptability
for a wide pH range are vital characteristics for the heterogeneous
catalyst.
The pyrite (FeS2) is regarded as a sustainable iron source for the EF
process, and it has been successfully applied to the LEV [41], and sul-
famethazine (SMT) by Barhoumi et al. [26] In the latest research,
Barhoumi et al. improved the pH of TC decay by CuFeS2, and clarify the
Fenton’s-like reaction for Cu2+ alone with Fenton reaction in the EF
degradation [22]. The natural pyrite and chalcopyrite should be sieved
with a filter of less than 80 μm after ground finely and then the pyrite
power must accept the sonication in 95% ethanol for 5 min and rinse
with deionized water and 95% ethanol after being washed by 1 M HNO3
and finally dried at 30 °C. Moreover, both of the best doses of the pyrite
and chalcopyrite are figure out and efficiently improve the conven-
tional EF process.
Besides, the noble metal (e.g., Pd and Pt) introduced in the EF
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Chemical Engineering Journal 347 (2018) 379–397
process would oxidize the H2 into H2O2, for example, the Fe3O4 and Pd
nanoparticles (Fe3O4-Pd) could be combined and use to catalyze the
electrochemical-heterogeneous Fenton (EC-HF) process [59,60].
Moreover, the iron doped carbon fiber materials (e.g., FeCx/N-doped
carbon fiber composites (FeCx/NCNFs) [23] and iron(II) phthalocya-
nine polyacrylonitrile (FePc/PAN) nanofibers [61]) seem to enhance
the heterogeneous catalysis efficiency by extra adsorption of the pol-
lutant. Obviously, the highly efficient natural mineral could be devel-
oped as practical heterogeneous catalyst for the EF process, and nearly
no carbon based catalyst adopts to the antibiotic removal by EF.
3.2.3. Cathode and generation efficiency of H2O2
The efficiency of EF process is largely depended on the cathode
which largely affected the production of hydrogen peroxide. The carbon
felt (CF) and graphite felt (GF) are the most common and convenient
cathode for the degradation of antibiotics (Table. 2). The electro-
chemically active surface area (ECSA) of CF/GF is considerable, and the
reduction of the Fe3+ could be accomplished instantly (Eq. (19)). Thus,
X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Fig. 3. Schematic illustration of the degradation of antibiotics under irradiation by Fenton like process: (A) Fe3O4 and oxalate, reprinted with permission from ref
[53]. Copyright 2017 Elsevier. (B) C3N4@MnFe2O4-graphene nanocomposites, reprinted with permission from ref [54]. Copyright 2017 Elsevier.

the generation efficiency of H2O2 is an important characteristic for the
cathode, bringing out numerous researches on the modification and
activation method. Interestingly, the GF with high ECSA were used as
anode for the degradation of SMT, found a great apparent rate constants
at low current (50 mA) [43]. However, the GF might burn for a higher
current (> 100 mA) while common used anode could reach a more
complete TOC removal with a higher current.
CF, graphite and reticulated vitreous carbon (RVC) were compared
for the reduction of Fe3+ and generation of the hydrogen peroxide in
the EF process by means of a Merck specific analytical test (Fig. 6a).
Although the RVC shows the distinctive electrocatalytic activity, the
cost of CF is well below the RVC cathode, indicating a practical value
for the further study [62]. The modification of the GF cathode could be
accomplished by hydrothermal synthesis with C2H5OH and N2H4·H2O
(Fig. 6b), exhibiting an obvious improve of the TOC removal for the
degradation of LEV during EF process [14]. The surface of GF was
corroded and etched during the heated process in the mixture of
C2H5OH and N2H4·H2O, generating vacancies and edge planes for the
improvement of the oxygen and nitrogen containing functional groups
[63]. The hydrophilic property and the electro-catalytic activity were
improved by the nanoparticles, nitrogen and oxygen containing func-
tional groups attached to the surface of cathode (Fig. 6c). With regard
to the modification substance in EF process, Ling et al. compared the
improvement of Fe loading by modification of acid potassium dichro-
mate, hydrogen peroxide, nitric acid, concentrated sulfuric acid and
sodium hypochlorite for the active carbon felt (ACF) [64].
Besides, the anodized GF materials prepared by electrochemical
treatment [65], and KOH activation method [66], resembling to the
function of modification method in the EF process. Meanwhile, the
carbon fiber is suitable for the cathode membrane, and has been applied

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X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Fig. 4. (a) The deep mineralization of antibiotic effluent after MBR though solar PF process, reprinted with permission from ref [11]. Copyright 2016 Elsevier. (b)
The pretreatment of antibiotic wastewater for the SBR though PF process, reprinted with permission from ref [52]. Copyright 2011 Elsevier.

Table 2
The key parameters of the EF process for degradation of antibiotics.
Antibiotics pH Anode Cathode Iron source (catalyst) Applied current Ref.

Tetracycline 3.0 Ti/RuO2-IrO2 CF FeSO4·7H2O 200–500 mA [69]

Pt
BDD
Levofloxacin 3.0 RuO2/Ti ACF FeSO4·7H2O 2.22–9.26 mA cm−2 [94]
Levofloxacin 3.0 Pt CF FeSO4·7H2O 60–500 mA [93]
Levofloxacin 3.0 BDD CF Pyrite 100–400 mA [41]
Enoxacin 3.0 Pt CF FeSO4·7H2O 50–300 mA [95]
Norfloxacin 3.0 Pt CF BDD FeSO4·7H2O 30–500 mA [72]
BDD Pt
Sulfamethazine 3.0 BDD GF FeSO4·7H2O 100–1000 mA [43]
Pt
DSA
Sulfamethazine 3.0 BDD CF Pyrite 100–1000 mA [26]
Pt
−2
Tetracycline Natural Anode chamber (graphite particles) Cathode membrane FeOOH/TiO2/GAC 0–350 mA m [57]
Amoxicillin 3.0 Ti4O7 CF FeSO4·7H2O 10–120 mA [17]
Tetracycline Natural Pt CF Chalcopyrite 50–500 mA [22]
BDD
Ciprofloxacin 3.0 Pt CeO2/RGO composite FeSO4·7H2O 100–450 mA [13]
Ciprofloxacin 3.0 Pt CexA1−xO2 (A = Zr, Cu and Ni) modified CF FeSO4·7H2O 100–500 mA [68]
Ciprofloxacin 3.0 Cylindrical Pt mesh CF FeSO4·7H2O 60–500 mA [74]
Levofloxacin 3.0 Ti/RuO2-IrO2 N-doped GF FeSO4·7H2O 100–400 mA [14]

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X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Fig. 5. Schematic illustration of the natural pH system for the degradation of antibiotics by EF process: (a) Combination of microbial of fuel cell (MFC) technology by
FeOOH/TiO2 granular activated carbon (FeOOH/TiO2/GAC) for the tetracycline, reprinted with permission from ref [57]. Copyright 2017 Elsevier. (b) Chalcopyrite
degradation mechanism of the tetracycline and the time-course of pH, reprinted with permission from ref [22]. Copyright 2017 Elsevier.

Fig. 6. (a) Comparison of the graphite, carbon felt, reticulated vitreous carbon (RVC) cathode, reprinted with permission from ref [62]. Copyright 2016 Elsevier. (b)
Flow diagram of the degradation of antibiotic by modified cathode, reprinted with permission from ref [14]. Copyright 2017 Elsevier. (c) Schematic illustration of the
mechanism of modification of cathode, reprinted with permission from ref [63]. Copyright 2014 Elsevier. (d) Sandwiched structure of the membrane stack cathode,
reprinted with permission from ref [67]. Copyright 2015 American Chemical Society.

