Journal of Environmental Management 246 (2019) 51–62

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Journal of Environmental Management

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

Review

Insights on the current status of occurrence and removal of antibiotics in T

wastewater by advanced oxidation processes
R. Anjali, S. Shanthakumar∗
Department of Environmental and Water Resources Engineering, School of Civil Engineering, Vellore Institute of Technology (VIT), Vellore, 632014, India

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

Keywords: Antibiotics are considered as the significant group of pharmaceuticals which causes a serious hazard to the
Emerging pollutants environment and human health in recent years. Due to the inefficient treatment technologies, conventional
Ozonation wastewater treatment plants (WWTPs) are unable to remove many antibiotics from wastewater. This review
Fenton process encapsulates the current status of antibiotics occurrence in influent and effluent of WWTPs globally. Specifically,
Ciprofloxacin
β-lactams, fluoroquinolones, macrolides, sulfonamides, tetracyclines classes of antibiotics are found to be high in
Degradation mechanism
wastewater. An overview of physicochemical properties, generation classifications of antibiotics, and different
Hydroxyl radicals
advanced oxidation processes (AOPs) available for the removal of emerging pollutants are presented. Besides,
the removal efficiency of diverse antibiotics by various AOPs are discussed. The combination such as UV/H2O2,
UV/H2O2/Fe2+ and ozonation are reported for maximum removal of antibiotics. However, when compared to
simulated wastewater, limitations are persisted for the removal of antibiotics in real wastewater, owing to its
difficulty in assessing and observing the compound under mixed nature. AOPs assisted degradation mechanism
for ciprofloxacin antibiotic in wastewater is presented and the necessity of research on antibiotic removal is
highlighted.

1. Introduction hormones, anti-inflammatory drugs, beta-blockers, lipid regulators,

Worldwide, water scarcity has become an immense problem with
increasing population, climate change, urbanization and over-
exploitation, which cause freshwater demand. To meet this demand,
utilization of source water for industrial and other applications can be
reduced by providing appropriate treatments and recycling of waste-
water (Besha et al., 2017). In this concern, most of the studies are
conducted on the removal of nutrients, microorganisms, heavy metals
and significant pollutants in water and wastewater which cause po-
tential adverse effects on the aquatic environment and human being
(Ahmed, 2017; Cabeza et al., 2012; Lei et al., 2015; Meffe and de
Bustamante, 2014; Petrie et al., 2014; Roberts et al., 2016; Rodriguez-
Narvaez et al., 2017; Stuart et al., 2012; Wang and Wang, 2016). Now a
days, emerging contaminants (ECs) becomes ubiquitous with regard to
pharmaceuticals, personal care products, pesticides, landfill leachate,
surfactants, seepage from sewers, storm runoff, and discharge of was-
tewater treatment plant effluents (Jurado et al., 2012; Liu and Wong,
2013; Murray et al., 2010; Yang et al., 2014). As a consequence,
pharmaceuticals are considered as one of the most important group of
ECs which encompasses antibiotics, analgesics, steroids, anti-
depressants, antipyretics, stimulants, antimicrobials, painkiller,
contrast media, and impotence drugs (Balakrishna et al., 2017; Q Bu
et al., 2013; Kaplan, 2013; Sui et al., 2015; Wang and Chu, 2016).
Amongst pharmaceuticals, antibiotics are addressed specifically and
gained more attention in the environment since 1990s. Antibiotics are
the natural or synthetic compounds occurs in the environment with
antimicrobial activity (Kemper, 2008). Nearly 250 different antibiotics
are recorded and used as human and veterinary medicine (Kümmerer,
2009). Globally, extensive production and usage of antibiotics have
been increased for therapeutic treatment and prevention of bacterial
infections in humans and animals, for their healthy living condition
(Carvalho and Santos, 2016; Kasprzyk-Hordern et al., 2009; Liu et al.,
2018). The main sources of antibiotics are households, hospitals, ani-
mals husbandry, agricultural, aquaculture, raw and treated wastewater,
sewer leakage, surface runoff and pharmaceutical industry through
which it enter into the environment (Ahmed, 2017; Ngan et al., 2018;
Kumar and Pal, 2018; Tran et al., 2018).
As per the latest report, 0.1 to 0.2 million tons per annum of anti-
biotics have been utilized all around the world (Kumar and Pal, 2018).
China is the highest consumption and production of antibiotic in the
world when compared to western countries, Europe, UK and the United
States (Qiao et al., 2018). In 2013, China consumed 92,700 tons of

∗
Corresponding author.
E-mail address: shanthakumar.s@vit.ac.in (S. Shanthakumar).

