Separation and Purification Technology 347 (2024) 127458

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Separation and Purification Technology

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

Review

Pharmaceuticals wastewater treatment via different advanced oxidation

processes: Reaction mechanism, operational factors, toxicities, and cost
evaluation – A review
Jibran Iqbal a, *, Noor S. Shah b, *, Javed Ali Khan c, Mu. Naushad d, Grzegorz Boczkaj e, f,
Farrukh Jamil g, h, Shamshad Khan i, Long Li j, Behzad Murtaza k, Changseok Han l, m, *
a
College of Natural and Health Sciences, Zayed University, P.O. Box 144534, Abu Dhabi, United Arab Emirates
b
Department of Chemistry, COMSATS University Islamabad, Abbottabad Campus 22060, Pakistan
c
Department of Chemistry, Abdul Wali Khan University Mardan, Mardan 23200, Pakistan
d
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
e
Gdańsk University of Technology, Faculty of Civil and Environmental Engineering, Department of Sanitary Engineering, G. Narutowicza 11/12 Str, 80-233 Gdańsk,
Poland
f
EkoTech Center, Gdansk University of Technology, G. Narutowicza St. 11/12, 80-233 Gdansk, Poland
g
Department of Chemical Engineering, COMSATS University Islamabad, Lahore Campus, Raiwind Road, Lahore 54000, Pakistan
h
Biomass and Bioenergy Research Group, Sustainable Energy and Power System Research Centre, Research Institute for Sciences and Engineering, University of Sharjah,
Sharjah, United Arab Emirates
i
School of Geography and Resources Science, Neijiang Normal University, Neijiang, 641100, China
j
Institute of Chemistry, Co., Ltd, Henan Academy of Sciences, Zhengzhou 450002, China
k
Department of Environmental Sciences, COMSATS University Islamabad, Vehari Campus 61100, Pakistan
l
Department of Environmental Engineering, INHA University, Incheon 22212, Korea
m
Program in Environmental & Polymer Engineering, Graduate School, INHA University, Incheon 22212, South Korea

A R T I C L E I N F O A B S T R A C T

Keywords: Pharmaceuticals comprises different drugs used for treating different infections in human being and animals. The
Water pollution huge quantities of pharmaceuticals used are found to discharge into different water resources and cause different
Pharmaceuticals health and environmental problems. The continuous and large-scale discharge of pharmaceuticals increases their
Treatment technologies
persistency which can consequently make them more toxic. The different advanced oxidation processes (AOPs)
AOPs
•
OH and SO•−
were found to effectively treat pharmaceuticals contaminated water. The AOPs showed high efficiency in the
4
treatment of acetaminophen, sulfamethoxazole, metronidazole. ciprofloxacin. sulfadiazine, sulfamethazine,
amoxicillin, ibuprofen, carbamazepine, and tetracycline. The pharmaceuticals, amitrole, norfloxacin, atenolol,
chloramphenicol, berberine, diclofenac, and sulfadiazine showed persistency to some AOPs. The AOPs yield
different reactive radicals with predominantly hydroxyl radical (•OH)- and sulfate radical (SO•− 4 ) which showed
fast reactivity with pharmaceuticals. Different mechanistic approaches were systematically reviewed which
verify the yield, reactivities, and degradation pathways of •OH and SO•− 4 . Different factors, such as pH, dose of
peroxides and activators, level of pharmaceuticals contamination, and common inorganic anions were found to
influence the effectiveness of AOPs. The effectiveness of the AOPs in term of cost and detoxification of target
pharmaceuticals suggested to select preferably AOPs which are economical and form non-toxic and/or less toxic
products. The different challenges, such as treatment of mixture of pharmaceuticals and treatment in real
wastewater which can further increase potential of treatment are discussed.

* Corresponding authors at: College of Natural and Health Sciences, Zayed University, P.O. Box 144534, Abu Dhabi, United Arab Emirates (J. Iqbal); Department of
Chemistry, COMSATS University Islamabad, Abbottabad Campus 22060, Pakistan (N.S. Shah); Department of Environmental Engineering, INHA University, Incheon
22212, Korea (C. Han).
E-mail addresses: [email protected] (J. Iqbal), [email protected] (N.S. Shah), [email protected] (C. Han).

https://doi.org/10.1016/j.seppur.2024.127458
Received 13 February 2024; Received in revised form 9 April 2024; Accepted 9 April 2024
Available online 11 April 2024
1383-5866/© 2024 Elsevier B.V. All rights reserved.
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

1. Introduction [7,14,17–21]. The pharmaceutical contaminated waters are reported to

show different physical properties, such as pH, biological oxygen de­
Water is a natural, scarce, and indispensable source of the Universe mand (BOD), chemical oxygen demand (COD), total organic carbon
which is essential for preserving human life and environmental sus­ (TOC), total dissolved solid (TDS), and total suspended solids (TSS) as
tainability. However, pollutants and waste discharged from different shown in Table 1 [22]. The pharmaceutical contaminated waters
sources are rapidly deteriorating the available water resources [1–4]. collected from different sources and analyzed by different in­
Among the different pollutants, those contributing at large level strumentations for estimating concentration of the drug and the physical
comprise wastes from industrial discharge, such as pharmaceutical in­ properties as listed in Table 1.
dustries. Active pharmaceutical ingredients (APIs) containing drug Due to large-scale and continuous contamination, many APIs acquire
products referred to as pharmaceuticals, which are formulated to cure non-biodegradable nature as well as “pseudo presence” which render
various diseases in animals as well as humans, are discharged in huge the conventional treatments inefficient leading towards the further rise
quantities into different water resources [5,6]. The pharmaceutical in the existence of parent-drugs as well as their metabolites in terrestrial
wastes are reportedly less toxic, however, their large-scale and contin­ and aquatic environments [34–36]. The release of these ineffectively
uous contamination in water bodies include them in important classes of treated effluents and their usage by end-users for irrigation of soil can
emerging water pollutants [7,8]. Pharmaceuticals contamination in impose serious threats to soil, crops, biota, and humans [36]. Thus,
water resources at high and increasing rate is becoming one of the key pharmaceuticals are considered as significant environmental pollutants
and alarming environmental issue. Varying levels of different pharma­ which necessitate the research for efficiency and advancements in
ceuticals ingredients are reported in different water resources technologies for their removal from water streams and ultimately from
throughout the world [7–10]. After recognition of pharmaceuticals ex­ environment.
istence in the environment, interests have been developed for the The conventional technologies, such as adsorption, biodegradation,
investigation of their impacts, fate, toxic behavior as well as potential incineration, chlorination, and reverse osmosis which simply transfer
approaches for their removal from contaminated waters and prevent the pollutants from one phase to another, result into secondary pollu­
further discharge into freshwater resources. Environmental concerned tions, affected by toxicities of pollutants, and require high operational
pharmaceutical groups comprise of antibiotics, antidepressants, anti­ costs are not favored [8,12,37]. Contrary, the advanced oxidation pro­
epileptic drugs, beta blockers (b-Blockers), non-steroidal anti-inflam­ cesses (AOPs) which are based on the in-situ yield of highly reactive
matory drugs (NSAIDs), blood lipid lowering agents, hormones, species, such as superoxide radical (O•2), hydroperoxyl radical (HO•2),
antihistamines etc. [11–13]. The main source identified are Wastewater hydroxyl radical (•OH) and sulfate radical (SO•– 4 ) etc. are reported to
Treatment Plants (WWTPs) as being collectors of discharges from have great potential in the treatment of wide range of emerging pol­
households, industries, hospitals, veterinaries as well as pharmacies lutants [38–43]. The AOPs are reported to cause complete breakdown of
[14–16]. Because of different physiochemical characteristics of APIs, the toxic organic pollutants into non-toxic and/or less toxic smaller and
design of WWTP as well as the composition of sewage including the easily degradable products and even mineralization into carbon dioxide,
effectiveness of treatment methods can differ significantly demanding a water, and inorganic ions in some cases [12,44]. The different classes of
wide-ranging removal protocol. The existence of drug products in in­ AOPs and the reactive radicals produced from each AOPs are listed in
fluents as well as effluents of WWTPs is reported in many studies Fig. 1.

Table 1
Physiochemical properties of different wastewater contaminated with pharmaceutical wastes. Reproduced with permission from [22].
pH BOD COD TOC TDS TSS Main compound and Analysis Method Source/location Reference
mg/L mg/L mg/L mg/L mg/L conc. (mg/L)

6.8 8600 16,240 NA* NA* 400 Ampicillin (3.5) HPLC Fuzhou Pharmaceutical [23]
Company, China
6.6 350 2300 NA* NA* 30 Aureomycin (4.6) HPLC Fuzhou Pharmaceutical [23]
Company, China
6.9 140 540 NA* 1760 680 NA* BOD/COD Pharmaceutical industry [24]
analysis in
Dewas, India
5.8–7.8 20–620 128–960 NA* 650–1250 230–830 NA* BOD/COD ETP plant, India [25]
analysis
NA 10,184 ± 16,547 ± 8083 ± 24,899 ± 285 ± Triethylamine (987 ± GC Pharmaceutical [26]
2574 1827 578 1758 175 2142) company in
Singapore
7.18 NA* 2840 ± 634 ± 42 846 ± 311 ± Ampicillin (12.34 ± 1.32) HPLC Pharmaceutical factory, [27]
135 108 0.83 Ceftriaxone (2.61 ± 0.22) Lanzhou, China
Amoxicillin (18.68 ± 0.97)
Cefazolin (8.74 ± 0.75)
6.8 466 3500 NA* 600 360 Paracetamol (48) HPLC Pharmaceutical industry [28]
12.8 21,560 ± 37,410 ± 8250 ± 21,340 ± 6780 ± NA* BOD/COD Pharmaceutical [29]
160 225 145 450 180 analysis manufacturing
unit, Derabassi, Punjab
India
13–14 NA* 34,348 ± 17,215 ± 64,383 ± 433 ± Antibiotics (penicillin COD Pharmaceutical factory, [30]
1425 1784 2113 120 family) analysis Singapore
6.5–8.5 30 60 NA* 3000 100 NA* COD, BOD, TDS Hospital wastewater, [31]
analysis etc. Tanzania
7.2 22 80 NA* 134 70 NA* TDS Hospital wastewater, [32]
analysis Nigeria
7.8 3500–3800 5900–6140 2365–2393 NA* 297–346 Amoxicillin (150–180) HPLC Pharmaceutical Industry, [33]
Brazil

NA*= Not applicable, HPLC = High performance liquid chromatography, GC = Gas chromatography.

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J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

than 22,700 tons of antibiotics in 2001 [52]. The pharmaceutical con­

sumption is reported to be possibly increased by 67 % till 2045 in
Germany and this huge increase in consumption of pharmaceuticals
with time to meet the increasing population may led to severe water
pollution issues [53]. The high and large-scale use of different phar­
maceuticals throughout the world led to their contamination in different
water resources, e.g., drinking, surface, and ground water [54–58]. Due
to advancement in analytical technologies, the contamination of phar­
maceuticals in different water resources has been possible at very low
concentration. The pharmaceuticals analyzed in wastewater from
different sources follow the trend of industrial discharge > hospital
discharge > wastewater treatment plants > surface water > ground
water > drinking water [8]. The level of different pharmaceuticals
detected in water resources vary with location, e.g., painkillers are
predominantly detected in Europe while antibiotics predominate in Asia
[59,60]. The level of different pharmaceuticals detected in different
water sources in different regions of the world is illustrated in Fig. 3.
The pharmaceuticals contamination in water resources is found
mainly at lower level, however, their continuous discharge makes their
presence in water resources an issue of great concern [61]. The guide­
lines and daily acceptable level of different pharmaceuticals proposed
by Australia in water are listed in Table 3. The high biological activity,
high level contamination, greater persistency, and stability and resis­
Fig. 1. Different AOPs used with predominant reactive oxygen species pro­ tance to degradation make pharmaceutical contamination a great source
duced. Figure reproduced from [45] which is open access and permits unre­ of numerous health and environmental issues [62,63]. It is reported that
stricted use of materials under the terms of the Creative Commons CC-BY. even modest contamination of pharmaceuticals in water causes endo­
crine disruption, reproductive oddities, bacterial resistance, and envi­
The objective of this review was to discuss in detail the sources and ronmental toxicities [62]. Table 4 illustrate the toxicities of different
issues of different pharmaceuticals contamination in water resources as groups of pharmaceuticals contamination in water.
well as their chemistry, properties and usages and suggest different In addition to target pharmaceuticals toxicities, their intermediate
conventional and advanced treatment. Different •OH and SO•− 4 -based
products are sometime more toxic than parent compounds. and reported
AOPs are simultaneously discussed for treatment of pharmaceuticals to cause severe health and environmental issues as listed in [62,64,65].
under different conditions of process parameters, such as pH, effects of The pharmaceuticals contamination in water is grouped into
anions, and concentrations of peroxides, catalysts, and target contami­ different classes depending on their persistency to degradation, e.g.,
nant. The detail mechanism involved in the yield of the both •OH and hardly removable, lower removable, moderately removable, and readily
SO•−
4 by the selected AOPs, reactivities of OH and SO4 with pharma­
• •− removable [8,66]. The treatment technologies applied are considered
ceuticals, and participation of •OH and SO•−4 in the degradation of these based on the types and levels of contamination. The different technol­
pharmaceuticals are discussed. In addition, in this review, the potential ogies commonly applied for the treatment of pharmaceuticals contam­
of different AOPs in term of toxicities evaluation and cost estimation are inated water are discussed below.
also discussed in detail. Contrary, previous review are mostly focused on
single •OH or SO•− 4 -based AOPs and discussed briefly about the phar­ 3. Conventional technologies for the treatment of
maceutical contamination, impacts of process parameters. pharmaceuticals