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X. Liu et al.
to the EF process for the sequential influent treatment [67]. As illu-
strated in Fig. 6d, a sandwiched structure of membrane stack was
consist of carbon nanotube (CNT) separated by polytetrafluoroethene
(PTFE) layer, and 3 pieces of CNT membrane seem to represent the
cathode, bulk solution and anode, respectively. Interestingly, the fab-
rication of cathode chamber could be achieved by cathode membrane,
and the modification of the poly (vinylidene fluoride) (PVDF) would
strengthen the physical and chemical stability of the carbon fiber cloth
[57].
Moreover, the rare earth elements have been introduced to the
degradation of antibiotics in EF system, combined with the carbon-
based material as cathode. Li et al. fabricate a 3D cerium oxide/reduced
graphene oxide (3D CeO2/RGO) cathode to degrade the CIP, and the
generation of the hydroxyl radical and superoxide from the cycle of
Ce4+/Ce3+ are investigated, respectively [13]. In the recent research,
the same team produce lattice defects in the CeO2 by doping transition
metal (Zr, Cu and Ni), improving the O2 diffusion on the CexA1-xO2
(A = transition metal ions) cathode [68]. Exactly, the transition metal
replaces the Ce in the precursor, and the Ce0.75Zr0.25O2 has the best
electrocatalytic activity and electrosorption feature for the degradation
of CIP. The modification and activation of cathode are economical and
durable methods for a better antibiotic decay in EF system, and the CF/
GF has been considered as the ideal cathode for further improvement.
Actually, the non-metallic reagents could increase the nitrogen or
oxygen functional groups to generate more H2O2, whereas the metallic
modified method would introduce the cooperation with other metal
ions.
3.2.4. Anode and applied current
Compared to the cathode materials, the high performance of anodes
are relatively expensive (e.g., boron-doped diamond (BDD), Pt) to
produce more available heterogeneous hydroxyl radical (Eq. (20)).
Oturan et al. firstly carried out a comprehensive comparison of the
anode materials for the degradation of TC by EF and electrochemical
oxidation (EO) process, including Ti/RuO2-IrO2, Pt and BDD anode, and
BDD was the best anode in the EF and EO process [69]. The generation
of M(%OH) on the anode is mainly depending on the overvoltage for
oxygen evolution, and the overvoltage for the BDD is higher than Pt
indicating more M(%OH) generation under the same current density
(Fig. 7a). Moreover, the physisorbed BDD(%OH) is more reactive and
available for the degradation of the organics than the chemisorbed Pt
(%OH) on the anode surface [70,71]. Interestingly, the BDD and Pt were
tried as cathode to the degradation of NOR with EF treatment, showing
that Pt is more suitable for the cathode than BDD in terms of the gen-
eration of H2O2 [72]. Indeed, the effective surface of the Pt is higher
than BDD for the ORR, giving a logical explanation for the highest
Fig. 7. Schematic diagram of anode materials: (a) Conventional anode for the removal of sulfamethazine, reprinted with permission from ref [26]. Copyright 2016
Elsevier. (b) Novel Ti4O7 anode for the degradation of amoxicillin, reprinted with permission from ref [16]. Copyright 2016 Elsevier.
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Chemical Engineering Journal 347 (2018) 379–397
efficiency of the CF/GF cathode with considerable ECSA.
The Pt anode is made up of expensive precious metal while the
synthesis of BDD anode requires the strict condition, and both of them
hinder the realization of industrialization [73]. The Pt mesh anode
possessing cylindrical shape seems to provide large ECSA with less
consumption of precious materials [74]. Nevertheless, the dimension-
ally stable anode (DSA) could hardly reach equivalent efficiency as Pt
or BDD anode for the less generation of DSA(%OH) and unexpected
firmer adsorption on the surface of anode in the EF process for de-
gradation of SMT [43]. The coating technology and other strategies for
the preparation of conventional DSA (e.g., Ti/RuO2-IrO2, RuO2/Ti) are
sophisticated enough for the industrialization with a much lower ex-
pense [75].
Aiming at a balance between the high efficiency of BDD and low
cost of DSA, the ceramic anode with deposition of Ti4O7 plasma pro-
duced Ti4O7(%OH) are fabricated for the degradation of amoxicillin
(AMX) by EF process (Fig. 7b). The TiO2 were put into a hydrogen
plasma plume ionized by 38 kW electric arc generated from copper
annular anode and tungsten cathode, and the argon was used as carrier
gas at rate of 30 g min−1 [16]. Melted TiO2 particles are quenched by
the cold titanium plate, and the results of XRD show that the main
phase of the plasma coating is Ti4O7 instead of Ti3O5, Ti5O9, Ti6O11.
The Ti4O7 anode has a similar performance to the commercial BDD
anode mineralization of AMX in the EF process, and the source of the
Ti4O7 is highly abundant TiO2 and the production cost is relatively low
[17].
Nevertheless, most of the mentioned system is integral for the EF
system, and the fabrication of dual-chamber could combined with MFC
[57], and bioelectrochemical system (BES) by porous clapboard and
cationic exchange membrane [64], respectively. The graphite particles
were added in the anode chamber while the FeOOH/TiO2/GAC,
FeOOH/GAC or GAC was used to fill the cathode chamber, and the
energy for the MFC were supplied by 4 electron ORR on the GAC sur-
face (Eq. (36)), generally considered as an unexpected reaction com-
peted with 2 electron transfer (Eq. (15)) in EF process on the cathode
[57]. Meanwhile, the anode chamber of BES reactor is consist of gra-
phite fiber brushes and anaerobic sludge, and the wastewater was
treated mainly by cathode chamber [64].
O2 + 4H+ + 4e− → 2H2 O (36)
Furthermore, there are some interesting findings in terms of the
relationship between the electrode materials and optimum applied
current or current density for the EF process, since the definition and
fundamental of the applied current or current density for the EAOPs
have been well detailed [9]. The range of applied current or current
density of the degradation of antibiotics by EF process was illustrated in
X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Table. 2, and the common applied current seem to be range from 100 to
400 mA. Generally, the removal of antibiotics would be more complete
with an increasing current. Nevertheless, it could not be indefinite for
the Eq. (22) as well as the adsorption characteristics of different het-
erogeneous %OH on the anode. The analysis of the applied current range
from 100 to 1000 mA for the SMT decay shows that the optimum ap-
plied current for the Pt and DSA seem to be 500 mA with GF cathode,
whereas the optimum current for BDD might be higher than 1000 mA
[43]. This excellent electric property of BDD highly attributed to the
highest overvoltage and physisorption of heterogeneous %OH [76].
Interestingly, the effective current for the degradation of OXA is
relatively low (10–120 mA) for the vulnerable moiety, which is in
agreement with the previous hypothesis in PF process under relatively
neutral pH [17,45]. Besides, the optimum current would be affected by
the 3D CeO2/RGO cathode, and the reduction of Ce4+ might compete
with the generation of H2O2 when the applied current is higher than
400 mA [13]. Moreover, the electric current generated from the 4e− on
the GAC is extremely low and unstable, and the modification of TiO2
and FeOOH certainly ensure the stability of TC effluent quality [57].
The high performance anode significantly improve the removal effi-
ciency and stability of EF system, but the unacceptable expend of anode
is not suitable for the large scale antibiotic degradation. The optimal
applied current for the antibiotic degradation should meet the reg-
ulatory limits and pursue the waste of energy as low as possible. The
MFC has been investigated for the EF process, indicating an alternative
to the DC power.
3.3. The degradation of antibiotic by PEF and SPEF process
3.3.1. Basic parameters
The pH and iron source are usually limited to the 3.0 and
FeSO4·7H2O for the most investigations on the antibiotics decay by
PEF/SPEF process (Table. 3). Moreira et al. comprehensively in-
vestigated the degradation of trimethoprim (TMP) in the PEF process,
figuring out the function of the pH and Fe3+ speciation coordinated
with carboxylate complexes [77]. The theoretical Fe3+ speciation could
avoid the formation of Fe(OH)3 precipitation in the PEF system, and the
optimum pH should be set lower than 5.5 despite the species of ligand
(e.g., citrate, oxalate, malate and tartrate) and molar ratio (Fig. 8).
Moreover, the solution of TMP and Fe3+ has an absorption peak at
wavelength of 270 nm further enhanced by the introduction of ligands.
Indeed, both of the stability in the EF process and photo-activity in the
PF process are required for the iron based catalyst of the PEF process,
and the iron containing (metal organic frameworks) MOFs materials
seem to be a good solution for the characteristics of multifunction [40].
The current density would be associated with the flow rate and
electrode to achieve an equivalent efficiency. Guinea et al. compared
the anodic oxidation (AO), EF and SPEF for the degradation of enro-
floxacin (ENR), and the constant current density was selected as
50 mA cm−2 with the 20 cm2 BDD and Pt anode [78]. The TOC removal
of ENR in the SPEF could reach 80% after 2 h under the flow rate of
200 L h−1 in the recirculation flow plant. Meanwhile, Pérez et al. car-
ried out the degradation of metronidazole (MTZ) by SPEF process with
a 90.2 cm2 Pt anode area at the current density of 55.4 mA cm−2,
achieving a 36% DOC removal after 5 h treatment of SPEF process
under 200 L h−1 [79]. Nevertheless, the applied current density in the
PEF process for the removal of TMP is 5 mA cm−2, and the nearly
complete removal is achieved after 2.5 h degradation with 10 cm2 BDD
at the flow rate of 40 L h−1 [77]. Moreira et al. accomplish a complete
degradation of TMP after 0.5 h SPEF treatment with the 10 cm2 BDD
and Pt anode, and the flow rate was set as 40 L h−1 at the maximum
current density of 150 mA cm−2 [80]. Moreover, Pérez et al. investigate
the SPEF process using the FM01-LC flow reactor for the ERY decay,
and the electrodes were 64 cm2 platinized Ti plate anode and 517 cm2
cathode [81]. The optimum cathodic current density for the SPEF
system was found at 0.16 mA cm−2, reaching a 69% DOC removal after
5 h treatment under flow rate of 180 L h−1. The PEF and SPEF system
was usually carried out by pilot-scale equipment, and the control of
volume and flow rate for the reactor must receive enough attention. It
seems to maintain the stable operation that the heterogeneous catalysts
have not been applied to the PEF and SPEF so far.
3.3.2. Electrode
Carbon-PTFE air-diffusion cathode is the most common electrode
for the PEF/SPEF process, and the general ACF/GF could also be
adopted as well (Table. 3). The carbon-PTFE air-diffusion cathode is
usually embedded in the equipment combined with a same size anode
(Fig. 9a). Interestingly, the 2-ethylanthraquinone (2-EAQ) in the PTFE
electrode could highly improve the generation of H2O2 ensuring the
enough ORR in the flow plant (Fig. 9b), and 2-EAQ has been success-
fully adopted for the modification of the carbon cathode [82]. Mean-
while, the air-diffusion cathode is a special gas diffusion electrode for
the wastewater degradation, improving the ORR reaction with lower
energy consumption [83]. Moreover, the multifunctional iron con-
taining MOFs would be modified on the carbon cathode for the SPEF
process to introduce the photo activity to the conventional EF process
(Fig. 9c). Zhao et al. fabricate a MOF(2Fe/Co)/carbon aerogel (MOF
(2Fe/Co)/CA) for the SPEF process, and the characteristic of the gen-
eration of electron-hole pair on the semiconductor enhance the de-
composition of in-situ H2O2 with the hole scavenger of CCl4 [84].
The main functionality of anode materials for the PEF/SPEF process
is similar to the EF process to generate the M(%OH). Despite the un-
acceptable expense, the BDD and Pt are more suitable for continuous
flow plant than the DSA due to the highly stable and efficient feature.