https://doi.org/10.1016/j.jenvman.2019.05.090
Received 5 January 2019; Received in revised form 2 May 2019; Accepted 22 May 2019
0301-4797/ © 2019 Elsevier Ltd. All rights reserved.
R. Anjali and S. Shanthakumar
antibiotics in which 48% are consumed by humans and the remaining
52% are by animals (Zhang et al., 2015). The mass production, over-
utilization, misuse, and residue of antibiotics created a negative effect
on the environment (Yidong et al., 2017). Also, many antibiotics are
excreted by animals and human through urine and feces as the parent
compounds might be complete or incomplete metabolites and trans-
formation products (Bouki et al., 2013; Chen et al., 2017). The release
of excreted antibiotics reaches the wastewater treatment plants
(WWTP) most of which are not designed to remove the antibiotics
(Hirsch et al., 1999; Kümmerer, 2009; Lorenzo et al., 2018; Sun et al.,
2016). The continuous discharge of antibiotics leads to a potential
threat to the environment even at low concentration (ng L−1 to μg L−1)
(Ahmed et al., 2015; Babić et al., 2017; Homem and Santos, 2011; Liu
et al., 2018) and it has been detected in the aquatic environment such
as lakes, rivers, groundwater, and wastewater (Ngan et al., 2018). Also,
previous literature reported that antibiotics are bioaccumulated in
living organisms, for example, green algae (ciprofloxacin), cyno-
bacterium, duckweed, crustacean, daphniamagna and fathead minnow
(fluoroquinolone antibiotics) (Balakrishna et al., 2017; Ebele et al.,
2017; Ewadh et al., 2017). This bioaccumulation causes a potential
impact on male fish feminization and reduces the reproduction process
(Naghdi et al., 2018; Sophia and Lima, 2018).
The presence of antibiotics led to the development and widespread
of antibiotic steered to promote the growth of antibiotic-resistant genes
(ARG) and antibiotic-resistant bacteria (ARB) which pose a serious risk
to the environment and human health (Inyinbor et al., 2018). A recent
report indicates 700,000 demises yearly by drug-resistant pathogens
and it is estimated 10 million people would die each year by 2050
(Lorenzo et al., 2018). Hence, the antibiotics to be removed before
discharge into the environment (Ahmed et al., 2015). In this perspec-
tive, advanced oxidation processes (AOPs) becomes an emerging, and
prominent methods for the removal of antibiotics in the effluents
(Kumar and Pal, 2018; Liu et al., 2019). It includes different treatment
technologies such as ozonation (O3), UV/H2O2, Fenton (Fe2+/H2O2),
photo-Fenton processes (Fe2+/H2O2/UV) and other methods (ultra-
sonic, radiation) have been effectively used for the treatment of was-
tewater (Bethi et al., 2016; Sun et al., 2019). AOPs gathered potential
significant for large production of highly reactive hydroxyl radicals
(•OH), short-lived and more attractive for degradation of high strength
organic and recalcitrant compounds (Hassan et al., 2018; Moreira et al.,
2017). •OH is a powerful oxidizing tool for oxidization and miner-
alization of organic compounds into CO2, H2O and the stable end
products (Kurt et al., 2017). So, AOPs is the effective oxidation pro-
cesses for the degradation of antibiotics in the wastewater (Kumar and
Pal, 2018).
With this in view, the present review focuses on the occurrence and
removal of antibiotics in municipal wastewater treatment plants by
AOPs, and the degradation mechanism of ciprofloxacin compound is
presented. An overview of physiochemical properties and AOPs treat-
ment methods are discussed. Finally, appropriate further research needs
are highlighted.
2. Classification, generation and properties of antibiotics
Antibiotics are treated as the important discovery of the 20th cen-
tury (Carvalho and Santos, 2016). Fig. 1 shows the possible pathway of
antibiotics in the environment. Antibiotics are categorized based on
their chemical structure or mechanism of action and divided into dif-
ferent classes. Table 1 present the important core structure and gen-
erations of antibiotics. Antibiotics are divided into various classes such
as β-lactams, fluoroquinolones, macrolides, sulfonamides, tetracyclines,
aminoglycosides, carbapenems and cephalosporins, chloramphenicol,
imidazoles, lincosamides and others (Ahmed et al., 2015; Bouki et al.,
2013). Fluoroquinolone and tetracyclines are important antibiotics
consumed by humans and animals. Sulfonamides are extensively used
to treat acute urinary tract infections and other various bacterial
52
Journal of Environmental Management 246 (2019) 51–62
infectious diseases. β-lactams widely used as antibacterial agents to
treat the infectious problem caused by the susceptible organism
(Ahmed, 2017; Liu et al., 2018; Yu et al., 2016). Table 2 exhibits the
main classifications and physicochemical properties of antibiotics.
3. Occurrence of antibiotics in domestic wastewater
WWTPs are not primarily designed to remove ECs in the water.
There is no federal regulation and discharge limits for pharmaceuticals.
However, few antibiotics such as erythromycin and macrolide anti-
biotics (azithromycin, clarithromycin and erythromycin) are listed in
the USEPA's Drinking Water Contaminant Candidate List 4 and the
watch list of European Decision (2015)/495/EU (Babić et al., 2017;
Henrique et al., 2018; Kim et al., 2017). Hence, this substance requires
further research to monitor the occurrence in the aquatic environment
and confirm their potential effects (both acute and chronic effects) in
order to minimize the impacts on the environment. Also, it helps to set
the list of priority substance and regulatory limits for the pollutants
(Luo et al., 2014; Pereira et al., 2015). The concentration of antibiotics
vary in the range of ng L−1 to μg L−1 in wastewater and its presence is
addressed in many countries, for instance Greece, USA, Spain, China,
Singapore, Korea, UK, Finland, India, Germany, Canada, Sweden, and
Italy. The antibiotics detected in the raw and treated effluent include β-
lactams, fluoroquinolones, macrolides, sulfonamides, tetracyclines,
lincosamides, trimethoprim, imidazoles, chloramphenicol and Cepha-
losporin. The concentration of antibiotics (in ng L−1) in the wastewater
are presented in Table 3. Based on the literature, it has been identified
that the β-lactams (Ampicillin) are detected at high concentration
(12680 ng L−1) in WWTP effluent in India. Fluoroquinolones (cipro-
floxacin, ofloxacin, and norfloxacin) are observed in eight nations in the
range of not detectable (ND) to 8000 ng L−1. Among, 3 compounds in
fluoroquinolones, ciprofloxacin has the highest concentration in India
(8000 ng L−1) and lowest in Sweden (31.5 ng L−1) effluents. Ofloxacin
is noticed high in Italy (400 ng L−1) and low in Sweden (10 ng L−1)
WWTP effluents. The occurrence of macrolides (clarithromycin, ery-
thromycin, azithromycin, and roxithromycin) are detected in 6 coun-
tries among this clarithromycin is maximum (7000 ng L−1) and roxi-
thromycin is minimum (9.3 ng L−1) in Canada. Eight out of 13
countries are majorly detected with sulfonamides (Sulfamethoxazole,
Sulfamerazine, Sulfamethazine) in the range of ND to 2000 ng L−1.
Among sulfonamides, the maximum concentration of sulfamethoxazole
and Trimethoprim (trimethoprim) were found to be 2000 ng L−1 and
2469 ng L−1 (Table 3). With the reported concentration in many
countries, the compounds such as ciprofloxacin, sulfamethoxazole and
trimethoprim are commonly found in the effluent (Fig. 2).
4. Overview of AOPs treatment technologies for the removal of
emerging pollutants
Previous literature revealed that several treatment techniques are
available to remove emerging pollutants in water and wastewater
treatment plants, which includes coagulation, flocculation, sedimenta-
tion, filtration, chlorination, activated carbon (AC) adsorption, carbon
nanomaterials (CNMs) (e.g., carbon nanotubes (CNTs), and graphene
oxides (GOs), membrane filtration, ozonation, ultraviolet (UV) irra-
diation, ultrasonication and biological processes (Jung et al., 2015).
Advanced oxidation processes (AOPs) such as ozonation (O3/H2O2),
photocatalysis (UV/TiO2), ultraviolet (UV/H2O2), and Fenton/photo-
Fenton, ultrasonic (US) treatment has been recently recognized as an
advanced treatment process for the removal of complex inorganic and
organic contaminants in water and wastewater (Chu et al., 2017). Fig. 3
illustrates the overview of AOPs adopted for the removal of ECs. AOPs
have been significantly gained attention to remove the endocrine dis-
rupting chemicals, personal care products, pharmaceuticals such as
antibiotics (Sharma et al., 2018). It provides alternated solutions to
remove antibiotics compared with conventional treatment processes.
R. Anjali and S. Shanthakumar Journal of Environmental Management 246 (2019) 51–62