2. Pharmaceuticals contamination in water and their effects The treatment of pharmaceuticals contaminated waters by conven­
tional technologies includes the use of different technologies, such as
Pharmaceuticals constitute a group of different biologically active physical, chemical, and biological treatment. In the physical treatment
compounds which differ widely in structure, function, and properties process, e.g., filtration the pollutants are not completely degraded but
and are used to provide safe and healthiest environment to human being involves only phase transfer [7,67]. The different physical processes, e.
and other living organisms [46,47]. Pharmaceuticals include wide va­ g., reverse osmosis, micro-, nano-, and ultrafiltration have been suc­
riety of different groups, the most prominent are antibiotics, analgesic, cessfully used in the removal of different pharmaceuticals [62,68,69].
beta-blockers and psychoactive, non-steroidal anti-inflammatory drugs, The reverse osmosis-based treatment occurs due to the driving force
and endocrine disruptors [11–13,48–50]. This classification of different produced as a result of the pressure difference between filtrate and feed
groups of pharmaceuticals is based on their structure, functional groups, sites [8,70]. However, in ultra- and nanofiltration the charged surfaces
activity, pharmacological actions, biological entity, and ameliorative undergo ion repulsion which produces driving forces for separation of
functions. Table 2 illustrates some of the commonly used pharmaceu­ the target pharmaceuticals [8]. The removal mechanism by filtration is
ticals with CAS number, molecular formula, structure, molar mass, not exactly known but it’s reported to involve several processes, e.g.,
classification and therapeutic applications, critical environmental con­ adsorption, electrostatic effects, and steric hindrance [8,71]. Besides,
centrations (CEC), and physical properties. They are extensively used the removal by filtration is affected by several factors of pharmaceuticals
throughout the world to treat different diseases. The increased world and filtrate, e.g., charge, size, permeability, polarity, and solubility etc.
population at high rate consequently led to increase demand of phar­ [8,72,73]. Due to these influencing factors and the different driving
maceuticals. The consumption report given in Fig. 2 illustrate huge forces, the extent of removal of pharmaceuticals by the different phys­
quantities (tons) of different pharmaceuticals utilized throughout the ical processes vary widely. The high operational cost, high energy de­
world. It is reported that that in Germany 5000 drugs were registered in mand, and mere phase transfer of pollutants discourage the role of
2001, out of which about 2700 drugs were consumed more than 90 % physical process in the treatment of pharmaceuticals [8,74].
[51]. Similarly, a report revealed that United Stated consumed more In the case of chemical treatment, the removal of target contami­
nants includes the use of different chemical species, such as chlorination

3
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Table 2
Physiochemical properties, molecular structure, molecular formula, and molar masses of different pharmaceuticals. Reproduced from [8] which is open access and
permits use of contents under ACS Author Choice License.
Pharmaceuticals Classification/ Chemical LogKow Predicted critical pKa Molecular Structure
(CAS Number) Therapeutic function formula environmental
with molar concentration
mass (g/mol) (ng/L)

Acetaminophen Analgesic/Antipyretic/Humna C8H9NO2 0.46 2.4 × 107 9.3

(103–90-2) and veterinary use (151.163)

Acebutolol Beta-blockers/ C18H28N2O4 1.53 Not reported 13.8

(37517–30-9) antihypertensive/human use (336.432)

Albuterol (18559–94- Bronchodilator/human use C13H21NO3 0.64 27,669 10.3

9) (239.3)

Amoxicillin Antibacterial/antibiotic/beta- C16H19N3O5S 0.87 7.4 × 106 3.2,

(26787–78-0) lactums/humane use (365.4) 11.7

Carbamazepine Anti-epileptic/neuropathic C15H12N2O 2.45 366,496 13.9

(298–46-4) pain/antipsychotic (236.2)

Cetirizine (83881–51- Antihistamine/antiallergic/ C21H25ClN2O3 1.70 423,061 2.70,

0) human use (388.892) 3.57,
7.56

Ciprofloxacin Antibiotic/fluoroquinolone/ C17H18FN3O3 0.28 1.9 × 107 6.09,

(85721–33-1) human use (331.3) 8.74

Clarithromycin Antibiotic/macrolide/human C38H69NO13 3.16 7267 8.99

(81103–11-9) use (747.964)

Clofibric acid Lipid lowering metabolites/ C10H11ClO3 2.9 Not reported 3.2
(882–09-7) human use and plants growth (214.6)
promotors

Diazepam (439–14-5) Benzodiazepine/Antianxiety C16H13ClN2O 2.9 16,219 3.4

drug/human use (284.7)

Diclofenac NSAIDs/human and veterinary C14H11Cl2NO2 4.51 4560 4.15

(15307–86-5) use (296.1)

(continued on next page)

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J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Table 2 (continued )
Pharmaceuticals Classification/ Chemical LogKow Predicted critical pKa Molecular Structure
(CAS Number) Therapeutic function formula environmental
with molar concentration
mass (g/mol) (ng/L)

Erythromycin Antibiotic/macrolide/human C37H67NO13 3.06 Not reported 8.88

(114–07-8) and veterinary use (733.937)

Famotidine Antihistamine/antagonist/ C8H15N7O2S3 7.5 452,408 − 1.95

(76824–35-6) human use (337.435)

Fluconazole Antifungal C13H12F2N6OS3 11.0 5.0 × 106 0.25

(86386–73-4) (306.277)

Ibuprofen (15687–27- NSAIDs C13H18O2 (206.2) 3.97 194,711 4.91

1)

Metronidazole Antibiotic/antiprotozoal/ C6H9N3O3 (171.1) − 0.02 2.3 × 107 2.38

(448–43-1) nitroimidazole

Naproxen (22204–53- NSAIDs C14H14O3 (206.2) 3.18 827,999 4.15

1)

Norfloxacin Antibiotic/fluoroquinolone/ C16H18FN3O3 0.46 6.4 × 106 6.34,

(70458–96-7) human use (206.2) 8.75

Omeprazole Antacid/proton pump C17H19N3O3S 2.23 3.48 × 107 1.2, 7.4

(73590–58-6) inhibitor/human use (345.417)

Sulfamethoxazole Broad spectrum antibiotic/ C10H11N3O3S 0.89 9.8 × 107 1.6, 5.7
(723–46-6) sulfa drug/human and (253.576)
veterinary use

and coagulation [8,74–76]. Chlorination is one of the widely used Biodegradation is another conventional treatment which uses
chemical-based conventional processes for treatment of different con­ different microorganisms to degrade target pharmaceuticals [84–86].
taminants. The chlorination is reported to be effective in degradation of The microorganisms degrade pharmaceuticals and use them as a source
wide classes of organic pollutants including antibiotics [8,13]. Fig. 4 of carbon and/or nitrogen [8]. The use of different biodegradation is
depicts chlorination-based treatment of ciprofloxacin (CIP) by and the used to cause effective degradation of wide-classes of different phar­
resulting degradation products. maceuticals even at very high concentration and results into the for­
The function of chlorination-based treatment is influenced by mation of numerous degradation products [87–89]. A study by Dawas-
different factors, such as pH, ammonia, free chlorine, and suspended Massalha et al. [90] investigated the kinetics of the degradation of
solids [77]. Chlorination being effective in treatment of wide classes of five different pharmaceuticals by biodegradation and found to be first-
pharmaceuticals, its role is limited to less polluted water [78]. Besides, order. Fig. 5 depicts the degradation of pharmaceutical compound,
the formation of chlorinated products which are reported to be some clarithromycin by fungal strains and found to form several degradation
time more toxic discourage the use of chlorination [79–81]. In addition products.
to chlorination, clarification is another chemical-based conventional Although biodegradation is effective in degradation of numerous
treatment used to destabilize colloid particle and promote their coagu­ pharmaceuticals, however, some pharmaceuticals, e.g., antibiotics is
lation as well as settling down [82,83]. reported to affect the activity of microorganisms [91].

5
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Fig. 2. Consumption percentage of different pharmaceuticals worldwide. Figure reproduced from [8] which is open access and permits use of contents under ACS
Author Choice License.

need to be explored in detail further. A suitable AOPs used for the

treatment of any target pollutant is selected keeping in view the nature,
types and concentration of pollutants, discharge limit of wastewater,
and cost of treatment applied etc. The different types of AOPs used
include chemical-, photochemical-, and energy-based and are selected
based on the properties of pollutants, e.g., biodegradability, solubility
etc. as discussed in detail below [106]. Table 5 depicts the treatment of
different pharmaceuticals by different classes of AOPs with the experi­
mental conditions and degradation efficiencies achieved.
The details of the mentioned AOPs are discussed in detail below in
the sections (a) to (j) with detail of the yield of reactive radicals and their
mechanistic role in the degradation of different pharmaceuticals.

a) Photolysis of pharmaceuticals

The photolytic degradation of pharmaceuticals is grouped into two

types, direct photolysis and indirect photolysis [135]. In the case of
Fig. 3. Analyzed concentrations (ng/L) of non-steroidal anti-inflammatory direct photolysis, the wastewater contaminated with pharmaceuticals
drugs (NSAIDs), i.e., ibuprofen, naproxen, diclofenac, ketoprofen and acet­ wastes are treated with high energy radiations, such as UV and visible
aminophen in surface water samples from different countries. Figure repro­ irradiation. The irradiation interacts with the target pollutants and cause
duced from [61] which is open access and permits use of contents under a their excitation into high energy state which subsequently passes
Creative Commons license. through series of reactions and give degradation products (DPs) as
shown in reaction (1) and (2) [136].
4. Pharmaceuticals removal studies with advanced oxidation
processes (AOPs) Pharmaceuticals + hv→Pharmaceuticals* (1)

Advanced oxidation processes are a group of different advanced Pharmaceuticals* + hv→DPs (2)
treatment technologies which rely on the use of highly reactive radicals, Fig. 7 depicts the degradation mechanism of the direct and indirect
such as •OH and SO•– 4 for degradation of different classes of persistent photolytic degradation of sulfonamide pharmaceuticals, e.g., sulfa­
and toxic organic pollutants [2,92–102]. The AOPs are advantageous as methoxazole, sulfisoxazole, sulfamethizole, and sulfathiazole [136]. The
the target pollutants are degraded into non-toxic and/or less toxic critical parameters necessary in analyzing the potential of direct
degradation products or even mineralized with minimum and/or no photolysis of pharmaceuticals degradation are reported to be molar
formation of secondary pollutants [12,103–105]. The total number of absorptivity of the target contaminants (ελ), quantum yield ((Φ)), in­
review publications on the different advanced oxidation processes-based tensity of radiation, and functional groups of the target pollutants
degradation of pharmaceuticals for 10 years (2013 to 2023) are pre­ [137,138].
sented in Fig. 6 (Source Web of Science). It is evident from Fig. 6 that The extent of light absorption and quantum yield measure the rate of
small number of review articles are published on the proposed topic and