Table 3
The key parameters of the PEF process for degradation of antibiotics.
Antibiotics pH Electrode Iron source Light source Device Ref.

Enrofloxacin 3.0 Anode: Pt and BDD FeSO4·7H2O Solar photoreactor 2.5 L flow plant [78]
Cathode: Carbon-PTFE air-diffusion Philips TL/6W/08 fluorescent black light
Trimethoprim 3.0 Anode: Pt and BDDn FeSO4·7H2O Compound parabolic collector 2.2 L flow plant [80]
Cathode: Carbon-PTFE air-diffusion Philips TL 6 W/08 fluorescent black light
Trimethoprim 3.5–5.5 Anode: BDD Fe(III)-carboxylate Compound parabolic collector 2.2 L flow plant [77]
Cathode: Carbon-PTFE air-diffusion complexes UVA lamp
Metronidazole 3.0 Anode: Pt FeSO4·7H2O Compound parabolic collector 10 L solar plant [79]
Cathode: Carbon-PTFE air-diffusion
Trimethoprim 2.8 Anode: BDD FeSO4·7H2O UVA and UVC lamp 2.2 L flow plant [85]
Cathode: Carbon-PTFE air-diffusion
and Pt
Trimethoprim 3.0 Anode: RuO2/Ti FeSO4·7H2O Sunlight Photo-voltaic [42]
Cathode: ACF cell
Erythromycin 3.0 Anode: Platinized Ti FeSO4·7H2O Filter-press FM01-LC flow reactor with compound 10 L solar plant [81]
Cathode: GF parabolic collector

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X. Liu et al.
Fig. 8. The theoretical function of the solution pH and actual Fe3+ speciation: 35.8 μM Fe3+ with (a) 107 μM oxalate, (b) 35.8 μM citrate, (c) 35.8 μM tartrate and (d)
35.8 μM malate, reprinted with permission from ref [77]. Copyright 2015 Elsevier.
The coating technique is a sophisticated method for the dispersion of
noble metal on the electrode, compensating the electrochemical prop-
erty by larger area. The platinized Ti plate anode with an area of 64 cm2
was adopted for degradation of ERY with conventional 517 cm2 GF
cathode, and the cost of this pilot plant would be more practical [81]. In
addition, the photovoltaic cell was introduced to the SPEF process for
the TMP decay with RuO2/Ti mesh anode and ACF cathode possessing a
size of 20 cm2 area [42]. It is noteworthy that the gas diffusion property
makes the electrode adaptable to the flow plant, and the size of elec-
trode must act in concert with the entire pilot plant during the anti-
biotic decay by PEF and SPEF process.
3.3.3. Light source and pilot-scale device
The PEF/SPEF procedure is a suitable subject for the further in-
vestigation on the pilot-scale device, promoting the utilization of en-
ergy input such as the sunlight, UV light, applied current, and the
aeration. Moreira et al. comprehensively compared the AOPs and
EAOPs for the effluent after secondary treatment with additional 5 mg/
L TMP [85], including the UVC, H2O2/UVC, AO, AO-H2O2, AO-H2O2/
UVC, PEF-UVC, PEF-UVA in 2.2 L flow plant (Fig. 10a). Both of the PEF-
UVC and PEF-UVA processes were investigated at the neutral pH or at
the pH = 2.8, and the PEF-UVC in the acidic condition and the H2O2/
UVC are superior to the other treatment. Interestingly, the excellent
performance of H2O2/UVC is attributed to the generation of %OH from
extreme high cleavage of H2O2. The wavelength of the UVA, UVB and
UVC was 320–400 nm, 275–320 nm and 200–275 nm, respectively,
whereas the light source of PF process is usually carried out under UVA
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Chemical Engineering Journal 347 (2018) 379–397
and UVB section for the photo reduction of Fe2+ (Eqs. (11–13)) due to
the excess energy input of UVC makes no difference for the PF [10].
In addition to the combination of the solar heterogeneous photo-
catalysis (SPC) for the SPEF [86], the utilization of sunlight could in-
crease by the CPC in the SPEF due to the natural light irradiation is not
concentrated enough to make an obvious improvement [79,81]. The
CPC usually equip with a recirculation of pilot device for the solar
photoreactor instead of the static treated solution [87], including the
pump, air pump, heat exchangers, power supply, electrochemical cell,
reservoir and rotameter (Fig. 10b). In the recent research, Pérez et al.
adopted the FM01-LC flow plant equipped with CPC photoreactor for
the degradation of ERY, and the low applied current density
(j = 0.16 mA/cm2) achieve 75% current efficiency with convenient Pt
coating anode and GF cathode [81].
Interestingly, there is a novel photovoltaic cell that could supply the
EF process under sunlight as solar assisted PEF process, and Zhang et al.
employed it to the degradation of TMP with a comparison of the AO,
AO-H2O2, EF and SPEF processes [42]. As illustrated in Fig. 10c, 72
mono-crystalline silicon solar cells with an active surface area of
12 × 10 cm2 per cell connected in 6 columns and 12 rows were used to
construct the panel. Moreover, the solar cell is superior to the men-
tioned MFC for the degradation of antibiotics without the electricity
input due to the limited current density to the electrode [57]. As
compared to the EF and PF processes, the recent research on the PEF
and SPEF processes for the antibiotic removal tend to introduce pilot-
scale device for the practical application, including the CPC photo-
reactor and photovoltaic cell.
X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Fig. 9. Schematic illustration of highly efficient cathode: (a) Carbon-PTFE air diffusion cathode in the pilot device, reprinted with permission from ref [80].
Copyright 2016 Elsevier. (b) The function of 2-ethylanthraquinone (2-EAQ) in the PTFE cathode, reprinted with permission from ref [82]. Copyright 2014 Elsevier.
(c) The iron containing MOFs based cathode for the introduction of photo-activity, reprinted with permission from ref [84]. Copyright 2017 Elsevier.

4. The degradation pathway of antibiotics
The degradation of antibiotics in aqueous matrices has been re-
viewed by Homem et al., giving an overview of the conventional re-
moval process and a detailed classification and comprehensive en-
vironment analysis [31]. The common investigated structure of
antibiotics in the EF/PF/PEF is summarized in Fig. 11, giving an in-
tuitive understanding of the degradation pathway. The studies on the
antibiotic degradation by EF and PF process are so limited for the
complex structure, i.e. the degradation mechanism must be measured
by LC-MS/MS, HPLC/ESI-MS or GC–MS. The introduction of MS
certainly required a volatile mobile phase (e.g., ammonium formate
buffer or ammonium acetate buffer) for the electrospray ionization
(ESI). Therefore, the common mobile phase for the HPLC (e.g., phos-
phate buffer) can’t reach a well-defined peak due to the poor volatility
that hindered the precise determination of the intermediates. Hence,
the solid-phase extraction (SPE) is usually introduced to the pretreat-
ment of the sample to concentrate the antibiotic in solution avoiding
the interference of non-volatile salt [88–90].

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X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Fig. 10. (a) Comparison of the pilot plant of UV, H2O2-UV, AO, AO-H2O2, and PEF, reprinted with permission from ref [85]. Copyright 2016 Elsevier. (b) Schematic
diagram of compound parabolic collector (CPC) in the SPEF, reprinted with permission from ref [87]. Copyright 2011 Elsevier. (c) Novel photovoltaic cell driven
SPEF process reprinted with permission from ref [42]. Copyright 2016 Elsevier.

4.1. PF degradation pathway 4.2. EF and PEF degradation pathway

The mentioned antibiotics in the investigation of the PF process The EF and PEF are more convincing for the discussion of complete
include AMX [51], ampicillin [51], cloxacillin (CLX) [51], OXA [45], degradation pathway, and final conversion of AMX (Eq. (37)) [17], LEV
TC [24], CIP [47], CEX [49], ERY [11], CLA [11], SMX [12], TMP [12], (Eq. (38)) [14], SMT (Eq. (39)) [26], NOR (Eq. (40)) [72], ERY (Eq.
NOR [50], LEV [20], penicillins [91] and tinidazole [92]. Since the PF (41)) [81], TMP (Eq. (42)) [80], CEX (Eq. (43)) [27], ENR (Eq. (44))
process cannot always achieve complete mineralization, the discussion [78], TC (Eq. (45)) [22] and CIP (Eq. (46)) [74] were figured out to
on the degradation pathway is limited to the OXA [45], CIP [28], CEX calculate of the mineralization current efficiency (MCE) during the EF
[49], and tinidazole [92]. Serna-Galvis et al. proposed six possible and PEF process by Eq. (47). Moreover, following reactions are con-
pathways for the degradation of OXA by PF process [45], (P1) hydro- cluded from the ion chromatography, ion exclusion chromatography
xylation of the aromaticring, (P2) opening of the β-lactam ring, (P3) and TOC analyser, and time course of these inorganic ions could be
oxidation of the thioether moiety, (P4) isomerization of OXA, (P5) considered as mineralization indicators.
breakdown of the central secondary amide and (P6) decarboxylation
C16 H19 N3O5 S+ 40H2 O→ 16CO2 + 3NO−3 + SO24− + 99H+ + 94e− (37)
(Fig. S3). Villegas-Guzman et al. compared the degradation of CIP by
H2O2/UV, Fe2+/H2O2/UV and TiO2/UV [28], and illustrated the de- C18 H20 FN3O4 + 41H2 O→ F− + 3NO−3 + 102H+ + 98e− (38)
gradation pathway based on attack of the %OH (P1–P3) and the oxida-
tion of photo-induced holes (P4-P6) (Fig. S4). The CEX decay in the C12 H14 N4 O2 S+ 26H2 O→ 12CO2 + 4NH+4 + SO24− + 50H+ + 52e−
combination of PF and photo catalysis was analyzed with the frag- (39)
mentation of 8 intermediates (Fig. S5). Velo-Gala et al. investigated the
degradation mechanism of tinidazole for the obtaining of selected by- C16 H18 FN3O3 + 29H2 O→ 16CO2 + 3NH+4 + F− + 64H+ + 66e− (40)
products, including C9H11N2O2, C11H14NO2S, C16H27N4O7S2 [92]. Sin- C37 H67 NO13 + 64H2 O→ 37CO2 + NO−3 + 195H+ + 194e− (41)
cerely, these antibiotic degradation pathways suggested that the PF
process just bring about the primary break of structure rather than C14 H18 N4 O3 + 31H2 O→ 14CO2 + 2NH+4 + 2NO−3 + 72H+ + 72e− (42)
complete mineralization.
C16 H17 N3O4 S+ 41H2 O→ 16CO2 + 99H+ + 3NO−3 + SO24− + 94e− (43)

