Science of the Total Environment 780 (2021) 146608

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Science of the Total Environment

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

Removal of ibuprofen from aqueous media by adsorption: A

comprehensive review
Stephen N. Oba a, Joshua O. Ighalo a,b, Chukwunonso O. Aniagor a, Chinenye Adaobi Igwegbe a,⁎
a
Department of Chemical Engineering, Nnamdi Azikiwe University, P. M. B. 5025, Awka, Nigeria
b
Department of Chemical Engineering, University of Ilorin, P. M. B. 1515, Ilorin, Nigeria

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

• The empirical findings on the adsorp-

tion of IBP were reviewed
• Carbon-based adsorbents are the best
class for the uptake of IBP
• The highest reported adsorption capac-
ity for IBP is 496.1 mg/g by SWCNTs
• Mechanism of uptake was also reviewed.

a r t i c l e i n f o a b s t r a c t

Article history: Ibuprofen (IBP) is a non-steroidal anti-inflammatory drug released into the environment through hospital and
Received 7 January 2021 medical effluents, pharmaceutical wastewater and veterinary use. The aim of this paper is to review the empirical
Received in revised form 11 March 2021 findings on the adsorption of IBP from aqueous media. A preliminary ecotoxicological assessment confirmed the
Accepted 16 March 2021
environmental risk of IBP in the aqueous environment. Open literature works considered in this review were for
Available online 19 March 2021
the past decade (2010−2020). Carbon-based adsorbents are the best class of adsorbent for the uptake of IBP and
Editor: Dimitra A Lambropoulou the highest reported maximum adsorption capacity (qmax) for IBP is 496.1 mg/g by SWCNTs. The range of adsorp-
tion capacities for IBP uptake in this review is between 0.0496 and 496.1 mg/g. The mechanism of uptake is ma-
jorly by hydrophobic interactions, π – π stacking, hydrogen bonds, electrostatic interactions and dipole-dipole
Keywords: interaction. IBP uptake was best fit to a wide variety of isotherm models but was well suited to the pseudo-
Adsorption second order kinetics model. The thermodynamics of IBP uptake depends majorly on the nature of the adsorbent
Biosorption and desorption from the solid phase is based on an appropriate choice of the eluent. Knowledge gaps were ob-
Environmental pollution served in used adsorbent disposal and process improvement. In the future, interest would increase in scale-up,
Ibuprofen
industrial applications and practical utilisation of the research findings which would help in sustainable water re-
Water treatment
source management.
© 2021 Elsevier B.V. All rights reserved.

Abbreviations: AC, Activated carbon; AOPs, Advanced oxidation processes; BDST, Bed-depth service time; BOD, Biochemical oxygen demand; BSA, Bovine serum albumin; DFT, Density
functional theory; CNT, Carbon nanotubes; COD, Chemical oxygen demand; FA, Fulvic acid; GA, Gallic acid; GAB, Guggenheim–Anderson–de Boer model; HA, Humic acid; IBP, Ibuprofen;
IUPAC, International union of pure and applied chemistry; Log Kow, Octanol-water partition coefficient; MIEX, Magnetic ion-exchange resin; MIP, Molecularly imprinted polymer; MOF,
Metal organic frameworks; MWCNT, Multi-walled carbon nanotubes; NOM, Natural organic matter; NSAID, Non-steroidal anti-inflammatory drug; pKa, Acid dissociation constant;
SWCNT, Single-walled carbon nanotubes; TA, Tannic acid; TOC, Total organic carbon.
⁎ Corresponding author.
E-mail addresses: sn.oba@unizik.edu.ng (S.N. Oba), jo.ighalo@unizik.edu.ng (J.O. Ighalo), co.aniagor@unizik.edu.ng (C.O. Aniagor), ca.igwegbe@unizik.edu.ng (C.A. Igwegbe).

https://doi.org/10.1016/j.scitotenv.2021.146608
0048-9697/© 2021 Elsevier B.V. All rights reserved.
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al. Science of the Total Environment 780 (2021) 146608

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Ecotoxicology of IBP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Overview of mitigation strategies for IBP uptake . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4. Adsorbent performance for IBP uptake . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5. IBP adsorption mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.1. Generalised IBP adsorption mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.2. Mechanism of IBP adsorption regarding adsorbent surface functional groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
6. Equilibrium isotherm and kinetics modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
6.1. Isotherm modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
6.2. Kinetic modelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
7. Thermodynamics modelling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
8. Desorption and reusability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
9. Competitive adsorption studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
10. Column adsorption studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
11. Adsorption modelling by computational strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
12. Knowledge gap and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
13. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Funding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Compliance with ethical standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Declaration of competing interest. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

1. Introduction In a bid to achieve environmental sustainability, environmental en-

Due to changing lifestyle patterns, emerging contaminants in water
have now become a serious environmental issue (Stuart et al., 2012;
Bolong et al., 2009). These emerging contaminants include herbicides
and pesticides (Cosgrove et al., 2019; Ighalo et al., 2021a), personal
care products (Kaur et al., 2018), endocrine disruptors (Tijani et al.,
2016), micro-plastics (Wu et al., 2018a) and pharmaceuticals (Yang
et al., 2017). There is a need for the protection of the environment due
to these new pollutants arising from human pollution growth and its re-
sultant lifestyle changes (Ighalo et al., 2020a; Ighalo et al., 2021b).
Ibuprofen (IBP) is a colourless, crystalline solid with a characteristic
odour (De Oliveira et al., 2019). More details of its properties are given
in Table 1 and its general chemical structure is shown in Fig. 1. It is a
non-steroidal anti-inflammatory drug (NSAID) (Bancos et al., 2009)
used in the treatment of fever, muscle pain and inflammation
(Rainsford, 2009). Ibuprofen was discovered by Stewart Adams in
1961 (Halford et al., 2012) and it remains one of the most prescribed
NSAID in contemporary times (Gaffar et al., 2020).
Based on carefully monitoring and assessment of water, re-
searchers can now identify the sources of pollution of certain con-
taminant species (Ighalo and Adeniyi, 2020a; Ighalo et al., 2021c).
NSAID usually appear in the environment in ng/L and μg/L concen-
trations and can possess negative ecotoxicological effects even at
these levels (Davarnejad et al., 2018). Due to their wide use in clini-
cal practice and in agriculture, NSAID like IBP is very common in the
aqueous environment and has been also been regularly occurring be-
cause of their stability and hydrophilicity (Ahmed, 2017). IBP, like
other pharmaceutically active compounds, gets into the environ-
ment through hospital and medical effluents (Caicedo et al., 2020),
pharmaceutical wastewater (Davarnejad et al., 2018) and veterinary
use (Han et al., 2020). IBP at a relatively higher concentration levels
than other pharmaceuticals in WTP effluents (Balakrishna et al.,
2017) (albeit in India). In fact, in estuaries globally, IBP has one of
the highest concentration which was around 18–6297 ng/L
(Letsinger et al., 2019). These suggest a serious threat to the flora
and fauna of the environment due to their ecotoxicity. Of 26 pharma-
ceutical and personal care compounds investigated by De García
et al. (2014), IBP was in the upper half (classed as harmful to aquatic
organisms) based on standard ecotoxicological tests.
gineers have been exploring a variety of techniques for pollutant re-
moval from water (Guo et al., 2017; Shi et al., 2017). Techniques
explored for IBP uptake includes persulfate-based oxidation (Yin et al.,
2018), Fenton oxidation (Hussain et al., 2020), photocatalytic degrada-
tion (Candido et al., 2016), ozonation (Jothinathan and Hu, 2018), chlo-
rination (Noutsopoulos et al., 2015), and constructed wetlands (Zhang
et al., 2017). Adsorption is one of the oldest and popular techniques
for pollutant removal from water (Hevira et al., 2021; Hevira et al.,
2020). Adsorption is low-cost, less energy-intensive, does not require
chemicals and is easy to implement (Ighalo et al., 2020b; Kausar et al.,
2018). It is effective for removing NSAID in water (Ighalo and Adeniyi,
2020b).
There is no available review in literature examining the empirical
findings on the adsorption of IBP (based on the authors thorough
search). Its regular occurrence in water sources as a pollutant and the
vast amount of literature on its mitigation by adsorption raises a need
for a comprehensive review on the subject. The aim of this paper is to
review the empirical findings on the adsorption of Ibuprofen (IBP)
from aqueous media. The review first looks at the ecotoxicology of the
compound as a justification for its negative effect on the environment.
It then presents an overview of other mitigation strategies to help justify
the choice of adsorption as the subject of the review. The review is thor-
ough as it analyses every aspect of the empirical findings on IBP adsorp-
tion published in open literature in the past ten years.
2. Ecotoxicology of IBP
In this section, the ecotoxicology of IBP is discussed to understand
the negative implications of its presence in the aquatic environment.
IBP is commonly detected in surface waters at ng/L and the major con-
tamination source is pharmaceutical effluent (Aguilar-Romero et al.,
2020). Cleuvers (2003) observed that acute effects of IBP in the aquatic
environment is unlikely but could be significant in combination with
diclofenac (another NSAID). IBP affected algae and Daphnia by non-
polar narcosis and follows the concept of concentration addition
(Cleuvers, 2003). IBP has been shown to affect metabolism and sub-
strate attachment abilities of Baltic Sea blue mussels (Mytilus edulis
trossulus) (Ericson et al., 2010). Bio-magnification was observed as the
concentration of IBP was higher in the animal cells than in the polluted