6
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Table 3 Table 4
Australia guidelines for the use of different pharmaceuticals. Reproduced from Pharmaceuticals contamination in water and their effects on environment and
[8] which is open access and permits use of contents under ACS Author Choice human. Reproduced with permission from [13].
License. Pharmaceuticals Impacts on human health and environment
Pharmaceuticals Lowest daily Surrogate acceptable Drinking Class
therapeutic dose daily intake (S-ADI, water
Antibiotics Invertebrates show low toxicity in the presence of
(LDTD, mg/day) μg/kg/day) guidelines
antibiotics, increased oxidative stress, block the electron
(DWG, μg/L)
chain of photosynthesis II, develop emerging resistance, and
Cefaclor 500 7.1 250 affect algae and aquatic plants
Chloramphenicol 3500 5 175 Analgesics and Inhibits CYP2M in Cyprinus carpio, changes the breeding
Ciprofloxacin 500 7.1 250 NSAIDS pattern in Oryzias latipes
Chloramphenicol 3500 5 175 Anti-cancer Cytotoxic, mutagenic, genotoxic, and teratogenic in
Clindamycin 600 8.6 300 eukaryotic organisms; visceral organ damage; and genetic
Demeclocycline 600 8.6 300 abnormality.
Naladixic acid 2000 28.4 1000 Beta-blockers Embryonic development issues in crustacean, mortality in
Norfloxacin 800 11.4 400 algae
Roxithromycin 300 4.3 150 and fish, growth development abnormality in algae, and
Fenoprofen 900 12.9 450 immobilization in Daphnia similis.
Ibuprofen 800 11.4 400 Endocrine disruptors Cancer, obesity, thyroid disturbance, and Alzheimer’s
Indomethacin 50 0.71 25 disease.
Naproxen 440 6.3 220 Anti-retrovirals Nausea, anemia, nephrotoxicity, hypersensitivity, and
Betaxolol 20 0.28 10 rashes.
Bisoprolol 1.25 0.018 0.63
Metoprolol 50 0 0.71 25
Nadolol 40 0.57 20
Propranolol 80 1.14 40 [136,139,141,142]. Some of the common sensitizers in indirect
Timolol 20 0.28 10 photolysis are NO–3 and dissolve organic matters (DOMs) [8,143,144].
17α-ethinyl 0.03 4.3 × 10–5 0.0015
estradiol
These sensitizers are abundantly found in water resources and their
Equilenin 0.6 8.6 × 10–4 0.03 photoexcitation upon absorption of incident radiations yield varieties of
Equilin 0.6 8.6 × 10–4 0.03 reactive intermediates, such as reactive oxygen species, hydroxy radical
Estriol 1 1.4 × 10–3 0.05 (•OH), singlet oxygen (1O2), peroxy radical (ROO•), and super oxide
Estrone 0.6 8.6 × 10–4 0.03
radical anion (O•–2 ) and triplet (excited) DOM and hydrated electrons
Mestranol 0.05 7.1 × 10–5 0.0025
Norethindrone 5 7.1 × 10–3 0.25 (e–aq) [8,141]. The reactivities of these reactive intermediates with target
Alprazolam 0.5 0.0071 0.25 contaminants is dictated by their steady state concentrations and
Antipyrine 2000 28.4 1000 second-order rate constants. The photolytic degradation of serval
Atorvastatin Atorvastatin 10 0.14 5 pharmaceuticals studied showed their effective degradation into
Bezafibrate 600 8.6 300
Carbamazepine 200 2.8 100
degradation products which were found due to direct photolysis by the
Cimetidine 400 5.7 200 absorption of light and indirect photolysis due to reactive radicals
Clofibric acid 1500 21.4 750 [8,141,145].
Codeine 100 1.4 50
Cyclophosphamide 70 0.1 3.5
b) UV/peroxide-based AOPs
Dehydronifedipine 40 0.57 20
Diazepam 5 0.071 2.5
Diltiazepam 120 1.7 60 In the UV peroxide-based AOPs, the degradation of pharmaceuticals
Enalprilat 2.5 0.036 1.25 proceeds by the incident UV irradiation in the presence of peroxides,
Fluoxetine 20 0.28 10 such as H2O2, S2O2−8 , and HSO5 [146–150]. These peroxides, H2O2,
−
Gemfibrozil 1200 17 600 2−
Iohexol 1440 20.6 720
S2O8 , and HSO5 possess O-O bonds and are reported to effectively
−

Iopamidol 800 11.4 400 absorb UV irradiation due to their high molar extinction coefficient and
Iopromide 1500 21.4 750 consequently undergo homolytic cleavage leading to the formation of
Isophosphamide I70 0.1 3.5 OH and SO•−4 with high quantum yield of the later as illustrated in Eqs.
•
Metformin 500 7.1 250
(3) to (5) [151,152].
Salbutamol 6 0.086 3
Stigmastanol 2000 28.4 1000 H2 O2 + hv→• OH Φ = 1.0 (3)
Sulfasalazine 1000 14.2 500
Terbutaline 9 0.13 10 0.14 5
4.5 S2 O2−8 + hv→SO•−4 Φ = 1.8 (4)
Terbutaline 9 0.13 4.5
HSO−5 + hv→• OH + SO•−4 Φ = 1.04 (5)

degradation of target pollutants, thus pharmaceuticals which absorb The cleavage of the peroxides by the UV irradiations and the yield of the
high quantum of incident radiation consequently give high degradation •
OH and SO•−4 depends on the O-O bond length, bond energy, and molar
rate and vice versa. Owing to these facts, some pharmaceuticals which extinction coefficient of the peroxides [151–156]. Among the three
absorb effectively direct radiation have short half-lives within the range peroxides, the S2O2−
8 show lower O-O bond length and bond energy and
of minutes while compounds with low absorptivity show high short-lives high molar extinction coefficient and consequently lead to high yield of
of several hours to several days [139]. As a result of direct photolytic reactive radicals as well as higher degradation efficiency as shown in
reactions, the bonds in target pharmaceuticals are cleaved and results Fig. 8 [152,155,157]. The •OH and SO•−4 produced from the activation of
into DPs formation through different reactions [140]. The direct H2O2 and S2O2−8 , respectively, cause degradation of the target pharma­
photolysis of the five membered ring sulfonamides shown in Fig. 7 ceuticals into degradation products and finally mineralization into
initiated with the cleavage of S–N bond [136]. inorganic fragments as shown in Fig. 8 [158]. The use of the peroxides,
In the case of indirect photolytic degradation, the incident light is S2O2−
8 , HSO5 and H2O2 with UV irradiations have resulted into effective
−

absorbed by sensitizer which reacts directly with the target pollutants or degradation of several classes of target organic pollutants
produce reactive radicals that led to reactions with the target pollutants

7
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Fig. 4. Chlorination based treatment of CIP. Figure reproduced from [8] which is open access and permits use of contents under ACS Author Choice License.

Fig. 5. Biodegradation of clarithromycin. Figure reproduced from [8] which is open access and permits use of contents under ACS Author Choice License.

[95,146,147,149,150,158]. Besides, the SO•− 4 is reported to have higher between saccharine and SO•− 4 , the H2O2-based AOPs caused higher
oxidation potential than •OH and due to these factors S2O2− 8 showed degradation of saccharin than S2O2−
8 in the study conducted by Ye et al.
higher degradation of thiamphenicol than H2O2 [152,153,157]. The [159].
degradation of pharmaceuticals by UV peroxide-based AOPs is reported
to depend on the reactivities of reactive radicals with pharmaceuticals c) Gamma-irradiation based AOPs
and pH of reacting solutions also [95,155].
Owing to the higher reactivities between •OH and saccharine than Gamma-irradiation are highly energetic radiation with high pene­

8
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Sonolysis is an important type of AOPs which are dictated by the use

of ultrasound radiation (US) as illustrated in reactions (13) to (15)
[167–169]. It is shown that the use of US irradiation to treat aqueous
solution of pharmaceuticals produce •OH that attack the target con­
taminants [167–169].
H2 O + )))→+• OH+• H (13)

2OH • →H2 O2 (14)

2OH • →H2 O + O (15)

The symbol))) in reaction (13) illustrate US irradiation. The sonolysis is

found to yield •OH and the later attack the target pharmaceuticals
[167,169]. The presence of promoters of reactive oxygen species (ROS),
e.g., peroxides, ozone and photocatalysts with ultrasound radiation in­
crease the yield of ROS and consequently facilitate the degradation of
target contaminants [170]. Fig. 10 illustrates the sonolytic degradation
of antibiotics contaminated waters in the presence of peroxides, ozone,
and photocatalysts which depicts enhanced formation of reactive radi­
cals [170]. The rate of the reactive radicals produced in sonolysis de­
pends on the frequency and power of the applied ultrasound radiations
Fig. 6. Different publications on the treatment of pharmaceuticals by AOPs.
(US) [167,171–173]. The degradation of levodopa and paracetamol by
Data taken from the web of science for the period from 2013 to 2023.
sonolysis was conducted at different frequencies, e.g., 574, 860 and
1134 kHz and the results obtained showed decline in the degradation
tration power and reported to produce oxidizing specie (e.g., hydroxyl
efficiency (%) with increasing ultrasound frequencies [167]. The
radical, •OH) as well as reducing reactive species (e.g., hydrated electron
increasing frequency inhibit the cavitational effect which in return
(e−aq) and hydrogen atom (•H)) as shown in reaction (6) [160,161].
lower the rate of formation of reactive radicals and achieve lower
H2 O→ ⋅ OH(0.29) , e−aq(0.28) , ⋅ H(0.06) , H3 O+
(0.32) , H2 O2(0.07) , H2(0.05) (6) degradation efficiency of target contaminants [167]. On contrary, the
power of ultrasonic irradiation enhanced degradation efficiency of
The oxidizing and reducing reactive species react with the target con­ target contaminants [167]. The ultrasonic degradation of levodopa and
taminants and degrade them into target contaminants. The gamma paracetamol was conducted at different ultrasonic powers, i.e., 9, 17, 22
irradiation-based degradation of several pharmaceuticals is conducted and 32 W and the results showed linear increase in the degradation ef­
and found to achieve appreciable degradation [122,162,163]. Among ficiency of levodopa and paracetamol with elevated ultrasonic power
the reactive species, the reductive species are found to be more effective and vice versa [167].
in the degradation of halogenated compounds [160]. However, in the This is because at high power, the rate of formation of reactive
presence of air (oxygenated solutions), the reductive species are scav­ radicals increases which in return lead to rapid collision with the target
enged and converted into secondary and less reactive species [160]. contaminant molecules [167]. However, it is reported that beyond op­
However, the oxidative radicals are found to be more efficient in the timum power, the sonolysis rate is slowed down and consequently led to
degradation of different pharmaceuticals conducted in previous studies decline in the removal efficiency [167]. The rate of sonolytic degrada­
[135–137]. The oxidative degradation of pharmaceuticals by gamma- tion of organic pollutants is reported to be facilitated by the addition of
irradiation were found to be facilitated by the •OH and SO•− 4 , pre­ peroxides, H2O2, S2O2−8 , HSO5 [170,173,174,175]. The possible reason
−

cursors, e.g., H2O2, S2O2−

8 , and HSO5 [122,162,163]. The H2O2, S2O8 ,
− 2− is that US irradiation decompose the peroxides into •OH and SO•− 4 and
and HSO−5 are found to yield •OH and SO•− 4 by reaction with e −
aq (re­ consequently the rate of formation of reactive radicals is enhanced
actions (7) to (12)), thereby, increasing the concentrations of •OH and [171,174,175]. This enhancement in the rate of formation of reactive
4 [122,162–165]. The study further showed that high concentra­
SO•− radicals led to increased degradation of target pollutants. The coupling
tions of H2O2 and S2O2−8 led to faster degradation of target contaminants of other ROS activators, such as ozone (O3) and photocatalysts (e.g.,
by gamma irradiation possibly due to the high rate of formation of •OH TiO2) with US also facilitate the yield of reactive radicals and led to high
and SO•−4 [122,162,163]. Fig. 9 highlights the degradation of diclofenac degradation of target pharmaceuticals [170].
by ionic irradiation-based peroxides which show that activated perox­
ides effectively yield •OH and SO•− 4 and the later involve in the degra­ e) Ozone based AOPs
dation of diclofenac into degradation products [166].
Ozone (O3) is a powerful oxidant due to its high redox potential and
H2 O2 + e−aq →• OH+− OH (7) found to degrade wide classes of different organic pollutants
[98,176,177]. However, ozone alone is found to produce less concen­
H2 O2 +• H→• OH + H2 O (8) tration of •OH and reportedly degrade recalcitrant organic pollutants at
slow rate [176–178]. To improve the capacity of ozone to yield high
S2 O2−8 + e−aq →SO•−4 + SO2−4 (9)
concentrations of •OH and effectively mineralize organic pollutants, it is
coupled with UV radiations, i.e., UV/O3 or catalysts [178]. Ozone ab­
S2 O2−8 +• H→SO•−4 + SO2−4 ++ H (10) sorbs UV-C radiation effectively and shows high molar absorptivity in
the order of 3300 M− 1 cm− 1 [178]. The UV/O3 process is reported to be
HSO−5 + e−aq →SO•−4 +− OH (11)
one of effective AOPs processes for degradation of organic pollutants
without yield of secondary pollution [67]. The reactions of ozone in the
HSO−5 + e−aq →• OH + SO2−4 (11) presence of UV-C irradiations leading to the yield of •OH are shown in
reactions (16) and (17) as below.
d) Sonolysis O3 + hv→O2 +1 O (16)