Veterinary Agricultural Pharmaceutical Medicine Prescriptions Human

Hospitals
antibiotics crops industry antibiotics

Manufacturing

Wastewater
Livestock Manure Wastewater
Excreta

Excreta Field
WWTP
Drinking

Soil
Effluent Landfill

Biosolids
Runoff Leachate

ARG &
Surface water Ground water ARB

Drinking water Drinking To protect animals and

Humans WWTP design
treatment plants human health

Fig. 1. Probable pathway of antibiotics in the environment.

Table 1
Important core structures and generation of antibiotics.
Classes Core structure Names 1st generation 2nd generation 3rd generation References

Aminopenicillin Amoxicillin (Etebu and

Penicillinase-resistant Ampicillin Arikekpar, 2016;
penicillin Holten and Onusko,
Natural Cloxacillin 2000)
Cephalosporin Penicillin V Cefuroxime

Fluoroquinolones Ciprofloxacin Gatifloxacin (King et al., 2000;

Enrofloxacin Levofloxacin Klahn and Brönstrup,
Norfloxacin Moxifloxacin 2017)
Ofloxacin Sparfloxacin

Macrolides Erythromycin Azithromycin & (Baran et al., 2018;

Clarithromycin Kaneko et al., 2007)

Tetracycline Tetracycline & Doxycycline (Baran et al., 2018;

Oxytetracycline Fuoco, 2012)

53
 Table 2
Classification and physiochemical properties of antibiotics.
Classification Name Symptoms* Chemical Formula CAS Molecular weight Vapor Pressure (mm log Kow pKa References
(g/mol) Hg) 25 °C

β-Lactams Amoxicillin Allergic reactions to C16H19N3O5S 26787-78-0 365.4 4.69 × 10−14 0.87 3.2 Papageorgiou et al. (2016)
Ampicillin humans and animals C16H19N3O4S 69-53-4 349.4 2.84 × 10−13 1.45 2.5 Papageorgiou et al. (2016)
Cloxacillin C19H18ClN3O5S 61-72-3 435.9 _ _ 2.78 NCBI
R. Anjali and S. Shanthakumar

Penicillin V C16H18N2O5S 132-98-9 350.4 _ 1.4 2.73 (Qingwei Bu et al., 2013);

NCBI
Fluoroquinolones Ciprofloxacin Arthropathies in young C17H18FN3O3 85721-33-1 331.3 2.85 × 10−13 0.28 6.09 Wang and Wang (2016)
Enrofloxacin animals C19H22FN3O3 93106-60-6 359.401 _ _ _ (Qingwei Bu et al., 2013)
Gatifloxacin C19H22FN3O4 112811-59-3 375.4 _ 2.6 _ (Qingwei Bu et al., 2013)
Levofloxacin C18H20FN3O4 100986-85-4 361.373 9.8 × 10−13 −0.39 6.24 NCBI
Moxifloxacin C21H24FN3O4 354812-41-2 401.4 2.35 10.68 Papageorgiou et al. (2016)
Norfloxacin C16H18FN3O3 70458-96-7 319.336 _ 0.46 6.34; 8.75 (Qingwei Bu et al., 2013)
Ofloxacin C18H20FN3O4 82419-36-1 361.4 9.84 × 10−13 −0.39 5.97, 9.28 (Qingwei Bu et al., 2013;
Wang and Wang, 2016)
Sparfloxacin C19H22F2N4O3 110871-86-8 392.407 _ _ _ (Qingwei Bu et al., 2013)
Macrolides Azithromycin Allergic reactions C38H72N2O12 83905-01-5 748.996 2.65 × 10−24 4.02 8.74 (Qingwei Bu et al., 2013)
Clarithromycin C38H69NO13 81103-11-9 748 2.32 × 10−25 3.16 8.99 (Qingwei Bu et al., 2013;
Chen et al., 2016)
Erythromycin C37H67NO13 114-07-8 733.9 2.12 × 10−25 3.06 8.9 Papageorgiou et al. (2016)
Roxithromycin C41H76N2O15 80214-83-1 837.1 _ 2.75 8.8 Papageorgiou et al. (2016)
Tylosin C46H77NO17 1401-69-0 916.1 1.98 × 10−34 1.63 7.73 Wang and Wang (2016)
Sulfonamides Sulfadimethoxine Nephrotoxic (destructive C12H14N4O4S 122-11-2 310.3 _ 1.63 _ (Qingwei Bu et al., 2013)
Sulfachloropyridazine to the kidneys) C10H9ClN4O2S 80-32-0 284.7 _ _ _ (Qingwei Bu et al., 2013)
Sulfadiazine C10H10N4O2S 68-35-9 250.3 _ −0.09 6.36; 2.1 Papageorgiou et al. (2016)
Sulfamerazine C11H12N4O2S 127-79-7 264.3 _ 0.14 7.14 Chen et al. (2016)

