Journal of Hazardous Materials 400 (2020) 122961

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Journal of Hazardous Materials

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

Conventional and emerging technologies for removal of antibiotics from T

wastewater
Bao Lee Phoona, Chong Cheen Ongb,c, Mohamed Shuaib Mohamed Saheedb,c, Pau-Loke Showd,
Jo-Shu Change,f,g, Tau Chuan Lingh, Su Shiung Lami, Joon Ching Juana,j,*
a
Nanotechnology & Catalysis Research Centre (NANOCAT), Level 3 Block A, Institute for Advanced Studies, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Department of Fundamental & Applied Sciences, Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Perak Darul Ridzuan, Malaysia
c
Centre of Innovative Nanostructures & Nanodevices (COINN), Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Perak Darul Ridzuan, Malaysia
d
Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham Malaysia Campus, Jalan Broga, 43500 Semenyih, Selangor
Darul Ehsan, Malaysia
e
Department of Chemical and Materials Engineering, College of Engineering, Tunghai University, Taichung 407, Taiwan
f
Center for Nanotechnology, Tunghai University, Taichung 407, Taiwan
g
Department of Chemical Engineering, National Cheng Kung University, Tainan 701, Taiwan
h
Institute of Biological Sciences, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
i
Pyrolysis Technology Research Group, Institute of Tropical Aquaculture and Fisheries (AKUATROP) & Institute of Tropical Biodiversity and Sustainable Development (Bio-
D Tropika), Universiti Malaysia Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia
j
School of Science, Monash University, Sunway Campus, Jalan Lagoon Selatan, Selangor Darul Ehsan, Malaysia

GRAPHICAL ABSTRACT

Abbreviations: AC, activated carbon; AEF, adsorption-electro-Fenton; AFT, anodic Fenton treatment; AMP, ampicillin; AMX, amoxicillin; AnBEMR, anaerobic bio-
entrapment membrane bioreactor; AnMBR, anaerobic membrane bioreactor; AnSBR, anaerobic sequencing batch reactor; AOP, advanced oxidation process; ARB,
antibiotic resistance bacteria; ARG, antibiotic resistance genes; AZTY, azithromycin; BCOT, biological contact oxidation tank; BDD, boron-doped diamond; CASS,
cyclic activated sludge; CBT, closed bottled test; CFU, colony-forming unit; COD, chemical oxygen demand; CPF, ciprofloxacin; CSTR, completely stirred tank reactor;
DC-HCl, deoxycycline hydrochloride; DFT, density function theory; DNA, deoxyribonucleic acid; ENR, enrofloxacin; ER, erythromycin; FLU, flumequine; FQ,
fluoroquinolone; GAT, gatifloxacin; GDE, gas diffusion electrode; GF, gemifloxacin; HGT, horizontal gene transfer; LVX, levofloxacin; MBR, membrane bioreactor;
MBF, marbofloxacin; MOF, metal-organic framework; MWCNT, multiwalled carbon nanotube; NHAR, novel micro-aerobic hydrolysis acidification reactor; NHE,
normal hydrogen electrode; OFL, ofloxacin; OLR, organic loading rate; OTC, oxytetracycline; PAC, powdered activated carbon; PF, photo-assisted Fenton; PEF, photo-
electro-Fenton; PFC, photocatalytic fuel cell; PM, photocatalytic membrane; PMR, photocatalytic membrane reactor; POP, persistent organic pollutant; SA, sulfo-
namide; SBR, sequencing batch reactor; SC, sludge derived carbon; SDM, sulfamethoxine; SFD, sulfadiazine; SIM, sulfisomidine; SMA, specific methanogenic activity;
SMP, soluble microbial products; SMX, sulfamethoxazole; SPEF, solar photo-electro-Fenton; SSA, specific surface area; TC, tetracycline; TDX, tinidazole; TMT,
trimethoprim; TOC, total organic carbon; TPAD, two-phase anaerobic digestion; UASB, upflowing anaerobic sludge blanket; UASR, up-flow anaerobic stage reactor;
UF, ultrafiltration; UN, United Nation; WHO, World Health Organization; WWTP, wastewater treatment plant; XRD, X-ray diffraction; ZIF-8, zeolitic imidazolate
frameworks
⁎
Corresponding author at: Nanotechnology & Catalysis Research Centre (NANOCAT), Level 3 Block A, Institute for Advanced Studies, University of Malaya, 50603
Kuala Lumpur, Malaysia.
E-mail address: jcjuan@um.edu.my (J.C. Juan).

https://doi.org/10.1016/j.jhazmat.2020.122961
Received 26 February 2020; Received in revised form 26 April 2020; Accepted 12 May 2020
Available online 19 May 2020
0304-3894/ © 2020 Elsevier B.V. All rights reserved.
B.L. Phoon, et al. Journal of Hazardous Materials 400 (2020) 122961

ARTICLE INFO ABSTRACT

Editor: Jörg Rinklebe Antibiotics and pharmaceuticals related products are used to enhance public health and quality of life. The
wastewater that is produced from pharmaceutical industries still contains noticeable amount of antibiotics, and
Keywords:
this has remained one of the major environmental problems facing public health. The conventional wastewater
Antibiotics
Wastewater treatment remediation approach employed by the pharmaceutical industries for the antibiotics wastewater removal is
Advanced oxidation process unable to remove the antibiotics completely. Besides, municipal and livestock wastewater also contain un-
Biological treatment metabolized antibiotics released by human and animal, respectively. The antibiotic found in wastewater leads to
Advanced treatment antibiotic resistance challenges, also emergence of superbugs. Currently, numerous technological approaches
have been developed to remove antibiotics from the wastewater. Therefore, it was imperative to critically review
the weakness and strength of these current advanced technological approaches in use. Besides, the conventional
methods for removal of antibiotics such as Klavaroti et al., Homem and Santos also discussed. Although,
membrane treatment is discovered as the ultimate choice of approach, to completely remove the antibiotics,
while the filtered antibiotics are still retained on the membrane. This study found, hybrid processes to be the best
solution antibiotics removal from wastewater. Nevertheless, real-time monitoring system is also recommended
to ascertain that, wastewater is cleared of antibiotics.

1. Introduction 2008) as well as the determination and measurement of various kinds of

antibiotics (Hao et al., 2007). However, although, there are several
In recent years, pharmaceuticals and its related products have be- review articles on the advanced oxidation technologies for removal of
come chemicals of in emerging environmental challenges (Richardson pharmaceutical waste (Klavarioti et al., 2009), and advanced biological
et al., 2005). Currently, one of the most significant environmental processes (Homem and Santos, 2011), but there is lack of critical review
concern is wastewater. Pharmaceuticals and antibiotics are used to of the current technologies approach to remove or treat the trace of
enhance quality of life in public health and around the world. Never- antibiotics and unmetabolized antibiotics found in wastewater. In this
theless, the pharmaceutical industry may produce a high concentration work, various technologies to remove antibiotic from wastewater
of antibiotic wastewater and release it to the environment. It was found treatment are critically evaluated and discussed.
that, the pharmaceutical wastewater treatment plant (WWTP) effluent
that receives wastewater from 90 pharmaceutical manufacturers in
1.1. Antibiotics
India, contains a high level of ciprofloxacin, which was 31 mg/L
(Larsson et al., 2007). The antibiotic resistance genes (ARG), were de-
Antibiotics are considered efficient, when they inflict harm on a
termined to be relatively high in the effluent receiving wastewater in
targeted pathogen with minimal damage inflict to the host. The most
the pharmaceutical industry (2.36 × 107 copies/mL), which is far
efficient toxicity is achieved, when an antibiotic inhibits metabolic
higher than municipal wastewater (9.50 × 105 copies/mL) (Guo et al.,
pathway is not found in the host cell, or one that differs drastically from
2018). This indicates that the current (WWTP) from the pharmaceutical
the host, known as selective toxicity. This toxicity could be achieved by
industry is not adequately effective enough to remove traces of anti-
targeting either different organelles or structures that are not present in
biotics from wastewater (Hou et al., 2019). Apart from that, the in-
eukaryotic cells, but present in prokaryotic cells. This can also be
complete metabolism of antibiotics in humans has led to the large
achieved by targeting variable regions of shared DNA sequences. As
amounts of pharmaceutical drugs released into municipal WWTP. The
shown in Table 1, listed among the top ten common classes of anti-
environmental challenges caused by improper management can bring
biotics, structures, and its uses.
serious problems to humans and animals. Due to their usage in both
human and animal treatment as well as subsequent excretion of anti-
biotics in the feces and urine, the existence of antibiotics in wastewater 1.1.1. History
is ubiquitous. Apart from water, antibiotics is also frequently found in a While there is documentation of the unintentional antibiotic use in
different environment, such as soil and sludge, which increases the alternative medicines, the start of the antibiotic surge can be traced to
spread and speed up the antibiotic resistance development in the en- Salvarsan, a sulfa drug used to treat Syphilis in the 1910s. Back in 1928,
vironment. This is responsible for an increased risk to human disease
prevention and control (Hou et al., 2019). Therefore, wastewater
treatment is considered most effective to release antibiotics into the
environment.
The world consumption of antibiotic has risen rapidly in the past 10
years (Borghi and Palma, 2014). On the other hand, the metabolites
excretion in their original form has also risen drastically. After ingestion
by animals and humans, most antibiotics only partially metabolized,
providing that, 25 %–75 % of the antibiotics fraction may excrete from
the bodies in an unchanged form after consumption (Khan and Ongerth,
2004; Rivas et al., 2011; Watkinson et al., 2009). From the year
2000–2015, between these 15 years, it was reported that, the anti-
biotics consumption went up by 65 % (Klein et al., 2018). In addition,
the World Health Organization (WHO) collected data on world anti-
biotics consumption, based on 5 regions in the year 2018, the data was
mainly derived from import, sales, and reimbursement databases. Ac-
cording to Fig. 1, the world antibiotics consumption was up to
14,272 tons. Fig. 1. The world antibiotics consumption from 5 regions. (Source: WHO report
Previously, numerous studies have been reviewed and published on on surveillance of antibiotic consumption: 2016-2018 early implementation)
the effects and occurrence of antibiotics in our environments, (Kemper, Adapted from Ref. Organization (2018).

2
B.L. Phoon, et al. Journal of Hazardous Materials 400 (2020) 122961

Table 1
The commonly classes of antibiotics. Adapted from Ref. Homem and Santos (2011).
Class Core structure Structure

Aminoglycosides Consists of a two or more amino sugars joined by a glycosidic linkage to a hexose nude of the drug.

Carbapenems The structure is similar to penicillin but the sulfur position has been replaced by a carbon.

Cephalosporins Consist of a cephem nucleus to which 2 side chains are linked: one linked to the nucleus (R3) and another one esterifies
the carbamate group (R1).

Lincomycins Carbohydrate-containing antibiotic produced by the actinomyces Streptomyces lincolnensis.

Macrolides Highly substituted monocyclic lactone with 1 or more saccharides glycosidically attached to hydroxyl groups.

Penicillins Consists of a thiazolidine ring connected to a β-lactam ring, to which a side chain is attached.

Quinolones This structure consists of 2 fused rings with a ketone and carboxylic acid group.

Sulfonamides Consist of sulfonyl group connected to an amine group.

Tetracyclines Consist of an octrahydronaothacene ring skeleton, containing 4 fused rings.

the Penicillin antibiotics were discovered by Alexander Fleming. He future discoveries.

noticed in his laboratory that, the bacteria would not have activity near
some fungus, which had accidentally found its way into his experiment.
This discovery earned him the Nobel prize in 1945 and helped
humanity to develop a key antibiotic which has saved countless lives.
From there, the “golden era” of antibiotic discovery from 1945 to 1960
commenced, during which the majority of the chemical classes of an-
tibiotics, now in clinical use were first characterized. Synthetic synth-
esis of antibiotics allowed for the discovery of additional antibiotics,
after the initial surge of naturally discovered antibiotics began to
dwindle. However, though, proven effective, these techniques of pro-
ducing antibiotics were limited to culturable organisms. Lately, Ling
et al. described teixobactin, which is a new class of antibiotics, using a
culture-free approach (Ling et al., 2015). Due to a decrease in recent
novel antibiotics discovery, culture-free detection holds promises for
1.1.2. Impacts to the environment and human health
The major reasons for the bacteria resistance development are in-
judicious and indiscriminate to employ antibiotics in ecosystems (W.H.
Organization, 2018). According to WHO, the number of antibiotics for
non-human consumption (e.g. growth promoters for poultry production,
aquaculture, and agriculture) was more than half of the global pro-
duction of antibiotics (W.H. Organization, 2018). The widespread of
antibiotics used in humans and animals has proven potential increase in
antibiotic resistance (Goossens, 2009). As we share the same environ-
ment, the widespread application of antibiotics for poultry, also con-
duce to develop antibiotic resistance, that can also affect human. This is
because, antibiotics resistance is the link between animals, as well as a
human in the natural ecosystem. Thus, the bacteria that was resisted