9
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Table 5
Different AOPs used for treating different pharmaceuticals with removal efficiencies and detail experimental conditions.
AOPs type Pharmaceuticals Experimental conditions Results References
2
UV Photolysis Acetaminophen Low-pressure Hg lamp, λ = 254/185 nm, flux = 5 mW/cm , time = 100 % removal [107]
80 min
UV Photolysis Triclosan VUV/UV-C light sources, UV 100 % removal [108]
Dose = 0.8 J/cm2
UV Photolysis Sulfamethoxazole Medium-pressure Hg lamp (200–300 nm), C0 = 23.69 mM Removal = 89 % at UV dose = [109]
200 mJ/cm2
UV/H2O2 Carbamazepine (CBZ) Low-pressure Hg lamp (254 nm), C0 = 20 mM, [H2O2]0 = 5 mM, Removal = 100 % after 4 min [110]
pH5
UV/H2O2 Sulfamethoxazole Low-pressure Hg lamp (254 nm), C0 = 2.24 mg/L, [H2O2]0 = 5 mM, Removal = 100 % after 1 min [111]
pH7.4
UV/H2O2 Paracetamol Low-pressure Hg lamp (254 nm), C0 = 0.01 mM, [H2O2]0 = 5 mM, Removal = 90 % after 1.3 h [112]
pH7.4
UV/H2O2 Metronidazole Low-pressure Hg lamp (254 nm), C0 = 6 mM, [H2O2]0 = 50 mg/L, Removal = 65 % after 2.5 min [113]
pH6
UV/PS Sulfamethoxazole Medium-pressure Hg lamp (2.8 kW, 200–300 nm); C0 = 23.69 mM; Removal = 96 % at UV dose [109]
[PS]0 = 1 mM, of 200 mJ/cm2
pH 6.24
UV/PS Oxcarbazepine Low pressure UV lamp (254 nm); C0 = 20 mM; CPS ¼ 1 mM, pH Removal = 99 % at 120 min [114]
UV/PS CBZ UV lamp (254 nm); C0 = 21.16 mM; [PS]0 = 1 mM, pH 5.48 Removal = 98.9 % after 90 [115]
min
UV/PS Sulfamethazine UV lamp (254 nm); C0 = 0.02 mM; [PS]0 = 0.2 mM Removal = 96.5 % after 45 [116]
min
UV/PMS Atenolol C0 = 0.02 mM, 0.08 mM PMS, UV lamp (2 5 4), pH7, Removal > 80 % after 0.5 h [117]
UV/PMS Sulfamerazine; sulfamethizole; C0 = 0.2 μg/L, 1.0 mg/L PMS, UV lamp = 254, pH 7.5 Removal = 100 % after 0.5 h [118]
sulfachloropyridazine
Gamma-irradiation Ciprofloxacin C0 = 4.6 mg/L, dose rate = 290 Gy/h, N2-saturated, pH6.5 Removal = 100 % at 870 Gy [119]
Gamma-irradiation Sulfamethoxazole C0 = 0.1 mM, dose rate = 6 kGy/ h Removal = 99.9 % at 5.0 kGy [120]
Gamma-irradiation Cefaclor C0 = 30 mg/L, dose rate = 14,300 Gy/h. Removal = 100 % at 1 kGy [121]
Gamma- Carbamazepine C0 = 0.04 mM; [PMS]0 = 0.8 mM; pH 3.2 Radiation dose needed for [122]
irradiation/PMS 100 % removal reduced
from 800 to 300 Gy in the
presence of 0.8 mM PMS
Sonolysis Diclofenac C0 = 1 mg/L, US frequency = 40 kHz Removal = 70.3 % at 120 min [123]
Sonolysis Sulfadiazine C0 = 0.07 mM, [PS]0 = 1.84 mM, US frequency = 20 kHz, US power Removal = 13.7 % at 60 min [124]
= 40 W, pH5
Sonolysis Tetracycline C0 = 0.112 mM, [PS]0 = 4.0 mM, US frequency = 35 kHz, US power 96.5 % removal at 120 min [40]
hydrochloride = 500 W, pH10
Sonolysis Diclofenac C0 = 5 mg/L, Power density = 3.5 W/cm. pH = 6.0; T = 30 ◦ C; Removal = 97 % at 240 min [125]
[PS]0 = 120 mg/L
Sonolysis Carbamazepine C0 = 25 μM/L, Frequency = 40 kHz, power = 50 W. pH = 3.0, T = Removal = 43.8 % at 120 min [125]
50 ◦ C, [PS]0 = 1 mM
Sonolysis Sulfamethazine C0 = 50 mg/L, Frequency = uniformed, power = 600 W. pH = 7.5, Removal = 99.5 % at 30 min [126]
T = 25 ◦ C, [PS]0 = 0.6 g/L
Ozone-AOPs Caffeine 32 W UV lamp (365 nm), C0 = 40 mg/L, O3 gas flow of 60 L/h, O3 Removal = 95 % at 22.5 min [127]
constant supply of 1.0 g/h
Ozone-AOPs Estrone Low pressure UV lamp (254 nm), C0 = 5 mg/L, [O3]0 = 1.31 mg/L, Removal = 100 % at 15 min [128]
pH6.5
Ozone-AOPs Berberine(BRB) [H2O2]0 = 0.5–4.0 mM, Low-pressure mercury vapor lamp (λ = 254 Removal of 94.1 % [129]
nm), pH = 5–11
Ozone-AOPs Chlortetracycline [O3]0 = 0.012 mM, [H2O2]0 = 0–5.9 mM, Low-pressuremercury Removal = 100 % in less than [129]
vapor lamp (λ = 254 nm), pH = 8.5 15 min
Ozone-AOPs Penicillin G [O3]0 = 0.03 mM, [H2O2]0 = 3 mM, Low-pressure mercury vapor Removal ~ 80 % in 30 min [129]
lamp (λ = 254 nm)
Electrochemical Tyrosol Boron-doped diamond (BDD) anode, [Fe2+]0 = 0.50 mM, pH 3, C0 Removal = 100 % at 70 min [130]
= 723 mM
Electrochemical Metronidazole Ce/SnO2-Sb coated anode, graphite bar cathode, [Na2SO4]0 = 0.1 100 % removal after 80 min [130]
M, [Fe2+]0 = 0.50 mM, C0 = 0.34 mM, pH 3
Electrochemical Paracetamol Electrochemical cell with a Pt anode and air-diffusion cathode, 99 % removal in 55 min [130]
coupled with a
compound parabolic collector (CPC) as solar photoreactor. C0 =
157 mg/L, [Na2SO4]0 0.05 M, [Fe2+]0 = 0.40 mM, pH 3
Fe2+ and UV- Ciprofloxacin C0 = 0.15 mM, [Fe2+]0 = 2.25 mM, [H2O2]0 = 22.5 mM, pH 3.5 Removal ˃80 % after 45 min [130]
peroxides
Fe2+ and UV- Metronidazole C0 = 6 mM, [Fe2+]0 = 11.76 mM, [H2O2]0 = 29.4 mM, pH 3.5 Removal = 76 % after 5 min [130]
peroxides
Fe2+ and UV- Amoxicillin 2+
21 W low-pressure Hg lamp (254 nm), C0 = 400 mg/L, [Fe ]0 = 1 Removal = 100 % after 40 min [130]
peroxides mM, [H2O2]0 = 20 mM, pH 3
Fe2+ and UV- Ciprofloxacin UV lamp (254 nm), light intensity 12 W/m2, C0 = 0.15 mM, [Fe2+]0 Removal ˃94 % after 45 min [130]
peroxides = 2.25 mM, [H2O2]0 = 22.5 mM, pH 3.5
Zerovalent metals Ciprofloxacin C0 = 0.15 mM, [PS]0 = 3.62 mM, nZVI = 120 mg/L, pH = 4.5 Removal = 94 % at 60 min [40]
Zerovalent metals Chloramphenicol C0 = 10 mg/L, [PMS]0 = 0.2 mM, nZVI = 500 mg/L, pH = 7 Removal = 95.2 % [131]
Zerovalent metals Metronidazole C0 = 0.14 mM, [PS]0 = 1.85 mM, nZVI = 500 mg/L, pH = 3 Removal = 90.3 % at 30 min [40]
Carbonaceous Sulfamethoxazo C0 = 0.019 mM, [PS]0 = 4 mM, Biochar = 0.05 g/L, pH = 6 Removal = 100 % [40]
materials
(continued on next page)

10
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Table 5 (continued )
AOPs type Pharmaceuticals Experimental conditions Results References

Carbonaceous Norfloxacin C0 = 0.031 mM, [PS]0 = 3.72 mM, Biochar = 0.8 g/L, pH = 6.5 Removal = 90 % [40]
materials
Carbonaceous Tetracycline C0 = 0.02 mM, [PS]0 = 2 mM, Biochar = 0.4 g/L, pH = 3 Removal = 100 % [40]
materials
Carbonaceous Chlortetracyckine C0 = 0.1 mM, [PS]0 = 11.48 mM, Activated carbon = 0.2 g/L, pH = Removal = 88 % [40]
materials 5
Photocatalysis Sulfamethoxazole UV-A (324 ≤ λ ≤ 400 nm), C0 = 100 mM, [TiO2 ]0 = 0.1 g/L, pH 3 Removal = 95 % at 60 min [130]
Photocatalysis Ibuprofen Light λ = 365 nm, [TiO2] = 20 mg/L, [PDS] = 0.5 mM, C0 = 20 µM, Rate constant = 0.388 1/min [132]
pH = 5 at 25 min
Photocatalysis Sulfaclozine Light λ = 365 nm, [TiO2] = 2.5 g/L, [PDS] = 12.5 g/L, C0 = 25 mg/ Removal = 100 % at 60 min [133]
L, pH = 7
Photocatalysis Amitrole Simulated solar light, Photocatalyst = N doped TiO2, [PMS] = 0.05 Removal = 82 % at 120 min [134]
mM, C0 = 8 mg/L, pH = 5.8

organic pollutants. In addition, the use of UV-C with O3 is useful as it can

degrade the target contaminant by direct photolysis and additionally
excite the target contaminant which is reported to be more susceptible to
•
OH [173,179]. Fig. 11 illustrates the degradation of sulfamethoxazole
by different ozone-based AOPs [180]. It is shown that sulfamethoxazole
is efficiently degraded into degradation products by all the ozone (O3)-
based processes. Among the different O3-based AOPs, the best perfor­
mance is shown by coupling radiation/O3 with H2O2, possibly due to the
high rate of formation of •OH [180]. A similar increase in degradation
efficiency of target organic pollutant is observed in other study also
using UV/O3/H2O2 [181]. Ho et al. [182] studied the mineralization of
sulfonamides drugs by UV/O3/PS and showed high degradation rate
constants, i.e., 0.0802 min− 1 (at pH5) and 0.0802 min− 1 (at pH7) as
compared to that by UV/O3 only, i.e., 0.0101 min− 1 (at pH5) and
0.08116 min− 1 (at pH7). The presence of PS is reported to increase the
rate of formation of reactive radicals by coupling with UV/O3
Fig. 7. Direct and indirect photolysis for degradation of sulfonamides. Figure [182,183].
reproduced with permission from [136]. In the case of catalytic ozonation, the catalysts activate the decom­
position of ozone and promote the yield of •OH as shown in (20) and
1
O + H2 O→2• OH (17) (21) [184].

Fe2+ + O3 →FeO2+ + 2O• (20)

The O3 can undergo indirect reactions and also yield •OH as shown in
reactions (17) and (19).
FeO2+ + H2 O→ + F 3+ +• OH+− OH (21)
O3 + H2 O→O2 + H2 O2 (17)
f) Electrochemical-based AOPs
H2 O2 + hv→2• OH (19)

The high rate of formation of •OH led to rapid degradation of target The electrochemical based AOPs is one of the important processes
which yield reactive radicals without the utilization of chemicals and

Fig. 8. UV/H2O2 and UV/PS processes for degradation of thiamphenicol. Figure reproduced with permission from [158].