2
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al. Science of the Total Environment 780 (2021) 146608

Table 1
Properties of Ibuprofen (PubChem, 2020; Davarnejad et al., 2018).

Property Values

CAS ID 15,687-27-1
IUPAC Name 2-(4-Isobutylphenyl) propanoic acid
Chemical Formula C13H18O2
Molar mass 206.28 g/mol
Specific gravity 1.03
Solubility in water (at 25 °C) 21 mg/L
pKa 4.91
Log Kow 3.97
Melting point 75–77 °C
Boiling point 157 °C

aqueous environment. Though not toxic, De García et al. (2014) ob-

served that IBP and its sodium salt is harmful to aquatic organisms
based on tests on Vibrio fischeri, Algae, crustaceans and biomass of
wastewater treatment plant. The summary of their ecotoxicity findings
is shown in Fig. 2.
Based on the investigations of Han et al. (2010), IBP was observed to
have an endocrine disruption effect on Japanese medaka (Oryzias
latipes) and freshwater cladocerans Daphnia magna and Moina
macrocopa. A high genotoxic potential that is greater than other
NSAID like paracetamol and diclofenac has been observed for IBP
using in vitro biomarker investigations on the haemocytes freshwater
bivalve zebra mussel (Dreissena polymorpha) (Parolini et al., 2009).
Using the same species, a chronic cyto-genotoxic effect was observed
by cell gel electrophoresis assay, the DNA diffusion assay, the micronu-
cleus test and neutral red retention assay) of the mussel haemocytes
(Parolini et al., 2011). Pomati et al. (2004) observed that IBP stimulated
the growth of cyanobacterium Synechocystis spp. but inhibited the
growth of the duckweed Lemna minor. Acute and chronic effects have
been observed for Keeled rams horn snails (Planorbis carinatus)
(Pounds et al., 2008). IBP has been shown to inhibit the chloroplastic en-
ergy transduction and electron transport chain in of the diatom
Phaeodactylum tricornutum (Silva et al., 2020). The drug has also been
shown to be slightly toxic on Aliivibrio fischeri (Zuriaga et al., 2019).
Based on these, it can be surmised that IBP needs to be mitigated from
hospital and medical effluents, and pharmaceutical wastewater before
environmental release. This, the relevance of this review is justified.
3. Overview of mitigation strategies for IBP uptake
In this section, the different mitigation methods used for IBP were
addressed. This would help to define and point out the importance of
adsorption and its importance over the other IBP mitigation methods,
thereby encouraging the focus of this review (adsorption) to be se-
lected. The treatment methods adopted by different authors for the
management of IBP polluted waters may be grouped into physical,
chemical and biological techniques (Table 2). The physical methods
may include the membrane filtration processes (such as ultrafiltration,
microfiltration, and nanofiltration processes) (Vergili, 2013; Higgins
and Duranceau, 2020; Maryam et al., 2020; Licona et al., 2018), reverse
Fig. 1. General chemical structure of Ibuprofen.
Fig. 2. Ecotoxicology of IBP and its sodium salt (adapted from De García et al. (2014)).
osmosis (Licona et al., 2018), and adsorption (Essandoh et al., 2015;
Rafati et al., 2018). In physical processes, the pollutants nature is not
changed or degraded (also termed as non-destructive processes (Crini
and Lichtfouse, 2019)). Membrane filtration processes involve the use
of semipermeable materials to remove pollutants. These membrane fil-
ter types differ in pore diameters which separates their purposes in
water treatment. Studies have proved that the nanofiltration process
is more efficient for the removal of pharmaceutics than the
microfiltration and ultrafiltration since the later processes require lesser
energy to operate (Davarnejad et al., 2018; Vergili, 2013). Complete IBP
rejection (100%) was reported when graphene oxide membrane was
used (Bahamon and Vega, 2019).
Chemical methods that have been used by authors for IBP removal
include the advanced oxidation processes (AOPs) (Kwon et al., 2015;
Saeid et al., 2018; Jallouli et al., 2018), coagulation-flocculation
(Suarez et al., 2009; Carballa et al., 2005), electrocoagulation (Khadir
et al., 2020a; Mission et al., 2010), chemical oxidation (Adityosulindro
et al., 2018), and ion exchange (Wang et al., 2015). AOPs include a
group of mitigation processes such as ozonolysis, hydrolysis, sonolysis,
photolysis, sonocatalysis, photocatalysis, Fenton (photo-Fenton,
electro-Fenton, and sono-Fenton), persulfate and chlorine processes
etc. The advanced oxidation processes (AOPs) are advanced methods
that make use of highly oxidative radicals such as sulfate radicals
(SO•− •
4 ) and hydroxyl radical ( OH) formed during the treatment of pol-
lutants. AOPs are known to degrade and mineralise highly resistant pol-
lutants at a fast rate (Ahmadi et al., 2020). Many researchers have tested
various AOPs on IBP removal. For instance, Ghauch et al. (2012) investi-
gated IBP removal via persulfate process; they obtained 85% IBP degra-
dation at pH 4, temperature of 333 K, initial IBP concentration value of
20.36 μM, and persulfate concentration of 1 mM. Also, some authors
(Farzaneh et al., 2020) used another AOP (O3/H2O2) to remove IBP
from sewage effluent for reuse which led to 80% IBP reduction when
1.5 mg/L O3 dose and O3:H2O2 ratio of 1:1/4 were used. More than
96% IBP mineralisation (% TOC) was achieved by Loaiza-Ambuludi
et al. (2014) via the photo-Fenton process at constant conditions of
Fe3+ and H2O2 concentrations of 0.25 and 10 mM, respectively. The
coagulation-flocculation treatment process was not effective for IBP re-
moval. Only 23% IBP reduction was observed by Suarez et al. (2009) and