3
B.L. Phoon, et al.
from antibiotics may be developed and spread from animals to the
environment (soil and/or water to humans) (van den Bogaard and
Stobberingh, 2000; Swartz, 2002).
There are more than a thousand tons of pharmaceutical products
that are being used around the world every year, but its potential after-
effects of their usage are little-known. Recently, researchers found
traces of antibiotics in the wastewater and surface water (Diwan et al.,
2010; Fatta-Kassinos et al., 2011; Martínez, 2008). Since the antibiotics
are still biologically active, even, in a very low concentration, there is a
concern of these trace antibiotics in the aquatic ecosystem. This is be-
cause, they have potential to increase the resistance among the natural
populations of bacteria and thus, given a negative impact on public
health (Ding and He, 2010). As we are aware, the antibiotics could
trigger allergic reactions, if they are present in drinking water
(Kümmerer, 2009). In 2017, UN environmental experts were warned
that, the careless disposal of antibiotics could produce “ferocious su-
perbugs”. Antibiotics can also affect the ecosystem of aquatic plants,
animals, and microorganisms. Yang et al. reported that chlortetracy-
cline could potentially bring influence on the growth of green alga
growth in freshwater systems (Yang et al., 2008). The bacterial re-
sistance towards antibiotics could be obtained in 2 ways, which are (i)
by horizontal gene transfer (HGT) and/or (ii) by mutation (Ding and
He, 2010; Summers, 2006). The amount of antibiotics in the natural
ecosystem is usually low. In natural environments, the low concentra-
tions of antibiotics are significant for the maintenance and enrichment
of resistance in bacterial populations (Gullberg et al., 2011).
Modern medicine has done a great job in achieving antibiotics
against the illness, that resulted from bacteria. Nevertheless, when it is
really needed, the bacteria are becoming less responsive and resistant to
antibiotic treatment (Bush et al., 2011; Jean and Hsueh, 2011;
Livermore, 2012). The resistance of antibiotics is the capability of
bacteria, to develop a tolerance for a particular antibiotic, to which
they were once susceptible (Van Boeckel et al., 2019; Povolo and
Ackermann, 2019; Fahrenkamp-Uppenbrink, 2016; MacLean and San
Millan, 2019). The increase of resistant antibiotics to bacteria (ARB) is
the main issue in public health as the infections caused by resisted
bacteria have become hard and costly for treatment (Andersson and
Hughes, 2010; French, 2010; Finch and Sharland, 2009; Ashley et al.,
2011). Extensive personal travel, medical tourism, as well as hospital-
acquired infections, are posing new threats in the propagation of ARB
around the world (Andersson and Hughes, 2011; Arias and Murray,
2012; Fisher and Mobashery, 2016). Considering the severity of the
issue, it has become a global concern, as declared by WHO “Anti-
microbial resistance” the World Health Day theme in 2011.
2. Remediation methods
2.1. Technology of antibiotics removal from wastewater
The process of wastewater treatment is to transform wastewater into
a useful effluent, which to enable reuse, by returning to the water cycle.
As shown in Fig. S1, traditional wastewater treatment basically can be
categorized into 3, and these are the biological, chemical, and physical
methods. The biological method consists of anaerobic digestion, aerated
lagoons, activated sludge, fungal treatment, trickling filters, and sta-
bilization. These biological treatments usually rely on bacteria, nema-
todes, or other small organisms, to transform the biodegradable organic
contaminants that contains in wastewater, into simple substances and
additional biomass by breaking down organic pollutants using normal
cellular processes (Grady et al., 2011). Chemical wastewater treatment
is of 2 types of properties as advantageous, which are (i) the char-
acteristics of the reaction products between treated chemicals and
contaminants, regarding their volatility, solubility, or other properties,
that relate to inability to stay in suspension and/or water stream, and
(ii) the pollutants chemical characteristics, regarding their tendencies
to interact with, or react with that chemicals that are meant to treat
4
Journal of Hazardous Materials 400 (2020) 122961
pollutants. Basically, catalysis, electrolysis, ion exchange, neutraliza-
tion, oxidation, and reduction belong to the chemical process (Lin and
Chen, 1997). Meanwhile, wastewater treatment by physical method is
accomplish by substances removal with the use of naturally occurring
forces, for example, van der Waals forces, electrical attraction, and
gravity, as well as using physicals barriers. Generally, physical treat-
ment does not cause the change of the chemical structure of the pol-
lutant substances. However, there are exceptions also, physical state is
changed in some cases, such as dispersed chemicals, that possibly
caused to agglomerate, as frequently found in the filtration and va-
porization steps. Sedimentation, coagulation, membrane treatment,
adsorption, distillation, and filtration belong to the physical method
(Shimizu et al., 1996).
The residues of antimicrobial can outflow the environment by sev-
eral paths. The incomplete metabolized antibiotics, that was excreted
through feces and urine into sewage, was up to 80 %. These effluents
outflow into sewage treatment plants that are also treating water from
industrial facilities and hospitals. Yet, current conventional WWTPs are
not designed to clear up the pharmaceutical products, and antibiotics
from wastewater. At the end, the surface water contains the remaining
drugs being released. Besides that, antibiotics that was applied to food-
producing animals are excreted via manure, therefore antimicrobial
plays a role in agriculture. This is because, it can spread onto fields as
fertilizer, and able to be carried into nearby oceans, streams and lakes,
with others unprocessed agricultural runoff. On top of that, approxi-
mately three-quarters of antibiotics that was adopted in aquaculture
might be lost to surrounding waters. It was suggested by the UN on
environment that, the antimicrobial stewardship should play a role, by
reducing the quantity of antibiotics that get into wastewater. Besides
that, some approaches that had been tried to lessen the problem, has
varying levels of effectiveness, which include heat treatment, UV dis-
infection and ozonation This varying level of effectiveness is to remove
antibiotics and bacteria, membrane filtration, secondary and tertiary
wastewater treatment facilities. In addition, Kümmerer was reported
that, starting with the medicinal product life cycle, 3 activities should
be thought over, in which solutions to the issue addressed able to put in
effects, which are (i) drug development, (ii) handling of drugs, and (iii)
technical emission control, in urban water management (Kümmerer,
2009). Also, the pharmaceutical professionals adopt a wide array of
disposal and wastewater treatment techniques (Struzeski, 1980). Waste
stream reduction at the source, along with recycling the water re-
clamation of some part of these wastes, is a desirable option. A few
reports have been generated, on the endocrine-disrupting chemicals
and pharmaceutical compounds treatments in the last decades (Liu
et al., 2009).
It was reported that, the rate of hydrolysis is important for pre-
dicting the environmental persistence of antibiotics. Hydrolysis can be a
significant degradation pathway in the environment for some organic
compounds, such as amides and esters. Antibiotics that contain amides
and esters functional group, may be of less bio-accumulative than the
parent compound, due to the high polarity. This resulted in high solu-
bility in water, and low octanol water partition coefficients (Lin et al.,
2007). The rate of hydrolysis is a function of environmental conditions,
with pH and temperature that are the most important factors, for ex-
ample, the rate of hydrolysis typically increases with temperature. Base-
catalyzed hydrolysis predominates over neutral and acid-catalyzed
hydrolysis for many organic compounds (Mabey and Mill, 1978). Even
though, hydroxide anion and water are attracted to electron-deficient
atoms, hydroxide anion is a stronger nucleophile than water. Alter-
natively, hydrolysis may catalyze in acidic solutions, when protons shift
the electron density of a molecule, so that, a susceptible site can be
attacked through water molecules. Besides that, ionic strength is an-
other factor that affects the hydrolysis such as presence of clays, oxide
surface, and divalent metal ions. Hydrolysis of labile functional groups
is a major degradation pathway in systems without a large micro-
organism population, such as ground waters, rivers, and streams (Li
B.L. Phoon, et al.
et al., 2011a).
Besides that, most of the conventional technologies deal with the
wastewater treatments from processes of fermentation and chemical
(Gadipelly et al., 2014). Therefore, the following section of this review
would discuss to date, the several common technologies and their
performances in antibiotics wastewater treatment.
2.2. Advanced oxidation process (AOP)
The commonly used processes for wastewater treatment are not
valid enough to clear up pharmaceutical products completely, because,
most of the biodegradability of such species is low. These treated ef-
fluents that is discharged into water streams can get polluted with these
contaminants (Kümmerer, 2008). Advanced oxidation processes (AOPs)
are efficient to treat various organic pollutants and toxic, as to have the
chemical structure of pollutants, i.e., emerging concern like deleterious
contaminants, dyes, pesticides, and naturally occurring toxins to be
fully destroyed. AOPs refer to a set of water treatments with oxidation,
that is applied for treating hazardous effluents at WWTP, hospitals, and
at industrial level. Different AOPs for the miscellaneous recalcitrant
compounds’ removal has been looked back from time to time. There are
2 kinds of AOPs, these are nonphotochemical AOPs (e.g. ozonation,
Fenton, and electrolysis) and photochemical AOPs (e.g. photolysis,
photocatalysis, and photo-Fenton) (Ameta and Ameta, 2018).
With the TiO2 electrode and UV radiation, the water splitting by the
photocatalysis phenomenon was discovered in 1972, by Fujishima and
Honda. This discovery marks the beginning of a new generation in
heterogeneous photocatalysis (Fujishima and Honda, 1972). Due to the
high efficiencies, the abundance of solar light, and comparatively in-
expensive, light driven AOP is an attractive technique to treat waste-
water. In general, organic contaminants interact with hydroxyl radical,
through hydrogen abstraction or addition routes, causing in carbon-
centered radicals. This would form a peroxyl radical, that undergoes
subsequent reactions, by reacting with oxygen molecule, to creates a
host of oxidation products like alcohols, aldehydes, or ketones. In AOPs,
the most effective species and efficient is hydroxyl radical. By ab-
stracting an electron from electron-rich substrates. This can also form
radical cations, that can hydrolyze like in aqueous medium giving an
oxidized product. The oxidized products are more susceptible to bior-
emediation, as well as, less toxic such as, inorganic salts, water, and
CO2. AOPs are advantageous to other methods of treatment, because,
the compound that is found in wastewater are broken down, rather than
transferred into diffused phase or concentrated. Therefore, it prevents
the production and disposal of secondary waste material.
2.2.1. Heterogeneous photocatalysis
The reaction of photocatalysis is primarily relies on the catalyst and
light energy or wavelength. Generally, the catalyst which performs as
sensitizers for the irradiation of light stimulated redox process is
semiconducting materials, because of their electronic structure (Fig. 2).
Fig. 2. The photocatalytic mechanism for wastewater treatment.
5
Journal of Hazardous Materials 400 (2020) 122961
When the energy of light falls on the surface of the semiconductor, and
if the incident ray energy is higher than or equivalent to the semi-
conductor bandgap, valence band (VB) electrons are excited and move
to the semiconductor conduction band (CB). Then, holes would be left
in the semiconductor VB. The VB can oxidize donor molecules with the
holes and react with water to produce hydroxyl radicals, whereas, the
CB electrons are able to form superoxide ions by reacting with dissolved
oxygen species and these electrons induce the reactions of redox
(Saravanan et al., 2017).
Table 2 shows the antibiotics that undergo photocatalytic de-
gradation, with different photocatalysts. According to Table 2, it was
known that, researchers attempted to treat antibiotics wastewater in
different semiconductors. However, until today, photocatalytic de-
gradation still has some challenges, such as the rate of recombination
and light absorption wavelength. Many of the photocatalysts are more
photoactive in UV regions such as TiO2 and ZnO due to the wide
bandgap. For example, Ahmadi et al., attempted to use MWCNT/TiO2
for TC degradation with UV-C lamps (Ahmadi et al., 2017), Rimoldi
et al. synthesized TiO2/WO3 for TC removal with UV lamp (Rimoldi
et al., 2018), while Wang et al. tested the performance of TC de-
gradation by using ZnO under UV irradiation (Wang et al., 2016a).
Some of the research work for photocatalytic TC degradation, under UV
light that was given a good performance; such as the research work
published by Xu et al. with utilizing carbon quantum dots and ZnIn2S4
composites, and it was successful to remove more than 80 % of TC
within half an hour (Xu et al., 2018a).
Nevertheless, if UV light performance is compared with solar light
performance the later performance would need light for some im-
provement. This is because, the solar only contributes 4–5 % of UV, 46
% of visible light, and the rest are IR irradiation. Therefore, numerous
technologies have been adopted to make them absorb lower energy
photons. For example, Tang et al. attempted anionic doped TiO2 to
narrowing the bandgap (Tang et al., 2018). Wang et al. successfully
degraded more than 90 % of TC, within an hour with Ag/Ag3PO4/AC
photocatalyst under artificial solar (Wang et al., 2015a). Initially,
Ag3PO4 is only able to absorb the light up to blue, however, Ag can
generate the surface plasma resonance, causing in high electron-hole
pairs separation and strengthen the photodegradation performance
(Teng et al., 2012). Moreover, the activated carbon (AC) is the het-
erostructure, that can improve the photocatalyst specific surface area
(SSA), which leads to many active sites for photocatalysis as presented
in Fig. S2. According to Wang et al., the function of AC here does not
only provide great SSA and active sites but also enhanced the light
absorption. Under UV-Diffusion absorption spectra (DRS) analysis
(Fig. 3(a)), the spectrum of AC has a high light absorption, over the
range of wavelength 200−800 nm (Wang et al., 2015a). This may due
to the color of the AC itself is black. Compared with the UV-DRS
spectrum of Ag3PO4 photocatalyst (Fig. 3(b)), the optical absorption of
Ag3PO4 becomes weak from 300 nm onwards. This indicates that, the
Ag3PO4 itself is highly active under the irradiation of UV-C only.
 Table 2
The performance of antibiotics degradation with different photocatalysts.
Photocatalyst Mass (g) Light source Target pollutant/ concentration/ Volume of target Degradation time/ Rate Reactive species Ref. (year)
pollutant (mL) efficiency (Most > Least)
B.L. Phoon, et al.

Ag/Bi3TaO7 0.05 250 W Xe lamp (λ > Tetracycline/10 mg L−1 120 min/85.42 % 0.0162 min−1 OH⦁ > O2⦁− > h+ (Luo et al., 2015) (2015)
420 nm)
−1 −1 +
AgI/BiVO4 0.03 300 W Xe lamp (λ > Tetracycline/20 mg L 100 60 min/94.91 % 0.0547 min h > O2 > >O2⦁− (Chen et al., 2016a)
420 nm) OH⦁ (2016)
Ag/Ag3PO4/ AC 0.1 300 W Xe lamp Tetracycline/10 mg L−1 100 60 min/96.54 % 0.06181 min−1 O2⦁− > e- > h+ > (Wang et al., 2015a)
OH⦁ (2015)
mp-Bi2WO6 0.01 350 W Xe lamp Tetracycline/20 mg L−1 20 120 min/97 % (Chu et al., 2016)
(2014)
−1
In2S3/NaTaO3 0.05 300 W Xe lamp Tetracycline/10 mg L 100 180 min/75 % 0.02798 min−1 h+ > O2⦁− > OH⦁ (Xu et al., 2018b)
(2018)
Ag/K2Ta2O6 0.1 300 W Xe lamp (λ > Tetracycline/20 mg L−1 100 300 min/49.59 % 0.0019 min−1 h+ > OH⦁ (Xu et al., 2015) (2015)
425 nm)
Mn-SrTiO3 0.1 250 W Xe lamp (λ > Tetracycline/10 mg L−1 100 60 min/66.7 % 0.0166 min−1 h+ > OH⦁ (Wu et al., 2015) (2015)
420 nm)
WO3/NaTaO3 0.025 500 W Xe lamp (λ > Tetracycline/20 mg L−1 100 420 min/60.88 % O2⦁− > h+ > OH⦁ (Qu et al., 2016) (2016)
420 nm)
−1 −1 + ⦁ ⦁−
N-TiO2/MoS2 0.025 Visible light Tetracycline/10 mg L 50 120 min/84 % 0.01443 min h > OH > O2 (Kumar et al., 2017)
(2017)
ZnO Low pressure Hg lamp (32 W, Tetracycline/0.16 mM 200 180 min/94.6 % (Wang et al., 2016a)
450 μW cm−2) (2015)
N-TiO2/rGO 0.05 300 W Xe lamp (λ > Tetracycline/10 mg L−1 100 60 min/98 % 0.05655 min−1 O2⦁− > h+ > OH⦁ (Tang et al., 2018)
400 nm) (2018)
CQD/ZnIn2S4 NF 0.02 350 Hg lamp (λ < 356 nm) Tetracycline/10 mg L−1 80 30 min/84 % O2⦁− > h+ > OH⦁ (Xu et al., 2018a)
(2018)