11
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Fig. 9. Degradation of diclofenac by ionizing irradiation coupled with H2O2 and PS. Figure reproduced with permission from [166].

Fig. 10. Sonolytic degradation of antibiotics contaminated water in the presence of peroxides, ozone, and photocatalysts. Reproduced from [170] which is open
access and permits use of contents under a Creative Commons license.

consequently without the formation of secondary wastes [12,185]. The chlorine, H2O2 and S2O2– 8 and catalysts activate the efficiency of the
electrochemical advanced oxidation process (EAOPs) proceeds through anodic oxidation process [186,187]. The direct and indirect electro­
two different pathways; (1 direct oxidation of pharmaceutical com­ chemical AOPs-based degradation of pharmaceutical drug, lamivudine
pounds (R) at the anode through direct transfer of charge between the is represented in Fig. 12. In the EAOPs, the second prominent reaction
anodic surface and the pharmaceuticals as depicted in reaction (22) involve the cathodic reactions in which the oxidants, like H2O2 is
[186]. generated through two-electrons reduction of oxygen (bubbled air) as
shown in reaction (25) [186,188]. The H2O2 formed further reacts in
Rads →ze− + Pads (22)
aqueous solutions with catalysts etc. and yield •OH [186,188]. The re­
In the indirect EAOPs, the pharmaceuticals are oxidized through the actions involving the use of catalytic decomposition of H2O2 is called
electrogenerated reactive oxygen species (ROS), such as •OH and/or electrochemical-Fenton reaction which is illustrated in reaction (26).
SO•–
4 at the anode [186] which occur through physiosorbed ROS (reac­ O2 (g) + 2H + + 2e− →H2 O2 (25)
tion (23) or chemisorbed active oxygen species formation reaction (24)
[186]. Fe2+ + H2 O2 →Fe3+ +• OH+− OH (26)
⋅
M + H2 O→M( OH)+ OH + e − −
(23)
Several studies conducted on the use of EAOPs for degradation of
pharmaceuticals received encouraging results and the target pharma­
⋅
M( OH)→MO + H + e + −
(24)
ceuticals are reported to be degraded into products [186–189].
In the anodic oxidation process, the mass of the target contaminants
transferred from the bulk to the anode surface or its vicinity influence g) Ferrous and peroxides coupled with irradiation based AOPs
the removal rate [186]. In addition, the addition of oxidants, such as
This process involves the use of Fe2+ and peroxides (i.e., H2O2, S2O2–
8 ,

12
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Fig. 11. Degradation of sulfamethoxazole by different O3-based AOPs. Figure reproduced with permission from [180].

As a result, HSO–5 is reported to generate high rate of reactive radicals

and lead to effective degradation of target pollutants than other two
peroxides. The process is recyclable and the Fe2+ used is regenerated as
shown in reactions (30) and (23) [193].

Fe3+ + H2 O2 →Fe2+ + HO•2 + H + (30)

Fe3+ + HSO−5 →Fe2+ + SO•−5 + H + (31)

The use of UV light with Fe2+ and peroxides is reported to promote the
yield of •OH and/or SO•– 4 and consequently cause high degradation ef­
ficiency of target contaminants than UV-C and/or Fe2+-catalyzed
peroxides-based processes [193]. The possible reason of this high per­
formance of the UV-mediated Fe2+-catalyzed peroxides-based processes
looked to be the involvement of three processes, i.e., UV and Fe2+, UV
and peroxides, and Fe2+ and peroxides which all are reported to yield
reactive radicals.
Fig. 12. Schematic presentation of electrochemical AOPs-based degradation of The photo-Fenton and photo-Fenton-like process give effective
lamivudine: Figure reproduced with permission from [187]. degradation of pharmaceuticals than both UV-C-peroxides and Fe2+/
Fe3+-peroxides-based processes. Fig. 13 the mechanism of the yield of
•
OH in the photo-Fenton process and reaction of •OH with ciprofloxacin
and HSO–5) under irradiation for the degradation of pharmaceuticals. which led to degradation of the later into products [194]. The resulting
Among the Fe2+-catalyzed peroxides-based processes, the reaction degradation product of the ciprofloxacin is identified by interpretation
involving the use of Fe2+ and H2O2 is called Fenton reaction which yield of its mass spectra as shown in Fig. 13. In another study, the degradation
•
OH as shown in reaction (26) [178,190–193]. The •OH produced sub­ of norfloxacin was investigated by UV-C/Fe2+-catalyzed peroxides, i.e.,
sequently causes the degradation of target contaminants. Among the UV-C/Fe2+/H2O2, UV-C/Fe2+/S2O2– 2+
8 , and UV-C/Fe /HSO5 and the re­
–

Fe2+-peroxides-based processes, the reactions involving the use of Fe2+ sults obtained showed significant degradation of norfloxacin by all the
with S2O2–8 and/or HSO5 is called Fenton-like reactions and lead to the
– three processes [195]. The three processes were found to yield •OH and
yield of •OH and/or SO•–4 as shown in reactions (27) to (29) [193]. SO•–4 which caused degradation of norfloxacin. Both the OH and SO4
• •–

showed high reactivity with norfloxacin [195]. In the three different

Fe2+ + S2 O2−8 →Fe3+ + SO•−4 + SO2−4 (27) processes, the fast degradation of norfloxacin was caused by UV-C/Fe2+/
HSO–5 followed by UV-C/Fe2+/S2O2– 2+
8 and then UV-C/Fe /H2O2 [195].
Fe2+ + HSO−5 →Fe3+ + SO•−4 +− OH (28) The possible reason for the fast degradation by UV-C/Fe2+/HSO–5 was
found due to faster activation of HSO–5 by UV-C and Fe2+ [195].
Fe2+ + HSO−5 →Fe3+ + SO2−4 +• OH (29)

The catalytic decomposition of H2O2, S2O2–

8 , and by Fe2+
HSO–5 h) Zerovalent metals based AOPs
2+
proceeds through transfer of electrons from the Fe into the lower
unoccupied molecular orbital (LUMO) of the peroxides [190]. The Zerovalent metals (ZVMs) are strong reductants with high reduction
peroxide HSO–5 is reported to have the lowest LUMO among the perox­ potential and easily loss electrons which can effectively reduce heavy
ides and consequently reported to be easily catalyzed by Fe2+ [153,193]. metals and halogenated organic compounds [196,197]. In addition, the

13
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Fig. 13. Degradation of ciprofloxacin by photo-Fenton process. Figure reproduced with permission from [194].

high reduction capacity of ZVMs led them to catalyze peroxides (e.g.,

H2O2, S2O2–
8 and HSO5) through electron transfer reactions and yield
–
•
OH and/or SO•–
4 as show in reactions (32) to (36) [197–200]. The
produced •OH and SO•– 4 attack the target pharmaceuticals and degrade
them into degradation products. The process is recyclable and the M2+
needed for catalytic decomposition of peroxides is regenerated by the
zerovalent metals following the reaction (37) [93,197,199].
0
M(s) 2+
+ H2 O + O2 →M(aq) + 2OH − (32)

2+
M(aq) 3+
+ H2 O2 →M(aq) +• OH+− OH (33)

2+
M(aq) + S2 O2−8 →M(aq)
3+
+ SO•−4 + SO2−4 (34)

2+
M(aq) 3+
+ HSO−5 →M(aq) + SO2−4 +• OH (35)

2+
M(aq) 3+
+ HSO−5 →M(aq) + SO•−4 +− OH (36)
Fig. 14. Treatment of pharmaceuticals contaminated waters by Fe0 in the
0
M(s) 3+
+ 2M(aq) 2+
→3M(aq) (37) presence of PS. Figure reproduced with permission from [201].

The use of zerovalent metals are found to be highly efficient in the

degradation of different pharmaceuticals mostly halogenated [93,197]. and 653.6 eV are due to the Mn2+ and Mn3+, respectively [93].
In the presence of peroxides, the reactive radicals produced by reactions The ZVMs are magnetic and easily recoverable which consequently
of zerovalent metals led to enhanced degradation of target pharma­ enable it for reuse in activating peroxides and degradation of pharma­
ceuticals [93,197,201]. Lumbaque et al. [201] studied the degradation ceuticals. The studies of reusability and stability of the ZVMs are con­
of pharmaceuticals contaminated waters in the presence of H2O2 and ducted and found the materials to be highly reusable with potential
S2O2–8 which showed successful formation of OH and SO4 and the later
• •–
degradation efficiency for several cycles as well as led into low (Fig. 16)
caused degradation of pharmaceuticals into transformation products leaching of metal ions [93,202].
(TPs). Fig. 14 illustrate the degradation of pharmaceuticals contami­
nated waters by zerovalent iron (Fe0)-catalyzed S2O2– 8 -based processes, i) Carbonaceous materials activated peroxides based AOPs
the yield of •OH and SO•– 4 and the degradation of pharmaceuticals by
these pharmaceuticals into TPs [201]. The increasing level of zerovalent The carbon-based materials, such as biochar are reported to be
metals and peroxides is reported to improve further the degradation efficient activators of peroxides (i.e., H2O2, S2O2– 8 and HSO5) and
–

efficiency [93,101]. consequently decompose them into reactive radicals, OH and SO•–
•
4
The zerovalent metals are produced by borohydride-based (BH–4) [100,203]. The possible reasons looked to be that these carbonaceous
chemical reduction method as illustrated in reaction (38) [199]. materials possess abundant functional groups with pi-electron and can
efficiently donate electrons [203]. The peroxides are reported to be
2+
M(aq) 0
+ 2BH4− + 6H2 O→M(s) + 2B(OH)3 + 7H 2 (38)
efficient electrons acceptors and consequently accept the electrons lost
by the carbonaceous materials. The use of these carbonaceous materials
The formation of the prepared ZVMs are verified by different charac­
are reported to be of significant importance due to their high surface
terization techniques. Fig. 15 illustrate the Fourier transform infrared
area, porous structure, high chemical and thermal stability, and low cost
spectroscopy (FTIR) and x-ray photoelectron spectroscopy (XPS) ana­
[204]. Besides, these materials are metals free and consequently render
lyses of the prepared zerovalent manganese (ZVMn) [93]. The FTIR
minimum chances of secondary pollution [205]. The doping of hetero­
results of the zerovalent manganese (ZVMn) illustrate peak due to Mn
atoms, such as nitrogen and oxygen-containing functional groups (e.g.,
bonding at a wavelength of 620 cm− 1 [93]. Similarly, the XPS spectra of
hydroxyl, carbonyl, and carboxyl) with abundant lone pair of electrons
the ZVMn is given in Fig. 15 in which the peak shown at a binding en­
promote the electron donating capability of the carbonaceous materials
ergy of 639.5 eV is due to the zerovalent manganese while that 645.2
and enhance the decomposition of H2O2 (HP), S2O2– 8 , (PS, PDS), and

14
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Fig. 15. FTIR and XPS analyses of ZVMn. Figure reproduced with permission from [93].

Fig. 16. Mechanistic pathways involved in the degradation of tetracycline by biochar-catalyzed peroxydisulfate. Figure reproduced from [208] which is open access
and permits use of contents under a Creative Commons license.