3
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al.
Table 2
Advantages and setbacks of each method used for IBP mitigation.
Process Advantages
type
Physical Membrane filtration (such as • Cost of energy is low
nanofiltration and ultrafiltration) • Can perform effectively at low
temperatures
• Easy to scale up
Reverse osmosis • Cost of energy is low
• Requires less labour since they
are fully automated
• Maintenance cost is low
• Installation cost is also high
Adsorption • Easy operation
• Low cost of application
• High performance
• Simple equipment
• Can easily be coupled with the
other treatment techniques
Chemical Electrocoagulation • Requires less time
• May not need chemicals to give a
good performance
• easy to operate,
• Low sludge production
AOPs • Ability to degrade recalcitrant
pollutants
• Rapid rates of reaction
• Complete mineralisation is
certain
Chemical precipitation • Good for COD reduction
• Simplicity of operation
• Very effective
Ion exchange • Very effective for softening of
water
• Low maintenance cost
• Resins possess long life and
proper magnetic separation
features
Chemical coagulation- • Simple process
flocculation • Not expensive to operate
• Very effective for colloidal particles
• Good for organic pollutants (TOC,
COD and BOD) reduction
Biological • Simplicity of operation and eco-
nomical
• Effective for removal of biode-
gradable matter
• High removal of suspended par-
ticles and BOD
10–25% IBP reduction was obtained by Carballa et al. (2005). Moreover,
coagulation is a preliminary treatment technique mostly for the re-
moval of colloidal and suspended solids (Igwegbe and Onukwuli,
2019). Electrocoagulation is fast coagulation with the help of the use
of electricity (Zaied et al., 2020). The dissolved electrodes in water act
as the coagulant. Recently, Negarestani et al. (2020) investigated the re-
moval of IBP from underground water through electrocoagulation
equipment. The removal of IBP reached 50.96% at 2 A, pH 5, electrolysis
time of 110 min, electrodes spacing of 3 cm and IBP concentration of
40 ppm and shaker speed of 200 rpm. The efficiency was improved to
78% when double electrocoagulation step was used (Negarestani et al.,
2020). Another author, Mission et al. (2010) studied the removal of
IBP and COD using Al and Fe as the sacrificial electrodes. Highest IBP
and COD removals of 64.18 and 32%, respectively were achieved with
the Fe electrode at pH 6, and 21.4 V. Martins et al. (2020) combined
electro-oxidation with resin adsorbent to reduce 100 ppm IBP. 73% IBP
removal was removed after the electrochemical reduction followed by
85% reduction using the ion exchange process; this combination re-
duced the initial IBP concentration from 100 to 4 ppm (96%).
Biological methods involve the use of microorganisms' cultures to
biodegrade pollutants. This method is very simple and has been well
established (Crini and Lichtfouse, 2019). The biological processes used
for the management of wastewater is grouped as aerobic (requires
Science of the Total Environment 780 (2021) 146608
Disadvantages Ref.
• Prone to membrane fouling (Lippi et al., 2018; Reverberi et al., 2014)
• High equipment cost
• Not applicable for concentrated solutions (Lippi et al., 2018; Reverberi et al.,
2014; Nwabanne et al., 2018)
• Moderate high investment cost (Crini and Lichtfouse, 2019; Igwegbe
• Performance is dependent on the type of pol- et al., 2020a; Igwegbe et al., 2020b)
lutant and adsorbent
• Adsorbent regeneration is costly
• Cost of electricity is high (Crini and Lichtfouse, 2019; Nwabanne
• High cost of sacrificial electrodes et al., 2018; Igwegbe et al., 2019)
• Electrode passivation
• Needs more treatment to remove the elevated
concentrations of the metal electrodes used
• Expensive chemical reagents are needed (Crini and Lichtfouse, 2019; Ahmadi
• High cost of energy, investment, and operation et al., 2020)
• Unknown products can be formed.
• Expensive chemicals are needed (Crini and Lichtfouse, 2019)
• High volume of sludge
• High operational cost (Shuang et al., 2012; Igwegbe et al.,
• The acidity level of water is increased 2020c)
• Buffer is required
• Generation of high sludge volume (Crini and Lichtfouse, 2019)
• Chemicals may be required as coagulants and
flocculants
• The process takes time (in days) with very (Crini and Lichtfouse, 2019; Igwegbe
slow process kinetics et al., 2020c)
• Poor degradability for some compounds
• Microbiological process complexity
• Not impressive for colour reduction
oxygen) and anaerobic (does not require oxygen) treatments. Under
anaerobic or aerobic conditions, nitrogenous and organic compounds
in the wastewater can act as nutrients for accelerated microbial devel-
opment (Vymazal, 2007). IBP is biologically degradable (Davarnejad
et al., 2018) and high removals are usually obtained using this process
(Langenhoff et al., 2013). Many researchers have investigated the effec-
tiveness of this process on IBP degradation Langenhoff et al. (2013) ex-
amined the removal of 0.25 g/L IBP through a membrane bioreactor
which was biodegraded within four days to untraceable concentrations
(that is, 100% IBP removed). Also, Hasan et al. (2016) reported 63 to 90%
IBP degradation using an aerobic suspension-sequencing batch reactor
at 24 h hydraulic retention times and aeration rate of 1 L/min.
The advantages and setbacks of each type of technique or process are
stated in Table 2. Most of these approaches are very costly and not very
effective in lowering water pharmaceuticals concentrations in water
(Ighalo et al., 2021d). The adsorption method, however, enables the in-
corporation of wastes (which has little or no economic viability) and
other inexpensive, sustainable and renewable materials (Choi, 2019;
Umembamalu et al., 2020). Materials like nano-adsorbents (Hanbali
et al., 2020; Banerjee et al., 2016; Vicente-Martínez et al., 2020), poly-
mers (Zhang et al., 2020a), clays (Martín et al., 2019; Ghemit et al.,
2019; Malvar et al., 2020), activated carbon (Mestre et al., 2007;
Guedidi et al., 2017), un-activated wastes (Chakraborty et al., 2018a;
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S.N. Oba, J.O. Ighalo, C.O. Aniagor et al. Science of the Total Environment 780 (2021) 146608

Table 3
Adsorption capacities of different adsorbents for aqueous IBP uptake.

Adsorbent qmax (mg/g) pH Temp (°C) Method of determination Ref.

SWCNTs 496.1 4.0 NS Experiment (Cho et al., 2011)