6
MWCNT/ TiO2 0.1 2 × 6 W UVC lamps (λ Tetracycline/5 mg L−1 1000 20 min/72.62 % (Ahmadi et al., 2017)
=240 nm) (2017)
Ag3PO4/ CuBi2O4 0.05 300 W Xe lamp (λ > Tetracycline/10 mg L−1 100 60 min/75 % 0.0201 min−1 O2⦁− > OH⦁ > h+ (Shi et al., 2017a)
420 nm) (2017)
PbMoO4 (1 × 1 cm) Thin 35 W Xe lamp Tetracycline/10 mg L−1 7 180 min/55 % 0.0595 min−1 (Obregón et al., 2018)
film (2018)
C-TiO2 0.3 g/L 25 W visible LED light strip (λ Tetracycline/5 mg L−1/200 m L 200 120 min/70 % 0.0099 min−1 OH⦁ (Oseghe and Ofomaja,
=450 nm, 46 W m−2) 2018) (2018)
TiO2/WO3 0.05 UV lamp, 30 mW cm−2 Tetracycline/35 mg L−1 1000 45% O2⦁− (Rimoldi et al., 2018)
(2018)
W-BaTiO3 0.01 UV lamps Tetracycline/20 mg L−1 50 180 min/80 % 0.0833 min−1 OH⦁ (Demircivi and Simsek,
2019) (2019)
ZnO/MTMN 0.1 Tetracycline/120 mg L−1 100 200 min/94 % (Zyoud et al., 2017)
(2017)
−1
Bi4Ti3O12 0.1 360 W halogen lamps (λ > Tetracycline/0.01 mM L 100 114 min/63.9 % (Khodadoost et al.,
420 nm) 2017) (2017)
NiS/MoS2/GCN 250 W halide lamp Ciprofloxacin/10 mg L−1 10 120 min/71.3 % 0.0084 min−1 (Lu et al., 2018) (2018)
(λ > 400 nm)
GCN 0.05 300 W Xe lamp (λ > Sulfonamide/10 μM 100 40 min/100 % 0.078 min−1 OH⦁ (Song et al., 2017)
400 nm) (2017)
−1 −1 ⦁− +
mp-GCN/CQD 0.5 g/L 350 W Xe lamp (λ > Ofloxacin/8 mg L 50 120 min/90.1 % 0.035 min O2 > h > e- (Wang et al., 2018)
420 nm) (2018)
0D/2D plasmonic Cu2-xS/ 0.05 Xe lamp AM1.5 Levofloxacin/20 mg L−1 50 20 min/100 % (Zhou et al., 2020)
GCN NS (2020)
Bi7O9I3/GCN 0.05 300 W Xe lamp Deoxycycline hydrochloride /20 mg L−1 100 120 min/80 % 0.0125 min−1 O2⦁− > OH⦁ > h+ (Zhang et al., 2020a)
(λ > 420 nm) (2020)
MoS2/GCN/Bi24O31Cl10 0.01 300 W Xe lamp Tetracycline/20 mg L−1 50 50 min/90 % 0.06429 min−1 O2⦁− > h+ > OH⦁ (Kang et al., 2020)
(λ > 420 nm) (2020)
(continued on next page)
Journal of Hazardous Materials 400 (2020) 122961
B.L. Phoon, et al. Journal of Hazardous Materials 400 (2020) 122961

Note: AC: Activated carbon; mp: Mesoporous; rGO: Reduced graphene oxide; CQD: Carbon quantum dots; NF: Nanoflower; ⦁O2−: superoxide radical; ⦁OH: hydroxyl radicals; h+: trapping holes; e−: electrons; MWCNT:
(Solehudin et al., 2020)

(Faisal et al., 2020)

(Ma et al., 2020a)
Ref. (year)

(2020)

(2020)

(2020)
h+ > OH⦁ > O2⦁−
O2⦁− > h+ > OH⦁
Reactive species
(Most > Least)

0.0222 min−1

0.6935 min−1

Fig. 3. The UV-DRS spectra of different samples. Reproduced form Ref. Wang
et al. (2015a).
Rate
Degradation time/

240 min/95.43 %
100 min/85.6 %

180 min/80 %
efficiency
Volume of target
pollutant (mL)

150

Multi-walled carbon nanotube; LED: Light-emitting diode; GCN: Graphitic carbon nitride; MTMN: Montmorillonite.
10
Target pollutant/ concentration/

Sulfamethoxine /20 mg L−1

Tetracycline/10 mg L−1

Gemifloxacin /0.02mM

Fig. 4. The photoluminescence (PL) spectra of Ag3PO4 composites. Reproduced

form Ref. Wang et al. (2015a).

However, when both AC and Ag3PO4 are combined (Fig. 3(c)), the
optical absorption becomes strong again over the whole spectrum
(200−800 nm). When the Ag3PO4/AC was further combined with Ag
nanoparticles, the recombination rate was suppressed (Fig. 4). In
250 W high pressure Hg lamp

overall, the Ag/Ag3PO4/AC can break down TC up to 97 % in 20 m.

Besides that, Sturini et al. conducted a research of enrofloxacin
(ENR) and marbofloxacin (MBF) photodegradation by using clay mi-
55 W Xe lamp, HID

nerals, which was montmorillonite (MTMN) and kaolinite (KLN), due to

500 W Xe lamp
(λ > 420 nm)

(λ > 420 nm)

it existed in soil naturally (Sturini et al., 2015). It was found that, both
Light source

MTMN and KLN have good adsorption ability, majorly because of the
high SSA. Regarding the photodegradation part, it was found that, both
antibiotics would initially attach and bonded to the interlayer spacing
and external surface of the clay. This was proven by XRD (Fig. 5). First
of all, the d-spacing of MTMN (0 0 1) has been expanded, when ad-
sorbed by antibiotics. Then, when the sunlight irradiates, the antibiotics
Mass (g)

would slowly break down, and the interplanar d-spacing value of (0 0

1 g/L
0.15

0.01

1) would start to shrink after the photodegradation ended. The per-

formance of EF (55 mg/g) degradation with MTMN is about 40 % after
(0 1 0) BiVO4 plate with Fe

sunlight irradiation of 180 h. Similar research was reported by Wu et al.

Polythiophene doped ZnO

in 2015, but the targeted pollutant was ciprofloxacin (CPF) (Wu et al.,
Table 2 (continued)

2018). According to Wu et al., photodegradation of CPF in water is

slow, but in the interlayer space of MTMN is more rapid.
oxydroxide
MGCN/UGCN
Photocatalyst

Some researchers think that, MTMN itself might not have high
performance in antibiotics degradation. In 2017, Zyoud et al. attempted
to make a ZnO nanocomposite with MTMN to treat TC wastewater

7
B.L. Phoon, et al. Journal of Hazardous Materials 400 (2020) 122961

Fig. 5. The XRD patterns of MTMN enriched with ENR antibiotics before and after irradiation of sunlight. Reproduced from Ref. Sturini et al. (2015).

(Zyoud et al., 2017). It was found that, the performance of ZnO/MTMN sulfadimethoxine (SDM of 90 % was achieved within 4 h, which is far
nanocomposite is 2.3-fold better than MTMN itself, in terms of TC better than pure BiVO4. Since FeOOH received a charge carrier from
(120 mg/L) adsorption. This clearly shows that, MTMN itself has a BiVO4, the Fe3+ was converted to Fe2+ and the electron holes were
lower SSA. The enlargement of ZnO/MTMN is presumably due to two transferred, to BiVO4 to generate more effective hydroxyl radicals.
factors, which are: (i) extra area added by ZnO nanoparticles on the Furthermore, Fe(II)/Fe(III) are able to reach a dynamic equilibrium
surface and (ii) grinding of MTMN during stirring. Meanwhile, MTMN rapidly under visible light irradiation, allowing the antibiotics pollutant
and ZnO themselves have low photocatalytic activity. When these 2 to be efficiently degraded by h+ active species (Ma et al., 2020a).
components are combined, the mineralization can be up to 94 %. Be- Nowadays, some scientist prefers to conduct adsorption and pho-
sides that, Li et al. conducted a nanocomposition of g-C3N4/MTMN (Li todegradation studies simultaneously, which is able to remove the
et al., 2016). Li et al. proposed that, there are many negative charges wastewater effectively in a shorter period, and flow back the treated
covered on the MTMN surface. The photogenerated charge carriers can wastewater into the water stream. Due to the tunable structure, high
migrate effectively, because of the electrostatic repulsion between the porosity, and SSA, metal-organic frameworks (MOFs), have earned
MTMN layers and electrons, which significantly resulted in the decrease much attention from scientists. For example, GCN/ZIF-8 nanocomposite
of charge carrier recombination and this was proven by photo- able to break down TC up to 96 %, with only an hour of sunlight ir-
luminescence (PL) spectroscopy (Fig. 6) (Li et al., 2016). radiation (Panneri et al., 2017). Also, Wang et al. reported that, there
G-C3N4 is a two-dimensional material, that normally in sheet-like was a synergistic effect between In2S3 and MIL-125(Ti), which could be
shape. Recently, Zhou et al. attempted to bind zero-dimension Cu2-xS on attributed to an efficient charge transfer (Wang et al., 2016b). In 2018,
the surface of g-C3N4. When localized surface plasmon resonances He et al. reported to degrade TC by using MIL-100(Fe)/TiO2 (He et al.,
(LSPR) is mentioned, expensive noble metals, such as, Ag and Au are 2018). It was found that, a certain amount of MIL-100(Fe) could en-
involved. However, Zhou et al. managed to introduce Cu2-xS nanodots hance of optical absorption of TiO2. As shown in Fig. 7, pristine TiO2 is
to enhance the overall photocatalytic activity. It was found that, the only photoactive at 400 nm and lower, but, with integrated MIL-
LSPR effect of Cu2-xS, was better than expensive noble metal such as Ag 100(Fe), absorption of light for TiO2 nanocomposite was greatly
and Au. This is because, the LSPR effect Cu2-xS can expand to NIR (near
infrared) which Ag and Au unable to do so. Zhou et al. tried to pho-
todegrade LVX (levofloxacin) in three different kinds of light sources,
which are: (i) AM 1.5 full spectrum, (ii) Xe lamp
(400 nm < λ < 780 nm), and (iii) Xe lamp (λ < 780 nm). Under the
irradiation of AM1.5, the 20 mg/L of LVX is able to fully degrade in
20 min., which is far better than pure g-C3N4 (26.88 %). Surprisingly,
when shifted the light irradiation to λ < 780 nm, photodegradation
does happen, while the pure g-C3N4 does not work. This has proven
that, the incorporation of Cu2-xS is able to enhance the light-harvesting
effect in NIR (Zhou et al., 2020).
In order to enhance charge separation, most researchers prefer to
utilize cost effective metal oxide onto the photocatalyst surface. Herein,
Ma et al. attempted to employ FeOOH and NiOOH as co-catalyst.
Oxyhydroxide promoters were commonly used in the hydrogen pro-
duction process, to boost its performance (Takata et al., 2015; Yu et al.,
2015). This is because, the metal ions in the metal oxyhydroxide is able
to capture electrons and undergo a reduction process to be deposited on
the photocatalyst (Li et al., 2013). The usage of FeOOH as co-catalyst
with BiVO4 has improved the photocurrent density, which delay the Fig. 6. The PL spectroscopy of bulk g-C3N4 and g-C3N4/MTMN nanocomposite.
electron charge recombination. Meanwhile, photodegradation of Reproduced from Ref. Li et al. (2016).

8
B.L. Phoon, et al.
Fig. 7. The UV spectrum for TiO2 and its nanocomposites. Reproduced from
Ref. He et al. (2018).
enhanced to 600 nm.
In this recent, photocatalytic fuel cell (PFC) has gained attention
from scientists (Li et al., 2019a; Zeng et al., 2018; Deng et al., 2018).
Basically, PFC is a combination technology of fuel cells and photo-
catalysis., the photogenerated electrons from photoanode, would
transfer to the cathode through an external circuit, and undergo a re-
duction of substances, such as H+ to H2 under light illumination.
Meanwhile, the photogenerated hole is left on photoanode can be a
strong oxidant and to degrade pollutants. As a result, PFC not only can
break down pollutants, it can generate hydrogen energy as well. In
2019, Nahyoon et al. attempted to treat TC with Fe/GTiP nano-
composite (GTiP = graphene oxide and titanium phosphate) photo-
anode and ZnIn2S4 as a photocathode. According to Nahyoon et al., the
contaminants and electricity generation are working on the basis of
mismatched Fermi levels between both photoanode and photocathode
band potential (Nahyoon et al., 2019). According to Fig. 8, the CB value
of Fe/GTiP is -0.16 V and VB is +2.90 V (vs. NHE) while the CB of
ZnIn2S4 is -0.91 V and VB is +1.19 V (vs. NHE), which has inferior bias
for the PFC. The photogenerated electron flowing from anode to
Fig. 8. Schematic diagram of proposed PFC mechanism using Fe/GTiP photoanode and ZnIn2S4 photocathode for solar illumination. Reproduced from Ref. Nahyoon
et al. (2019).
9
Journal of Hazardous Materials 400 (2020) 122961
cathode was driven by internal bias. Since photoanode has a high value
of VB value, it is capable of producing powerful holes to oxidize con-
taminants. According to the result presented by Nahyoon et al., the PFC
system was managed to break down 89 % of TC within 90 min
(Nahyoon et al., 2019). Then, in the same year, Li et al. proposed to add
peroxymonosulfate (POMS) in the PFC system (Li et al., 2019b). The
reason to do so was to fasten the contaminant break down process.
POMS is a strong oxidant, with higher redox potential compare to H2O2
(Jiang et al., 2018). It can simply be activated by ultrasonic, UV, as well
as, heat to generate sulfate radicals (SO4%−), which is component that,
higher redox has potential than the well-known hydroxyl radicals, OH%.
In this case, Li et al. proven that, adding POMS into the PFC system can
achieve better performance in degradation, with the similar condition
with Nahyoon et al., Li et al., managed to break down 90 % of TC in
60 min.
Discharge of antibiotics without proper and complete treatment into
water bodies, can cause health and environmental risk. Sometimes,
antibiotics that undergo photodegradation is possible to produce highly
toxic compounds, compare with their parent pollutants. Therefore, the
toxicity test is a useful and important procedure for the WWTP.
Previously, some researchers preferred to examine the total organic
carbon (TOC), and chemical oxygen demand (COD), to indicate the
mineralization and carbon residue of treated wastewater (Hu et al.,
2016; Wang et al., 2016c; Zhan and Jiang, 2016). Palmisano et al. re-
ported the use of a respirometric biosensor, to evaluate the toxicity of
treated antibiotic wastewater in 2015 (Palmisano et al., 2015). In re-
cent years, some researchers attempted to run toxicity assessments
(Zhou et al., 2019). In 2019, Naraginti et al. conducted phytotoxicity
studies with V. radiata after photodegrading the target pollutant
(Naraginti et al., 2019), which was azithromycin (AZTY). According to
Naraginti et al., the germination index (GI) of the AZTY parent com-
pound is relatively low (12.3 %) before conducting the photodegrada-
tion experiment. However, the GI straight increased to 81.1 % after a
photocatalytic reaction of 8 h, which is nearly detoxification. Mean-
while, Ge et al. conducted the antibacterial activity assessment, by
using E. coli for gatifloxacin (GAT) photodegradation on 3 types of
water bodies, which are: pure water, seawater, and freshwater (Ge
et al., 2018). It was found that, the parent GAT compound could de-
grade fast, but the antimicrobial activity will persist longer time (Fig.
S3).
B.L. Phoon, et al.
2.2.2. Fenton oxidation
In 1894, Henry John Horstman introduced the Fenton reaction,
which is reaction that is related to encompassing reaction with per-
oxides. Normally, a species of active oxygen is formed and oxidize in-
organics or organics with the presence of Fe ions and H2O2. The sig-
nificance of hydroxyl radical (OH%) reactions is well-known in the last
few decades, and the rate constant was more than thousands for OH%
reactions with inorganic and organic materials in the aqueous medium,
which has been tabulated. Since the past decade, the Fenton reaction
was treated effectively for wastewater that contains, dangerous organic
compounds (Babuponnusami and Muthukumar, 2014). The traditional
process of Fenton relates to the use of a catalyst, and one or more
oxidizing agents (e.g. metal salts or oxides, normally Fe) in acidic
conditions. Meanwhile, the photo-assisted Fenton (PF) process relates
to artificial or solar irradiation. The traditional Fenton process has the
benefits that apply Fe, as a catalyst which is low toxic and highly
abundant. Moreover, the oxidant (H2O2) is lower cost, compared to
other oxidants (Hung et al., 2012). Different kinds of wastewater con-
sisting of miscellaneous pollutants namely: amines, chlorophenols, and
phenols have been examined for Fenton oxidation. Nevertheless, there
are many compounds that are refractory to Fenton oxidation, for ex-
ample, acetone, ethanoic acid, and maleic acid (Bautista et al., 2008).
During the wastewater treatment, the Fenton process can be in-
tegrated with the electrochemical process (EF). Brillas, thoroughly in-
troduced the process of EF and suggested that, the capacity of oxidation
for EF was from the (OH)-O-center dot attack at the anode and in the
medium, where Fenton reaction took place (Brillas, 2014). The source
of catalyst and oxidant for EF is diverse. Initially, H2O2 was produced in
situ, through reduction of two-electron from the dissolved oxygen, at
cathode under the acidic condition for both homogenous and hetero-
geneous Fenton process, when the electrochemical process was applied
(Eq. 1) (Wang et al., 2012). Apart from that, in situ H2O2 production is
advantageous, to enhance the performance of organic contaminant
degradation. On top of that, in the EF process, this type of H2O2 was
Fig. 9. Schematic diagram of different types of homogeneous EF like setup. Reproduced from Ref. Brillas et al. (2009).
10
Journal of Hazardous Materials 400 (2020) 122961
used to break it down to water and oxygen. This property provides
higher selectivity towards the targeted reactions (Liu et al., 2013). In
addition, a homogeneous metal catalyst (Mn+) can either be supplied
by regeneration on the cathode surface, after the external addition of
metal ion or by sacrificing the corresponding metal anode directly. The
regeneration of active metal catalyst reaction at the cathode is pre-
sented in Eq. 2. EF process has been studied, and widely applied for
organic contaminant break down. For example, persistent organic
pollutants (POPs) (Roth et al., 2016), colorant (Labiadh et al., 2015),
antibiotics (de Souza Santos et al., 2015), herbicides (Lizama-Bahena
et al., 2015), and so on.
O2 +2H+ +2e− → H2O2 (1)
M(n+1)+
+e −
→M n+
(2)
Basically, homogeneous EF can be categorized into 4 by differ-
entiating the sources of H2O2 and Fe. Fig. 9(a) is a peroxi-coagulation
process, the in-situ production of H2O2 on the surface of the cathode by
bubbling oxygen/air, and the metal ion catalyst is supplied by a sacri-
fice anode. Fig. 9(b) is an EF-Fere process, both metal ion catalyst and
H2O2 added externally and the regeneration of metal ion catalyst is
through cathode reduction. Fig. 9(c) is electrochemical peroxidation
(ECP) and Fig. 9(d) is the anodic Fenton treatment (AFT) process. The
metal ion catalyst is supplied by a sacrifice anode and H2O2 is added
externally in these two processes. The gap between them simply arises
from an additional salt bridge.
Photo-Fenton (PF) reaction is to combine the UV light
(180−400 nm) with a homogeneous Fenton reaction. It shows the ef-
ficiency of the Fenton process has been improved. The positive impact
of illumination on the rate of degradation is because of Fe2+ ions from
Fe3+ photoreduction. Also, based on the mechanism that is shown in
Eq. 3, it can generate new hydroxyl radicals with H2O2 (Hung et al.,
2012). In general, the organic compounds degradation rate has fairly
risen in the PF. In the traditional Fenton process, the Fe3+ ions would
 B.L. Phoon, et al.