HSO–5 (PMS) [203]. Also, it is reported that the carbonaceous materials presence of HSO–5 and showed more than 80 % degradation in 15 min
(e.g., biochar, BP) adsorb the peroxides and the later are oxidized at the treatment time.
interface of the carbonaceous materials and water [203]. The enhanced Besides, the porous structure of these materials led to prompt
role of the carbonaceous materials effectively decomposes the peroxides interaction between the target pollutants and carbonaceous materials
and led to high-rate of formation of •OH and SO•– 4 which consequently which additionally enhance the removal of target pollutants [203]. The
led to high degradation of target contaminants. Different studies con­ porous nature of the carbonaceous materials is studied by porosity
ducted showed significant role of various carbonaceous materials meters, BET surface area analyzer. Zhang et al. [208] studied the
(doped and un-doped), such as activated carbon, biochar, multi-walled degradation of tetracycline by biochar-catalyzed peroxydisulfate based
carbon nanotubes, graphene oxide (GO)/reduced graphene oxide AOP and showed successful formation of reactive radicals which were
(rGO), and nitrogen-doped carbon fiber-aerogel etc. [203]. The study by verified by electron spin resonance (ESR) spectroscopy. The reactive
Huo et al. [206] synthesized nitrogen and sulfur co-doped porous carbon radicals participate in the degradation of tetracycline and caused its
and used for the oxidative degradation of tetracycline in the presence of degradation into several products.
S2O2–
4 with 100 % degradation efficiency in 60 min treatment time.
Similarly, other study conducted by Wu et al. [207] used magnetic j) Photocatalysis
nitrogen-doped carbon for the degradation of tetracycline in the

15
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Photocatalysts are heterogenous catalytic materials, such as titanium The activation of modified and un-modified TiO2 photocatalysts by
oxide (TiO2), zinc oxide (ZnO), and cerium oxide (CeO2) etc. which are light illumination, the yield of reactive radicals in the absence and
effectively used in degradation of different organic pollutants under UV, presence of peroxides is shown in Fig. 17.
solar, and visible light illumination [7,22,92,209–213]. The photo­ The metals and non-metals doping additionally promote the stability
catalytic materials are first synthesized using different approaches, such and reusability of the photocatalysts which enhance its potential prac­
as sol–gel, precipitation, microwave, and hydrothermal methods etc. tical applications and greenness and reduces treatment cost [7]. The
[7,214]. The prepared photocatalysts are characterized for studying FTIR analysis of used Fe and Ag doped ZnO used for photocatalytic
their physiochemical characteristics by different instruments, such as degradation of ibuprofen was compared with FTIR of fresh doped ZnO
FTIR, XRD, scanning electron microscope with energy dispersive x-ray and showed no changes (Fig. 18) [218]. The leaching of cerium ions in
spectroscopy (SEM-EDS), BET surface area analyzer, X-ray photoelec­ the prepared ceria and N-doped ceria in deep eutectic solvent (DES)
tron spectroscopy (XPS), and transmission electron microscopy (TEM). conducted in previous studies showed lower leaching of cerium ions by
Table 6 illustrate some of the characteristics, e.g., pore size, crystal size, the N-doped ceria [19]. Thus, doping promotes the reusability perfor­
pore volume, particle size, and BET surface area etc. of the prepared mance and physiological characteristics of photocatalysts.
TiO2, Fe0, and Fe0-doped TiO2 (Fe0/TiO2). The results show enhanced
characteristics of the doped TiO2 than un-doped. 5. Confirmation •OH and SO•–
4 formation and their involvement
The different studies on the use of different photocatalysts, such as in removal of pharmaceuticals
TiO2, ZnO, and CeO2 have achieved successful degradation of pharma­
ceuticals with enhanced removal efficiency [19,94,102,209]. Under The AOPs which rely on the in-situ formation of reactive radicals, e.
light illumination, the photocatalysts undergo activation and yield g., •OH and SO•– 4 , thus the yield of OH and SO4 in any AOPs and
• •–

conduction band electrons (e–cb) and valence band holes (h+ vb) as illus­ involvement of these reactive radicals in degradation of target pollutants
trated in reaction (39) [209]. The holes further react with water and give are analyzed by several studies. The most common among the various
•
OH as given in reactions (40) and (41) [209]. studies conducted include, radical trapping based on the analysis by
electron spin resonance spectroscopy (ESR), use of scavengers, and
Photocatalysts + hv→e−cb + h+ (39)
vb competition kinetics.
In the ESR analysis, the yield of •OH and SO•– 4 and other radicals in
h+ + •
vb + H2 O→H + OH (40)
the various AOPs are identified using radical trapping agents, e.g., 5,5-
dimethyl-1-pyrroline-N-oxide (DMPO) [208]. The DMPO form adduct
h+ − •
vb + OH → OH (41)
with the •OH and SO•– 4 which give signal in the ESR analysis. However,

In the presence of peroxides, H2O2, S2O2– in case of non-formation of the •OH and SO•– 4 , the adduct is not formed
8 and HSO5, the ecb produced
– –

attack the O-O bond of peroxides and decompose the later into •OH and and consequently no signals are observed. Guo et al [219] studied the
SO•– degradation of tetracycline by heterogenous catalyzed
4 as illustrated in reactions (42 to (45) [94,209,215].
peroxymonosulfate-based AOPs and concluded successful formation of
e−cb + H2 O2 →• OH + OH − (42) •
OH and SO•– 4 by the ESR study. Similarly, Zhang et al. [208] and Wang
et al. [220] used biochar-catalyzed peroxides-based processes for the
e−cb + HSO−5 →SO•−4 + OH − (43) degradation of pharmaceuticals and concluded successful formation of
reactive radicals through ESR analysis. Further, it was concluded that
e−cb + HSO−5 →SO2−4 +• OH (44) the reactive radicals facilitate degradation of target pollutants. The ESR
study showed no signals of DMPO-•OH and DMPO-SO•– 4 adduct when
e−cb + S2 O2−8 →SO2−4 + SO•−4 (45) only DMPO, activators and peroxides were used. However, sharp signals
were observed by the DMPO-•OH and DMPO-SO•– 4 adducts under the
The use of photocatalysts with peroxides is useful, it prevents the e–cb and
conditions of using both activators and peroxides (Fig. 19).
h+
vb recombination thus making hvb free for reaction and additionally
+
In the scavenger studies, different radical scavengers are used for
promote the yield of OH and SO•–
•
4 through reactions (42) to (45) identification of the resulting •OH and SO•– 4 in any AOPs. The most
[209,215]. One of the drawbacks of the metal oxide photocatalysts is
common scavengers used are alcoholic scavengers, such as isopropyl
that they are active mostly under UV irradiation due to their high band
alcohol (IPA) and tert-butyl alcohol (TBA) due to their higher second-
gap energy [209]. The band gap is lowered by doping the photocatalysts
order rate constants with •OH and SO•– 4 [42,221]. IPA is employed as
with metals and non-metals and consequently increase their efficiency
a scavenger of both •OH and SO•– 4 , i.e., (k•OH/IPA = 1.9 × 109 L/mol/s)
under solar and visible irradiations [209,211]. Khan et al. [212] pre­ 7
and (kSO•−4 /IPA = 8.2 × 10 L/mol/s), respectively, while TBA as the
pared TiO2 and N-TiO2 and showed lower band gap by N-TiO2 (i.e., 2.89
eV) than TiO2 (i.e., 3.23 eV) which suggest significant role of doping in scavenger of only •OH, i.e., (k•OH/TBA = 6.0 × 108 L/mol/s) [42,221].
reduction of the band gap of prepared photocatalysts. The doped pho­ The use of these alcoholic scavengers is reported to slow the reactivities
tocatalyst are found to facilitate removal of target contaminant [216]. of •OH and SO•– 4 with target contaminants [42]. The degradation of
And performance of the doped and un-doped photocatalysts are re­ clofibric acid by Bi/Cu0-catalyzed persulfate-based process in the pres­
ported to be further improved by coupling with peroxides [94,209]. Bibi ence of IPA and TBA is conducted and found to be significantly lower, i.
et al. [213] prepared zerovalent iron (Fe0) doped TiO2 and showed e., 34 and 47 % than that (85 %) in the absence of either of these alcohols
better performance than un-doped TiO2 and photocatalytic activity of as shown in Fig. 20 [42]. This was reported to be due to the competitive
the photocatalysts (both doped and un-doped) were found to be further effects caused by these alcohols with clofibric acid for reactive radicals.
improved by coupling with PMS. Further, experiments based on analysis of the second-order rate

Table 6
Different structural properties of TiO2 and N-doped TiO2. Reproduced from [212] which is open access and permits use of contents under a Creative Commons license.
Photocatalysts BET surfacearea Particle size (nm) Pore volume (cm3/g) Crystal size (nm) Porosity (%) D (1 0 1)(Å)
(m2/g)

TiO2 83.6 18.9 0.088 16.1 25.0 3.53

N-TiO2 131.8 12.0 0.140 10.9 34.7 3.52

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J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Fig. 17. TiO2 photocatalysts activated persulfate (PS and PMS). Figure reproduced with permission from [217].

Fig. 18. FTIR analysis of fresh and spent Fe and Ag doped ZnO. Figure reproduced with permission from [218].

constants of the pharmaceuticals with •OH and SO•– 4 are done using by •OH and SO•–
4 -based reactions are found and estimated the pathways
competition kinetics. In these experiments, competitors having known from the analysis of degradation patterns of the target pharmaceuticals
rate constants with •OH and SO•–4 are used [198,222]. The degradation and the resulting degradation products identification by mass spec­
of pharmaceuticals is performed by the AOPs in the presence of these trometry analysis as shown in Table 7 [40].
competitors and estimated the second-rate constants of •OH and SO•– 4
with the target pharmaceuticals. The second-order rate constants of 6. Factors affecting the functions of AOPs
various pharmaceuticals, e.g., CFA, tetracycline, and ciprofloxacin with
•
OH and SO•–
4 are estimated by these competition kinetic studies and The performance of the different AOPs have been found to be
found to show high second-order rate constants [42,168,198,222]. The affected by different factors, the most common in these include, pH,
high second order rate constants depict significant contribution of the concentration of peroxides, concentration of catalyst, concentration of
•
OH and SO•–
4 in the degradation of pharmaceuticals. contaminant, and inorganic ions.
The degradation pathways of different pharmaceuticals degradation

17
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Table 7
Degradation mechanism of different pharmaceuticals by •OH and SO•–
4 . Repro­
duced from [40] which is open access and permits use of contents under a
Creative Commons license.
Pharmaceuticals AOPs ROS Reaction mechanism References

Carbamazepine Gamma/PS •
OH Electron transfer [223]
and and hydroxylation of
SO•–
4 the aromatic rings
Chloramphenicol UV/PS •
OH Direct photolysis, [224]
and Hydrogen
SO•–
4 abstraction, Electron
transfer
Ciprofloxacin ɣ- SO•–
4 Oxidation of the [225]
Fe2O3–MnO2/ piperazine ring
PMS
Ciprofloxacin Biochar/PS •
OH Ring-opening [226]
and
SO4•–
Tetracycline US/PS •
OH Hydrogen [227]
and abstraction, Loss of
SO•–
4 methyl group, Loss
of amine group
Sulfamethoxazole Graphene/PS •
OH Ring-opening [228]
and
SO4•–
Fig. 19. ESR analysis of the biochar-catalyzed PMS. Figure reproduced with Tetracycline Fe3O4-doped •
OH Oxidation of double [229]
permission from [220]. biochar/PS and bonds and aromatic
SO•–
4 ring
Tetracycline UV/PMS •
OH Hydrogen [230]
abstraction,
hydroxyl addition
and electron transfer
Sulfamethoxazole Fe3O4/PS SO•–
4 Electron transfer, [231]
Ciprofloxacin •
OH ring-opening
and
SO•–
4
Sulfadiazine US-Fe0/PS SO•–
4 Hydrogen [124]
abstraction,
Oxidation of amine
group in the benzene
ring, Cleavage of
C–N bonds in the
heterocyclic ring,
Heterocyclic ring
opening,
Hydroxylation,
Cleavage of S–N
bond

degradation trend. The highest degradation was observed at pH of 9. In

the case of UV/PS process, the highest degradation efficiency and
Fig. 20. Use of IPA and TBA as a scavenger to verify formation of •OH and degradation rate constant was achieved at pH 9. AT high pH, PS exhibit
SO•–
4 . Figure reproduced from [42] which is open access and permits use of
high molar absorptivity and consequently led to high rate of formation
contents under a Creative Commons license. of •OH and SO•– 4 [222]. In addition, the deprotonated forms of TC
possess high density of electrons which consequently enhance the rate of
6.1. pH decomposition of PS [222]. The pH influences the redox potential of the
•
OH and SO•–
4 as well as the yield of the later which consequently could

pH is important factor which is reported to greatly influence the rate affect the degradation of target contaminants [232]. At high pH, the
of formation and reactivities of •OH and SO•– SO•–
4 reacts with OH and yield OH as given in reaction (46).
– •
4 [42,193,200]. The change
in pH affect the apparent charge on the target pollutant and conse­ SO•−4 +− OH→SO2−4 +• OH (46)
quently it is found in different ionic forms in aqueous solution which
consequently undergo different reactions with the catalyst, peroxides, In the case of photocatalytic reactions, the high pH promotes the
and reactive radicals [222]. Xu et al. [222] studied the degradation of yield of •OH as shown in reaction (41). Shah et al. [209] studied the
tetracycline (TC) by UV/PS at different pH, i.e., 5, 6, 7, 8, and 9 and degradation of norfloxacin by BiFe-ZnO catalyzed HSO=-based AOPs
found that TC exists in different ionic forms, i.e., protonated form and achieved maximum removal efficiency at slightly basic pH (pH 8.0).
(TCH+ 3 ) at pH < 5, neutral (TCH2) at pH = 6, and deprotonated, TCH
– The removal of norfloxacin was low at pH 2.0 and pH 11.0. The possible
and TC–2 at pH > 8 and pH > 9, respectively a shown in Fig. 21a. This reasons were reported to be repulsion between HSO=, norfloxacin, and
different distribution of TC in aqueous solution is due to its different pKa the catalyst as they exhibit identical charges at lower and higher pH
values. The different forms undergo different reactions with UV light conditions. However, high pH is reported to inhibit the yield of •OH and
2+
and the reactive radicals in UV/PS as shown in Fig. 21b. In the case of SO•–
4 in some cases as in Fenton reaction where Fe forms complex
UV condition only, the different ionic forms of TC exhibit different ab­ which consequently lower the availability of Fe2+ for the decomposition
sorption intensities and quantum yield and consequently show different of peroxides [190]. In the case of Fenton and Fenton-like reactions, the