Microporous activated carbon 495.0 3.0 13 Experiment (Guedidi et al., 2020a)
AC cloth 492.0 3.0 25 Experiment (Guedidi et al., 2017)
Physically activated coal 430.4 4.0 30 Langmuir (Mestre et al., 2009)
Chemical + steam activated carbon 416.7 2.0–4.0 25 Langmuir (Mestre et al., 2007)
Steam + chemically activated cork 378.1 4.0 30 Langmuir (Mestre et al., 2009)
Magnetised silica 321.8 6.0–8.0 20 Experiment (Wang et al., 2015)
MOFs 320.0 2.0 25 Experiment (Bhadra et al., 2017)
Oxygen pyrolysed biochar 311.0 7.0 25 Langmuir (Jung et al., 2015)
Physically activated wood 291.9 4.0 30 Langmuir (Mestre et al., 2009)
Nitrogen pyrolysed biochar 286.0 7.0 25 Langmuir (Jung et al., 2015)
Microwave activated Bamboo Waste 278.6 5.0 25 Langmuir (Reza et al., 2014)
AC 268.2 4.3 25 Experiment (Mansouri et al., 2015)
Physically activated PET 266.6 4.0 30 Langmuir (Mestre et al., 2009)
MIEX with polyacrylic matrix 266.1 7.0 25 Langmuir (Zhang et al., 2020a)
Amberlite resin 261.9 6–10 25 Experiment (Taleb et al., 2017)
Magnetised AC 261.4 2.0 25 Experiment (Fröhlich et al., 2019)
Rice husk acid-AC 239.8 – 30 Experiment (Álvarez-Torrellas et al., 2016)
Mesoporous MOFs 206.5 3.0 30 Langmuir (Van Tran et al., 2019)
Organobentonite 194.9 7.0 25 Experiment (Ghemit et al., 2019)
MWCNT 186.5 4.0 NS Experiment (Cho et al., 2011)
Ultrasonic modified AC 175.0 3.0 25 Experiment (Guedidi et al., 2020b)
Activated biochar 172.0 4.0 20 Experiment (Zhang et al., 2020b)
TiO2 modified AC 160.0 3.0 25 Experiment (Guedidi et al., 2013)
Palm shell AC modified with 3.8% Fe 157.3 7.0 25 Langmuir (Wong et al., 2015)
Chemical activated carbon 153.2 2.0–4.0 25 Langmuir (Mestre et al., 2007)
Physically + wet oxidated wood 149.1 4.0 30 Langmuir (Mestre et al., 2009)
C3N4/soot 148.8 NS NS Langmuir (Liao et al., 2018)
Chemically activated cork 145.2 4.0 30 Langmuir (Mestre et al., 2009)
Commercial AC 139.0 6.0 25 Experiment (Jedynak et al., 2019)
Modified magnetic nanomaterial 138.1 6.0 25 Langmuir (Kollarahithlu and Balakrishnan, 2019)
Sonicated AC 134.5 2.0 25 Experiment (Fröhlich et al., 2018a)
MOFs (UiO-66) 127.1 3.5 25 Experiment (Sun et al., 2019)
Bioactive hydroxyapatite nano-rods 127.0 7.4 37 Langmuir (Benedini et al., 2019)
Mesoporous carbon 120.1 6.0 25 Experiment (Jedynak et al., 2019)
Mesoporous carbon 120.0 3.0 25 Experiment (Ulfa et al., 2019)
Covalent organic framework 119.0 7.0 21 Experiment (Mellah et al., 2018)
AC 115.1 2.0 25 Experiment (Fröhlich et al., 2018a)
Palm shell AC modified with 8.6% Fe 114.7 7.0 25 Langmuir (Wong et al., 2015)
Ultrasound modified AC 107.1 2.0 25 Experiment (Fröhlich et al., 2018b)
AC 105.9 4.0 25 Experiment (Streit et al., 2020)
Modified CNT 103.1 2.0 20 Experiment (Lung et al., 2020)
Palm shell AC modified with 7.8% Fe 100.6 7.0 25 Langmuir (Wong et al., 2015)
Zeolite coated magnetic nanoparticle 97.37 2.0 30 Experiment (Attia and Hu, 2013)
AC 96.15 3.0 25 Langmuir (Nourmoradi et al., 2018)
CO2 activated mesoporous carbon 92.00 6.0 25 Experiment (Jedynak et al., 2019)
H2SO4-treated onion skin 91.99 6.5 25 Experiment (Abbas et al., 2017)
Standard AC 85.00 2.0 25 Experiment (Fröhlich et al., 2018b)
Oxidized AC 81.50 7.0 35 Langmuir (Ali et al., 2019)
H3PO4-treated onion skin 79.02 6.5 25 Experiment (Abbas et al., 2017)
Fe-loaded mesoporous silica 77.50 NS 20 Experiment (Ulfa et al., 2019)
Activated coconut husk 76.92 – 30 Langmuir (Bello et al., 2020)
Unmodified palm shell AC 72.70 7.0 25 Langmuir (Wong et al., 2015)
MOFs 72.30 3.5 55 Experiment (Jin and Row, 2005)
Chitosan-modified waste tire rubber 70.00 6.0 25 Experiment (Phasuphan et al., 2019)
HCl-treated onion skin 68.59 6.5 25 Experiment (Abbas et al., 2017)
Polyamidoamine functionaliased clay 68.34 6.0 25 Experiment (Kurczewska et al., 2020)
Alkaline AC 68.00 7.0 35 Langmuir (Ali et al., 2019)
AC 67.10 3.0 30 Langmuir (Kaur et al., 2018)
Modified Organo silica (G16-2-16-SiNSs) 64.19 4.0 25 Experiment (Zeng et al., 2018a)
Modified montmorillonite 64.00 6.5 20 Experiment (Malvar et al., 2020)
Hydrophobic functionalised AC 63.80 7.0 35 Langmuir (Ali et al., 2019)
Steam activated biochar 62.50 2.0 20 Langmuir (Mondal et al., 2016a)
AC (F400) 62.23 7.4 25 Langmuir (Delgado et al., 2015)
Molecularly imprinted membranes 61.80 NS 25 Experiment (Wu et al., 2018b)
Modified magnetic biochar 58.12 4.0 30 Experiment (Ai et al., 2020)
Powdered AC 54.00 3.5 55 Experiment (Jin and Row, 2005)
MOFs (UiO-66-NH2) 50.69 3.5 25 Experiment (Sun et al., 2019)
Acid-functionalised bean husk 50.00 4.75 50 Experiment (Bello et al., 2019)
Basic functionalised AC 48.00 7.0 35 Langmuir (Ali et al., 2019)
Functionalised clay mineral 45.84 6.0 25 Experiment (Kurczewska et al., 2020)
Untreated onion skin 41.66 6.5 25 Experiment (Abbas et al., 2017)
Oxidized MWCNTs 40.20 4.0 NS Experiment (Cho et al., 2011)
Modified Organo silica (G12-2-12-SiNSs) 40.14 4.0 25 Experiment (Zeng et al., 2018a)

(continued on next page)

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S.N. Oba, J.O. Ighalo, C.O. Aniagor et al. Science of the Total Environment 780 (2021) 146608

Table 3 (continued)

Adsorbent qmax (mg/g) pH Temp (°C) Method of determination Ref.

Modified silica aerogel 39.95 3.0–7.0 30 Experiment (Mohseni-Bandpei et al., 2020)

Clay 36.00 6.0 25 Experiment (Khazri et al., 2017)
Molecularly imprinted polymer 35.20 NS 25 Experiment (Zhou et al., 2013)
Modified mesoporous silica 34.96 3.0 25 Experiment (Choong et al., 2019)
Functionalised nano-clay 33.65 6.0 25 Experiment (Rafati et al., 2018)
Unmodified magnetic biochar 28.67 4.0 30 Experiment (Ai et al., 2020)
Biochar pyrolysed at 600 °C 26.13 7.0 25 Langmuir (Ocampo-Perez et al., 2019)
Microporous carbonaceous material 23.33 6.0 22 Langmuir (Sekulic et al., 2019)
Unmodified clay mineral 22.47 6.0 25 Experiment (Kurczewska et al., 2020)
W-biochar 21.70 4.0 NS Langmuir (Lin et al., 2017)
Sisal fiber 21.50 5.0 40 Experiment (Khadir et al., 2020b)
Molecularly imprinted membranes 21.36 NS 25 Experiment (Wu et al., 2018c)
AC 16.95 2.0 25 Langmuir (Dubey et al., 2010)
Biochar pyrolysed at 550 °C 16.64 7.0 25 Langmuir (Ocampo-Perez et al., 2019)
O-carboxymethyl-Nlaurylchitosan/γ-Fe2O3 15.20 7.0 40 Experiment (Chahm and Rodrigues, 2017)
Nanosheets-infiltrated membranes 13.80 NS 25 Experiment (Wu et al., 2018b)
Acid activated biochar 13.51 2.0 25 Langmuir (Chakraborty et al., 2018b)
Biochar pyrolysed at 450 °C 12.78 7.0 25 Langmuir (Ocampo-Perez et al., 2019)
Activated wood apple biochar 12.66 2.5 25 Langmuir (Chakraborty et al., 2018a)
Acid activated biochar 12.16 2.0 15 Langmuir (Chakraborty et al., 2019)
Acid activated date stone biochar 12.16 3.0 20 Experiment (Chakraborty et al., 2020)
Steam activated biochar 11.90 2.0 25 Langmuir (Chakraborty et al., 2018b)
β-cyclodextrin-grafted chitosan 11.23 2.0 27 Experiment (Bany-Aiesh et al., 2015)
Olive cake AC 10.83 2.01 25 Experiment (Baccar et al., 2012)
Pinewood biochar 10.74 3.0 35 Langmuir (Essandoh et al., 2015)
MOF, MIL-53(Fe) 10.67 2.6 25 Langmuir (Nguyen et al., 2019)
Chemically activated biochar 10.57 2.0 35 Langmuir (Show et al., 2020)
Steam activated date stone biochar 9.690 3.0 20 Experiment (Chakraborty et al., 2020)
Steam activated biochar 9.670 2.0 15 Langmuir (Chakraborty et al., 2019)
Graphene oxide nanoplatelets 9.319 6.0 35 Experiment (Banerjee et al., 2016)
Mesoporous carbon aerogel 8.847 4.0 25 Experiment (Abolhasani et al., 2019)
Raw biochar 8.640 2.0 35 Langmuir (Show et al., 2020)
Granular AC 8.000 7.3 24 Experiment (Iovino et al., 2015)
Modified aluminium mineral 7.610 5.0 35 Experiment (Dwivedi et al., 2011)
Montmorillonite 6.100 3.0 25 Experiment (Behera et al., 2012)
Non-imprinted membranes 6.000 NS 25 Experiment (Wu et al., 2018c)
Hydroxyl amine-functionalised MWCNT 5.800 4.0 25 Experiment (Hanbali et al., 2020)
Amino acid-functionalised MWCNT 5.610 4.0 25 Experiment (Hanbali et al., 2020)
Hydrazine functionalised MWCNT 5.430 4.0 25 Experiment (Hanbali et al., 2020)
Wood apple biochar 5.000 2.5 25 Langmuir (Chakraborty et al., 2018a)
Modified Organo silica (G8-2-8-SiNSs) 4.840 4.0 25 Experiment (Zeng et al., 2018a)
Living Phaeodactylum tricornutum biomass 3.790 8.2 18 Langmuir (Santaeufemia et al., 2018)
Chemically modified N-biochar 3.760 2.0 20 Langmuir (Mondal et al., 2016b)
Dead Phaeodactylum Tricornutum biomass 3.600 8.2 18 Langmuir (Santaeufemia et al., 2018)
α-FeOOH modified recycled rusted iron 3.470 7.0 25 Langmuir (Yin et al., 2018)
Modified montmorillonite 3.197 6.5 NS Experiment (Martín et al., 2019)
Kaolinite 3.100 3.0 25 Experiment (Behera et al., 2012)
Modified Mica 2.764 6.5 NS Experiment (Martín et al., 2019)
Lignosulfonate-based sorbent 2.320 2.0 25 Langmuir (Ciesielczyk et al., 2019)
Goethite 2.200 3.0 25 Experiment (Behera et al., 2012)
Molecularly imprinted polymer 2.010 4.6 NS Experiment (Madikizela and Chimuka, 2016)
Non-imprinted polymer 1.850 4.6 NS Experiment (Madikizela and Chimuka, 2016)
Synthetic α-FeOOH 0.7200 7.0 25 Langmuir (Yin et al., 2018)
Powdered AC (Norit SA Super) 0.4480 >7.0 20 Experiment (Puszkarewicz et al., 2017)
Powdered AC (Carbopol MB5) 0.3530 >7.0 20 Experiment (Puszkarewicz et al., 2017)
Iron nano-adsorbent 0.0660 7.0 25 Experiment (Ali et al., 2016)
Microwave irradiated activated shell 0.0496 12 40 Experiment (Sivarajasekar et al., 2017)