Table 3
The performance of antibiotics removal by using photo-Fenton-like process.
Target pollutant Treatment method Catalyst (Iron source) pH Amount of H2O2 Peformance/time Ref. (Year)

Oxacillin (OXC) PF (150 W UV lamp λ < 387 nm) FeSO4.7H2O 5.6 1000 μM TOC removal = 35 % (Serna-Galvis et al., 2016a)
(2016)
Tetracycline (TC) PF (4 W UV-C, Philips) Fe3O4@C 3 ± 0.2 3 mM TC = 87 % TOC removal = 37 % (Kakavandi et al., 2016) (2016)
Ciprofloxacin (CPF) PF (15 W black light lamp Iron citrate 4.5 100 μM CPF = 50 %; 90 min (de Lima Perini et al., 2017)
λ = 365−410 nm) (2017)
Oxacillin (OXC) PF (5 × 30 W Philips lamps, TL-D Actinic FeSO4.7H2O 5.6 1000 μM N/A (Serna-Galvis et al., 2016b)
BL) (2016)
Ciprofloxacin (CPF) PF (2 × 15 W Philip lamps, λmax FeSO4.7H2O 3.0 4.2 nM TOC removal = 60 % (Villegas-Guzman et al., 2017a)
=365 nm) (2017)
Cephalexin (CPH) PF (7 × 36 W Philips UV tube, λmax FeSO4·7H2O/ TiO2 immobilized clay 3.5 4.41 nM COD = 82 % CPH degradation = 89 (Bansal and Verma, 2017) (2017)
=365 nm) beads %
Tinidazole (TDX) PF (UV-C) FeSO4.7H2O 2.0/6.8 100−1500 μM TOC removal = 100 % (Velo-Gala et al., 2017) (2017)
Penicillins (PEN) PF (Black lamps, Philips) FeSO4.7H2O 3.0 10 mM N/A (Villegas-Guzman et al., 2017b)

11
(2017)
Norfloxacin (NFX) PF (300 W Xe lamp) Fe3O4-multiwalled carbon NTs 3.0 98 mM TOC removal = 80 %; 180 min (Shi et al., 2017b)
(2017)
Sulfadiazine (SFD) PF (UV254, 100 μW cm−2) α-FeOOH 10 mM L−1 Mineralization: 80 %; 60 min (Sun et al., 2020)
(2020)
Swine wastewater (TMT ∼ 90 μg Biodegradation and Fenton-like oxidation FeSO4·7H2O 6.0 1.5 mM Removal: 74 %; 120 min (Qian et al., 2020)
L−1) (2020)
Tetracycline (TC) PF (LED λ > 420 nm) ZnFe2O4 0.2 mL (30 wt%) Removal: 94.2 %; 40 min (Xiang et al., 2020a)
(2020)
Sulfamethoxazole (SMX) Phyto-Fenton (phragmites australis) Micro-sized Fe3O4 fine particles Constructed wetland Removal: 50 %; 29 days (Ranjusha et al., 2020)
(2020)
Tetracycline (TC) PF (300 W Xe lamp, λ > 400 nm) g-C3N4/FeOCl 20 μL Removal: 90 %, 20 min (Zhao et al., 2020)
(2020)
Ofloxacin (OFL) PF (500 W Hg lamp, λ < 420 nm) Biogenic Fe-Mn oxides Removal: 98.1 %, 120 min (Du et al., 2020)
(2020)

Note: PF: Photo-Fenton; N/A: Not available; TMT: Trimethoprim; LED: Light-emitting diode; SMX: Sulfamethoxazole.
Journal of Hazardous Materials 400 (2020) 122961
 B.L. Phoon, et al.

Table 4
The performance of antibiotics removal by using electro-Fenton-like process.
Target pollutant Treatment method Catalyst (Iron source) pH Materials for anode/cathode Peformance/time Ref. (Year)

Levofloxacin (LFX) EF (100−400 mA) FeSO4·7H2O 3.0 Anode: Ti/RuO2-IrO2 Cathode: N-GF TOC removal = 90 %; 480 min (Liu et al., 2017) (2017)
Ciprofloxacin (CPF) EF (100−500 mA) FeSO4·7H2O 3.0 Anode: Pt Cathode: CexA1−xO2 (A = Zr, Cu TOC removal 97.45 %; 360 min (Li et al., 2017a) (2017)
and Ni) modified CF
Ciprofloxacin (CPF) EF (100−450 mA) FeSO4·7H2O 3.0 Anode: Pt Cathode: CeO2/RGO TOC removal: 91 %; 390 min CPF: 100 (Li et al., 2017b) (2017)
nanocomposite %
Tetracycline (TC) EF (50−500 mA) Chalcopyrite Natural Anode: Pt Cathode: CF TOC removal: 98 %; 360 min (Barhoumi et al., 2017)
(2017)
Amoxicillin (AMX) EF (10−120 mA) FeSO4·7H2O 3.0 Anode: Ti4O7 Cathode: CF TOC removal: 84 % (Oturan et al., 2017)
(2017)
Tetracycline (TC) EF (0−350 mA/m2) FeOOH/TiO2/GAC Natural Anode: Graphite Cathode: Cathode membrane TC: 90 % (Li et al., 2017c) (2017)
Sulfamethazine (SMX) EF (100−1000 mA) Pyrite 3.0 Anode: BDD Cathode: CF TOC removal: 96 % (Barhoumi et al., 2016)

12
(2016)
Sulfamethazine (SMX) EF (100−1000 mA) FeSO4·7H2O 3.0 Anode: BDD Cathode: GF TOC removal: 98.5 % (Sopaj et al., 2016) (2016)
Norfloxacin (NFX) EF (30−500 mA) FeSO4·7H2O 3.0 Anode: Pt Cathode CF BDD TOC removal: 97.7 % (Özcan et al., 2016)
(2016)
Enoxacin (ENX) EF (50−300 mA) FeSO4·7H2O 3.0 Anode: Pt Cathode: CF ENX: 98 %; 60 min (Annabi et al., 2016)
(2016)
Erythromycin (ERT) PEF (Filter-press FM01-LC flow reactor with compound FeSO4·7H2O 3.0 Anode: Ti Cathode: GF TOC removal: 69 % (Pérez et al., 2017) (2017)
parabolic collector/Solar plant)
Trimethoprim (TMTP) PEF (Sunlight/PV cell) FeSO4·7H2O 3.0 Anode: RuO2/Ti Cathode: ACF TOC removal: 80 %; 360 min (Zhang et al., 2016)
(2016)
Tetracycline (TC) EF M type SrFe12O19 7.0 Anode: Carbon felt Cathode: Carbon felt Removal: 85.9−88.2; 17 h TOC (Hassan et al., 2020)
removal: 74.8−87.2% (2020)