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X. Liu et al.
Fig. 11. The illustration of common investigated antibiotics in EF, PF and PEF/SPEF processes.
C19 H22 FN3O3 + 35H2 O→ 19CO2 + F− + 3NH+4 + 80H+ + 82e− (44)
C22 H24 N2 O8 + 36H2 O→ 22CO2 + 2NH+4 + 88H+ + 90e− (45)
C17 H18 FN3 O3 HCl·H2 O·+ 30H2 O→17CO2 + F− + Cl− + 3NH4+ +
69H+ + 70e− (46)
nFVSΔ(TOC)exp
MCE(%) = × 100
4.32 × 107mlt (47)
It is noteworthy that the degradation pathway of LEV in the EF
process has been discussed by three papers from different aspects,
whereas the decarboxylation, demethylation, and de-piperazinyl are
regarded as the basic reaction (Fig. S6–8). Yahya et al. investigated the
specific intermediate of LEV according to the different mass-to-charge
ration resulted from mass spectra (MS), and the possible intermediates
were figured out based on the analysis of the structure and the results of
MS [93]. In addition, Gong et al. give a more comprehensive by-product
analysis for the fragment of LEV intermediates, which might have the
same retention time (tR) as the complete structure in the results of
UPLC-QTOF-MS chromatogram [94]. Moreover, the latter’s matching of
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Chemical Engineering Journal 347 (2018) 379–397
the tR and intermediates might be more convincing than the former for
the recognition of the degradation pathway. Although the hydrogen
evolution reaction (HER) was discussed as a compete reaction for the
consumption of the proton and electron (Eq. (18)), the additional HER
with no slash on the ORR seem to be effective for the N atom directly
connected on the ben ring. In the recent research, Liu et al. firstly
characterized the HER during the degradation of LEV, proposing the
interesting mechanism for the enhancement of the modified electrode
[14].
Moreover, the degradation pathways of SMT [26], TC [22], NOR
[72], enoxacin (ENO) [95], CEX [27] and MTZ [96] during the EF
process were detailed in the recent investigation. Barhoumi et al. in-
vestigated the mechanism of SMT in the pyrite EF process based on the
BDD(%OH) mineralization [26]. The results of GC–MS provide the tR
with the specific molecular mass, and suggest that the cleavage of N-C
bond, N-S bond and the desulfonation on the benzene ring led the main
pathway (Fig. S9). Recently, Barhoumi et al. proposed the degradation
pathway of TC during the EF process based on the attack of homo-
genous %OH with the catalyst of solid chalcopyrite [22]. HPLC-MS and
GC–MS are adopted to identify high molecular weight polar byproducts
X. Liu et al.
and the lower molecular weight polar and non-polar byproducts, re-
spectively, and the multiple hydroxylation reactions, demethylation
and decarboxylation are essential to the complete mineralization (Fig.
S10).
Besides, Özcan et al. concluded the main reaction pathway of the
NOR in the EF process from both of the LC-MS and GC–MS analysis
[72]. Substitution of fluoride as well as hydroxylation was two parallel
reactions in the beginning (Fig. S11), and the hydroxylation would be
detailed in the LEV with the similar structure as illustrated in Fig. 11.
Annabi et al. illustrate the possible by-products of ENO in the EF pro-
cess with the data of UPLC-MS/MS [95], giving the comprehensive
analysis of the intermediates. The similar reaction for the generation of
ENO I, II, III, IV can be found during the mineralization of LEV (Fig.
S12). Coledam et al. proposed the degradation mechanism of the CEX
on the BDD anode according to the data of retention time, molecular
ion and main fragment ions from LC-MS/MS [27]. The hydroxylation,
breakdown of the cephem group and oxidation of substituent methyl
group are attributed to the total mineralization of CEX (Fig. S13).
Ammar et al. investigated the MTZ decay mechanism on the BDD anode
[96], reaching the complete mineralization by denitration and hydro-
xylation (Fig. S14).
Meanwhile, the degradation mechanism of TMP and MTZ were in-
vestigated in the SPEF process. Zhang et al. determine the tR and the by-
products of TMP by UPLC-QTOF-MS/MS chromatograms [42], and the
main reactions were concluded as carbonylation, hydroxylation and
demethylation (Fig. S15). Pérez et al. combined the results of LC-MS
and previous study on the TMP [79], giving a good reference to the
TMP decay by EAOPs (Fig. S16). Furthermore, the same group identi-
fied the intermediates of ERY by GC–MS during the SPEF process
without investigation on the degradation pathway [81]. The EF, PF and
SPEF could achieve complete mineralization of antibiotics in several
hours, and the investigations on the intermediates provide a clear re-
cognition of degradation mechanism and predict the potential toxicity.
4.3. The toxicity evaluation of antibiotics in PF and EF
The toxicity of antibiotics arouses an indirect threat to the medical
treatment, because the remaining toxicity of antibiotic containing ef-
fluents would increase the antibiotic resistance. The growth inhibition
tests were firstly introduced to evaluate the sulfonamides (SNs) after
the electrochemical treatment by the duckweed of Lemna minor and
green algae of Scenedesmus vacualatus (Fig. S17), and the L. minor test
confirmed that the eco-toxicity of the sulfathiazole (STZ) and SMT was
obviously increased for the high growth inhabitation [25].
Instead of the evaluation of the eco-toxicity, the assessment using
the Microtox methods for several of bacterial are more frequent. The
Vibrio Fischeri bacteria was adopted to comprehensively investigate the
toxicity during the EF process (Fig. S18), and the highest toxicity was
observed as 90 min and 60 min for the SMT [26] and AMX, respectively
[17]. Indeed, the luminescence inhibition has an unpredicted trend due
to the various of intermediates generated in the degradation process
lead a change of the toxicity. Besides, Escherichia coli cell was employed
to assess the degradation product of CEX by growth inhibition assays
[27], and the inhibition index indicates that the 3 h of electrolysis
caused no damage to the cephem functional group (Fig. S19). In the
recent research, Escherichia coli and Staphylococcus aureus were chosen
to evaluate AA of CIP treated by TiO2/UV, H2O2/UV and PF process
(Fig. S20), and the PF process shows a strong removal of the AA after
5 min treatment [28]. In conclusion, the complete structure of anti-
biotic is not the symbol of the highest toxicity, and there should be
more comprehensive evaluation on the treatment residual to avoid an
unnatural emergency of toxicity.
5. The cost aspects of EF and PF and other processes
Cost aspects are vital for the practical application, since a
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Chemical Engineering Journal 347 (2018) 379–397
comprehensive comparison of EF and PF processes and those of other
wastewater processes are valuable to choose the best strategy accord-
ingly. Generally, the optimal pH for the EF and PF process is always
acidic without any modification ensuring the oxidation state and so-
lubility of iron catalyst, and the pretreatment of acidification and sec-
ondary treatment for the neutralization might increase the budget
[8,30]. Therefore, an economical alternative to promote the suitability
of catalyst in the mild or broad pH should be investigated for EF and PF
processes, respectively. For example, the utilization of NOM in the
wastewater might improve the solubility of Fe2+/Fe3+ [19], whereas
the introduction of O2%– for the production of H2O2 is more effective
[21]. The photolysis and EO processes seem to be available in the mild
pH, but the removal efficiency is not satisfied as compared to EF and PF
processes.
Moreover, the raw materials for the synthesis of heterogeneous
catalyst certainly increase cost, especially for the less durable and
poorly recyclable catalyst. Some of noble metal loading catalysts show a
higher removal rate of EF process [59], whereas the natural mineral
catalysts are more practical for the improvement of efficiency [22,41].
The semiconductor improves the utilization of hv for the PF process,
and the heterogeneous catalyst could be immobilized on the stable
semiconductor to achieve a better recyclability. In addition, the mul-
tifunctional iron containing MOFs possess considerable efficiency both
in the PF and EF processes, but the high cost for the preparation and
poor stability might hinder the practical application [40].