Jaafar et al., 2020), and composites (Rafati et al., 2018; Hanbali et al.,
2020) were employed for the removal of IBP. Adsorption possesses ex-
cellent capacity to get rid of broad types of pollutants with fast process
kinetics (Crini and Lichtfouse, 2019). Another great advantage of the ad-
sorption process is its ease and low cost of operation/equipment
(Table 2). All through years, the implementation of the adsorption pro-
cedure for the reduction of IBP has been generously (than the other
treatment techniques mentioned above) and successfully assessed
(which is fully discussed in the subsequent sections).
4. Adsorbent performance for IBP uptake
This section presents the review of findings on the different adsor-
bent performances towards aqueous IBP. For this discussion, the adsor-
bent performance is reported in terms of maximum adsorption capacity
(qmax) instead of removal efficiency, as the former provides useful in-
sight on the intrinsic suitability of the adsorbents (Igwegbe et al.,
2020c). Meanwhile, the removal efficiency is more affected by initial
concentration and adsorbent dosage (and these can vary widely from
one study to another). As shown in Table 3, the different adsorbent
qmax was determined either from isotherm models (predominantly
Langmuir model) or experimental predictions. Consequently, the de-
pendence of adsorption capacity on the adsorbate characteristics, pre-
vailing process conditions and nature of adsorbent, have been
highlighted (Baccar et al., 2012).
According to Moreno-Castilla (2004), molecular size, solubility, dis-
sociation constant (pKa) etc., are some of the factors with major influ-
ence on the adsorbate characteristics. The adsorbent pore accessibility
during adsorption is well related to the adsorbate molecular size,
while the adsorbates ionisation behaviour (for electrolytes) are