18
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Fig. 21. Effects of pH on the distribution of TC (a) and degradation of TC by UV and UV/PS (b). Figures reproduced with permission from [222].

catalytic activity of Fe2+ and decomposition of peroxides is promoted at It is also shown that both UV/H2O2– and UV/PS-based AOPs resulted
acidic and lower at highly basic pH [95,190]. However, it is reported into higher degradation rate constants and degradation efficiency than
that at very low pH, formation of oxonium ion, possibly of bonding with UV only condition (i.e., absence of H2O2 and PS). The degradation of
O-O bond of peroxides and scavenging of the reactive radicals by ciprofloxacin by UV-C/Fe2+/HSO–5 at different concentrations of HSO–5
hydrogen ion occur which inhibit the removal efficiency of target showed high degradation of ciprofloxacin (i.e., 98 %) at a HSO–5 dose of
contaminant [95]. In the case of degradation of ciprofloxacin by zer­ 80 ppm compared to 67 % at 15 ppm of HSO–5 under identical experi­
ovalent manganese catalyzed S2O2= 8 -based AOPs, the degradation effi­ mental conditions [95]. Wang et al. [233] studied the degradation of
ciency was maximum (i.e., 95 %) at pH 2.0 while least, i.e., 27 % at pH ciprofloxacin by cobalt manganese oxide-catalyzed H2O2 and found
11.0 [93]. The pKa values of target contaminant and point of zero charge facilitated degradation with increasing H2O2 concentrations up to 68
of the catalysts which consequently influence the apparent charge at a mg/L and degradation was found to be 81 % at 68 mg/L H2O2 con­
given pH is also reported to influence the degradation of target con­ centration. However, it was found that further increase in H2O2 con­
taminants [93,95]. centrations beyond 68 mg/L inhibited removal efficiency of
ciprofloxacin and was found to be 64 % at 136 mg/L [233]. The
6.2. Concentrations of peroxides inhibited removal efficiency of ciprofloxacin at very high concentrations
of H2O2 was reported due to sacrificial effects of the peroxide towards
Peroxides, H2O2, S2O2–8 , and HSO5 act as a precursor of OH and SO4 OH caused by their high reactivities [233]. The degradation of sulfa­
– • •– •

under activation by irradiations and catalysts, thus increasing concen­ methazine and trimethoprim by gamma irradiation in the presence of
trations of peroxides is reported to promote the rate of formation of •OH different concentrations of H2O2 and PS were studied and showed
and SO•–4 [93,95,152,157]. The removal of different pharmaceuticals is facilitated degradation at high concentrations of peroxides than that at
studied at different concentrations of peroxides, H2O2, S2O2–8 , and HSO5
– lower concentration [162,163].
and the increasing dose of the later are found to facilitate removal ef­
ficiency of target contaminants [93,95,108,157,209]. Acosta-Rangel 6.3. Concentrations of catalysts
et al. [157] studied the degradation efficiency and degradation rate
constants of sulfonamide, sulfamethazine (SMZ) by UV/H2O2– and UV/ The catalysts act as an activator of peroxides in the catalytic
PS-based AOPs at different concentrations of H2O2 and PS, i.e., 1.47 and reactions-based AOPs cand is reported to facilitate the rate of formation
4.0 M. The results shown in Table 8 depict higher degradation efficiency of reactive radicals and consequently degradation of target contaminant
and degradation rate constant of sulfonamide at 4.0 M of H2O2 and PS [42,95,209]. In the case of photocatalysis-based AOPs in which light
than at 1.47 M. activation yield reactive radicals from the activation of photocatalysts
via e–cb and h+
vb generation is also reported to facilitate rate of formation
Table 8 of reactive radicals and consequently degradation of target contami­
Effects of H2O2 and PS concentrations on the degradation efficiency and nants [7,102]. Different studies conducted on the degradation of phar­
degradation rate constants of sulfamethazine reproduced with permission from maceuticals by catalysts based AOPs is reported to expedite removal
[157]. efficiency of target pharmaceuticals at high concentration of catalysts as
[Peroxide]0 [SMZ]0 Time Degradation rate % shown in Fig. 22 [19,42,95,102]. The reasons reported are the increase
(minutes) Constant (k, M–1 Degradation in rate of formation of reactive radicals at high concentration of the
s–1) catalysts [42,95,102]. However, it is reported that the catalysts pose
[H2O2]0 = 0 M 15 mg/ 60 - 77 dominant effects up to the optimal concentrations and beyond that led to
L inhibited removal efficiency of target contaminants [234].
[H2O2]0 = 1.47 × 15 mg/ 60 6.20 × 104 89 The reasons for the inhibited removal efficiency of target pollutants
104 M L
beyond the optimal concentration of catalysts is reported to inhibit light
[H2O2]0 = 4.0 × 15 mg/ 60 12.27 × 104 100
104 M L penetration, increased particles agglomeration, high light scattering,
[PS]0 = 0 M 15 mg/ 60 - 77 lower rate of e–cb and h+
vb formation, and scavenging of reactive radicals
L [234].
[PS]0 = 1.47 × 15 mg/ 60 4.42 × 104 80
104 M L
[PS]0 = 4.0 × 104 15 mg/ 60 12.89 × 104 100
M L

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J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

6.5. Inorganic anions

Inorganic anions are common constituents of natural water and some

are reported to react fast with •OH and SO•–
4 due to their high reactivities
as given in reactions (47) and (57) [93,95].
•
OH + NO−2 → − OH + NO2 • (k47 = 8.0 × 109 M− 1 s− 1 ) (47)

SO•−4 + NO−2 →SO2−4 + NO•2 (k48 = 8.8 × 108 M− 1 s− 1 ) (48)

•
OH + CO2−3 → − OH + CO3 •− (k49 = 4.0 × 108 M− 1 s− 1 ) (49)

SO4•− + CO2−3 →SO2−4 + CO•−3 (k50 = 4.1 × 106 M− 1 s− 1 ) (50)

Fig. 22. Degradation of ciprofloxacin by UV-C/PMS/Fe2+ at different concen­
trations of Fe2+ (A) Degradation of flumequine at different dose of N-doped •
OH + HCO−3 →CO•−3 + H2 O (k51 = 8.5 × 106 M− 1 s− 1 ) (51)
Ceria (B). Figure (A) and (B) reproduced with permission from [95] and [19],
respectively.
SO•−4 + HCO−3 →SO2−4 + CO•−3 + H + (k52 = 3.5 × 106 M− 1 s− 1 ) (52)

6.4. Concentrations of contaminants SO•−4 + NO−3 →SO2−4 + NO•3 (k53 = 5.0 × 104 M− 1 s− 1 ) (53)

The AOPs have been used to treat different concentrations of phar­ OH • + Cl− →ClOH •− (k54 = 4.3 × 109 M− 1 s− 1 ) (54)
maceuticals contaminants with an aim to optimize the selected AOPs for
efficient degradation of target pollutants at different concentrations SO•−4 + Cl− →Cl• + SO2−4 (k55 = 2.6 × 108 M− 1 s− 1 ) (55)
[95,102,209]. The results obtained showed that the •OH and SO•– 4 -based
removal of the target contaminant led to lower removal efficiency at SO2−4 + • OH→SO•−4 +− OH (k56 = 3.5 × 105 M− 1 s− 1 ) (56)
high concentration of the target contaminant than its lower concentra­
tion as shown in Fig. 23 [95]. The possible reasons are reported to be SO2−4 + SO•−4 →S2 O2−8 + e−aq (57)
that at high concentration of target contaminant, greater number of
molecules react with •OH and SO•– 4 than that at lower concentration Thus, presence of such inorganic ions is reported to compete strongly
[95]. This led to lowering in ratio of the •OH and SO•– 4 to with target with target contaminants and consequently influence the removal of
contaminant at high concentration than at lower concentration. Other target contaminants [93,95,221]. The degradation of different phar­
possible reasons found are that at high concentration, the concentration maceuticals, e.g., clofibric acid, norfloxacin, and ciprofloxacin is con­
of degradation products are expected to increase which consequently ducted by different AOPs in the presence of different inorganic anions
could led to high competition with target contaminants for reactive and the results obtained are found to show inhibited effects by some of
radicals and vice versa [95]. the anions [42,93,95,209].
Also, the high concentration of target contaminants is expected to Table 9 depicts the detailed effects of different inorganic ions, e.g.,
increase turbidity of the reacting solution which subsequently led to Cl–, HCO–, 2–
3 NO3, and SO4 on the degradation of different pharmaceuti­
–

decrease the penetration of light [95,152]. The reduced light penetra­ cals by different AOPs. The different anions are found to exhibit different
tion is reported to retard the activation of peroxides and catalysts and effects. The chloride ion is found to show dual functions, inhibit some­
consequently inhibit rate for formation of reactive radicals [152]. time, however, in some case it facilitates the degradation [40]. The
negative effects caused is due to the scavenging of the reactive radicals
by Cl–, formation of less reactive radicals, and inhibited adsorption of the
peroxides on the surface of the catalyst [40]. The positive impact caused
is possibly due to the activation of peroxides, PS and PMS by Cl–,
involvement of the chlorine radical in the degradation of pollutants and
the yield of •OH and SO•– 4 by reaction with water. The NO3 is found to
–

show no effect in some cased which could be due to its lower reactivities
with reactive radicals, however, in some cases it facilitated the degra­
dation which is possibly doe to its sensitization effect [144,184,221].
Similarly, the SO2–
4 is found to react slow with reactive radicals and yield
highly reactive, hydrated electron causes negligible ort smaller effect at
lower concentration. The positive impact caused by carbonate and/or
bicarbonate is found either due to decomposition of peroxides and for­
mation of carbonate radical [40,221].

7. Toxicity evaluation

One of the key points in suggesting any treatment technology is to be

environmentally friend and should not release secondary pollution. The
AOPs are reported to mainly eliminate the biological activity of target
contaminants and result into the formation of non-toxic and/or less toxic
products [12,44]. However, some degradation products evolved form
AOPs-based degradation of pharmaceuticals are reported to be toxic
[209]. Thus, it is highly essential to estimate step-by-step toxicity of
Fig. 23. Degradation of ciprofloxacin at its different concentration using UV-C/ contaminated water before and after treatment with proposed AOPs and
PMS/Fe2+ process. Figure reproduced with permission from [95]. propose guidelines for future researchers.

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J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Table 9
Degradation of different pharmaceuticals by different AOPs in the presence of different anions. Reproduced from [40] which is open access and permits use of contents
under a Creative Commons license.
Pharmaceuticals AOPs type Radical species Effects of anions
Cl– HCO–3 NO–3 SO2–
4 References

Ciprofloxacin Magnetic ɣ-Fe2O3–MnO2/PMS •

OH and SO•–
4 H (–) H (–) H (–) H (–) [225]
Tetracycline UV/PS •
OH and SO•–
4 H (–) (–) (–) (–) [235]
Norfloxacin AC-based CoFe2O4-SAC •
OH and SO•–
4 L (–), H (+) L (+), H (–) No effect – [236]
Nanocomposites/PMS
Tetracycline US/PS •
OH and SO•–
4 L (–) L (–) – – [227]
Erythromycin Gamma/PS •
OH and SO•–
4 H (–), L (–) H (–), L (–) H (–), L (–) H (+) [237]
Fluconazole Heat/PS •
OH and SO•–
4 H (–) H (–) – – [238]
Ciprofloxacin and Sulfamethoxazole Ferrous/PS •
OH and SO•–
4 – No effect – – [231]
Tetracycline Magnetic Ag/AgCl/modified •
OH and SO•–
4 H (–) – – – [239]
zeolite X/ PS
Oxytetracycline UV/PS •
OH and SO•–
4 H (–), L (–) H (+) No effect No effect [240]
Chloramphenicol Heat/PS •
OH and SO•–
4 H (–) H (–) No effect – [241]
Chloramphenicol UV/PS •
OH and SO•–
4 H (–), L (+) H (–) H (–) H (–) [224]
Cefixime UV/PMS •
OH and SO•–
4 – – – L (–) [242]

H-high concentration, L-low concentration, (+)–positive effect, (–)-negative effect.