The electric and photo current are essential for the EF and PF pro-
cesses, attributed to the cost of energy consumption. The DC power is
enough to carry out EF process, and the budget is largely determined by
the electrode materials showing a distinctive MCE values [43,69].
Nevertheless, most of the high performance anode certainly increases
the cost of device, let alone the corrosion on the traditional stainless
steel anode [36]. Therefore, the investigations on the modification of
cathode with accessible regent are more convincing to improve the
cheap but inefficient DSA anode. Generally, the energy consumption of
PF as well as other photocatalysis processes is lower than the EF and
related electrocatalysis processes, and the investigation on the service
life of device of light source for a continuous illumination is certainly
beneficial. The utilization of solar light requires investment on the pilot
equipment to enhance the hv in sunlight, providing valid photo-activity
for the PF process [11,79].
Purification of antibiotic wastewater by adsorption process is also a
common process, which seems to be cheaper as compared to the EF and
PF process [97]. The antibiotic concentrated on the adsorbent remains
the complete structure, and untimely separation of exhausted adsorbent
would cause a secondary pollution. Moreover, the regeneration of ex-
hausted adsorbent is necessary for the continuous removal of antibiotic
in wastewater. Apparently, the cost of complete treatment of adsorption
process shows no superiority to the EF and PF process, let alone the
unsatisfied time-consuming and final treatment of solution from the
regeneration process.
Biological treatment process might be the most practical and so-
phisticated process if the wastewater is degradable and debugging
process has been accomplished. The removal of different antibiotic in
the AS process shows distinctive characteristic for adsorption and bio-
degradation, and the low biodegradability of fluoroquinolones waste-
water increases the difficulty for the cultivation of microorganisms
[98]. It might cause much higher expend for control of sludge return
ratio, increasing the risk of destroying the balance of biological system.
In most case, the treated time of independent SBR for the antibiotics
seems to be much longer than EF and PF processes, and the effluent
after the biological treatment is still not in agreement with regulatory
limits [99].
6. The gaps need to be filled
Firstly, the contamination of natural water environment is often
X. Liu et al.
complex, and the assessment often involved with numbers of indicators,
leading pollution of surface water directly and groundwater mainly
through leaching and infiltration. Hence, it is also significant to remove
these unpredictable substances. Antonin et al. compared the EO, EF,
PEF and SPEF for the degradation of CIP in synthetic urine matrix and
sulfate medium [100], proposing a mechanism study of CIP by EAOPs
in sulfate medium (Fig. S21). The final mineralization efficiency has an
interesting improvement in the urine, indicating a well application of
EF, PF, PEF and SPEF to antibiotics in high urea content. Jojoa-Sierra
et al. investigated the degradation of NOR in urine, municipal waste-
water and seawater [101], giving a comparison of the AA as well (Fig.
S22).
Secondly, compared to the experiment for the degradation of or-
ganic micropollutants performed in the laboratory, the pilot-scale stu-
dies are more realistic for the remediation of the polluted wastewater at
a low antibiotic concentration [9]. Moreover, the pilot plant in the PEF
and SPEF are more convincing for the degradation of antibiotics at huge
flow rate (e.g., NETmix® photoreactors [12] and MBR in PF process
[11]). Nevertheless, most of research on the antibiotic decay in EF
process is at laboratory-scale [102], whereas the “filter”-type EF device
for the pilot-scale degradation has been proposed (Fig. S23). Facile
preparation method of the high performance carbon cathode seems to
be a possible approach to the development of pilot device [103]. Fur-
thermore, the detection of the SMX and TMP based on the electro-
chemical sensor is also benefit for the monitor of end-point of industrial
level wastewater [104].
Thirdly, the improvement of partial degradation of antibiotic ef-
fluent with a high concentration and low biodegradability could be
effective for lower energy consumption, followed by biological de-
gradation with a mixed culture of bacteria in the SBR or aerobic method
[99]. Olvera-Vargas et al. improved the ratio of BOD5/COD of the
metoprolol from 0.012 to 0.44 after 1 h EF treatment, and the further
aerobic treatment would achieve about 90% TOC removal [105]. Al-
though the 4 h EF treatment would complete the mineralization pro-
cedure, the combination of biological method would obviously cut the
cost. Interestingly, the recent papers simply supplement the data of
biodegradability without biological treatment, whereas the ratio of
BOD5/COD is enough for the assessment of pretreatment. Gong et al.
compared the partial degradation of EF process, anodic oxidation (AO),
and AO with electrogenerated H2O2 (AO-H2O2) by LEV [94]. The EF
process shows a convincing superiority for the TOC removal, and the
nearly zero BOD5 value of the LEV solution could achieve a pretty
biodegradability after 6 h EF treatment.
Fourthly, the spending high-performance anodes are not acceptable
mainly caused by the price of noble metal materials and complex
craftsmanship. To accomplish the BDD thin films, Mackul’ak et al.
added trimethylboron (TMB) into the 2% of CH4 in H2 gas activated by
five tungsten filaments (0.7 mm diameter) heated up to 2100 °C to ar-
chive the B/C ratio of 10,000 ppm. Then, the thin films were grown for
120 min with 3 kPa deposition pressure and substrate temperature
650 °C by Hot filament chemical vapor deposition (HFCVD), the
thickness was about 500 nm at both sides of a Si (10 9 10 mm) substrate
[73]. Although the strict condition and huge energy consumption have
been difficult to accomplish, the size of BDD thin films is still too lim-
ited to spread. Fortunately, there is a critical mini review on the elec-
trocatalytic properties of BDD, indicating a vital role of sp3/sp2 ratio for
the catalysis [106]. Since the possibility of reducing materials cost is
tiny, a better understanding of the potential window, molecular ad-
sorption and voltammetric background current for the impurities of sp2-
carbon seem to accelerate the formation of sophisticated fabrication
method of BDD practically.
Last but not the least, there is an emerging direction for the precise
by-products investigation with specific organic matter with various
characterization methods, and the antibiotics are suitable for the in-
vestigation due to the complex structure. The presence of 4-chlor-
ophenyl benzoate during the degradation of fluoxetine by PEF process
395
Chemical Engineering Journal 347 (2018) 379–397
confirmed the generation of HClO on the BDD anode [107]. The effect
of the Cl− can be attractive for the real wastewater purification, and the
incomplete oxidation might even change the toxicity for the un-
predicted intermediates. The formation of Fe3+-CIP chelate in the EF
process was evaluated by Chen et al., and the reduction of Fe3+ on the
cathode was promoted with the optimal chelate ratio (0.25 mM of Fe2+
and 1.50 mM of Fe3+) [108]. Meanwhile, the carcinogenicity of N-
containing pollutants aroused the interesting research on the amines
and nitro-derivatives. The quantification of N-volatile species in the
degradation of the N-containing pollutants could be assessed by dif-
ferential electrochemistry mass spectroscopy (DEMS) [109]. Interest-
ingly, the special structure of N-containing pollutants has its own be-
havior, affected by the HER on the modified cathode. In the latest
research, the degradation pathway of LEV was refined with the in-
troduction of HER, leading the conversion of the amino and nitro
groups on aromatic ring [14]. As a result, the additional HER reduced
the stability of LEV, showing in a 2.2 times higher value of initial MCE
and more complete mineralization.
Acknowledgements
The study was financially supported by the National Natural Science
Foundation of China (51709103), the National Program for Support of
Top-Notch Young Professionals of China (2012), the Program for New