6
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al.
governed by the pKa. The extent of adsorbent-adsorbate interactive hy-
drophobicity depends on the adsorbates' solubility and octanol/water
partition coefficient (Kow) values. Meanwhile, the direct proportionality
existing between the Kow and the adsorption capacity has been
highlighted (Hamdaoui and Naffrechoux, 2007). Furthermore, the influ-
ence of inherent functional groups and molecular structural properties
(in the case of organic molecules) on the different adsorbent perfor-
mances has been reported (Cho et al., 2011). For instance, due to the
presence of inherent ketone and carboxylic (an electron-withdrawing)
groups, IBP may have achieved a better complexation affinity (via elec-
tron donor-acceptor and π- π interactions) with carbon-based adsor-
bents (Baccar et al., 2012). This phenomenon could explain their
higher qmax when compared to other adsorbent types (Table 2).
The adsorption process conditions also bear significant influence on
a given adsorbents' performance (Igwegbe et al., 2020c). Explanation of
the different ways by which IBP adsorption process conditions could af-
fect the uptake performance is further elucidated herein. For instance, at
high initial adsorbate concentration, a large mass transfer driving force
is created due to concentration gradient; thus, resulting in improved
IBP uptake. Similarly, increased agitation of the adsorption set-up
could also help IBP molecules to overcome the mass transfer limita-
tion/resistance at the solid-liquid interphase on the adsorbent. During
adsorption, the diffusion of IBP from the bulk fluid phase to the adsor-
bent pores is strongly dependent on time. Thus, increased contact
time affords the resident time required for the equilibration of IBP up-
take. Generally, sorption processes are either favoured at increasing
(endothermic sorption) or decreasing (exothermic sorption) tempera-
tures. These temperature effects significantly shrink or widen the
boundary layer thickness, a factor which directly affects the uptake ca-
pacity. Also, the solution pH generally affects aqueous adsorbate, thus,
even at the same pH, adsorbents depict varied adsorption phenomenon
and capacities (qmax).
The influence of adsorbent nature on the adsorbate uptake perfor-
mance, (especially for organic compounds) has been extensively stud-
ied, with clear evidence to support the dependence of q max on the
adsorbent porosity (Baccar et al., 2012). Table 2 showed that apprecia-
bly high adsorption capacities were recorded mostly for the AC-based
adsorbent, of high surface area and porosity. The planar configuration
and molecular dimensions of the IBP molecule (in the range of
0.43–1.03 nm), may have permitted its (IBP molecules) ready adsorp-
tion onto the carbonaceous pores of these adsorbents via fill-pore mech-
anism (Quinlivan et al., 2005). The pore-filling mechanism conclusively
resulted in improved adsorption capacities either with homogenous
monolayer adsorption or heterogeneous multilayer adsorption (Chen
et al., 2007). Furthermore, the later discussion in Section 5.1, submitted
the relevance of the shape of the adsorption isotherm in determining
the nature of the adsorbate-adsorbent binding. ‘S type’ adsorption iso-
therm is indicative of the occurrence of competition between water
and IBP molecules for the sorption sites (Helmy et al., 1983). Increased
surface polarity on some adsorbents, mainly due to the presence of
hydrophilic active sites may result in the formation of clusters of
water molecules. Therefore, at increasing adsorbate-adsorbent hydro-
phobicity, these aggregate of water molecules readily adsorb onto the
hydrophilic adsorbent pores and mar the access of the relatively hydro-
phobic IBP compounds to the adsorption sites (Karanfil and Kilduff,
1999). Hence, adsorbents with acidic surface properties are expected
to depict a higher affinity towards the relatively hydrophilic ibuprofen
sodium salt molecule, compared to more basic adsorbents (Álvarez-
Torrellas et al., 2016).
Table 3 show the varieties of adsorbents that were utilised by re-
searchers for aqueous IBP uptake, with their adsorption capacities
sorted in decreasing order of magnitude. Based on the available data
(Table 3), the uptake performance of carbon-based adsorbents was out-
standing (and occurring at ambient temperature) when compares to
other adsorbents. Microporous AC (495.10 mg/g) (Guedidi et al.,
2020a), AC cloth (492 mg/g) (Guedidi et al., 2017), SWCNT
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Science of the Total Environment 780 (2021) 146608
(496.1 mg/g) (Cho et al., 2011), chemical & steam AC (416.7 mg/g)
(Mestre et al., 2007) and physically activated coal (430.2 mg/g)
(Mestre et al., 2009) depicted adsorption capacity that was >400 mg/g
(Table 3). This finding suggests that functionalisation enhances interac-
tions between the adsorbent and adsorbate for effective IBP removal
from solutions (Wang et al., 2020). By such specific interactions, stability
is enhanced and electrostatic repulsion of charges between molecules
reduced minimally. This accounts for the high adsorption capacities of
modified carbon-based adsorbents. If classed into carbon-based adsor-
bents, polymeric-resinous adsorbents and clay adsorbents (Ighalo
et al., 2021a; Ighalo et al., 2020a), it can be observed from the table
that carbon-based adsorbents are the best adsorbent class for the uptake
of IBP.
5. IBP adsorption mechanism
5.1. Generalised IBP adsorption mechanism
In this section, the mechanism of IBP uptake from aqueous media is
discussed. The structural orientation of IBP as shown in Fig. 3, consists of
hydrophilic and hydrophobic moieties, with dipolar natured functional
groups (Ulfa et al., 2019; Dwivedi et al., 2011; Lindqvist et al., 2005).
Based on the reviewed articles, IBP molecule is acidic, with a single
pKa which is commonly reported as 4.91. However, for some unknown
reasons, many authors reported the pKa of IBP as 4.35 (Phasuphan et al.,
2019), 4.4 (Abbas et al., 2017), 4.85 (Lin et al., 2017; Jun et al., 2019),
4.96 (Nourmoradi et al., 2018; Khazri et al., 2017), 4.92 (Abolhasani
et al., 2019) and 5.2 (Mellah et al., 2018). The IBP acidity is due to the hy-
drogen generated from the dissociation of its ionisable carboxylic group
at high pH (pH > pKa) (Dwivedi et al., 2011).
According to Tran et al. (2020), several mechanisms are involved
during the adsorption of organic compounds onto different adsorbents.
However, the primary adsorption mechanisms strongly depend on the
experimental adsorption conditions (pH, system equilibrium/kinetic,
thermodynamics, desorption etc.), adsorbate characteristics (solubility,
pKa, etc.), adsorbent properties (surface area, surface functional groups,
etc.). Thermodynamic ΔH0-parameter helps to gauge the adsorption
mechanism by elucidating the nature of the adsorbent-adsorbate inter-
actions (Igwegbe et al., 2020c). Desorption is also used to gauge the
probable adsorption mechanism. When distilled water or organic sol-
vent are applied as eluents, physical adsorption mechanism predomi-
nates. The effectiveness of strong acids and/or base shows chemical
adsorption mechanism. In some cases, the probable mechanism can be
defined based on the fundamental assumptions of the kinetics and iso-
therm model of best fit (Igwegbe et al., 2020c). Also, spectroscopic anal-
yses provide valuable insight into the specific functional groups and the
interaction site locations. This is especially important in isolating the ac-
tual chemical bonds that are responsible for chemical or physical inter-
action (Igwegbe et al., 2020c).
Furthermore, the information obtained from the degree of acidity
(pH), dissociation constant (pKa) and point of zero charges (pHpzc)
could offer a relevant explanation on the prevalent adsorption mecha-
nism, since these quantities relate to the state of the adsorbate and
the functional groups of the adsorbent (Essandoh et al., 2015; Bhadra
et al., 2017; Iovino et al., 2015). Consequently, Iovino et al. (2015)
highlighted the pKa dependence on temperature, while Bui and Choi
(2009) further attempted to establish the correlation between temper-
ature and pKa, as well as their influence on the sorption mechanism. It
was observed that temperature increase lowered the % ionisation of
IBP, such that the concentration of the non-ionised species increased
leading to unfavourable sorption mechanism. Furthermore, as a weak
electrolyte, IBP can coexist in different forms (acidic or basic) and the
proportion of its acidic or basic conjugates depend on the solution pH
and pKa of the acid form (Reijenga et al., 2013). For instance, IBP was
found to exist as neutral/hydrophobic/acidic/non-ionised species (at
pH < pKa), coexists as neutral and anionic species (at pH ≈ pKa), and
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al.
(a)
Fig. 3. Ibuprofen structure showing (a) the hydrophilic & hydrophobic moieties (b) dipolar nature (Dwivedi et al., 2011).
an anionic/hydrophilic/basic species (at pH > pKa) (Bui and Choi,
2009). By giving due consideration to aforementioned factors, as well
as findings from isotherm modelling, kinetics modelling, thermody-
namics modelling and spectroscopic analysis (like FTIR, XRD and XPS),
one can reasonably elucidate the mechanism of IBP uptake (Igwegbe
et al., 2020c).
IBP adsorption has been studied by many researchers using different
adsorbents as shown in Table 4. The review of these literature reports
showed the predominance of many mechanisms (depending on the ad-
sorbent characteristics and operating conditions). However, the major
mechanism involved includes electrostatic interaction, hydrophobic
(Van der Waals, π-π and electron donor-acceptor) interaction and hy-
drogen bonding (Table 4). Ciesielczyk et al. (2019) reported that elec-
trostatic interaction resulted mainly from the chemical bonds formed
between positively charged functional groups of an adsorbent and the
negatively charged IBP molecules. This mechanism is predominant
when either the pKa > pH > pHpzc or pKa < pH < pHpzc. Meanwhile,
the mechanism of interaction between the IBP and the different adsor-
bents are not limited to electrostatic interaction only but involves
other forms of interactions which will be elucidated further in subse-
quent paragraphs.
The hydrophobic interaction, as a form of sorption mechanism, is
non-pH responsive interaction. This mechanism is significantly acti-
vated during increased adsorbate-adsorbent repulsive effect (Oyetade
et al., 2018). Under this condition (high repulsive effect), the IBP uptake
can only occur onto adsorbents with substantive alkyl group via the af-
finity between the alkyl groups and the electrons of the IBP aromatic
ring (Bui et al., 2013; Bakr and Rahaman, 2016). Meanwhile, the ionic
strength has been found to bear significant influence on adsorbent-
adsorbate hydrophobic interaction. This is mostly due to the salting-
out effect and aggregation of adsorbents (Seo et al., 2016; Wong et al.,
2016). High ionic strength improves hydrophobic interaction but is det-
rimental for adsorption capacity (due to the loss of active sites by adsor-
bent clustering) (Jun et al., 2019). Chahm and Rodrigues (2017) further
reported that the presence of substantive competing ion in IBP adsor-
bate solution could disrupt the analytes solvation box. The oxygeneous
functional groups (like carbonyl, phenolic, etc.) can engage in donor-
acceptor interaction with the aromatic ring of IBP (Delgado et al.,
2015; Gregg et al., 1967) and adsorbent functionalisation affords such
relevant oxygeneous functional groups. Guedidi et al. (2013) reported
that the lone pair of oxygen electron found on oxidated AC adsorbent
was responsible for the formation of donor-acceptor complexes via a di-
pole moment interaction with IBP molecules. During this process, the
carbonyl groups of stronger dipole moment donated the electron
which was accepted by the IBP aromatic ring (Mattson et al., 1969). In
another scenario, the oxygeneous functional groups were involved in
Van der Waals and hydrogen bonds interaction with the carboxylic
groups of IBP, thus enabling dimer formation (Franz et al., 2000).
In the case of adsorbents with H-donor functional group (–OH), the
mechanism of IBP adsorption is based on the complexation between hy-
drogen bond and anionic IBP conjugate (H-acceptor). The aromatic
rings present on the adsorbent and the IBP molecules were responsible
for the establishment of π-π stacking and hydrogen bond interaction
8
Science of the Total Environment 780 (2021) 146608
(b)
mechanism at all pH ranges (Abolhasani et al., 2019). Conversely, due
to the presence of –COOH group, IBP molecules can as well serve as H-
donor during adsorption. This was demonstrated by Bhadra et al.
(2017) while adsorbing IBP onto a MOFs.
5.2. Mechanism of IBP adsorption regarding adsorbent surface functional
groups
As already expressed in the previous section, the adsorption capaci-
ties of various adsorbents for the IBP uptake is a function of their phys-
icochemical characteristics (such as surface area, porosity and surface
functional groups). To further elucidate the IBP adsorption mechanism
regarding the surface functional groups, the pre-and post-adsorption
surface chemistry (via FTIR spectra) of the adsorbents were studied.
Considering the high sorption capacities depicted by carbon-based ad-
sorbents (Table 2), our emphasis in this section will be on such a
group of adsorbents.
An overview of the FTIR spectra of the carbon-based adsorbents
showed the existence of common peaks at wavenumbers
>3200 cm−1 (hydroxyl groups), C-H stretching band group around
2900 to 2960 cm−1, C_O stretch of the carboxylic, ester, or ketone
around 1700 to 1780 cm−1, C_C stretching band around 1600 to
1690 cm−1 and C-O stretch (between 1300 and 1090 cm−1). The in-
volvement and significance of these functional groups during the ad-
sorption of IBP molecules were informed either by a slight to
moderate peak widening, variation in the absorption band intensity,
peak appearance/disappearance or shifting from a lower to a higher
wavenumber and vice versa. These indicators for a successful IBP sorp-
tion onto the respective carbon-based adsorbents are further discussed
in the subsequent paragraphs.
The IBP adsorption is accompanied by some obvious variation in the
intensity of the associated peaks (functional groups). The post-
adsorption FTIR analyses of F-400 activated carbon adsorbent
(Álvarez-Torrellas et al., 2016), activated biochar (Chakraborty et al.,
2018a; Chakraborty et al., 2018b) and NiFe2O4/activated carbon com-
posite (Fröhlich et al., 2019) showed an increment in the intensity of
the peak assigned to the hydroxyl, carboxylic and ketone/alkane groups.
Also, a decrease in the intensity of the peaks between 1500 and
1700 cm−1 (the C_O and C_C olefinic bonds), due to the interaction
and shielding effect of the adsorbed molecules was reported (Zhang
et al., 2020b).
An upward shift was observed in the wavenumbers around
1200 cm−1 (stretching vibration of –OH and/or C-O groups), thereby
suggesting the probable formation of relevant carboxylate and ether
complexes with the carbon-based adsorbent. This observation was not
only made for carbon-based adsorbents (Álvarez-Torrellas et al., 2016;
Abolhasani et al., 2019; Ali et al., 2016) but also chitosan-based adsor-
bent (Bany-Aiesh et al., 2015). Bello et al. (2019) and Abolhasani et al.
(2019) also observed a shift (from a lower to a higher wavenumber)
in the band corresponding to C_O groups (around 1700 cm−1) after
IBP adsorption. According to the authors, such observation is an indica-
tion of the involvement of carboxylic, ester and lactone groups during
adsorption. Also, a shift involving the peak at 2921 cm−1 after IBP
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al. Science of the Total Environment 780 (2021) 146608