54
Sulfamethazine C12H14N4O2S 57-68-1 278.33 6.82 × 10−9 0.89 7.59 Behera et al. (2011)
Sulfamethizole C9H10N4O2S2 144-82-1 270.3 2.06 × 10−9 0.54 2.1; 5.3 (Qingwei Bu et al., 2013)
Sulfamethoxazole C10H11N3O3S 723-46-6 253.3 6.93 × 10−8 0.89 5.7 Kosma et al. (2014)
Sulfamonomethoxine C11H12N4O3S 1220-83-3 280.3 _ _ _ (Qingwei Bu et al., 2013)
Sulfapyridine C11H11N3O2S 144-83-2 249.3 _ 0.35 8.43 Chen et al. (2016)
Sulfathiazole C9H9N3O2S2 72-14-0 255.31 4.22 × 10−8 0.05 2.2; 7.24 NCBI
Tetracyclines 4-Epitetracycline Hepatotoxic (destructive C22H24N2O8 79-85-6 444.4 _ _ _ NCBI
Doxycycline to liver cells) C22H24N2O8 564-25-0 444.4 _ −0.02 _ (Qingwei Bu et al., 2013;
Wang and Wang, 2016)
Oxytetracycline C22H24N2O9 79-57-2 460.4 9.7 × 10−25 −0.9 3.27 (Qingwei Bu et al., 2013);
NCBI
Tetracycline C22H24N2O8 60-54-8 444.4 _ −1.37 3.30 Wang and Wang (2016)
Lincosamides Clindamycin Gastro-intestinal C18H33ClN2O5S 18323-44-9 424.981 5.28 × 10−17 2.16 _ NCBI
Lincomycin problems C18H34N2O6S 154-21-2 406.5 1.34 × 10−17 0.29 7.9 Behera et al. (2011)
Trimethoprim Trimethoprim C14H18N4O3 738-70-5 290.3 9.88 × 10−9 0.91 6.8 Papageorgiou et al. (2016)
Chloramphenicols Chloramphenicol C11H12Cl2N2O5 56-75-7 323.1 1.7 × 10−12 1.14 9.61 Chen et al. (2016)
Imidazoles Metronidazole C6H9N3O3 443-48-1 171.2 3.1 × 10-7 −0.1 2.5 Papageorgiou et al. (2016)
Cephalosporin Cefuroxime C16H16N4O8S 55268-75-2 424.384 _ −0.8 _ NCBI
Others Carbadox C11H10N4O4 6804-07-5 262.2 6.20 × 10−10 0.13 _ NCBI
Cyclophosphamide C7H15Cl2N2O2P 6055-19-2 261.083 _ 0.63 _ NCBI
Danofloxacin C19H20FN3O3 112398-08-0 357.4 _ _ _ (Qingwei Bu et al.,
2013; Wang and Wang,
2016)
Glibenclamide C23H28ClN3O5S 10238-21-8 494.003 _ _ _ NCBI
Miconazole C18H14Cl4N2O 22916-47-8 416.123 _ 6.1 _ NCBI
Pirenzepine C19H21N5O2 28797-61-7 351.4 _ 0.6 _ NCBI
Tiabendazole C10H7N3S 148-79-8 201.247 4 × 10−9 2.47 4.64 NCBI

Log Kow: partition coefficient between water and octanol; pka: acid/base dissociation constant; PubChem: https://pubchem.ncbi.nlm.nih.gov/; * (Kemper, 2008).
Journal of Environmental Management 246 (2019) 51–62
R. Anjali and S. Shanthakumar Journal of Environmental Management 246 (2019) 51–62

Table 3
Occurrence of antibiotics in WWTPs.
Country Classification Name Influent Effluent Treatment methods References