Century Excellent Talents in University from the Ministry of Education
of China (NCET-11-0129), Project of Science and Technology of Hunan
Province (2016WK2010).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.cej.2018.04.142.
References
[1] M.J. Blaser, Antibiotic use and its consequences for the normal microbiome,
Science 352 (2016) 544–545.
[2] J.E. Michiels, d.B.B. Van, N. Verstraeten, J. Michiels, Molecular mechanisms and
clinical implications of bacterial persistence, Drug Resist. Update 29 (2016)
76–89.
[3] S. Aydin, B. Ince, O. Ince, Assessment of anaerobic bacterial diversity and its ef-
fects on anaerobic system stability and the occurrence of antibiotic resistance
genes, Bioresource Technol. 207 (2016) 332–338.
[4] J.L. Martínez, Antibiotics and antibiotic resistance genes in natural environments,
Science 321 (2008) 365–367.
[5] S. Tunç, T. Gürkan, O. Duman, On-line spectrophotometric method for the de-
termination of optimum operation parameters on the decolorization of acid red 66
and direct blue 71 from aqueous solution by Fenton process, Chem. Eng. J.
181–182 (2012) 431–442.
[6] S. Tunç, O. Duman, T. Gürkan, Monitoring the decolorization of acid orange 8 and
acid red 44 from aqueous solution using Fenton’s reagents by online spectro-
photometric method: effect of operation parameters and kinetic study, Ind. Eng.
Chem. Res. 52 (2013) 1414–1425.
[7] I. Sirés, E. Brillas, Remediation of water pollution caused by pharmaceutical re-
sidues based on electrochemical separation and degradation technologies: a re-
view, Environ. Int. 40 (2012) 212–229.
[8] M. Umar, H.A. Aziz, M.S. Yusoff, Trends in the use of Fenton, electro-Fenton and
photo-Fenton for the treatment of landfill leachate, Waste Manage. (Oxford) 30
(2010) 2113–2121.
[9] F.C. Moreira, A.R.B. Rui, E. Brillas, V.J.P. Vilar, Electrochemical advanced oxi-
dation processes: a review on their application to synthetic and real wastewaters,
Appl. Catal. B: Environ. 202 (2016) 217–261.
[10] V. Romero, O. González, B. Bayarri, P. Marco, J. Giménez, S. Esplugas,
Degradation of metoprolol by photo-Fenton: comparison of different photoreactors
performance, Chem. Eng. J. 283 (2016) 639–648.
[11] P. Karaolia, I. Michael-Kordatou, E. Hapeshi, J. Alexander, T. Schwartz, D. Fatta-
Kassinos, Investigation of the potential of a Membrane BioReactor followed by
solar Fenton oxidation to remove antibiotic-related microcontaminants, Chem.
Eng. J. 310 (2016) 491–502.
[12] M.J. Lima, C.G. Silva, A.M.T. Silva, J.C.B. Lopes, M.M. Dias, J.L. Faria,
Homogeneous and heterogeneous photo-Fenton degradation of antibiotics using
an innovative static mixer photoreactor, Chem. Eng. J. 310 (2017) 342–351.
[13] Y. Li, J. Han, B. Xie, Y. Li, S. Zhan, Y. Tian, Synergistic degradation of anti-
microbial agent ciprofloxacin in water by using 3D CeO2/RGO composite as
cathode in electro-Fenton system, J. Electroanal. Chem. 784 (2017) 6–12.
X. Liu et al.
[14] X. Liu, D. Yang, Y. Zhou, J. Zhang, L. Luo, S. Meng, S. Chen, M. Tan, Z. Li, L. Tang,
Electrocatalytic properties of N-doped graphite felt in electro-Fenton process and
degradation mechanism of levofloxacin, Chemosphere 182 (2017) 306–315.
[15] H. Zhao, L. Qian, X. Guan, D. Wu, G. Zhao, Continuous bulk FeCuC aerogel with
ultradispersed metal nanoparticles: an efficient 3D heterogeneous electro-Fenton
cathode over a wide range of pH 3–9, Environ. Sci. Technol. 50 (2016)
5225–5233.
[16] S.O. Ganiyu, N. Oturan, S. Raffy, M. Cretin, R. Esmilaire, E.V. Hullebusch,
G. Esposito, M.A. Oturan, Sub-stoichiometric titanium oxide (Ti4O7) as a suitable
ceramic anode for electrooxidation of organic pollutants: a case study of kinetics,
mineralization and toxicity assessment of amoxicillin, Water Res. 106 (2016)
171–182.
[17] N. Oturan, S.O. Ganiyu, S. Raffy, M.A. Oturan, Sub-stoichiometric titanium oxide
as a new anode material for electro-Fenton process: application to electrocatalytic
destruction of antibiotic amoxicillin, Appl. Catal. B: Environ. 217 (2017) 214–223.
[18] S. Giannakis, M.I.P. López, D. Spuhler, J.A.S. Pérez, P.F. Ibáñez, C. Pulgarin, Solar
disinfection is an augmentable, in situ -generated photo-Fenton reaction—Part 1: a
review of the mechanisms and the fundamental aspects of the process, Appl. Catal.
B: Environ. 199 (2016) 199–223.
[19] E.E. Daugherty, B. Gilbert, P.S. Nico, T. Borch, Complexation and redox buffering
of iron(II) by dissolved organic matter, Environ. Sci. Technol. 51 (2017)
11096–11104.
[20] A.A. Nogueira, B.M. Souza, M.W.C. Dezotti, A.R.B. Rui, V.J.P. Vilar, Ferrioxalate
complexes as strategy to drive a photo-Fenton reaction at mild pH conditions: a
case study on levofloxacin oxidation, J. Photochem. Photobiol. A 345 (2017)
109–123.
[21] L. Wang, M. Cao, Z. Ai, L. Zhang, Design of a highly efficient and wide pH electro-
Fenton oxidation system with molecular oxygen activated by ferrous-tetra-
polyphosphate complex, Environ. Sci. Technol. 49 (2015) 3032–3039.
[22] N. Barhoumi, H. Olvera-Vargas, N. Oturan, D. Huguenot, A. Gadri, S. Ammar,
E. Brillas, M.A. Oturan, Kinetics of oxidative degradation/mineralization pathways
of the antibiotic tetracycline by the novel heterogeneous electro-Fenton process
with solid catalyst chalcopyrite, Appl. Catal. B: Environ. 209 (2017) 637–647.
[23] H. Lan, J. Li, M. Sun, X. An, C. Hu, R. Liu, H. Liu, J. Qu, Efficient conversion of
dimethylarsinate into arsenic and its simultaneous adsorption removal over FeCx/
N-doped carbon fiber composite in an electro-Fenton process, Water Res. 100
(2016) 57–64.
[24] B. Kakavandi, A. Takdastan, N. Jaafarzadeh, M. Azizi, A. Mirzaei, A. Azari,
Application of Fe3O4@C catalyzing heterogeneous UV-Fenton system for tetra-
cycline removal with a focus on optimization by a response surface method, J.
Photochem. Photobiol. A 314 (2016) 178–188.
[25] A. Fabiańska, A. Białkbielińska, P. Stepnowski, S. Stolte, E.M. Siedlecka,
Electrochemical degradation of sulfonamides at BDD electrode: kinetics, reaction
pathway and eco-toxicity evaluation, J. Hazard. Mater. 280 (2014) 579–587.
[26] N. Barhoumi, N. Oturan, H. Olvera-Vargas, E. Brillas, A. Gadri, S. Ammar,
M.A. Oturan, Pyrite as a sustainable catalyst in electro-Fenton process for im-
proving oxidation of sulfamethazine. Kinetics, mechanism and toxicity assessment,
Water Res. 94 (2016) 52–61.
[27] D.A.C. Coledam, M.M.S. Pupo, B.F. Silva, A.J. Silva, K.I.B. Eguiluz, G.R. Salazar-
Banda, J.M. Aquino, Electrochemical mineralization of cephalexin using a con-
ductive diamond anode: a mechanistic and toxicity investigation, Chemosphere
168 (2016) 638–647.
[28] P. Villegasguzman, S. Oppenheimerbarrot, J. Silvaagredo, R.A. Torrespalma,
comparative evaluation of photo-chemical AOPs for ciprofoxacin degradation:
elimination in natural waters and analysis of pH effect, primary degradation by-
Products, and the relationship with the antibiotic activity, Water Air Soil Pollut.
228 (2017) 209–224.
[29] E. Brillas, I. Sirés, M.A. Oturan, Electro-Fenton process and related electrochemical
technologies based on Fenton's reaction chemistry, Chem. Rev. 109 (2009)
6570–6631.
[30] H. He, Z. Zhou, Electro-Fenton process for water and wastewater treatment, Crit.
Rev. Environ. Sci. Technol. 47 (2017) 2100–2131.
[31] V. Homem, L. Santos, Degradation and removal methods of antibiotics from
aqueous matrices–a review, J. Environ. Manage. 92 (2011) 2304–2347.
[32] M.A. Oturan, J.J. Aaron, Advanced oxidation processes in water/wastewater
treatment: principles and applications. a review, Crit. Rev. Environ. Sci. Technol.
44 (2014) 2577–2641.
[33] R.G. Zepp, B.C. Faust, J. Hoigne, Hydroxyl radical formation in aqueous reactions
(pH 3–8) of iron(II) with hydrogen peroxide: the photo-Fenton reaction, Environ.
Sci. Technol 26 (1992) 313–319.
[34] I. Grčić, S. Papić, K. Žižek, N. Koprivanac, Zero-valent iron (ZVI) Fenton oxidation
of reactive dye wastewater under UV-C and solar irradiation, Chem. Eng. J.
195–196 (2012) 77–90.
[35] E. Brillas, E. Llosa, J. Casado, R.M. Bastida, Electrochemical destruction of aniline
and 4-chloroaniline for wastewater treatment using a carbon-PTFE O2-fed
cathode, J. Electrochem. Soc. 142 (1995) 1733–1741.
[36] E. Brillas, C.A. Martínez-Huitle, Decontamination of wastewaters containing syn-
thetic organic dyes by electrochemical methods. An updated review, Appl. Catal.
B: Environ. 87 (2009) 105–145.
[37] C. Ridruejo, F. Centellas, P.L. Cabot, I. Sirés, E. Brillas, Electrochemical Fenton-