Table 4
Mechanism of aqueous IBP uptake (IBP pKa = 4.91).

Adsorbent Optimum pH Adsorption mechanism Ref.

Mesoporous carbon aerogel 4.0 Electrostatic interaction, π-π stacking interaction, hydrogen bonding (Abolhasani et al., 2019)
Olive cake AC 2.1 Hydrogen bonding and/or van der Waals interaction (Baccar et al., 2012)
O-carboxymethyl-N1 5.0–8.0 Electrostatic and hydrophobic interactions (Chahm and Rodrigues, 2017)
laurylchitosan/γ-Fe2O3
Lignosulfonate-based sorbent 2.0 Chemical bonds formation, weak physical and electrostatic interactions (Ciesielczyk et al., 2019)
AC (F400) 7.4 π-π dispersion interactions (Delgado et al., 2015)
AC 2.0 Dipole interaction (Dubey et al., 2010)
Modified aluminium mineral 5.0–7.0 Electrostatic interaction (Dwivedi et al., 2011)
Modified mesoporous silica 3.0 Electrostatic attraction; hydrogen bond (Choong et al., 2019)
Pine-wood biochar 3.0 Van der Waals dispersion forces, permanent dipole-dipole attractions, π-π interactions and (Essandoh et al., 2015)
hydrogen bonding.
Ultrasound modified AC 2.0 Donor–acceptor interactions (Fröhlich et al., 2018b)
Organobentonite 7.0 Hydrophobic interactions (Ghemit et al., 2019)
TiO2 modified AC 3.0 Dispersion interaction (Guedidi et al., 2013)
Microporous AC 3.0 Hydrophobic-hydrophobic interactions, electrostatic attraction (Guedidi et al., 2017)
Ultrasonic modified AC 3.0 Hydrophobic–hydrophobic interaction (Guedidi et al., 2020a)
Hydroxyl amine-functionalised 4.0 Dipole–dipole interaction, π–π interactions, n–π interactions, hydrogen bond (Hanbali et al., 2020)
MWCNT
Hydrazine functionalised 4.0 Dipole–dipole interaction, π–π interactions, n–π interactions, hydrogen bond (Hanbali et al., 2020)
MWCNT
Amino acid-functionalised 4.0 Dipole–dipole interaction, π–π interactions, n–π interactions, hydrogen bond (Hanbali et al., 2020)
MWCNT
Granular AC 2.0 π–π interactions (Iovino et al., 2015)
Commercial MIEX 7.0 Electrostatic interaction, H-bonding, van der Waals interactions, and π–π interactions (Jiang et al., 2015)
Synthesised MIEX 7.0 Electrostatic interaction, H-bonding, van der Waals interactions, and π–π interactions (Jiang et al., 2015)
Modified magnetic biochar 4.0 H-bond and hydrophobic interaction, electrostatic interaction and π–π electron (Jiang et al., 2015)
donor-acceptor interaction
MOFs 3.5 Hydrogen bonding, Lewis acid-base interactions, Coordination by framework metal, (Jun et al., 2019)
Electrostatic interactions and Hydrophobic interactions (π–π stacking)
Oxygen pyrolysed biochar 7.0 Hydrophobic interaction (Jung et al., 2015)
Nitrogen pyrolysed biochar 7.0 Hydrophobic interaction (Jung et al., 2015)
Aluminated mesoporous Silica 7.25 Hydrogen bonding, ligand-exchange adsorption, electrostatic interaction (Kamarudin et al., 2015)
nanoparticle
Mesoporous silica nanoparticle 7.25 Hydrogen bonding, ligand-exchange adsorption, electrostatic interaction (Kamarudin et al., 2015)
AC 3.0 Hydrophobic and π–π interactions (Kaur et al., 2018)
Sisal fiber 5.0 Electrostatic interaction (Khadir et al., 2020b)
C3N4/soot NS Electrostatic attraction, donor–acceptor interactions, (Liao et al., 2018)
W-biochar 4.0 π-π and H-bonding interactions (Lin et al., 2017)
Modified CNT 2.0 Hydrophobic interactions, π – π stacking, hydrogen bonds and polar interactions (Lung et al., 2020)
Modified montmorillonite 6.5 Electrostatic interaction (Malvar et al., 2020)
MOFs 2.0 Hydrogen bond formation, Hydrophobic and π – π interactions (Bhadra et al., 2017)
Chitosan-modified waste tire 6.0 Electrostatic interaction (Phasuphan et al., 2019)
rubber
Functionalised microporous 6.0 H-bonds, π–electron donor-acceptor interactions. (Sekulic et al., 2019)
carbonaceous material
Fe-loaded mesoporous silica NS π – π dispersive interactions, Electrostatic attractions (Ulfa et al., 2019)
MIEX 6.0–8.0 π – π bonding, cation- π bonding, H-bonding and hydrophobic interaction, (Wong et al., 2015)
Magnetised AC 7.0 Dispersive π-π interactions (Wong et al., 2015)