Greece β-Lactams Amoxicillin ND ND Screening; grit-removal; primary sedimentation; (Kosma et al., 2014; Papageorgiou et al.,
Ampicillin 1243 151 chemical & biological treatment. 2016)
Flouroquinolones Ciprofloxacin 152 199
Moxifloxacin 425 85
Sulfonamides Sulfamethoxazole 904.2a 30.6a
Trimethoprim Trimethoprim 138a 59.8a
USA Sulfonamides Sulfamethoxazole 3800a 304a Secondary treatment plants; oxidation ditches (Kwon and Rodriguez, 2014; Li et al., 2013)
Trimethoprim Trimethoprim 1170a 586a Bar screen; two aerated lagoons; filtration
Spain Flouroquinolones Ciprofloxacin _ 52 Tertiary treatment; ultrafiltration; reverse osmosis; Cabeza et al. (2012)
Ofloxacin _ 341 UV disinfection
Macrolides Erythromycin _ 39
Sulfonamides Sulfamethazine _ 74.33
Sulfamethoxazole _ 102.5
Sulfapyridine _ 54
China Flouroquinolones Ofloxacin 200 150 Primary sedimentation; secondary; UV Sun et al. (2016)
Tetracyclines Oxytetracycline 91 20 disinfection
Tetracycline 48 14
Sulfonamides Sulfamethoxazole 25 9
others Cyclophosphamide 13 14
Glibenclamide 1.4 1.9
Korea Lincosamides Lincomycin 16700a 14200a Conventional treatment processes (Behera et al., 2011; Sim et al., 2013)
Sulfonamides Sulfamethazine 164a 144a
Sulfamethoxazole 120a 57a
Sulfachloropyridazine 30 14
Sulfamonomethoxine ND ND
Sulfamerazine 48 33
Sulfathiazole 131 345
Trimethoprim Trimethoprim 261a 96a
UK Macrolides Erythromycin 274 _ Kay et al. (2017)
Singaporea Trimethoprim Trimethoprim 880 _ Tran et al. (2013)
Finland Flouroquinolones Ciprofloxacin 600 60 Conventional activated sludge (CAS) treatment Vieno et al. (2007)
Norfloxacin 120 ND
Ofloxacin 100 14
India β-Lactams Amoxicillin 172.6 62.5 Conventional treatment methods (Akiba et al., 2015; Balakrishna et al., 2017;
Ampicillin 104200 12680 Mutiyar and Mittal, 2014, 2013; Singh et al.,
Flouroquinolones Ciprofloxacin 20060 8000 2014; Subedi et al., 2017)
Gatifloxacin 2740 1220
Levofloxacin 107900a _
Norfloxacin 18200a _
Ofloxacin _ 285
Sparfloxacin 22490 140
Macrolides Azithromycin 176900a _
Sulfonamides Sulfamethoxazole 2260a 637a
Cephalosporin Cefuroxime 3420 220
Lincosamides Clindamycin 1870a 952a
Lincomycin 730a 430a
Trimethoprim Trimethoprim 4010a 2469a
others Miconazole 1410a 1020a
Tiabendazole 123a 79a
Germanyb Chloramphenicol Chloramphenicol _ 560 Hirsch et al. (1999)
Macrolides Clarithromycin _ 240
Erythromycin-H2O _ 6000
Roxithromycin _ 1000
Sulfonamides Sulfamethoxazole _ 2000
Trimethoprim Trimethoprim _ 660
(continued on next page)

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R. Anjali and S. Shanthakumar Journal of Environmental Management 246 (2019) 51–62

Table 3 (continued)

Country Classification Name Influent Effluent Treatment methods References

Canada b
β-Lactams Cloxacillin 50 50 Facultative lagoon; chemically-assisted primary Guerra et al. (2014)
Penicillin V 64 27 treatment; secondary activated sludge; biological
Flouroquinolones Ciprofloxacin 2500 620 nutrient removal; aerated lagoon
Enrofloxacin 15 5.3
Ofloxacin 2800 210
Macrolides Azithromycin 2500 1300
Clarithromycin 8000 7000
Erythromycin 600 270
Roxithromycin 4.4 9.3
Tylosin _ 47
Sulfonamides Sulfadiazine 42 _
Sulfamerazine 9.3 _
Sulfamethazine 45 _
Sulfamethizole 6.5 87
Sulfamethoxazole 3100 1800
Tetracyclines 4-Epitetracycline 120 46
Doxycycline 78 53
Tetracycline 120 36
Lincosamides Lincomycin 110 65
Trimethoprim Trimethoprim 810 580
Others Carbadox – 78
Miconazole 43 27
Tiabendazole 220 140
Sweden Fluoroquinolones Ciprofloxacin 320 31.5 Conventional activated sludge (CAS) treatment Zorita et al. (2009)
Norfloxacin 18 < LOD
Ofloxacin 22.5 10
Italy Fluoroquinolones Ciprofloxacin 2200 630 Verlicchi et al. (2014)
Norfloxacin 210 150
Ofloxacin 980 400
Macrolides Azithromycin 120 130
Clarithromycin 200 280
Erythromycin 46 15
Roxithromycin 66 290
Trimethoprim Trimethoprim 59 40
Imidazoles Metronidazole 42 28

a a
Mean concentration (max); < LOQ - Below detection limit; ND - Not Detected. - Concentration Range.
b
-Maximum value; concentrations are in ng L−1.

The advanced chemical treatment process provides maximum removal Fenton (Fe2+/H2O2), photo Fenton (UV/H2O2/Fe2+), UV/H2O2, solar
efficiency. photo Fenton. Table 4 presents the removal efficiency of antibiotics in
the effluent by AOPs.

4.1. Removal of antibiotics by advanced oxidation processes

AOPs treatment is explained in two ways: one is a generation of
hydroxyl radical (•OH) which is a strong oxidant and other is oxidative
radicals react with the molecules. Therefore, it is possible to oxidize and
mineralize the targeted compounds into carbon dioxide, water and in-
organic ions (Su et al., 2012; Yonar, 2006). AOP includes ozonation,
4.1.1. Ozonation
Ozonation has been frequently used for disinfection (bacteria,
viruses, algae and fungi and organic matter) in water and wastewater
(Mutseyekwa et al., 2017; Rosal et al., 2009). In advance oxidation
process, ozonation (O3) and other ozone combinations such as (O3/
H2O2), (O3/UV) or (O3/H2O2/UV), and with catalysts (O3/catalysts) are

Canada Germany India Korea Spain USA Greece

Trimethoprim

Ciprofloxacin

Sulfamethoxazole

0 1 2 3 4 5 6 7 8 9 10
Concentration (μg/L)
Fig. 2. Commonly identified compounds in WWTPs effluent.