Note: EF: Electro-Fenton; PEF: Photo-Electro-Fenton; N/A: Not available; NTs: Nanotubes; GF: Graphite felt; CF: Carbon felt; ACF: Active carbon felt; GAC: Granular activated carbon; BDD: Boron doped diamond; PV:
Photovoltaic; Pt: Platinum.
Journal of Hazardous Materials 400 (2020) 122961
B.L. Phoon, et al.
start to precipitate as OH in higher pH. So, the main drawback of the PF
is the requirement to conduct the experiment at pH 3–4. Velo-Gala et al.
attempted to remove tinidazole (TDX) from the water with UV-C, and
they were successful, to fully mineralize contaminants (Velo-Gala et al.,
2017). According to Velo-Gala et al., excessive hydroxyl radicals would
not help to boost up the degradation performance, because, a high
concentration of hydroxyl radicals can cause radical recombination to
repeat formation of H2O2 (Velo-Gala et al., 2017). On the other hand,
the wastewater remediation cost can increase up to 50–60%, due to the
UV radiation lamps energy cost (Centi et al., 2000). In terms of mini-
mizing the cost of energy consumption, the UV-C radiation replaces the
visible light was gained interest. In theory, solar illumination is pre-
dicted to have higher efficiency, when it diminishes the Fe ions con-
centration after treatment. Meanwhile, the Fe3+ complexes were able
to be broken down and let the Fe3+ ions to take part in the Fenton
catalytic cycle (Soon and Hameed, 2011). Then, Shi et al. proposed the
use of Fe3O4/MWCNT (multiwalled carbon nanotubes), as a catalyst to
treat organic contaminants with Xe solar stimulators. The reason to
choose MWCNT as nanocomposite is to consider the high SSA and based
on the outcome, Shi et al. managed to remove 80 % of TOC within 3 h
(Shi et al., 2017b).
hv
Fe3 + + H2 O Fe 2 + + OH • + H+ (3)
Meanwhile, some researchers started to develop photo-electro-
Fenton (PEF) (Zhao et al., 2017a; Garza-Campos et al., 2018; Flores
et al., 2016). The UV prefers to break down contaminants, due to its
boosts Fe2+ regeneration and hydroxyl radical generation from Fe
(OH)2+ photoreduction. However, the UV lamps set up in the system
would increase the cost. However, this problem could be solved by
using solar, at a low cost and sustainable energy source. The process
was named the “solar PEF” (SPEF) process (Garza-Campos et al., 2016;
Paz et al., 2020), for example, the research work carried out by Zhang
et al. to degrade trimethoprim (TMT) (Zhang et al., 2016). The set up
basically the used photovoltaic (PV) solar panel to receive sunlight.
Another corporation method is adsorption-electro-Fenton (AEF) pro-
cess, which the experiment conducted by Roth et al. (2016). Roth et al.
carried out this experiment by firstly to remove contaminants through
adsorption, then only comes to EF procedure. Besides that, the gas
diffusion electrode (GDE) was fabricated by microtubular CNT because
of the considerable SSA (Roth et al., 2016). Table 3 and 4 summarize
the performance of antibiotics degradation by using the Fenton-like
method.
Iron sulfate is a common catalyst for the Fenton process, because,
the Fe ion in the aqueous solution is able to generate hydroxide ion by
oxidizing Fe(II) to Fe(III), and forming hydroperoxyl radical. Recently,
Xiang et al. introduced yolk-shell structure ZnFe2O4 as photo-Fenton’s
catalyst. As mentioned by Jiang et al. in 2016, the optical properties
could be enhanced with a yolk-shell structure, due to the multiple light
reflections in the interior surface (Jiang et al., 2016). On top of that, the
performance of yolk-shell ZnFe2O4 in the photo-Fenton system, was five
times better than bulk ZnFe2O4, which proved that the hierarchical
structure played an important role (Xiang et al., 2020a).
Besides of PF, EF, and PEF, Ranjusha et al. firstly reported new
method of phyto-Fenton. Phyto-Fenton is a process that uses the en-
dogenous H2O2 in plants to break down contaminants. They tried to
degrade the antibiotic in constructed wetlands system. However, the
concentration of antibiotics shows some increase in second month
(Ranjusha et al., 2020). This might be due to several factors that in-
fluence the degradation, such as: amount of H2O2 from the plant, pH,
and hydroxide ions production due to the dynamic environment system.
Therefore, more studies are needed in this new phyto-fenton method.
To solve the drawbacks of iron leaching that happened during the
homogeneous Fenton water treatment process, a heterogeneous Fenton
process was introduced. For the heterogeneous Fe catalyst, was carried
out by coating iron oxide or iron ions into supporting materials, that are
13
Journal of Hazardous Materials 400 (2020) 122961
porous to avoid leaching. The chemical changes and physical steps
occurred at the active sites of catalyst, where mass transfer limited the
adsorption of reactant molecules occurs, for the heterogeneous process.
The desorption of product molecules from the surface occurs at the end
of the reactions, so that, it would be available for a new set of reactant
molecules, to attach to the active sites to achieve the reaction (Soon and
Hameed, 2011). For the heterogeneous Fenton reaction, various Fe
containing solids are used (e.g. Fe2O3 and Fe2Si4O10(OH)2). Fe2+ sus-
tained on different supports like zeolites, Al2O3, and SiO2, with also
different types of non-mineral and mineral carriers, namely, steel dust
and hematite were proposed, as active supports for Fenton reagent
(Virkutyte et al., 2010). A good heterogeneous Fe catalyst should meet
2 requirements, which are (i) low Fe dissolution, and (ii) high catalytic
activity. As a result of this, heterogeneous Fenton is solving the major
disadvantages that homogeneous Fenton has.
2.2.3. Ozonation
To remove toxic compounds effectively, ozonation is a technique
that is able to make refractory organic compounds mineralization
(Liotta et al., 2009). Ozone, (under acidic conditions, E(O3/
O2) = 2.07 V) is a good oxidizing agent, and it is the main component
for the ozonation process. In comparison with all other AOPs, that have
applied for color removal, odor control, and disinfection. The use of
ozonation to treat wastewater has witnessed the great majority of ap-
plication (Rice et al., 1981). During ozonation, there are 2 mechanisms
involved in pollutant degradation (Ikehata and El-Din, 2004). First, the
ozone direct oxidation, which is a low rate of reaction with the highly
selective process (Hoigné, 1998). The reactions of molecular ozone are
predominant at lower pH, where the electrophilic attack occurs on
organic compounds and breakdown into fatty acids. The reactions of
molecular ozone are selective to the compounds having nucleophile
moieties, namely: C]C, −OCH3, −CH3, −OH, and other sulfur,
phosphorus, oxygen, and nitrogen-bearing functional groups (Alvares
et al., 2001). The second mechanism is an indirect mechanism, to
generate hydroxyl radical (Eq. 4.1) at high pH (> 8). The formed hy-
droperoxyl radical is in the state of equilibrium (Eq. 4.2). The O2−%
(superoxide radical) and O3 then react to form O3−% (ozonide radical)
(Eq. 4.3), which then straightaway break down into O2 and OH% (Eq.
4.5) (Gottschalk et al., 2009). Generally, 3 O3 molecules theoretically
produce 2 OH% as shown in Eq. 4.6.
O3 + OH • O2• + HO2• (4.1)
HO2• O2• + H+ (4.2)
O3 + O2• O3• + O2 (4.3)
O3• + H+ HO3• (4.4)
HO3• OH • + O2 (4.5)
Overall reaction:
3O3 + OH + H+ 2OH • + 4O2 (4.6)
Feng et al. attempted to study the breakdown of flumequine (FLU)
from aqueous by ozonation in 2016 (Feng et al., 2016). In this research,
up to 20 mg L−1 of FLU was fully broken down within 240−300 s. The
FLU removal mechanism was proposed to involve hydroxylation, dec-
arboxylation, as well as defluorination. However, it would generate
degraded by-products, and these by-products have the propensity to
accumulate in water which further needs treatment. Formation of
hidden hazardous by-products reacts with background compound in
water, one which, bromate is regulated and suspected carcinogenic is
the major drawback of the ozonation process (Von Gunten and Hoigne,
1994; Boorman, 1999). To avoid the toxic by-product formation, it is
significant to do optimization for both the oxidation process and the
disinfection of ozonation. Then, Feng et al. also carried out a toxicity
assessment for degraded FLU. It was found that, FLU showed less
B.L. Phoon, et al.
toxicity, after the ozonation reaction (Feng et al., 2016). Currently, the
ozonation method is commonly used to break down microorganisms
(Sousa et al., 2017), antibiotic resistance genes (ARG) (Chu et al.,
2020), and ARB (Alexander et al., 2016). Iakovides et al. reported on
ozonation continuously on urban wastewater, that contains antibiotic-
resistant Escherichia coli, ARG, and antibiotics (Iakovides et al., 2019).
Besides that, Sousa et al. carried out the ozonation of urban wastewater
together with UV-C radiation (Sousa et al., 2017).
2.2.4. Electrochemical oxidation
Electrochemical oxidation for organic component destruction in
aqueous medium has not only been tested in a laboratory, but also pilot
plant scale. Due to its high operational cost, it is yet to be applied
commercially (Mieluch et al., 1975; Boudenne et al., 1996; Brillas et al.,
1998). In this electrochemical process, the electrons that are given or
used up within the electrodes, given with a clean reactant, that does not
raise the amount of the chemical molecule to relate in the process is one
of the main advantages. Nevertheless, they present some of the draw-
backs, which are: (i) the effluent must be conductive, thus in case that
the wastewater does not have low conductivity, thus, some salts are
advised to be added, and (ii) the mechanism in water is complex, and
by comparing it with other processes, electrochemical treatment is
higher in cost. The organic compounds’ electrochemical oxidation is
thermodynamically favorable, against the competitive reaction of
oxygen production by water oxidation. Nevertheless, the kinetics of
organic compounds oxidation is slower than the kinetics of water oxi-
dation, among other reasons, due to its concentration is much higher.
Generally, 3 stages are involved in the electrochemical process me-
chanism, which: (i) electrocoagulation, (ii) electroflotation, and (iii)
electrooxidation as shown in (Eqs. 5.1–5.3).
e
RH RH+ (5.1)
H+
RH+ R• (5.2)
R• + R• R R (5.3)
In general, the anodic oxidation is a direct method, that involves
transferring electrons from contaminants to the electrode, so that, the
cationic radical is generated. In a direct method, the nature of the
electrodes, the pH, and the fate of the cationic radical, has effects in a
decisive manner on the formed products. The latter radical-radical
combinations have been noticed often. A few numbers of articles have
mentioned the electrochemical process application in industrial textile
wastewater, (Jojoa-Sierra et al., 2017) and the performance of dye
degradation with this technique has been proven by many of them
(Zappi et al., 2000; Gutierrez et al., 2001).
In 2015, Körbahti and Taşyürek reported a research about electro-
chemical oxidation of sulfadiazine antibiotics, with boron-doped dia-
mond (BDD) anode (Körbahti and Taşyürek, 2016). BDD is an inactive
electrode, that exhibits good stability and activity (Moreira et al., 2017;
Chaplin, 2014). Besides that, Körbahti and Taşyürek also mentioned
that BDD could effectively breakdown ampicillin (AMP) in the same
year (Körbahti and Taşyürek, 2015). According to Körbahti and Ta-
şyürek, the temperature parameter for the electrochemical oxidation
reaction was insignificant for the energy consumption, and the perfor-
mance to remove sulfadiazine pollutants. Nevertheless, the current
density and electrolyte concentration, can bring positive influences on
the sulfadiazine (SFD) degradation. This is because of in situ redox re-
agents production of HOCl and OCl- in the aqueous medium, and
weakly adsorbed OH% generated at BDD anode (Körbahti and Taşyürek,
2016). Meanwhile, in 2016, Yu et al. reported a study on combined Fe
electrodes, and that persulfate system can produce better performance
than electrocoagulation alone (e.g. without the presence of persulfate)
(Yu et al., 2016). As proposed by Xie et al. in 2017 that, the persulfate
can produce additional sulfate radicals by reacting OH% on the surface
of the anode (Equation 6) (Xie et al., 2017). Then, Frontistis,
14
Journal of Hazardous Materials 400 (2020) 122961
Mantzavinos, and Meriç conducted research on the combined electrode
with BDD and sodium persulfate in 2018 (Frontistis et al., 2018). It was
managed to fully remove 1.1 mg L−1 of AMP within 10 min (0.1 M of
Na2SO4, 25 mA/cm2, and inherent pH).
k = 1.2 x 107
S2 O82 HSO4 + SO4• + 0.5 O2 (6)
In 2016, Zhu et al. performed fluoroquinolone antibiotics (FQs)
electrochemical oxidation on the BDD electrode. It was proposed that,
the OH% has significantly attacked piperizinyl moiety of FQs, and the
FQs antibacterial activity was greatly reduced, when the reaction had
ended. Besides that, Zhu et al. also evaluated the toxicity of FQs after
the electrooxidation process (Zhu et al., 2016). It was found that, the
toxicity of FQs on green algae (D. subspicatus) increased or remained
compared to their parents’ compounds. This indicates that, the piper-
izinyl ring oxidation is unable to eliminate the toxicity of the FQs and
can produce hazardous by-products.
2.2.5. Wet oxidation
In the last few years, AOP has received outstanding attention (Li
et al., 2017d). Catalytic wet peroxide oxidation (CWPO), is attractive
and cost-effective AOP technology. Under the aqueous medium, both
inorganic and organic components are oxidized in the wet oxidation
process, with the condition of air/oxygen, at extreme pressure and
temperature. The pressure goes from 20 and up to 200 bar whereas, the
temperature relies on the nature of the components to achieve break
down. It is usually in between 150−350 °C and the COD removal
ranges from 75 to 90 % (Li et al., 1991). The wet oxidation mechanism
has been studied thoroughly, and this process occurs by means of free
radical process. It depends on the electrons transference from a suitable
catalyst to H2O2 molecules, in order to facilitate their processes of
breaking down, through the reduction of H2O2 to OH− and OH%
(Navalon et al., 2010). It was well-known that, CWPO was a particular
case of the Fenton process, characterized by the production of OH% from
the reaction between homogeneous Fe2+ and H2O2 under the condition
of low pH (Fenton, 1894). However, the use of homogeneous Fe2+
often resulted, in the need for a complicated final separation step for the
removal or recovery of Fe2+/Fe3+ ions. It is frequently noticed that,
concentration is being more than the limits allowed by common EU
Directives, for treated to be discharged into natural receiving water
bodies (2 mg L-1). Among the components that have been listed as
readily oxidizable by means of wet oxidation are aliphatic, and ali-
phatic chlorides, and aromatics that, do not include halogenated
functional groups, for example, anilines and phenols. Components that
consists of nitro functional groups and halogens are noticed to be hard
to decomposed by this method (Scott, 1997). In the wet oxidation ex-
perimental results of wastewater treatment are expected to be more
than 90 % removal of phenolic compounds such as phenol is achiev-
able.
In 2016, Ribeiro et al. studied the sulfamethoxazole (SMX), by using
magnetic carbon xerogels with the CWPO process. In the study, Ribeiro
et al. noticed that, the corporation of Fe and Co in the carbon xerogel
was able to improve the overall catalytic performance. This result was
attributed to the higher accessibility of Fe species, boosted by the si-
multaneous incorporation of Co catalysts used in CWPO included het-
erogeneous and homogeneous catalysts (Kavitha and Palanivelu, 2005).
Heterogeneous catalysts could get rid of those disadvantages that
homogeneous have, such as: (i) secondary pollution, caused by soluble
metals, and (ii) unable to be reused (Yang et al., 2018). Variety of
catalytic supports that have been developed including AC (Wang et al.,
2015b) and zeolites (Yan et al., 2014). Nonetheless, the major limita-
tion is, its expensiveness. It was found that, after the pyrolysis process,
sludge derived carbon (SC) consists of many active substances (e.g. Fe
and Al) (Daorattanachai et al., 2018; Gu et al., 2017; Wang et al.,
2017). Therefore, SC is a potential low-cost catalyst in the degradation
reaction. In terms of cost minimization, Liu et al. carried out research
 B.L. Phoon, et al.

Table 5
The performance of antibiotics removal with different adsorbents.
Adsorbent Mass Target pollutant/Concentration/volume (mL)/pH Adsorption time/ Adsorption capacity/rate constant Ref. (year)
Percentage removal

MTMN 4 mL of 450 mg L−1 MTMN TC/5 × 10−4 mol L-1/10 mL/3 1440 min/90 % (Parolo et al., 2008) (2008)
dispersion
Silica (BET: 700 m2/g) TC/1 × 10−4 mol L-1/N.A/4 (Turku et al., 2007) (2007)
CTS 2 g L−1 TC/1 × 10−4 mol L-1/25 mL/5 1440 min/30 % 93.04 mmol kg−1 (Kang et al., 2010) (2010)
GO 0.181 mg mL−1 TC/8.33 mg L−1/8 mL/3.6 313 mg g−1/0.065 g mg−1 h−1 (Gao et al., 2012) (2012)
MTMN 4 mL of 9 × 10−4 kg L-1 MTMN TC/0.76 mM/2.2 mL/N.A 1440 min/N.A (Parolo et al., 2012) (2012)
dispersion
AC (derived from tyre pyrolysis char) 0.004 g TC/100 mg L−1/25 mL/6.5−7.5 1440 min/N.A 312 mg g−1/0.004 g mg−1 h−1 (Acosta et al., 2016) (2016)
Rice husk ash 2 g L−1 TC/5 mg L−1/20 mL/5 600 min/83.52 % 8.37 mg g−1 (Chen et al., 2016b) (2016)
AC (derived from apricot nut shells) 0.005 – 0.3 g TC/100 mg L−1/50 mL/1.5−8.5 1440 min/N.A 166.66 mg g−1/6.407 g mg−1 min−1 (Marzbali et al., 2016)
(2016)
GO/calcium alginate composite fibers 0.25 g TC/30 mg L−1/50 mL/2−9 300 min/70 % 131.6 mg g−1/0.0233 g mg−1 min−1 (Zhu et al., 2018) (2017)
NiFe (derived from Punica granatum peel) 0.3 g L−1 TC/20 mg L−1/100 mL/N.A 90 min/93 % 61 mg g−1 (Ravikumar et al., 2019)
(2019)
Honeycomb tubular biochar (derived from 0.05 g TC/80 mg L−1/100 mL/7 90 min/90 % 146.68 mg g−1/0.007 g mg−1 min−1 (Ma et al., 2018) (2018)
fargesia leaves)

15
Fe3O4@SiO2-CTS/GO nanocomposite 0.02 g TC/1 × 10−4 mol L-1/50 mL/3−10 1440 min/N.A 59.38 mmol kg−1/0.0004 kg mol−1 min−1 (Huang et al., 2017) (2017)
Zeolite-hydroxyapatite-activated oil palm 0.2 g TC/50−400 mg L−1/250 mL/3−13 1800 min/N.A 186.09 mg g−1 (Khanday and Hameed,
ash composite 2018) (2018)
Polypyrrole modified Calotropis gigantea fiber 0.01 g ENR/100 mg L−1/120 mL/6 180 min/ N.A 78.27 mg g−1 (Duan et al., 2019) (2019)
CPF/100 mg L−1/120 mL/6 180 min/N.A 76.61 mg g−1
NFX/100 mg L−1/120 mL/6 180 min/N.A 68.90 mg g−1
Magnetic biochar-based manganese oxide 0.05 g NFX/10 mg L−1/25 mL 1440 min/N.A 6.94 mg g−1 (Li et al., 2018b) (2018)
composite CPF/10 mg L−1/25 mL 1440 min/N.A 8.37 mg g−1
ENR/10 mg L−1/25 mL 1440 min/N.A 7.19 mg g−1
MOF-polymer SAs/ (Shih et al., 2016) (2016)
Spent coffee grounds based biochar and 0.1 g SMX/500 μg L−1/30 m L 1440 min/N.A 130 μg g−1 (Afreen et al., 2020)
hydrochar (2020)
Manganese ferrite modified biochar from 0.1−2.0 g/L CIP 90.4 mg g−1/0.0021 min−1 (Xiang et al., 2020b)
vinasse (2020)
Polymer of Intrinsic Microporosity (PIM) 0.002 AMX/200 μM 208.6 mg g−1/0.00023 min−1 (Alnajrani and Alsager,
2020)
(2020)
Carbon nanotubes/Graphene oxide/sodium CIP/200 mg L−1/20 mL 200 mg g−1 (Ma et al., 2020b) (2020)
alginate