based treatment of tetracaine in synthetic and urban wastewater using active and
non-active anodes, Water Res. 128 (2017) 71–81.
[38] W. Liu, J. Ma, C. Shen, Y. Wen, W. Liu, A pH-responsive and magnetically se-
parable dynamic system for efficient removal of highly dilute antibiotics in water,
Water Res. 90 (2016) 24–33.
[39] H. Barndõk, L. Blanco, D. Hermosilla, Á. Blanco, Heterogeneous photo-Fenton
396
Chemical Engineering Journal 347 (2018) 379–397
processes using zero valent iron microspheres for the treatment of wastewaters
contaminated with 1,4-dioxane, Chem. Eng. J. 284 (2016) 112–121.
[40] X. Liu, Y. Zhou, J. Zhang, L. Tang, L. Luo, G. Zeng, Iron containing metal-organic
frameworks: structure, synthesis, and applications in environmental remediation,
ACS Appl. Mater. Interfaces 9 (2017) 20255–20275.
[41] N. Barhoumi, L. Labiadh, M.A. Oturan, N. Oturan, A. Gadri, S. Ammar, E. Brillas,
Electrochemical mineralization of the antibiotic levofloxacin by electro-Fenton-
pyrite process, Chemosphere 141 (2015) 250–257.
[42] Y. Zhang, A. Wang, X. Tian, Z. Wen, H. Lv, D. Li, J. Li, Efficient mineralization of
the antibiotic trimethoprim by solar assisted photoelectro-Fenton process driven
by a photovoltaic cell, J. Hazard. Mater. 318 (2016) 319.
[43] F. Sopaj, N. Oturan, J. Pinson, F. Podvorica, M.A. Oturan, Effect of the anode
materials on the efficiency of the electro-Fenton process for the mineralization of
the antibiotic sulfamethazine, Appl. Catal. B: Environ. 199 (2016) 331–341.
[44] H. Shemer, K.G. Linden, Degradation and by-product formation of diazinon in
water during UV and UV/H2O2 treatment, J. Hazard. Mater. 136 (2006) 553–559.
[45] E.A. Serna-Galvis, J. Silva-Agredo, A.L. Giraldo, O.A. Flórez, R.A. Torres-Palma,
Comparison of route, mechanism and extent of treatment for the degradation of a
β-lactam antibiotic by TiO2 photocatalysis, sonochemistry, electrochemistry and
the photo-Fenton system, Chem. Eng. J. 284 (2016) 953–962.
[46] E.A. Sernagalvis, J. Silvaagredo, A.L. Giraldo, O.A. Flórezacosta,
R.A. Torrespalma, Comparative study of the effect of pharmaceutical additives on
the elimination of antibiotic activity during the treatment of oxacillin in water by
the photo-Fenton, TiO2-photocatalysis and electrochemical processes, Sci. Total
Environ. 541 (2016) 1431–1438.
[47] P. Jal, S. Bce, A.L. Tonetti, N. Rfp, Photo-Fenton degradation of the pharmaceu-
ticals ciprofloxacin and fluoxetine after anaerobic pre-treatment of hospital ef-
fluent, Environ. Sci. Pollut. R. 24 (2017) 1–8.
[48] N. Klamerth, S. Malato, A. Agüera, A. Fernándezalba, Photo-Fenton and modified
photo-Fenton at neutral pH for the treatment of emerging contaminants in was-
tewater treatment plant effluents: a comparison, Water Res. 47 (2013) 833–840.
[49] P. Bansal, A. Verma, Synergistic effect of dual process (photocatalysis and photo-
Fenton) for the degradation of Cephalexin using TiO2 immobilized novel clay
beads with waste fly ash/foundry sand, J. Photochem. Photobiol. A 342 (2017)
131–142.
[50] T. Shi, J. Peng, J. Chen, C. Sun, H. He, Heterogeneous photo-Fenton degradation of
norfloxacin with Fe3O4-multiwalled carbon nanotubes in aqueous solution, Catal.
Lett. 147 (2017) 1–10.
[51] E.S. Elmolla, M. Chaudhuri, Degradation of the antibiotics amoxicillin, ampicillin
and cloxacillin in aqueous solution by the photo-Fenton process, J. Hazard. Mater.
172 (2009) 1476–1481.
[52] E.E.S. Elmolla, M. Chaudhuri, Combined photo-Fenton–SBR process for antibiotic
wastewater treatment, J. Hazard. Mater. 192 (2011) 1418–1426.
[53] M. Huang, Z. Tao, X. Wu, J. Mao, Distinguishing homogeneous-heterogeneous
degradation of norfloxacin in a photochemical Fenton-like system (Fe3O4/UV/
oxalate) and the interfacial reaction mechanism, Water Res. 119 (2017) 47–56.
[54] X. Wang, A. Wang, J. Ma, Visible-light-driven photocatalytic removal of antibiotics
by newly designed C3N4@MnFe2O4-graphene nanocomposites, J. Hazard. Mater.
336 (2017) 81–92.
[55] M. Pérez, F. Torrades, X. Domènech, J. Peral, Fenton and photo-Fenton oxidation
of textile effluents, Water Res. 36 (2002) 2703–2710.
[56] S. Giannakis, M.I.P. López, D. Spuhler, J.A.S. Pérez, P.F. Ibáñez, C. Pulgarin, Solar
disinfection is an augmentable, in situ-generated photo-Fenton reaction—Part 2: a
review of the applications for drinking water and wastewater disinfection, Appl.
Catal. B: Environ. 198 (2016) 431–446.
[57] Y. Li, L. Liu, F. Yang, Destruction of tetracycline hydrochloride antibiotics by
FeOOH/TiO2 granular activated carbon as expanded cathode in low-cost MBR/
MFC coupled system, J. Membr. Sci. 525 (2017) 202–209.
[58] J. Jiang, G. Li, Z. Li, X. Zhang, F. Zhang, An Fe–Mn binary oxide (FMBO) modified
electrode for effective electrochemical advanced oxidation at neutral pH,
Electrochim. Acta 194 (2016) 104–109.
[59] K. Kim, P. Qiu, M. Cui, J. Khim, Development and application of Fe3O4–Pd na-
nospheres as catalyst for electrochemical-heterogeneous Fenton process, Chem.
Eng. J. 284 (2016) 1165–1173.
[60] B. Huang, C. Qi, Z. Yang, Q. Guo, W. Chen, G. Zeng, C. Lei, Pd/Fe3O4 nanocatalysts
for highly effective and simultaneous removal of humic acids and Cr(VI) by
electro-Fenton with H2O2 in situ electro-generated on the catalyst surface, J. Catal.
352 (2017) 337–350.
[61] Z. Zhu, C. Yi, G. Yan, W. Fei, W. Lu, T. Xu, W. Chen, Catalytic degradation of
recalcitrant pollutants by Fenton-like process using polyacrylonitrile-supported
iron(II) phthalocyanine nanofibers: intermediates and pathway, Water Res. 93
(2016) 296–305.
[62] E. Petrucci, A.D. Pozzo, L.D. Palma, On the ability to electrogenerate hydrogen
peroxide and to regenerate ferrous ions of three selected carbon-based cathodes
for electro-Fenton processes, Chem. Eng. J. 283 (2016) 750–758.
[63] L. Zhou, M. Zhou, Z. Hu, Z. Bi, K.G. Serrano, Chemically modified graphite felt as
an efficient cathode in electro-Fenton for p-nitrophenol degradation, Electrochim.
Acta 140 (2014) 376–383.
[64] T. Ling, B. Huang, M. Zhao, Q. Yan, W. Shen, Repeated oxidative degradation of
methyl orange through bio-electro-Fenton in bioelectrochemical system (BES),
Bioresource Technol. 203 (2016) 89–95.
[65] L. Zhou, M. Zhou, C. Zhang, Y. Jiang, Z. Bi, J. Yang, Electro-Fenton degradation of
p -nitrophenol using the anodized graphite felts, Chem. Eng. J. 233 (2013)
185–192.
[66] Y. Wang, Y. Liu, K. Wang, S. Song, P. Tsiakaras, H. Liu, Preparation and char-
acterization of a novel KOH activated graphite felt cathode for the electro-Fenton
X. Liu et al.
process, Appl. Catal. B: Environ. 165 (2015) 360–368.
[67] G. Gao, Q. Zhang, Z. Hao, C.D. Vecitis, Carbon nanotube membrane stack for flow-
through sequential regenerative electro-Fenton, Environ. Sci. Technol. 49 (2015)
2375–2383.
[68] Y. Li, J. Han, X. Mi, X. Mi, Y. Li, S. Zhang, S. Zhan, Modified carbon felt made using
CexA1−xO2 composites as a cathode in electro-Fenton system to degrade cipro-
floxacin, RSC Adv. 7 (2017) 27065–27078.
[69] N. Oturan, J. Wu, H. Zhang, V.K. Sharma, M.A. Oturan, Electrocatalytic destruc-
tion of the antibiotic tetracycline in aqueous medium by electrochemical advanced
oxidation processes: effect of electrode materials, Appl. Catal. B: Environ. 140–141
(2013) 92–97.
[70] B. Marselli, J. Garcia-Gomez, P.A. Michaud, M.A. Rodrigo, C. Comninellis, elec-
trogeneration of hydroxyl radicals on boron-doped diamond electrodes, J.
Electrochem. Soc. 150 (2003) D79–D83.
[71] M.S. Çelebi, N. Oturan, H. Zazou, M. Hamdani, M.A. Oturan, Electrochemical
oxidation of carbaryl on platinum and boron-doped diamond anodes using electro-
Fenton technology, Sep. Purif. Technol. 156 (2015) 996–1002.
[72] A. Özcan, A.A. Özcan, Y. Demirci, Evaluation of mineralization kinetics and
pathway of norfloxacin removal from water by electro-Fenton treatment, Chem.
Eng. J. 304 (2016) 518–526.
[73] T. Mackuľak, M. Vojs, R. Grabic, O. Golovko, A.V. Staňová, L. Birošová,
A. Medveďová, J. Híveš, M. Gál, A. Kromka, Occurrence of pharmaceuticals, illicit
drugs, and resistant types of bacteria in hospital effluent and their effective de-
gradation by boron-doped diamond electrodes, Monatsh. Chem. 147 (2016)
97–103.
[74] Y. Msh, N. Oturan, K.K. El, K.M. El, C.T. Aravindakumar, M.A. Oturan, Oxidative
degradation study on antimicrobial agent ciprofloxacin by electro-Fenton process:
kinetics and oxidation products, Chemosphere 117 (2014) 447–454.