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R. Anjali and S. Shanthakumar Journal of Environmental Management 246 (2019) 51–62

Advanced Oxidation
Processes (AOPs)

US – Fenton Processes
UV - Photolysis O3 - Ozonation Oxidation
Ultrasonic/Sonolysis (H2O2/Fe2+)

Catalytic Photo Fenton

UV/H2O2 UV/O3 US/Fe2+
oxidation Process

Photo electro
UV/TiO2 O3/H2O2 H2O2/US Wet oxidation
Process

Catalytic wet
UV/HClO4 UV/H2O2/O3 US/UV/Fe2+ Electro Fenton
oxidation

Electrochemical Heterogeneous
UV/Chlorine TiO2/UV/O3 US/Fenton/TiO2
oxidation Fenton

US/O3

Fig. 3. Overview of chemical treatment methods adopted for the removal of pollutants.

extensively used and studied to remove the antibiotics (Bethi et al., 2006). The Fe2+ reacted with H2O2 to form the Fe3+ and •OH with the
2016). Ozone has a strong capability to oxidize hydroxyl radicals (•OH) intermediates. The complete reaction process is explained in equations
to remove antibiotics and usually performed at high pH values to in- (3) and (4) (Bethi et al., 2016; Giri and Golder, 2014a; Rakhshandehroo
crease the production of •OH (Lofrano et al., 2017). Ozone along with et al., 2018).
hydrogen peroxide (H2O2) is employed to promote a large number of
Fe 2 + + H2 O2 → Fe 3 + + OH− + •OH (3)
•OH (Wang and Wang, 2016) which removes a wide range of pollutants
in water and wastewater (Gomes et al., 2017). The major factors in- Fe3 + + H2 O2 → HO2· + H+ (4)
fluencing the ozonization processes are pH, ozone dosage and tem-
perature affect the mineralization of the pollutants. The •OH reacts with Fe 2+
to form the Fe 3+
and able to react with
The simple reaction mechanism of O3 is given in equations (1) and the organic pollutants (R) to convert to the non-toxic. The reactions are
(2) (Kurt et al., 2017). presented in equations (5) and (6).
•OH + Fe 2 + → Fe 3 + + OH− (5)
O3 + H2 O → 2•OH + 4O2 (1)

If the O3 reacts with H2O2, the general reaction involves as •OH + R → R·+H2 O + CO2 (6)

H2 O2 + 2O3 → 2•OH + 3O2
Ozonation is applied as a principal treatment to enhance the de-
gradability of pollutants. The advantages of using ozonation are less
energy and water recovery up to 99% without waste production (Gomes
et al., 2017). However, it has the potential drawback of high energy
demand and high cost to implement (Ahmed et al., 2017).
(2) This process is a feasible treatment for industrial wastewater (Wang
and Wang, 2016). Meanwhile, iron is available plenty and harmless.
Fenton processes is a safe, fastest, economic and environmentally
friendly for oxidizing the targeted pollutants and it became the re-
presentative AOPs (Hassan et al., 2018; Pan et al., 2018). The removal
of ofloxacin by Fenton process is achieved as 100% in wastewater ef-
fluent (Michael et al., 2010).

4.1.2. Fenton process
Among AOPs, Fenton processes is an important and very effective
method for the treatment of wastewater. These processes have been
conducted at the laboratory and plant/pilot scale for the treatment of
antibiotics (Huang et al., 2016). The reaction occurs in the acidic
medium (2.8–3.0) (Moreira et al., 2017) by the mixture of H2O2 as
oxidant and Fe2+ as a catalyst to produce •OH which are more reactive
and responsible for the oxidation of organic pollutants and considered
as the dominant oxidant. The chain reaction takes place in the presence
of Fe2+ and H2O2 is decomposed (Huang et al., 2016; Shemer et al.,
4.1.3. Photo Fenton and solar photo Fenton
Photo Fenton process occurs in the presence of UV radiation or
sunlight with the combination of H2O2 and Fe2+ or Fe3+ to enhance the
additional •OH production (Pouran et al., 2015, 2014; Sharma et al.,
2018). This process is different from Fenton process, which converts the
complex Fe3+ to regeneration Fe2+, and further react to form a weak
oxidizing species as superoxide anion radical, CO2 anion radical and
H2O2 (Moreira et al., 2017). In this process, the iron salts act as a
photocatalyst and H2O2 act as an oxidizing agent. Usually, the photo
Fenton process is studied in acidic or neutral conditions for aquatic

57
 Table 4
Removal efficiency of antibiotics in wastewater by AOPs.
Methods Classifications Names Removal efficiency (%) Experimental conditions References

2+
Fe or Fe (mg/L) H2O2 (mg/L) Ozone (mg/L) time (min) pH Energy humic acid (mg/L) T (°C)
R. Anjali and S. Shanthakumar

Solar Photo Fenton Fluoroquinolones Ciprofloxacin 95.5–97 5 50 144 3, 7 30 W/m2 10 _ Klamerth et al., 2013
Ofloxacin 95.5–97
Ofloxacin 98 5 54 20 2.3 kJ/L _ _ Prieto-Rodríguez et al., 2013
Ofloxacin 90 5 50 _ _ _ _ _ Klamerth et al., 2012
Sulfonamides Sulfamethoxazole 95.5–97 5 50 144 3, 7 30 W/m2 10 _ Klamerth et al., 2013
Sulfamethoxazole 90 5 50 _ _ _ _ _ Klamerth et al., 2012
Trimethoprim 95.5–97 5 50 144 3, 7 30 W/m2 10 _ Klamerth et al., 2013
Trimethoprim Trimethoprim 98 5 54 20 2.3 kJ/L _ _ Prieto-Rodríguez et al., 2013
UV/H2O2 Macrolides Azithromycin 100 _ 50 30 2.5 550 W/m2 _ 17 Cruz et al., 2012
Clarithromycin 100
Erythromycin 100 _ 1.72 15 6.5 2768 mJ/L _ _ Kim et al., 2009
Fluoroquinolones Norfloxacin 100 _ 50 30 2.5 550 W/m2 _ 17 Cruz et al., 2012
Ofloxacin 100
Ciprofloxacin 100
Ciprofloxacin > 99 _ 20 _ 75 7.9 _ _ _ Afonso-Olivares et al. (2016)
Ciprofloxacin 93 _ 0.2* _ 18 S 2.5 170 J/L _ _ Rodríguez-chueca et al. (2019)
Sulfonamides Sulfamethoxazole 100 _ 50 30 2.5 550 W/m2 _ 17 Cruz et al., 2012
Sulfapyridine 100 _ 1.72 15 6.5 2768 mJ/L _ _ Kim et al., 2009
Sulfamethoxazole > 99 _ 20 _ 75 7.9 _ _ _ Afonso-Olivares et al. (2016)
sulfamethazine 97.3 0.3* 60 7 _ _ _ Pan et al. (2018)