Note: N.A: Not available; GO: Graphene oxide; AC: Activated carbon; TC: Tetracycline; ENR: Enrofloxacin; CPF: Ciprofloxacin; NFX: Norfloxacin; MOF: Metal-organic framework; SAs: Sulfonamide antibiotics; MTMN:
Montmorillonite; CTS: Chitosan; SMX: sulfamethazine; AMX: Amoxicillin.
Journal of Hazardous Materials 400 (2020) 122961
B.L. Phoon, et al.
on oxytetracycline (OTC) degradation, by using sludge to derive carbon
in 2019 (Liu et al., 2019). The conversion of OTC was achieved by 92.5
% after 260 min of reaction. Besides that, Liu et al. was the first to
conduct water toxicity evaluation with zebrafish embryos after the
catalytic oxidation process (Liu et al., 2019).
2.3. Advanced treatment
2.3.1. Adsorption
Adsorption shows as one of the very remarkable techniques for
pollutants removal and treatment, among the possible techniques for
water treatments. Adsorption is a mass transfer process, during which
chemicals are accumulated or adsorbed from the liquid into the solid
phase. This process was developed to treat drinking water, so that, to
remove compounds that are causing odor or make the water tasty,
color-forming organics, synthetic organic chemicals, and by-product
precursors disinfection. Besides that, it can also remove hazardous in-
organic substances, for example, heavy metals and perchlorate.
It was known that, the process of adsorption from the bulk liquid
phase into the adsorbent surface is assumed to include several steps,
which are: (i) adsorbate molecules mass transfer across the external
boundary layer, towards the solid particle, (ii) adsorbate molecules
transport from the surface of particle into the active sites, by diffusion
within the pore-filled liquid, and migrate along the solid surface of the
pore, (iii) solute molecules adsorption on the active sites on the interior
surfaces of the pores, and (iv) it might be moveable on the pore surface,
trough surface diffusion once the molecules adsorbed. Adsorbates can
be captured, by a physical attraction or chemical reaction into the
surface adsorbents. Physical adsorption is accomplished, by hydrogen
bonding, dipole interaction, and van der Waals forces. There is no ex-
change of electron between adsorbate and adsorbent. This is because,
physical adsorption does not require activation energy, but usually re-
quires very little time to reach equilibrium. Physical adsorption is a
process that is reversible and non-specific. Meanwhile, chemical ad-
sorption results from the chemical link between both the adsorbate and
adsorbent molecules are irreversible as well as specific. Also, the
properties of electronics as well as the chemical of adsorbent are
transformed. Binding covalent bonding between adsorbate and ad-
sorbent is a weak chemical adsorption, while the strong chemical ad-
sorption is usually binding by ionic bonding.
Table 5 shows the removal of the antibiotic by using different ab-
sorbents, that were carried out by another researcher. Until today, AC is
the major adsorbent applied in industry. Carbonized wood such as,
charcoal has been used as a purifying agent, medical adsorbent, and
drinking water filtration in Egypt and India, as early as, 1500 B.C. AC is
a black carbonaceous material that presents in solid form and porous.
Any carbonaceous solid precursor, natural or synthetic can also produce
AC. AC is able to prepare from abundant sources such as, petroleum
coke, bituminous coal, lignite, charcoal, black ash, peat, as well as,
coconut shells.
In 2016, Marzbali et al. prepared the AC from apricot nutshells
(Marzbali et al., 2016). Then, Acosta et al. reported to have produced
AC, by using tire pyrolysis char as a raw material in the same year, with
the TC adsorption capacity of 312 mg g−1 (Acosta et al., 2016). Besides
AC, some other adsorbent materials also have a good performance in TC
removal such as, the graphene oxide (GO) that was prepared by Gao
et al. in 2012, can achieve 313 mg g-1 of adsorption capacity (Gao et al.,
2012). It was known that, the aromatics was able to adsorb on graphene
and GO by π-π stacking from works of literature that was earlier re-
ported. TC contains 4 aromatic rings with several functional groups on
each ring, including amino, ketone, alcohol, and phenol (Zhang et al.,
2011).
With the agreement with the results of density functional theory
(DFT), Peng et al. mentioned that, the amount of aromatic rings on
antibiotics was the major reason to influence the rate of adsorption, the
major adsorption mechanism is based on the interactions of the π-π
16
Journal of Hazardous Materials 400 (2020) 122961
bond (Peng et al., 2016). Peng et al. deduced that, biochar that was
derived from lost cost materials, with additional aromatic ring area, can
remove the antibiotics faster and more efficient in 2016 (Peng et al.,
2016). Then, in the following year, Zhao et al. studied and quantified
the cation π-interaction between graphite and CPF antibiotics (Zhao
et al., 2017b). Zhao et al. proposed that, the ionic strength of water
bodies could affect the adsorption performance. This is because in the
aqueous medium, CPF is able to capture H+ from water and undergo
species transformation to form CPF(+1), after that, it would adsorb on
the surface of graphite and the uptake of the antibiotic was up to 72 %.
It is worth to know that, different processing conditions can produce
slightly different properties of biochar. Recently, Zhang et al. studied
the different processing techniques for those chars production from the
spent coffee ground, which are biochar and hydrochar (Zhang et al.,
2020b). The biochar and hydrochar were produced through pyrolysis
and hydrothermal carbonization (HTC) technique, respectively. It was
found that the biochar has a lower yield than hydrochar. On top of that,
biochar has lower surface oxygen, higher ash percentage, and more
carbon content, as compared to hydrochar. This suggested that, biochar
has the least polarity but higher aromaticity and good hydrophobicity.
Therefore, the adsorption mechanism of biochar and hydrochar was
mainly due to the π-π electron donor-acceptor interactions hydrogen
bonding, respectively (Zhang et al., 2020b).
Besides that, chitosan (CTS) was produced by chitin partial deace-
tylation, and it is a potential adsorbent for organic pollutants removal.
It was revealed that, CTS had a higher adsorptive capacity from a series
of studies (Olivera et al., 2016). In recent years, some researchers at-
tempted to combine CTS and photocatalyst to form a hybrid structure
for wastewater treatment. This is because, the CTS is able to raise the
light-harvesting and prolong the light absorption wavelength to
700 nm, as presented in Fig. 10 (Saravanan et al., 2018). In 2016, Shih
et al. conducted sulfonamide adsorption by using a composite of MOFs
and polymer (Shih et al., 2016). It was found that, the sulfonamide is
fully adsorbed by MOFs-polymer composite adsorbent. Nonetheless,
because of the interaction of strong Lewis acid-base, the adsorbent was
difficult to be desorbed.
Apart from that, Li et al. carried out a study in 2018 on the ad-
sorption of antibiotics on microplastics (MPs). Both antibiotics and MPs
are two classes of emerging contaminants, that would give negative
environmental impacts. Li et al. mentioned that, electrostatic interac-
tion, van der Waals force, hydrophobic interaction, and hydrogen
bonding were the major binding mechanisms between the microplastics
and antibiotics (Li et al., 2018a). On top of that, the physicochemical
properties such as, porosity, crystallinity, and SSA can affect the
Fig. 10. The UV–vis spectra of TiO2 and TiO2/CTS composites, (a) Pristine
TiO2, (b) TiO2/CTS (75:25), (c) TiO2/CTS (50:50), and (d) TiO2/CTS (25:75).
Reproduced from Ref. Saravanan et al. (2018).
B.L. Phoon, et al.
adsorption capacity as well. In the study, polyamide showed the best
adsorption performance in the freshwater bodies, this is because of the
hydrogen bonding. Meanwhile, in seawater, not all the pollutants can
be adsorbed, this may be due to the aqueous medium condition such as,
pH and ions that need to be further investigated. Besides that, we think
that, the separation technique to remove adsorbent from water bodies
after treatment still needs to be considered.
Most researchers conducted the antibiotics removal experiment in
the aqueous medium. Nevertheless, one of the facts that need to be a
concern is the possibility of antibiotics remains in the soil. Pan and Chu
carried out the first study about the adsorption, degradation, and per-
sistence of antibiotics in the agricultural soil (Pan and Chu, 2016). It
was found that, TC was the slowest degradation, but strongest ad-
sorption behavior, indicates that, TC is more persistent in the surface of
the soil and might cause higher environmental risks to organisms in the
topsoil. Meanwhile, SMX shows low adsorption and slower degradation
behavior implies that, SMX moving downward readily during waste-
water irrigation and/or manure application, causing higher risks of
groundwater contamination.
Until today, the adsorption technique remains a challenge and has
some drawbacks, because of the progressive capacity deterioration after
a number of treatment cycles. The main adsorption drawback is the
secondary waste formation, such as, the unusable recovered organic
compound, spent adsorbent, and organics in the wastewater, if steam is
used for regeneration. In addition, specialist disposal or off-site treat-
ment is necessary for secondary waste management (Sjoholm et al.,
2001).
Fig. 11. Schematic diagram of PMR configurations (a) submerged membrane PMR, (b) side pressurized membrane PMR, and (c) PM. Reproduced form Ref. Ganiyu
et al. (2015) and adapted from Ref. Sarasidis et al. (2014).
17
Journal of Hazardous Materials 400 (2020) 122961
2.3.2. Membrane treatment
Membrane technology directs to a few various parts of the process,
by separating chemical components using synthetic membranes. It was
recognized as the key technology for the separation of pollutant from
contaminated sources, that for original waters purification (Li et al.,
2011b). In recent years, membranes technology was dramatically en-
hanced with significant improved capabilities, and spread through ra-
pidly in commercial markets over the world. Physical separation is one
of the unusual benefits of the membrane separation process with che-
micals without change of phase, and non-addition in the feed stream
(Morão, 2008). Despite that, without any heating, it could be operated.
Thus, this process of separation is dynamically lower, than traditional
separation techniques, such as, crystallization and distillation. In the
separation industry, membrane separation processes play an important
role. The earliest industrial application of the pressure-driven mem-
brane process was water desalination, by reverse osmosis (RO) in the
1960s. Considering all, there is 4 pressure-driven membrane processes
allowing separation in the liquid phase, which are microfiltration (MF),
ultrafiltration (UF), nanofiltration (NF), and RO.
Wu et al. synthesized PVC membrane for UF of antibiotics and the
retention can be up to 80 % in 2016 (Wu et al., 2016). Then, in the same
year, Weng and co-workers have conducted antibiotics separation by
using zwitterionic polyamide NF membranes with the highest anti-
biotics’ retention of 96.5 % (Weng et al., 2016). It was mentioned by
Weng and co-workers that, zwitterion membranes were high hydro-
philicity and antifouling property, and thus becoming a new trend and
materials for NF membranes (Weng et al., 2016). However, membrane
B.L. Phoon, et al.
technology merely transforms antibiotics from one state to another. The
antibiotics may return to the environment and cause potential damage
in some areas, even, if the indirect or direct effusion of concentrate into
the environment is not regulated. However, some awareness has been
focusing on this issue in recent years (Pérez-González et al., 2012). In
addition, some innovations and further improvements are required,
especially in the antifouling membrane for wastewater treatment, ele-
ment and module design on membrane systems, morphological and
chemical design of membrane materials etc. (Li et al., 2011b). Liu et al.
were reported on the hybrid process on the removal of antibiotics with
the NF membrane and further process the NF concentrate by AOP.
Apart from that, the fouled contaminants that accumulate the surface
membrane and pores cause the membrane to become less durable and
cracks. Therefore, during the membrane filtration process, the result
shows a steep drop in the water flux sometimes (Xia and Ni, 2015; Wei
et al., 2012). Recently, some studies were carried out to improve the
antifouling and permeation effect (Saraswathi et al., 2017).
In order to get rid of the contaminant from the membrane, AOPs can
be used at the post-treatment stage. Especially for the concentrate
streams treatment, before discharge to water streams. The concentrated
contaminants in the concentrates provide an enabling condition for the
effective performance of the process since the majority of AOPs’ per-
formance is very effective (Ganiyu et al., 2015).
In recent years, hybrid systems incorporated with the membrane
technologies and photocatalysis have earned attention for the aqueous
wastewater treatment, in order to improve the wastewater effectiveness
(Sarasidis et al., 2017). Basically, this kind of integrated hybrid system
called photocatalytic membrane reactor (PMR) and can be broken into
two categories, (i) setup with the photocatalyst immobilized on/in the
membrane surface and (ii) with photocatalyst suspended in the was-
tewater medium. The second case is the most common system, by using
polymer membranes. Nonetheless, it has some serious disadvantages,
due to the polymeric membranes, that has a short life span under the
UV light, and the membrane surface might be attacked by hydroxyl
radicals (Chin et al., 2006; Darowna et al., 2017). Thus, some re-
searchers started to replace the polymeric membrane with ceramic
materials, due to high chemical stability, abrasion resistance, and
longer life span. Apart from that, the adsorption of organic pollutants
on the membrane layer also plays an important role (Kim et al., 2018).
Espíndola et al. conducted this hybrid system with UF for OTC removal
(Espíndola et al., 2019). In this case, the TiO2 was suspended in the
aqueous medium. It was found that, OTC managed to be fully removed
in 300 min and the mineralization was about 49 %. Furthermore, there
are two setups of PMRs have been mentioned in the research work
(Fig. 11), which are: (i) submerged membrane PMR, where the mem-
brane was buried in a slurry, that contains photo activated catalyst and
(ii) side pressurized membrane PMR, where suspended photocatalyst is
recirculated, through pressurized side membrane. Table 6 shows some
recent studies on PMRs.
Meanwhile, self-cleaning and photocatalytic membranes separate,
and mineralize organic pollutants in the feed stream at the same time.
Therefore, the system is more robust compared to PMR. Due to the
photocatalytic degradation ability, TiO2-based photocatalytic mem-
brane (PM) gained advantageous (Fig. 11(c)) such as, anti-fouling by
photodegradation of foulants, confining of the contaminants within the
Table 6
Summary of some recent studies on antibiotics removal by PMR.
Water system Experimental conditions Combined processes
Spiked water Continuous flow; 0.15−0.45 g of ZnIn2S4 Photocatalysis-PVDF membrane submerged PMRs
Spiked water Cross flow; 0.1 g of TiO2 Photocatalysis-UF membrane side pressurized PMRs
Spiked water N/A Photocatalysis nanofibrous membrane
Spiked water Continuous flow Photocatalysis-PVDF membrane side pressurized PMRs
Note: PVDF: Polyvinylidene fluoride; ARB: Antibiotic resistant bacteria; ARG: Antibiotic resistance genes; N/A: not available; TC: Tetracycline.
18
Journal of Hazardous Materials 400 (2020) 122961
photocatalytic chamber, high flexibility, that suitable for a variety of
membrane modules for industrial application, and no extras require-
ment for separation and recycling of the photocatalyst like in the case of
PMRs (Ma et al., 2010; Zhang et al., 2008).
2.4. Advanced biological treatment
Aside from physical and chemical treatment superiority, biological
treatment is still the foundation of any wastewater plant. In the case of
the removal of antibiotics, through biological treatment, it is obligatory
to evaluate the biodegradability of the substance. Biodegradability is
pertinent to the microorganisms’ activities; whereby, aerobic micro-
organism is measured by the amount of carbon dioxide produced, while
anaerobic microorganism is measured by the production of methane. A
simple closed bottled test (CBT), (Nyholm, 1991) is usually conducted
to ascertain the biodegradability of the antibiotic. Based on the Orga-
nisation for Economic Co-operation and Development (OECD), a sub-
stance is readily biodegradable, when oxygen used in the testing vessel
exceeds 60 % of theoretical oxygen in demand for a period of 28 days.
To complement CBT, a toxicity test using a colony-forming unit (CFU),
is also performed to determine the effect of antibiotics on bacteria ac-
tivity. It is significant to first determine the biodegradability of anti-
biotics, before implementing biological treatment because, generally, a
non-biodegradable antibiotic is less effective to be removed through
biological treatment.
2.4.1. Anaerobic treatment
Anaerobic treatment is a sequential step of chemical reaction that
involves biochemical processes such as, hydrolysis, acidogenesis, acet-
ogenesis, as well as, methanogenesis. In the hydrolysis stage, water-
insoluble organics’ chemical bonds are broken down into simple soluble
compounds, using water that is to be used by these bacterial cells
(Gerardi, 2003). Subsequently, acid-forming step (acidogenesis) or-
ganics are converted to a higher organic acid (e.g. butyric acid and
propionic acid), ethanoic acid, carbon dioxide, and hydrogen, by acid-
forming bacteria. Butyric acid and propionic acid are then converted to
ethanoic acid, through acetogenic bacteria. In the final stage, two re-
actions occur contemporaneously converting acetate to methane and
bicarbonate, as well as, carbon dioxide and hydrogen to methane. The
dominance of anaerobic treatment lies in the cost of the reactor, where
it needs no additional air circulation gear, less vitality venture, and
produces fewer amounts of overabundance ooze. In addition, the biogas
created amid anaerobic treatment could fill in, as an alluring wellspring
of sustainable power source to supplant petroleum derivative, while the
digestate can fill in as compost on farmland.
Among the contemporary anaerobic technologies developed in the
removal of pharmaceutical waste includes, upflowing anaerobic sludge
blanket (UASB), anaerobic sequencing batch reactor (AnSBR), anae-
robic bio-entrapment membrane bioreactor (AnBEMR), anaerobic
membrane bioreactor (AnMBR). Table 7 shows a summary of phar-
maceutical wastewater treatment, with the anaerobic process.
The advancement of AnMBR gives a promising potential, whereby,
it combined the anaerobic procedure and the layer of membrane to
generate solid free output, via complete biomass retention. In addition,
the by-product of AnMBR yields methane, which is an essential source
Efficiency Ref. (Year)
TOC removal = 57 % in 3 h (Gao et al., 2018) (2018)
ARB/ARG removal > 98 % (Ren et al., 2018) (2018)
TC removal > 90 % (Song et al., 2020) (2020)
TOC removal = 97.19 % (Liu et al., 2020) (2020)
 Table 7
Summary of anaerobic treatment for pharmaceutical wastewater treatment.
Type of wastewater Treatment Type of Bioreactor Hydraulic Retention COD Removal Target pharmaceutical Findings Ref. (year)
Time (HRT) (h) (%) compound removal (%)
B.L. Phoon, et al.