[75] T.L. Luu, J. Kim, J. Yoon, T.L. Luu, J. Kim, J. Yoon, A novel microwave-assisted
synthesis of RuO2-TiO2 electrodes with improved chlorine and oxygen evolutions,
Desalin. Water Treat. 77 (2016) 105–111.
[76] E. Brillas, B. Boye, I. Sirés, J.A. Garrido, R.M.A. RodríGuez, C. Arias, P.L. Cabot,
Comninellis, Electrochemical destruction of chlorophenoxy herbicides by anodic
oxidation and electro-Fenton using a boron-doped diamond electrode,
Electrochim. Acta 49 (2004) 4487–4496.
[77] F.C. Moreira, A.R.B. Rui, E. Brillas, V.J.P. Vilar, Degradation of trimethoprim
antibiotic by UVA photoelectro-Fenton process mediated by Fe(III)–carboxylate
complexes, Appl. Catal. B: Environ. 162 (2015) 34–44.
[78] E. Guinea, J.A. Garrido, R.M. Rodríguez, P.L. Cabot, C. Arias, F. Centellas,
E. Brillas, Degradation of the fluoroquinolone enrofloxacin by electrochemical
advanced oxidation processes based on hydrogen peroxide electrogeneration,
Electrochim. Acta 55 (2010) 2101–2115.
[79] T. Pérez, S. Garcia-Segura, A. El-Ghenymy, J.L. Nava, E. Brillas, Solar photo-
electro-Fenton degradation of the antibiotic metronidazole using a flow plant with
a Pt/air-diffusion cell and a CPC photoreactor, Electrochim. Acta 165 (2015)
173–181.
[80] F.C. Moreira, S. Garcia-Segura, A.R.B. Rui, E. Brillas, V.J.P. Vilar, Degradation of
the antibiotic trimethoprim by electrochemical advanced oxidation processes
using a carbon-PTFE air-diffusion cathode and a boron-doped diamond or pla-
tinum anode, Appl. Catal. B: Environ. 160–161 (2014) 492–505.
[81] T. Pérez, I. Sirés, E. Brillas, J.L. Nava, Solar photoelectro-Fenton flow plant
modeling for the degradation of the antibiotic erythromycin in sulfate medium,
Electrochim. Acta 228 (2017) 45–56.
[82] W. Wang, J. Yu, J. Zou, X. Yu, Mechanism for enhancing biodegradability of an-
tibiotic pharmacy wastewater by in-situ generation of H2O2 and radicals over MnO
x /nano-G/2-EAQ/AC cathode, Electrochim. Acta 191 (2016) 426–434.
[83] T. Liu, K. Wang, S. Song, A. Brouzgou, P. Tsiakaras, Y. Wang, New electro-Fenton
gas diffusion cathode based on nitrogen-doped graphene@carbon nanotube
composite materials, Electrochim. Acta 194 (2016) 228–238.
[84] H. Zhao, Y. Chen, Q. Peng, Q. Wang, G. Zhao, Catalytic activity of MOF (2Fe/Co)/
carbon aerogel for improving H 2 O 2 and OH generation in solar
photo–electro–Fenton process, Appl. Catal. B 203 (2017) 127–137.
[85] F.C. Moreira, J. Soler, M.F. Alpendurada, A.R.B. Rui, E. Brillas, V.J.P. Vilar,
Tertiary treatment of a municipal wastewater toward pharmaceuticals removal by
chemical and electrochemical advanced oxidation processes, Water Res. 105
(2016) 251–263.
[86] B. Garzacampos, E. Brillas, A. Hernándezramírez, A. Elghenymy, J.L. Guzmánmar,
E.J. Ruizruiz, Salicylic acid degradation by advanced oxidation processes.
Coupling of solar photoelectro-Fenton and solar heterogeneous photocatalysis, J.
Hazard. Mater. 319 (2016) 34–42.
[87] S. Garcia-Segura, L.C. Almeida, N. Bocchi, E. Brillas, Solar photoelectro-Fenton
degradation of the herbicide 4-chloro-2-methylphenoxyacetic acid optimized by
response surface methodology, J. Hazard. Mater. 194 (2011) 109–118.
397
Chemical Engineering Journal 347 (2018) 379–397
[88] J. Wu, L. Chen, P. Mao, Y. Lu, H. Wang, Determination of chloramphenicol in
aquatic products by graphene-based SPE coupled with HPLC-MS/MS, J. Sep. Sci.
35 (2012) 3586–3592.
[89] Q.T. Dinh, F. Alliot, E. Moreau-Guigon, J. Eurin, M. Chevreuil, P. Labadie,
Measurement of trace levels of antibiotics in river water using on-line enrichment
and triple-quadrupole LC-MS/MS, Talanta 85 (2011) 1238–1245.
[90] Y. Zhao, W. Li, J. Liu, K. Huang, C. Wu, H. Shao, H. Chen, X. Liu, Modification of
garlic peel by nitric acid and its application as a novel adsorbent for solid-phase
extraction of quinolone antibiotics, Chem. Eng. J. 326 (2017) 745–755.
[91] P. Villegasguzman, J. Silvaagredo, O. Florez, A.L. Giraldoaguirre, C. Pulgarin,
R.A. Torrespalma, Selecting the best AOP for isoxazolyl penicillins degradation as
a function of water characteristics: effects of pH, chemical nature of additives and
pollutant concentration, J. Environ. Manage. 190 (2017) 72–79.
[92] I. Velo-Gala, J.A. Pirán-Montaño, J. Rivera-Utrilla, M. Sánchez-Polo, A.J. Mota,
Advanced oxidation processes based on the use of UVC and simulated solar ra-
diation to remove the antibiotic tinidazole from water, Chem. Eng. J. 323 (2017)
605–617.
[93] Y. Msh, K.M. El, N. Oturan, K.K. El, M.A. Oturan, Mineralization of the antibiotic
levofloxacin in aqueous medium by electro-Fenton process: kinetics and inter-
mediate products analysis, Environ. Technol. 37 (2016) 1276–1287.
[94] Y. Gong, J. Li, Y. Zhang, M. Zhang, X. Tian, A. Wang, Partial degradation of le-
vofloxacin for biodegradability improvement by electro-Fenton process using an
activated carbon fiber felt cathode, J. Hazard. Mater. 304 (2015) 320–328.
[95] C. Annabi, F. Fourcade, I. Soutrel, F. Geneste, D. Floner, N. Bellakhal, A. Amrane,
Degradation of enoxacin antibiotic by the electro-Fenton process: optimization,
biodegradability improvement and degradation mechanism, J. Environ. Manage.
165 (2016) 96–105.
[96] H.B. Ammar, M.B. Brahim, R. Abdelhédi, Y. Samet, Green electrochemical process
for metronidazole degradation at BDD anode in aqueous solutions via direct and
indirect oxidation, Sep. Purif. Technol. 157 (2016) 9–16.
[97] Y. Zhou, X. Liu, Y. Xiang, P. Wang, J. Zhang, F. Zhang, J. Wei, L. Luo, M. Lei,
L. Tang, Modification of biochar derived from sawdust and its application in re-
moval of tetracycline and copper from aqueous solution: adsorption mechanism
and modelling, Bioresour. Technol. 245 (2017) 266–273.
[98] L. Bing, Z. Tong, Biodegradation and adsorption of antibiotics in the activated
sludge process, Environ. Sci. Technol. 44 (2010) 3468–3473.
[99] K.S. Jewell, S. Castronovo, A. Wick, P. Falås, A. Joss, T.A. Ternes, New insights
into the transformation of trimethoprim during biological wastewater treatment,
Water Res. 88 (2016) 550–557.
[100] V.S. Antonin, M.C. Santos, S. Garcia-Segura, E. Brillas, Electrochemical incinera-
tion of the antibiotic ciprofloxacin in sulfate medium and synthetic urine matrix,
Water Res. 83 (2015) 31–41.
[101] S.D. Jojoa-Sierra, J. Silva-Agredo, E. Herrera-Calderon, R.A. Torres-Palma,
Elimination of the antibiotic norfloxacin in municipal wastewater, urine and
seawater by electrochemical oxidation on IrO2 anodes, Sci. Total Environ. 575
(2016) 1228–1238.
[102] K.V. Plakas, S.D. Sklari, D.A. Yiankakis, G.T. Sideropoulos, V.T. Zaspalis,
A.J. Karabelas, Removal of organic micropollutants from drinking water by a
novel electro-Fenton filter: pilot-scale studies, Water Res. 91 (2016) 183–194.
[103] T.X.H. Le, C. Charmette, M. Bechelany, M. Cretin, Facile preparation of porous
carbon cathode to eliminate paracetamol in aqueous medium using electro-Fenton
system, Electrochim. Acta 188 (2016) 378–384.
[104] L.F. Sgobbi, C.A. Razzino, S.A.S. Machado, A disposable electrochemical sensor for
simultaneous detection of sulfamethoxazole and trimethoprim antibiotics in urine
based on multiwalled nanotubes decorated with Prussian blue nanocubes modified
screen-printed electrode, Electrochim. Acta 191 (2016) 1010–1017.
[105] H. Olvera-Vargas, T. Cocerva, N. Oturan, D. Buisson, M.A. Oturan, Bioelectro-
Fenton: a sustainable integrated process for removal of organic pollutants from
water: application to mineralization of metoprolol, J. Hazard. Mater. 319 (2016)
13–23.
[106] S. Garcia-Segura, E.V.D. Santos, C.A. Martínez-Huitle, Role of sp3/sp2 ratio on the
electrocatalytic properties of boron-doped diamond electrodes: a mini review,
Electrochem. Commun. 59 (2015) 52–55.
[107] C. Salazar, C. Ridruejo, E. Brillas, J. Yáñez, H.D. Mansilla, I. Sirés, Abatement of
the fluorinated antidepressant fluoxetine (Prozac) and its reaction by-products by
electrochemical advanced methods, Appl. Catal. B: Environ. 203 (2017) 189–198.
[108] Y. Chen, A. Wang, Y. Zhang, R. Bao, X. Tian, J. Li, Electro-Fenton degradation of
antibiotic ciprofloxacin (CIP): formation of Fe3+-CIP chelate and its effect on
catalytic behavior of Fe2+/Fe3+ and CIP mineralization, Electrochim. Acta 256
(2017) 185–195.
[109] S. Garcia-Segura, E. Mostafa, H. Baltruschat, Could NOx be released during mi-
neralization of pollutants containing nitrogen by hydroxyl radical? Ascertaining
the release of N-volatile species, Appl. Catal. B: Environ. 207 (2017) 376–384.