58
sulfadiazine 97.4 _ 0.3* _ 60 7 _ _ _ Pan et al. (2018)
Trimethoprim Trimethoprim 100 _ 1.72 15 6.5 2768 mJ/L _ _ Kim et al., 2009
Trimethoprim 100 _ 50 30 2.5 550 W/m2 _ 17 Cruz et al., 2012
Imidazole Metronidazole 100 _ 50 30 2.5 550 W/m2 _ 17 Cruz et al., 2012
Metronidazole 92 _ 20 _ 75 7.9 _ _ _ Afonso-Olivares et al. (2016)
Tetracycline Tetracycline ∼99 _ 1.72 15 6.5 2768 mJ/L _ _ Kim et al., 2009
Tetracycline 97.2 _ 0.3* _ 60 7 _ _ _ Pan et al. (2018)
oxytetracycline 97.3 _ 0.3* _ 60 7 _ _ _ Pan et al. (2018)
2+
UV/H2O2/Fe Fluoroquinolones Ciprofloxacin 100 5 50 _ 30 7.4 _ _ _ Cruz et al., 2012
Norfloxacin 100
Ofloxacin 100
Macrolides Azithromycin 100
Clarithromycin 93
Sulfonamide Sulfamethoxazole 100 5 50 _ 30 7.4 _ _ _ Cruz et al., 2012
sulfamethazine 99.6 0.3* 0.3* 60 7 _ _ _ Pan et al. (2018)
sulfadiazine 99.7 0.3* 0.3* _ 60 7 _ _ _ Pan et al. (2018)
Imidazole Metronidazole 100 5 50 _ 30 7.4 _ _ _ Cruz et al., 2012
Tetracycline Tetracycline 99.4 0.3* 0.3* _ 60 7 _ _ _ Pan et al. (2018)
oxytetracycline 99.5 0.3* 0.3* _ 60 7 _ _ _ Pan et al. (2018)
Fento process Fluoroquinolone Ofloxacin 100 5 3.714# _ _ 3 _ _ 25 Michael et al. (2010)
Ozonation Fluoroquinolones Ofloxacin 100 _ _ 390 _ 7.4 _ _ 25 Carbajo et al., 2015
Ofloxacin 98 _ _ 9.5 60 _ _ _ _ Prieto-Rodríguez et al., 2013
Trimethoprim Trimethoprim 98
Sulfonamide Sulfamethoxazole 100 _ _ 14 7.1 _ _ 17 Rodayan et al., 2010

Fe – Iron; H2O2 = Hydrogen peroxide; t = time; T = temperature; #mmol/L; *mM; S - Seconds.

Journal of Environmental Management 246 (2019) 51–62
R. Anjali and S. Shanthakumar Journal of Environmental Management 246 (2019) 51–62

solutions not containing organic matter. The mechanism involved in the Quinolone ring
photo Fenton reaction is to improve the hydroxyl radicals and iron can
be recycled at a higher rate to react with H2O2. The reaction process
involved in the photo Fenton method is shown in equations (7) and (8). Piperazine ring
hv
Fe3 + + H2 O → Fe 2 + + H+ + •OH (7)