Different techniques are used to measure the toxicity of different ion is non-toxic which suggest high usefulness of the AOPs in the
pollutants in wastewater before and after treatment. One such useful treatment of organic pollutants.
program is based on computer-based toxicity prediction, called as However, in some AOPs, the degradation products formed also show
Ecological Structure Activity Relationship (ECOSAR) program which significant toxicity. Jing et al. [98] conducted the degradation of
estimate toxicity of target contaminants and its DPs towards three ibuprofen (IBP) by three different AOPs, e.g., UV, O3, and UV/O3-based
different aquatic organisms, such as fish, daphnia, and green algae AOPs and evaluated toxicities of IBP and the resulting degradation
[209,243]. The ECOSAR is used to estimate the toxicities, i.e., acute and products at three different indexes, e.g., oral rat LD50, bioaccumulation,
chronic toxicities in the unit of mg/L of different contaminants based on and development toxicity using the United State Environmental Pro­
the European and Chinese hazard evaluation criteria as discussed in tection Agency (US EPA) Toxicity Estimating Software Tool. The results
previous studies [42,209,243]. The contaminants with lower acute and of the toxicity estimation of IBP degradation products by the different
chronic toxicities are assigned high toxicity while that with high acute AOPs at three different indexes are shown in Fig. 24(a to i). In the UV-
and chronic toxicities values are marked to be non-toxic [243]. The based AOPs process, the three toxicities of two products, P1 and P3
toxicities of different pharmaceuticals and its degradation products in are show in Fig. 24 (a to c) at three different indexes. The development
different AOPs is estimated by ECOSAR and the results obtained show toxicity of both P1 and P3 was higher than 0.5 which imply these
different toxicities exhibited by the degradation products with mostly products to be harmful to development [98]. The results in Fig. 24(d to
found as non-toxic [42,93,95,209]. Table 10 depicts the acute and e) illustrate more products of IBP in O3-based AOPs with decreased
chronic toxicities investigation of norfloxacin (NOR) and its products by bioaccumulation and development toxicities, however, many still
ECOSAR which depicts different toxicity levels of the products. The exhibited high development toxicities (Fig. 24e). The oral rat LD50
toxicities values are represented in color to identify toxicities level, blue values of the three products of IBP from O3-based AOPs, P7, P20, and
color (non-toxic), yellow color (harmful), and pink color (toxic). The end P21 were found to be lower than IBP (Fig. 24f) which suggest these
product of NOR degradation, labelled as TP15 and found to be acetate products to be more harmful. The products produced from the UV/O3-

Table 10
Acute and chronic toxicities estimation of norfloxacin degradation. Reproduced with permission from [209].

21
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Fig. 24. Study of the bioaccumulation (a to c), development toxicities (d to f), and oral rat LD50 (g to i) of IBP and its products at three different AOPs, UV, O3, and
UV/O3. Figure reproduced with permission from [98].

based AOPs showed smaller bioaccumulation feature (Fig. 24g) but antibiotic. The FOS contaminated waters were then treated with per­
some of them exhibited development toxicities (Fig. 24h) and lower oral sulfate (PS) and UV/PS processes using 20 µM of PS concentration and
rat LD50 values (Fig. 24i). the results obtained are shown in Fig. 25(b and c). In the case of treat­
In another study conducted by Wu et al. [244], the biological toxicity ment with PS only, the FOS contaminated waters containing 10 and 100
tests based on the use of E. coli was used to estimate toxicities of Fos­ µM of FOS showed identical bacterial inactivation compared to control
fomycin (FOS) and its degradation products. Fig. 25a depicts the sur­ (absence of PS). However, in the case of treatment with UV/PS pro­
vival curve of E. coli exposed to different concentrations of FOS, i.e., 0 to cesses, the toxicity of FOS contaminated waters containing both 10 µM
500 µM. The results showed significant effect of FOS on the inactivation and 100 µM of FOS was significantly reduced (Fig. 25b and 25c). In the
of E. coli and showed 80 % inactivation within only 8 h exposure time case of UV/PS process, the survival rate of E-coli exposed to both 10 and
(Fig. 25a). The inactivation of E. coli was found to be increased with 100 µM of FOS significantly increased even at lower treatment times, i.
increasing FOS concentrations. The high inactivation of E. coli caused by e., 2 and 5 min (Fig. 25b and 25c). This showed that FOS solutions
FOS even at lower concentration suggest significant toxicity of the treated with UV/PS-based AOPs led to fast degradation of FOS and

22
J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Fenton process to be more competitive than ozonation. It has been re­

ported that treatment of contaminants with AOPs at basic pH requires
more cost [194]. In the case of sonication based AOPs, the total cost
calculated is a function of capital, operational, and maintenance costs
[121]. Table 11 depicts the cost of different AOPs for treating pharma­
ceuticals wastewater.

9. Conclusions and final recommendations

Water resources were found to be severely contaminated with

different pharmaceuticals with concentration mostly exceeding the
acceptable level. The continuous and large-scale contamination of
pharmaceuticals find conventional technologies inefficient for their
treatment. The pharmaceuticals contaminated waters were found to be
successfully treated with advanced oxidation processes. The AOPs were
found to yield highly reactive •OH and SO•– 4 which reacted fast with
Fig. 25. Study of the sterilization of E.coli exposed to different concentrations
pharmaceuticals and causes their efficient degradation into different
of FOS for different times (a), study of the sterilization of E.coli exposed 10 µM
of FOS and treated with PS and UV/PS processes for different times at 20 µM of
degradation products. The peroxides, H2O2, S2O2– 8 , and HSO5 were
–

PS (b), study of the sterilization of E.coli exposed 100 µM of FOS and treated found to be used as a precursor of OH and SO4 under different acti­
• •–

with PS and UV/PS processes for different times at 20 µM of PS (c). Figure vation. The rate of formation of •OH and SO•– 4 were found to be influ­
reproduced with permission from [244]. enced by the concentrations of peroxides and activators. The use •OH
and SO•– 4 scavengers retarded their reactivities with target pharmaceu­
results into formation of mostly degradation products in solution which ticals. The •OH and SO•–4 were found to react with target pharmaceuti­
exhibited lower toxicity. cals through different pathways which subsequently caused their
degradation into degradation products. The AOPs were found to form
8. Cost evaluation less toxic and/or non-toxic end products. The degradation efficiency of
pharmaceuticals by the AOPs were influenced by pH of aqueous solu­
The cost of any AOPs is essential to be estimated to suggest its po­ tion, concentration of target contaminants, and common inorganic an­
tential practical applications for large-scale treatment of any target ions. The cost of the AOPs were found to be highly dependent on the
contaminant. The cost of any AOPs used for treatment of pollutants is nature and concentration of pollutants as well as properties of the
found to increase significantly when studying mineralization of the treated water. In addition to these facts, the following efforts needed to
selected pollutants [22]. Thus, it is highly useful to estimate the cost of be considered for effective and successful implementation of any AOPs
any AOPs used for efficient treatment and mineralization of toxic pol­ in treatment of pharmaceuticals contaminated water:
lutants. The total cost of the AOPs is calculated from the cost of chem­
icals and reagent used, electricity, labor, and waste disposal [22,101]. 1. Establish approaches for analyzing the toxicities of real wastewater
One of the costs calculated for AOPs-based degradation of different discharged from pharmaceutical industries and hospitals.
pollutants is electrical energy per order (EEO, kWh/m3/order) which is 2. Avoid unnecessary expenses in terms of time, facilities, and reagents,
calculated using equation (58) [245,246]. AOPs should be integrated with other treatments and only with
specific and clearly defined goals (i.e., the removal of recalcitrant
EEO =
Pt
(58) (micro)pollutants, the polishing of previously treated effluents, etc.).
V Furthermore, synergistic effects between processes should be studied
In Eq. (58), the terms P = power in kW, t is exposure time in h, and V at least at the pilot-scale.
is volume of the treated solution in m3. The EEO value is widely used to 3. Establish AOPs with lower energy cost in term of precursor materials,
compare the economic cost of different AOPs in treatment of wide-range energy, labor, and installation. Efforts are needed to utilize renew­
organic pollutants. For example, Paredes et al. [245] performed the able energy and precursor sources in the different energy and
photocatalytic and photolytic degradation of different pollutants and chemicals driven AOPs.
calculated the EEO values which were found to be 33 to 58 kWh/m3 and 4. Minimize the sludge formation in the different AOPs and find
49 to 79 kWh/m3, respectively. The EEO values depends on different different possible alternatives for the valorization of waste or sludge
factors, the most common include quality of water and properties of the formed.
target contaminant [246]. In photocatalytic degradation suing UV/TiO2, 5. In the catalytic-based AOPs, the materials prepared should be stable,
the cost of electrical energy per order is related to commercial lamps. In reusable, and environmentally friendly. Efforts are needed to prepare
other studies, the electrical energy cost for cost of energy per order is materials that undergo no physiological and chemical changes and
calculated for degradation of different pollutants using AOPs. For led to high treatment efficiency after use for several cyclic treat­
example, Miklos et al. [178] studied the degradation of mixture of ments. The materials should show sound stability and led to lower
different organic contaminants by UV/H2O2 and calculated the elec­ leaching into reacting solutions.
trical energy cost which was 1.08–2.84 kWh/m3. Lee et al. [174] 6. The wastewater discharged from different sources could contain
calculated the cost for ibuprofen degradation by ultrasound mediated mixture of different pharmaceuticals, thus, efforts are needed to
oxidants process which was 41.8 $/m3 per order of 263.5 kWh/m3. The investigated the performance of AOPs in treating water resources
cost associated with different AOPs for the treatment of wastewater in containing more than one pharmaceuticals.
the previous study are reported as H2O2 = 500 $/ton, sodium persulfate 7. To integrate the different processes with an aim to overcome the
= 1400 $/ton, 1100 $/ton for ZnO, and 1900 $/ton for TiO2 [247]. limitations caused by single pretreatment technology.
Similarly, Rizzo et al. [248] investigated degradation of different
emerging contaminants using solar photo-Fenton process and calculated CRediT authorship contribution statement
the cost for 90 % and 98 % removal which were found to be 0.188 €/m3
and 0.358 €/m3, respectively. The lower cost suggested the solar photo- Jibran Iqbal: Writing – original draft, Funding acquisition,
Conceptualization. Noor S. Shah: Writing – original draft, Visualization.

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J. Iqbal et al. Separation and Purification Technology 347 (2024) 127458

Table 11
Comparison of EEO values for degradation of pharmaceuticals by some AOPs. (– means not reported). Reproduced with permission from [249].
Pharmaceuticals AOPs [Oxidant]0 Removal (%) EEOUV (kWh/m3) EEOoxidant (kWh/m3) EEO (kWh/m3) References

Capecitabine (20 mg/L) UV/H2O2 0.1 mM 99 41.20 0.11 41.30 [250]

0.2 mM 99 10.90 0.23 11.10
0.5 mM 99 3.90 0.6 4.50
1.0 mM 99 2.00 1.10 3.10

Capecitabine (20 mg/L) O3 250 mg/h 99 – 1.8 1.8 [250]

500 mg/h 99 – 2.0 2.0

Carbamazepine (1 to 10 mg/L) UV/PMS 0.1 to 0.6 mM 100 0.30 to 2.53 0.02 to 0.08 0.38 to 2.55 [251]

Iopamidol (10 µM) UV 100 2.30 0 2.30 [252]

Atenolol (10 mg/L) UV/H2O2 10 mM 100 – – 4.24 [253]

UV/PDS 1.0 mM 100 – – 13.03
UV/H2O2/Fe2+ 10 mM/0.1 mM 100 2.56
UV/TiO2 1.0 g/L 100 – – 1.21

Ibuprofen (10 mg/L) UV/H2O2 10 mM 100 – – 2.36 [253]

UV/PDS 1.0 mM 100 – – 3.33
UV/H2O2/Fe2+ 10 mM/0.1 mM 100 – – 0.25
UV/TiO2 1.0 g/L 100 – – 3.18

Loperamde (10 mg/L) UV/H2O2 10 mM 100 – – 1.76 [253]

UV/PDS 1.0 mM 100 – – 1.94
UV/H2O2/Fe2+ 10 mM/0.1 mM 100 – – 0.28
UV/TiO2 1.0 g/L 100 – – 1.18

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