Pharmaceutical wastewater Anaerobic AnMBR 42.6 42.5 ± 4.3 – • Membrane fouling issue (Ng et al., 2014)
• High EPS and SMP (2014)
Pharmaceutical wastewater Anaerobic AnBEMR 42.6 47.2 ± 2.6 – • Lower rate of membrane fouling (Ng et al., 2014)
• Lower EPS and SMP at higher HRT. (2014)
Antibiotic waste (real) Anaerobic AnMBR 30.6 46.1−60.3 – • Improved performance in treating high saline (Ng et al., 2015)
and complex pharmaceutical wastewater. (2015)
• Lower particle size distribution and lower EPS
and SMP
Brewery waste pharmaceutical Anaerobic AnSBR – – 94.7−99.4 (ERY) • Presence of erythromycin resistance (Amin et al., 2006)
industry (synthetic) • The decrease in COD removal after a period of (2006)
time
• Accumulation of volatile fatty acids, soluble
microbial products and affect the overall system
instabilities
Synthetic antibiotic pharmaceutical Anaerobic AnSBR – – 85−94 (SMX, ERY & TC) • Viable post-treatment on AnSBR (Aydin, 2016) (2016)
waste (synthetic)
Pharmaceutical penicillin G Anaerobic UASB 168 80−85 – COD removal efficiency up to 120 days at (Rodríguez et al.,
−1
producing industry
• High
OLR of 1.5 g COD/ (L day ) 2005) (2005)
−1
• OLR higher than 2.09 g COD/ (L day ) affected
the performance.
Pharmaceutical fermentation Anaerobic UASB 13.5−38.5 83−91 – • Requires diluted pharmaceutical wastewater (Chen et al., 2014)
wastewater • Improved removal of COD as OLR increases (2014)
Pharmaceutical pre-treatment Anaerobic UASB 23.2 39−85 19−33 (6-APA) 13−47 • Potential to extend UASB in pre-treatment (Chen et al., 2011)
wastewater (amoxicillin) pharmaceutical wastewater (2011)

19
Pharmaceutical wastewater (real) Anaerobic UASR 96 70−75 95 (Tylocin) • Higher tylocin concentration results in lower (Chelliapan et al.,
(Tylosin and Avilamycin) COD removal 2006) (2006)
SMX Aerobic SBR – – 100 • SMX serves as carbon/nitrogen source to (Drillia et al., 2005)
enhanced microorganism performance. (2005)
TC Aerobic SBR 24 86.4 ± 8.7 • Removal of non-biodegradable TC (Kim et al., 2005)
(2005)
Pharmaceutical wastewater Anaerobic- UASB-CSTR 19.92 97 97−100 (Sulfamerazine) efficiency of suflamerazine increases (Sponza and Demirden,
(synthetic) aerobic
• -asRemoval
antibiotic concentration increases. 2007) (2007)
Pharmaceutical wastewater Anaerobic- TPAD-CSTR 12 (CSTR) 55 (UASB- 99 of high COD influent up to (Chen et al., 2008)
−1
(synthetic) aerobic AF) 5 (MBR)
• Removal
58,792 mg L with pH ranging from 4.3−7.2 (2008)
• Effluent can be directly discharged into natural
waters.
Pharmaceutical wastewater with high Anaerobic- UASB-MBR/SBR 48 94.7 • UASB-MBR shows slightly better performance in (Shi et al., 2014)
total dissolved solids aerobic COD removal compare to UASB-SBR (2014)
Pharmaceutical wastewater (real) Anaerobic-micro- UASB-NHAR-CASS- 1.35−23.5 97 97.2 (amoxicillin) • CASS contribute the most in amoxicillin (Chen et al., 2011)
aerobic BCOT-clarifier removal (2011)
Pharmaceutical wastewater Anaerobic- AMCBR-CSTR 48 95 99 (OTC) • - High removal of target compound (Sponza and Çelebi,
(synthetic) aerobic 2012) (2012)
−1
Pharmaceutical wastewater Anoxic-aerobic A/O MBR 6 89.2 ± 0.9 > 70 (SMX & TC) efficiency is > 70 % at 100 μg L (Zhu et al., 2017)
−1
(synthetic)
• Removalincrease concentration to 1000 μg L , it (2017)
• After
takes 2 weeks to recover the removal
performance to > 70%
Pharmaceutical wastewater Anaerobic- Anaerobic/ anoxic/ 16 94.7−98.4 93.9−97.5 (SAs) • Majority of antibiotics is removed under aerobic (Zhao et al., 2018)
(synthetic) anoxic-oxic oxic-MBR condition (2018)
• Under anaerobic condition, most target SAs
cannot be removed
(continued on next page)
Journal of Hazardous Materials 400 (2020) 122961
B.L. Phoon, et al. Journal of Hazardous Materials 400 (2020) 122961

Note: AnMBR: Anaerobic membrane bioreactor; AnBEMR: Anaerobic bio-entrapment membrane bioreactor; AnSBR: Anaerobic sequencing batch reactor; UASB: Upflow anaerobic sludge blanket; UASR: Upflow anaerobic

BCOT: Biological contact oxidation tank; AMCBR: Anaerobic multi-chamber bed reactor; TC: Tetracycline; OTC: Oxytetracycline; OLR: Organic loading rate; COD: Chemical oxygen demand; ER: Erythromycin; SMX:
stage reactor; SBR: Sequencing batch reactor; CSTR: Completely stirred tank reactor; TPAD: Two-phase anaerobic digestion; NHAR: Novel micro-aerobic hydrolysis acidification reactor; CASS: Cyclic activated sludge;
of clean energy attribute to its effective combustion properties
(Skouteris et al., 2012). Although, AnMBR sounds like a promising
(Han et al., 2020)
solution, membrane fouling remains an issue, that needs to be ad-
dressed. As an alternative, AnBEMR was developed to address this
Ref. (year)

concern, by using a reactor packed with bio-ball carriers. Ng et al.,

(2020)

investigated and compared the performance of AnBEMR over AnMBR,

and resulted in an improvement of 5–10 % COD removal efficiency with
15 % higher yield of methane (Ng et al., 2014). On top of that, AnBEMR
also produces less extracellular polymeric substances (mg L−1) (EPS)
and soluble microbial products (mg L−1) (SMP). EPS and SMP are the
of antibiotics is removed under

preeminent foulant agents for membrane bioreactors (Huang et al.,

2011). Besides that, the salinity of the influent, also influences the
performance of both AnMBR and AnBEMR, whereby, the higher the
salinity, the lowers the treatment process efficiency. Ng et al. dis-
covered that, AnMBR supplied from coastal silt could tolerate the high
anaerobic digestion.

salinity conditions with greater performance (Ng et al., 2015). This

could be ascribed to the way that the anaerobic microorganisms in the
B-AnMBR were emanated from a high salt concentration environment
that contained extensive measures of halophilic/tolerant microorgan-
• Majority

isms, and henceforth the biomass could adjust and flourish in the high
Findings

salt concentration environment during the wastewater treatment.

AnSBR is another biological method that was used to treat phar-
maceutical wastewater treatment, by using five-steps of the process
consists of fill, react, settle, decant, and idle in a single reactor in ab-
compound removal (%)

sence of light. A study of single antibiotic (erythromycin) influence on

Target pharmaceutical

anaerobic treatment was studied using a laboratory-scale AnSBR. The

findings revealed the anaerobic treatment in the presence of ery-
thromycin (ERY) is possible up to at least 7 weeks. Subsequently, a
slight reduction of COD removal was seen attribute to the increased
SMP. It was also discovered during the 7th days, that the specific me-
92

thanogenic activity (SMA) suggests the biomass developed resistance to

erythromycin. In addition, exposure of antibiotics influences the spe-
COD Removal

cific substrate degradation pathways, followed by the accumulation of

soluble microbial products, and volatile fatty acids. In another research,
a study was conducted on the influence of the concentration of anti-
(%)

95

biotic sulfamethoxazole (SMX) on the utilization of volatile fatty acids

using AnSBR (Cetecioglu and Orhon, 2017). The study discovered the
Hydraulic Retention

anaerobic treatment was efficient up to 40 mg L−1 of SMX, where fur-

Time (HRT) (h)

79.2 (3.3 days)

ther increase in concentration would result in toxicity for the micro-

organism. While anaerobic treatment was able to remove a significant
amount of antibiotic in the liquid phase, the solid phase may still
contain a considerable amount of antibiotic. Aydin carried out research
using white-rot fungi to remove ERY, SMX, and tetracycline (TC) from
the biosolids (Aydin, 2016). The findings suggested that, the use of T.
reactor-Aerobic SBR
Anaerobic digestion
Type of Bioreactor

versicolor and B. adusta fungi, as a post-treatment of AnSBR was viable,

as it could degrade the mentioned antibiotic effectively after the
anaerobic reaction.
UASB is by a long shot the most generally utilized high-rate anae-
robic framework for both domestic and industrial wastewater treatment
attribute to its simplicity, cost-efficient, adaptability and capacity to
withstand the change of pH and temperature (Chen et al., 2011). A
study in 2005 reveals that, organic loading rate (OLR) negatively affects
Anaerobic-
Treatment

the performance of COD removal when it increases from 1.5 to 2.09 g

aerobic

COD L−1 d−1). This is due to the accumulation of sulfides hinders the
methanogenic activity, as the pH increases more than 8, thus enables
Sulfamethoxazole; SAs: sulfonamides.

the sulfate-reducing bacteria, to flourish over methanogens in the UASB

(Rodríguez et al., 2005). In contrast with the aforementioned outcome,
another study reveals that, in an absence of sulfate and nitrate, a low
concentration pharmaceutical fermentation wastewater shows im-
Swine wastewater (real)

provement in COD removal, as OLR increases for continuous operation

Table 7 (continued)

of 140 days (Chen et al., 2014). UASB potential could be stretched to be

Type of wastewater

used as pre-treatment of pharmaceutical waste with high OLR from

12.57 to21.02 kg COD L−1 d−1 containing 6-aminopenicillanic acid (6-
APA) and amoxicillin with excellent removal percentage of 19−33 %
and 13−47 % respectively. Although, the system runs at high OLR, the
system still able to achieve COD removal of 39−85% (Chen et al.,

20
B.L. Phoon, et al. Journal of Hazardous Materials 400 (2020) 122961

2011). Moreover, an up-flow anaerobic stage reactor (UASR) is a de-
sign, consisting of a few UASB reactors connected in series. This ar-
chitecture enables the separation of acidogenesis and methanogenesis
resulting in better reactor performance. UASR could help to diminish
biomass washout, permit speedy recuperation from pressure-driven and
organic shock loads, and additional downstream type of equipment was
eliminated. UASR was tested as a pre-treatment option in pharmaceu-
tical wastewater, containing Tylosin with an antibiotic removal rate of
95 % and a COD removal rate of 70−75 %. However, it was also dis-
covered that a higher concentration of Tylosin results in a lower COD
removal rate (Chelliapan et al., 2006).
2.4.2. Aerobic treatment
In aerobic treatment, the organic compound would completely
break down into carbon dioxide, and water under aerobic conditions.
However, the treatment is limited to dilute wastewater and not viable
for high-strength wastewater from the antibiotic industry. Nevertheless,
Table 7 reveals that, some antibiotics can still be breakdown, by using
aerobic treatment. Among the antibiotic, SMX was observed to be
biodegradable, under aerated condition using a sequencing batch re-
actor (SBR). The removal efficiency achieved nearly 100 % on the 5th
day of the process. Besides that, TC also shows potential in removal by
using SBR up to 86.4 %, even though, the biodegradability test sug-
gested otherwise. As seen in Table 7, studies conducted on the single
aerobic system are limited and unsubstantial in comparison with the
anaerobic system. However, that does not mean the aerobic system is
insignificant in treating antibiotic wastewater, as it has usually been
used in smaller scale treatment facilities, with less than 20,000 m3
day−1. The advantages of aerobic digestion are the lower capital cost,
simplicity, flexibility, less risk of failure, and low production of odour
(Bernard and Gray, 2000).