hv (8)
FeOH 2 + → Fe 2 + + •OH + H+
This combined processes enhance the degradation efficiency of or-
ganic pollutants and reduce sludge waste (García-muñoz et al., 2019;
Mayyahi and AuthorAnonymous, 2018). Many pharmaceuticals com-
pounds have been removed and showed higher removal efficiencies Fig. 4. Chemical structure of CIP.
(95–100%) by photo-Fenton process except penicillin G (Ahmed et al.,
2015). Solar photo Fenton process removes the antibiotics in waste-
water effluent in the range of 90–98%. 2009).
Hence, the typical degradation begins when fluoroquinolone loses
its fluoride and carboxyl moiety (Klauson et al., 2010). The degradation
4.1.4. Combination of AOPs
of CIP is extensively described by previous researchers through AOP's
The combination of AOPs has recently gained attention for the re-
such as photocatalysis, photolysis, UV, H2O2, UV/H2O2, modified
moval of antibiotics in wastewater. The combination of AOPs with the
Fenton and photo-Fenton (An et al., 2010; Giri and Golder, 2014a; Li
other compounds like hydrogen peroxide, catalyst, solar or UV enhance
et al., 2018; Mondal et al., 2018; Wei et al., 2013), Fenton oxidation
the removal efficiency of wastewater. UV/H2O2, UV/H2O2/Fe2+ &
(Giri and Golder, 2014b), ferrous-activated persulfate (Ji et al., 2014).
ozonation approaches perceived high removal rate. These integrated
Generally, in AOPs the parent compound CIP is converted into
methods are employed in WWTPs effluent to remove at a high rate
daughter compounds by following possible degradation mechanism: (a)
compared with the single method. UV/H2O2 and ozonation method
Cleavage of piperazine ring followed by Oxidation, hydroxylation, and
showed the antibiotics are degraded up to 100% under different ex-
defluorination of Quinolone or b) Direct attack of Quinolone ring
perimental conditions expect Metronidazole (92%) and ciprofloxacin
through Oxidation, decarboxylation, hydroxylation, and defluorination
(93%). UV/H2O2/Fe2+ exposes the degradation value up to 100% in
as shown in Fig. 5. In mechanism (a), the piperazine ring cleavage
antibiotics expect Clarithromycin (93%). It can be further noted from
begins with the removal of –C2H2 to form the degradation product (DP
Table 4 that the high removal efficacy has been achieved in the com-
1) desethylene CIP, which is partially metabolized product of piper-
bination processes. Ozonation and other oxidation processes are usually
azine ring. Then the desethylene substituent will get oxidized to DP 2
used to remove antibiotics in water and wastewater. For the first time,
with the loss of nitrogen atom. Further, the quinolone ring degradation
ozonation has been used in raw milk to remove antibiotics (amoxicillin,
instigates to produce DP 3 through defluorination and so forth oxidized
doxycycline, ciprofloxacin, and sulphadiazine). This study confirmed
products (Sayed et al., 2016). In another mechanism (b) the quinolone
that ozonation is an efficient method for the removal of antibiotics
ring is directly degraded through hydroxylation process DP 4, de-
(Alsager et al., 2018).
fluorination process DP 5 (Ji et al., 2014; Li et al., 2016; Mondal et al.,
Ozonation, microfiltration, reverse osmosis and UV radiations are
2018). Successive decarboxylation and defluorination reactions on CIP
used in industries for disinfection in water and wastewater. But this
lead to the formation of DP 6 and DP 7 (Gupta and Garg, 2018). DP 8 &
advanced technology cannot eliminate antibiotic residues from waste-
DP 9 are the separate degradation products formed by the direct attack
water. The removal of antibiotics have been conducted on the pilot
of piperazine ring and fluoroquinolone during photolysis reaction,
scale in wastewater treatment plants using advanced oxidation pro-
where the carbonyl group (C]O) is introduced in the piperazine ring
cesses (Alsager et al., 2018; Borikar et al., 2015; Gomes et al., 2017;
and F atom in the quinolone ring is replaced by OH group (Vasconcelos
Roccamante et al., 2019; Rodríguez-chueca et al., 2019; Zhang et al.,
et al., 2009). Further, the intermediates formed are oxidized or mi-
2016). It has been observed from the previous studies, that there is no
neralized to carbon dioxide and water.
industrial level application on the removal of antibiotics. However,
further studies are required to identify the intermediates or by-products
being discharged into the environment. 6. Conclusion and future recommendations

5. Degradation mechanism of ciprofloxacin by AOPs
Based on the literature review, it has been identified that in WWTP
effluent, the most commonly found compounds are sulfamethoxazole,
trimethoprim, and ciprofloxacin (Fig. 2). Among these compounds, the
ciprofloxacin (CIP) showed higher concentration than other compounds
which necessitates to study the degradation mechanism of ciprofloxacin
by AOPs.
CIP is the second generation antibiotic of fluoroquinolone. The acid
and base property of CIP mainly depends on its solubility constant
because of the presence of carboxyl (Quinolone) and amine groups
(Piperazine) in its molecular structure (Giri and Golder, 2014a). The
piperazine contains the two nitrogen atoms (N1 and N4) opposite to
each other in the ring structure. In which N4 is highly prone to •OH
attack compared to N1 because of its weaker basicity (Zhang and
Huang, 2005). The Quinolone ring has two strong electrons with-
drawing nitrogen substituents i.e. fluorine and –COOH groups (Fig. 4)
which makes it more resistant towards degradation (Klavarioti et al.,
This review highlights the occurrence of antibiotics in WWTP ef-
fluent and the removal efficiency of antibiotics in wastewater by AOPs
are discussed. Based on the occurrence, the antibiotics β-lactams,
fluoroquinolones, macrolides, sulfonamides, tetracyclines classes are
predominantly detected in the wastewater effluent, since the conven-
tional treatment plants are not designed to remove such trace level
compounds. It will lead to the development of antibiotic-resistant genes
or bacteria in the ecosystem. Among the various treatment techniques,
the advanced chemical treatment technologies viz. ozonation, UV/
H2O2, UV/H2O2/Fe2+ and solar photo Fenton processes completely
remove antibiotics from effluents. Hence, it necessitates the im-
plementation of the advanced treatment methods to improve the
quality of effluent from WWTPs. The challenging task is to ensure the
toxicity reduction through studying the degradation mechanism and
byproducts formation involved in the treatment method. The primary
degradation mechanism of ciprofloxacin by AOPs is discussed. Hence,
to lessen the impact of antibiotics in the environment, more attention
has to be given over the sources and discharge of effluent. The further

59
R. Anjali and S. Shanthakumar
-F
DP 8
DP 9 Defluorination
-F
Defluorination
DP 5
Further -F
oxidation +OH
DP 3
Fig. 5. Major possible degradation mechanism of CIP in AOPs.
investigations on antibiotics occurrence in wastewater are necessary (i)
to establish the regulatory measures for discharging the antibiotics in
the environment, (ii) to identify the toxicological impacts of antibiotics
and its transformation products on the natural system, humans and
veterinary health effects, and (iii) to identify the impact of antibiotic-
resistant genes and bacteria in the ecosystem.
Acknowledgment
The author R. Anjali gratefully acknowledge the Council of
Scientific and Industrial Research (CSIR), Government of India for
awarding the CSIR-SRF Fellowship.
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