Table 8
Advantages and disadvantages of the current technologies in antibiotic wastewater removal.
Process (characteristics) Advantages Disadvantages

Heterogeneous Photocatalysis •Good stability of photocatalyst in the aqueous phase, for
(Destruction of organic contaminant example, TiO2, ZnO, and etc.
chemical structures using semiconductors •High activity and non-toxicity.
and light) •Efficient recovery & reasonable recyclability of photocatalyst.
•Low cost, easy to operate, and fully destroy the organic
pollutant chemical structure.
•Required abundant resources such as sunlight, oxygen and
photocatalyst.
Fenton •In-situ production of reactive radicals such as hydroxide ion.
(Destructive techniques with the aid of Fe •No production of sludge and mineralization of the organic
ion and H2O2) contaminants.
•Rapid degradation and efficiency for recalcitrant compounds.
Ozonation •This technology is able to break down antibiotics within a very
short period (240–300 s) (Feng et al., 2016).
Electrochemical oxidation •It is a zero-sludge process.
•It is not like Fenton technology, electrochemical oxidation can
be both unselective or selective, which depends on the oxidant
that is produced from the electrochemical cell (Bhuta, 2014).
Wet oxidation •Destruction of phenol in water solution.
(Destructive techniques) •Insoluble organic material is able to be converted to simpler
soluble compounds without hazardous substances emission.
•This technology is suitable for effluent that is too toxic for
biological treatment and also for effluent that is too low
concentration for the incineration process.
Adsorption •A high effective process with fast kinetics.
(Non-destructive technique by using a solid •Good ability to separate a wide range of contaminants (heavy
material to remove pollutants from metal & organic pollutant).
aqueous medium) •Adaptable to many treatment formats with simple equipment.
•Good quality of the treated effluent.
Membrane technology •Wide range of applications, for example, production of pure
(Non-destructive separation with waters & desalination (RO); ions & volatine/non-volatile
semipermeable barrier) organics removal (NF); polymers separation (UF); and sterile
filtration (MF) (Crini and Lichtfouse, 2019).
•Applicable for high concentrated wastewater and all types of
mineral derivatives, salts, and organic pollutants with high
selectivity.
•Simple, fast and efficient, no chemicals required for the
process.
Anaerobic treatment •Smaller reactor size (Compare to aerobic treatment).
•Produces methane as a by-product (a source of renewable
energy).
•Lower biomass yield.
Aerobic treatment •Higher loading rate.
•Greater performance in breaking down antibiotics (Compare to
anaerobic).
•Fast photogenerated electron-hole recombination.
•Limited visible light response.
•Poor treatment for high concentrated organic pollutants.
•The degraded by-product lack of study in terms of the
chemical structure and its toxicity.
•Formation of unknown by-products that need further
analysis and study.
•Laboratory scale.
•Technical constraints.
•A large amount of ferrous sludge produced.
•Formation of a high concentration of anions in the treated
wastewater.
•
Capital intensive process comparing to Fenton technology.
Because of different electrodes have varying capacities for
oxidants production, the selection of electrode is critical for
an efficient electro-oxidation process (Bhuta, 2014).
•High pressure and energy-intensive conditions.
•pH dependence.
•Unable to achieve full mineralization.
•Non-destructive and non-selective methods.
•The cost of regeneration is high and result in loss of material.
•The treatment process can be varied with different pH
values.
•Further process of adsorbent is required after wastewater
treatment, for example, incineration or regeneration.
•High energy requirements and limited flow rates.
•The high cost of investment for small medium-sized
industries.
•Fouling effect is possible especially for high concentrated
contaminants, and the concentrate needs a further process for
elimination.
•High operation and maintenance costs.
•The high flow rate used in cross-flow can damage shear
sensitive materials.
•High energy consumption
•High operating cost
•Low loading rate
•Does not digest all type of antibiotics efficiently. Required
combination with aerobic treatment for better removal
efficiency.
•High energy consumption.
•High operating costs.
•Does not digest all type of antibiotics efficiently. Required
combination with anaerobic treatment for better removal
efficiency.

21
B.L. Phoon, et al.
2.4.3. Hybrid anaerobic-aerobic treatment
As impressive as an anaerobic treatment in COD removal, the per-
formance also fluctuates according to influent conditions, such as sali-
nity, toxicity, and refractory compounds. These characteristics make it
hard to degrade under anaerobic conditions. To address this issue, a
combination of the hybrid anaerobic-aerobic system was developed,
whereby, anaerobic treatment removes most of the organic pollutants,
and aerobic treatment further remove organic residues together with
ammonia reduction. Among the combination of anaerobic-aerobic
treatment is the pairing of UASB and completely stirred tank reactor
(CSTR), where it demonstrates overall COD removal of 97 %, with
target compound removal rate of 97−100 % (Sponza and Demirden,
2007). Based on a study conducted by Demirer and Chen (2005), dis-
cover that, MBR is required to adapt to the requirements of reactor
condition by using the UASB hybrid system due to the different growth
rates, and optimum pH of acidogenic and methanogenic micro-
organism. Therefore, two-phase anaerobic digestion (TPAD) was in-
troduced showing significant performance in removing high COD in-
fluent up to 58,792 mg L−1 with 99 % removal efficiency. It was also
noted that the pH of effluent is ranging from 6.8 to 7.6, a condition can
be discharged to natural waters (Chen et al., 2008). Another research
conducted by Shi et al. also shows similar results by using MBR in a
succession of UASB with 94.7 % COD removal efficiency. The COD
removal of UASB only 41.3 %, this proves the MBR purpose in post-
treatment as significantly better (Shi et al., 2014). A further extension
of hybrid technology through a combination of UASB, novel micro-
aerobic hydrolysis acidification reactor (NHAR), a cyclic activated
sludge (CASS) and biological contact oxidation tank (BCOT) (Chen
et al., 2011). This combination achieves COD removal up to 97 %, with
CASS plays a major role in removing most part of it.
Another biological treatment combination is anoxic-aerobic mem-
brane treatment. Whereby, Zhu et al. (2017) implement 3 stages pro-
cess consisting of different concentrations of SMX and TC at each stage.
At stage 2, the concentration of SMX and TC is 100 μg L−1, the removal
efficiency is > 70 % for both SMX and TC. However, once the con-
centration increases to 1000 μg L−1 at stage 3, the efficiency of SMX
and TC is 50 % and 75 % respectively. This suggesting that, the system
implemented has the potential in treating wastewater that is produced
by the hospital with a high level of antibiotic concentration (Zhu et al.,
2017). A similar technique was employed by Zhao et al. (2018) with the
addition of oxic membrane bioreactor forming a three-membrane
system of anaerobic/anoxic/oxic-MBR to remove 9 types of sulfona-
mides (SAs). In this system, most of the antibiotic was removed under
aerobic condition. It was also observed that, sulfisomidine (SIM) and
sulfamethazine exhibited lower removal efficiency, compared to other
SAs. Recently, a study was conducted on swine wastewater, by using a
combination of anaerobic digestion reactor and aerobic sequencing
batch reactor (Han et al., 2020). It was discovered that, the total COD
and antibiotic removals are 95 and 92 % respectively, and anaerobic
digestion contributes a major part of the removal efficiency. This con-
tradicts the previously mentioned study, whereby, aerobic contributes
Table 9
The removal rate of the pharmaceutical compound using a combination of MBR and different treatment. (Reproduced from Ref. Baumgarten et al. (2007)).
Pharmaceutical compound MBR treatment in combination with
Ozone treatment
O3 conc / treatment period
−1 −1
40 mg L /20 min 40 mg L
Removal Rate (%)
Fluoroquinoloic acid 98.5 99.6
Ciprofloxacin 97.9 97.9
Enrofloxacin 98.8 98.8
Moxifloxacin 98.4 98.4
Journal of Hazardous Materials 400 (2020) 122961
more to the removal percentage. To put things to perspective, efficiency
in the removal of antibiotics, through biological treatment depends on
the type of antibiotic and wastewater. However, one constant similarity
between these studies is the utilization of both anaerobic and aerobic
treatment, which has shown much more superiority compare to in-
dividual performance.
2.5. Hybrid technologies
Section 2.2, 2.3, 2.4 has discussed various kinds of technologies to
treat antibiotic wastewater. Nonetheless, each of these individual
technologies remain certain advantages, but also disadvantages as
shown in Table 8. Each of these technologies has its own constraints not
only in terms of efficiency but also environmental impact, cost, feasi-
bility, as well as, reliability. Hybrid technology is possible to minimize
the disadvantages at the same time to improve the efficiency of anti-
biotics removal.
Hybrid technologies involving several combinations of several
technologies in removing antibiotics from wastewater. Among the ad-
vanced technology is the combination of ultrafiltration, reverse osmosis
and powdered activated carbon (PAC) in removing tetracycline. Nano-
filtration was utilized, as a pre-treatment and diminished the fouling in
reverse osmosis. The additional PAC increases the permeate flux and
reduction coefficient of reverse osmosis. In this system, tetracycline is
able to recover up to 72 % with 88 % (Zhang et al., 2006). A study
carried out to compare the combination of two technology of mem-
brane bioreactor (MBR) with ozone, PAC, or membrane technology.
Table 9 reveals the removal rate of the combination of two technologies
(Baumgarten et al., 2007). Another research was carried out on the
combination of the conventional method and the advanced method by
integrating activated sludge with microfiltration and reverse osmosis.
The overall removal of 28 types of antibiotics from activated sludge,
microfiltration, and reverse osmosis is 87 %, 43 %, and 94 % respec-
tively. A study was also carried out by using the Fenton and algal action
process in the removal of amoxicillin and cefradine. Using this tech-
nique, amoxicillin was removed up to 97.36 % when treated after 48 h
of algal treatment. However, in this case, the removal rate of cefradine
is unsatisfactory with only up to 22.52 % (Li et al., 2015). In a different
study by Du et al., removal of cefradine can be improved using UV-
algae treatment (Du et al., 2015).
As mentioned earlier, some AOPs technique may produce traceable
amount of undecomposed/incomplete antibiotic compounds, after the
reaction. In this case, real-time detection on the quality of the waste-
water is important. The treated antibiotic in wastewater might still be
harmful to human and environment, and thus should be closely mon-
itored before it is released into the water stream (Xu et al., 2020).
Therefore, these wastewaters should be further processed using a
membrane filtration, because, it removes all the harmful compounds. In
other words, AOPs provide the pretreatment of antibiotics, prior the
membrane filtration treatment. This would indeed extend the lifetime
and reduce the fouling of membrane treatment (Oh et al., 2019).
PAC addition Membrane treatment
PAC concentration Type of membrane/MWCO
−1 −1
/40 min 50 mg L 500 mg L NF/300 Da RO/100 Da
91.2 > 99.7 > 99.7 > 99.7
79.5 96.5 > 97.9 > 97.9
96.4 97.5 > 98.4 > 98.4
96.8 96.7 > 99.6 > 99.6
22
B.L. Phoon, et al.
Although, hybrid technologies have shown its significant improve-
ment in the removal of antibiotics, but, there are still room to invent.
Current research focusses on simple and cost-effective ways technology,
for the removal of antibiotics from wastewater. Recently, technologies
such as, nanomaterials have been widely used in recent years to remove
antibiotics from wastewater. Zhuang et al. (2019) utilized α-FeOOH
loaded on rGO as hydrogels rGO by combining it with α-FeOOH to form
α-FeOOH/rGO hydrogels to remove antibiotics through dual reaction-
Fenton like reaction. The high surface area promotes the removal of
antibiotics with the special π- π interaction between TC and rGO. They
also discovered that, the hydrogels could generate reactive oxygen
species without addition of H2O2. Nanocellulose from a waste straw has
also been used to remove TC by using the sonocatalyst technique
(Soltani et al., 2019). The integration of ZnO and on the nanocellulose
was able to achieve removal efficiency of 87.6 % of TC within 45 min.
This technique has proven to be a much time-efficient method, as
compared to the digestion by large method in a bioreactor. Similarly,
Afreen et al. (2020) used a much ‘greener’ approach through photo-
catalysis to treat TC and paracetamol. They utilized rGO/CdS quantum
dots, as nano-photocatalyst (Afreen et al., 2020). Interestingly, the re-
moval efficiency of TC and paracetamol under visible light are 84 and
90 %, respectively. Although, the reaction time is longer than sonoca-
talyst, the approach of using photocatalyst is much more energy effi-
cient.
The current trend of research is moving towards a simpler, cost-
saving and energy-effective technology. The introduction of nano-
technology has assisted in improving the removal efficiency of anti-
biotics. However, the challenge in the downstream process (recovering
nanomaterials) is still a major concern, especially the impact toward the
environment.
3. Conclusions and prospects
Pharmaceutical is the main industry that produces antibiotics. The
antibiotic wastewater from the pharmaceutical industry is hard to be
treated by conventional wastewater plant. Also, antibiotic is able to
improve the public health and quality of life, but it is unable to fully
metabolized by the human and animal body. The remaining un-
metabolized antibiotics may leave the bodies from excretion and pol-
lute the wastewater. Therefore, researchers introduced several alter-
native technologies for antibiotics removal.
Most of the technologies are commonly used for the removal of
antibiotics. Unfortunately, the mechanisms of antibiotic removal were
either ill-defined or incomplete. There is a need to emphasis more on
the fate of this antibiotic after treatment, in order to prevent secondary
pollutants. Since most of the commonly known antibiotics are odorless
and colorless, it is very difficult to determine whether the antibiotic
from the wastewater has been treated effectively. Therefore, that the
plausible suggestion is to carry out a real-time detection and monitoring
of pollutants removal with the current removal technologies. In addi-
tion, most AOP processes are able to destroy the chemical structure of
pollutants. However, a toxicity assessment should be conducted after
the experiment. As mentioned by Feng et al. (Feng et al., 2016) and Liu
et al. (Liu et al., 2019), sometimes these compounds were degraded,
but, the toxicity remained. These highly toxic effluents would bring
harm to the environment and ecosystem, once it flows to the water
stream. Advanced treatment can be categorized by adsorption and
membrane treatment; it can remove pollutants from wastewater effec-
tively in a short time. However, secondary pollutants would be gener-
ated because this process only transforms from one phase to another.
On the other hand, biological treatment is demonstrated to be a po-
tential solution for the removal of antibiotic from wastewater due to its
strong foundation and understanding. Unfortunately, the process of
biological treatment is not cost-effective and only target biodegradable
antibiotics. On the bright side, the generation of methane could be
useful, as part of our renewable energy source.
23
Journal of Hazardous Materials 400 (2020) 122961
Ultimately, various methods to remove antibiotics from wastewater
had been reported, and the author believes that, future research should
focus on simplifying the removal technique, by using emerging nano-
technology, to assist in improving the removal of antibiotics from
wastewater. However, the usage of nanomaterials in large quantity
raise a concern, especially on environmental impact. This remains a
challenge to be considered for future research. Apart from that, each of
the antibiotic wastewater technologies has its own pros and cons.
Therefore, based on this review, the best hybrid method is combination
of AOP system and membrane treatment, because, membrane treatment
can filter all the pollutants, which AOP is unable to degrade.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
The authors greatly acknowledged the support of Prototype
Research Grant Scheme (PR002-2016A) from the Ministry of Education
Malaysia and SATU grant (ST020-2019) from University of Malaya.
Student financial aid 2019 that sponsored by Institute of Research
Management & Services, University of Malaya.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2020.122961.
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