adsorption is related to the H-bond formation between the domicile
amide group and the adsorbent surface (Hanbali et al., 2020; Álvarez-
Torrellas et al., 2016).
Consequent upon IBP adsorption, the appearance and disappearance
of certain peaks were witnessed. Chakraborty et al. (2018a) observed
the appearance of an O-H stretching peak at 3442 cm−1 due to the pres-
ence of the adsorbed free alcoholic groups of IBP on the physically mod-
ified biochar surface. Also, the introduction of sharp peaks due to the
presence of free amide groups of IBP onto chemically modified biochar
surface and the masking of carboxyl peaks confirmed the chemical com-
plexation between carbon materials and the adsorbed IBP molecules
(Chakraborty et al., 2018b). The appearance of post adsorption biochar
peaks at 2927, 1718 and 1582 cm−1 suggest the slight stretching of
alkyl C-H group and aromatic C_C stretching upon interaction with car-
bon material during IBP adsorption (Chakraborty et al., 2018b;
Chakraborty et al., 2020). Furthermore, Dubey et al. (2010) reported
that the dipolar interaction between the methyl-substituted amide
(–CONHCH3) functional group of the mesoporous activated carbon
and the resonance stable IBP molecules could eliminate the later
via the formation of a six-membered stable ring as shown in Fig. 4.
6. Equilibrium isotherm and kinetics modelling
6.1. Isotherm modelling
The adsorption isotherm indicates how the adsorbate is distributed
between the liquid and the solid phases when the adsorption process
reaches an equilibrium state (Baccar et al., 2012). It also provides useful
information on the design of an industrial adsorption process and for
porous solids characterisation (Keller and Staudt, 2005). Isotherm
modelling can be achieved either via a linear or nonlinear regression ap-
proaches (Aniagor and Menkiti, 2019). For linear regression models, the
selection of the best fit model is made based on the closeness of their re-
spective coefficient of determination (R2) to unity. Nonlinear regres-
sion, as an iterative procedure, employs relevant computer software
for parametric data estimation (Menkiti et al., 2018a; Menkiti and
Aniagor, 2018). The closer the R2-values are to unity and the smaller
the error-values, the better the nonlinear model fit (Menkiti et al.,
2018b).
Consequently, the relevance of adsorption isotherm shape in diag-
nosing adsorption characteristics cannot be overemphasised. According

9
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al. Science of the Total Environment 780 (2021) 146608

Fig. 4. Schematic representation of IBU adsorption onto mesoporous activated carbon (adapted from Dubey et al. (2010)).

to Giles et al. (1974), there are four (4) main isotherm classifications qmax K L C e
qe ¼ ð2Þ
namely, L, S, H and C groups. Adsorption of pharmaceuticals has been re- 1 þ KLCe
ported to exhibit an ‘L’ curve pattern, with obvious indentation about
the x-coordinate which signifies progressive active site saturation where Ce = equilibrium concentration of adsorbate (mg/L),
during adsorption (Baccar et al., 2012; Cabrita et al., 2010). However, qe = adsorbed adsorbate per gram of the adsorbent at equilibrium
during the adsorption of IBP onto carbonaceous materials, Álvarez- (mg/g), q max = maximum adsorption capacity (mg/g), KL = Langmuir
Torrellas et al. (2016) reported the existence of an S-type isotherm isotherm constant (L/mg). Furthermore, Langmuir's dimensionless con-
curve pattern, an implication of vertical multi-layered adsorbate pack- stant (separation factor) which provides information on the nature of
ing onto the active sites. adsorption (unfavourable when RL > 1, linear when RL = 1, favourable
Table 5, shows that the Langmuir and Freundlich isotherms emerged when 0 < RL < 1 and irreversible when RL = 0) is expressed as Eq. (3)
mostly as the best fit model for describing IBP uptake by the various ad- (Langmuir, 1916).
sorbent, except for few studies. This observation implies the predomi- 1
nance of either homogenous monolayer or heterogeneous multilayer RL ¼ ð3Þ
1 þ KLC0
adsorption during IBP uptake onto different adsorbents. Meanwhile,
quite a large number of studies employed the linear regression model- where C0 = initial adsorbate concentration (mg/L) and KL = Lang-
ling approach (see Table 5). Accordingly, this linear regression approach muir constant.
is riddled with inherent bias which stems from the variations in the y-
 
(ii) Freundlich model
axis for the linear form of the Langmuir Cq e and Freundlich (ln qe)
e

model as shown in Eqs. (1) & (4), respectively. Therefore, the compari-
This model applies for the description of heterogeneous and revers-
son of isotherm plots with differing ordinates may be prone to error,
ible multilayer adsorption, with the occurrence of lateral interaction be-
hence, the superiority of the nonlinear form of the model since they
tween adsorbed molecule. For the Freundlich model, there is always a
have uniform y-axis parameter as shown in Eqs. (2) & (5). Conse-
rapid decline in energy distribution as the adsorption process pro-
quently, the emergence of Langmuir and Freundlich isotherms as the
gresses (Freundlich, 1907). The linear and nonlinear of this empirical
commonly reported model of best-fit calls for a detail elucidation of
equation is expressed as Eqs. (4) & (5), respectively (Freundlich, 1907;
their respective assumptions and theoretical.
Abonyi et al., 2019).
(i) Langmuir model
1
ln qe ¼ ln K F þ lnC e ð4Þ
n
Langmuir model is one of the most widely applied empirical models in
the sorption of aqueous pollutant (Aniagor and Menkiti, 2020; Langmuir, 1
qe ¼ K F C ne ð5Þ
1916). It thrives on the following assumptions (a) Monolayer adsorption
on distinct homogeneous adsorbent sites (b) Constant sorption energy
which is independent on the extent of active site saturation (c) rapid where ‘n’ = adsorption intensity (adsorption is assumed linear
weakening of the forces of attraction between adsorbate molecule with when 1n equals unity), ‘Ce’ = equilibrium adsorbate concentration
coverage (d) Existence of fixed sorption capacity on structurally homog- (mg/L), ‘qe’ = adsorbed adsorbate amount per gram of the adsorbent
enous adsorbents (e) Existence of identical and energetically uniform at equilibrium (mg/g) and ‘KF’ = Freundlich constant.
sites with the capacity for lateral interaction with adjacent sites
(Langmuir, 1916). The linear and nonlinear form of the Langmuir equa- 6.2. Kinetic modelling
tion is depicted in Eqs. (1) & (2), respectively (Langmuir, 1916).
Information on the sorption rate is useful for the design and subse-
quent scale-up of laboratory-scale experiments. This information is
Ce 1 Ce
¼ þ ð1Þ furnished from the fitting of experimental kinetic data to dedicated ki-
qe qm K L qm
netic models (Hashem et al., 2020). The estimation of the activation

10
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al. Science of the Total Environment 780 (2021) 146608

Table 5
Best fit isotherm and kinetic models for IBP uptake.

Adsorbent Isotherm models Kinetic models

Best fit Type R2 Best fit Type R2 Ref.

Untreated onion skin Freundlich Linear 0.924 PSO Linear 0.991 (Abbas et al., 2017)
H2SO4-treated onion skin Freundlich Linear 0.946 PSO Linear 0.996 (Abbas et al., 2017)
HCl-treated onion skin Freundlich Linear 0.966 PSO Linear 0.992 (Abbas et al., 2017)
H3PO4-treated onion skin Freundlich Linear 0.924 PSO Linear 0.981 (Abbas et al., 2017)
Mesoporous carbon aerogel Freundlich Linear 0.933 PSO Linear 0.999 (Abolhasani et al., 2019)
Iron nano-adsorbent Freundlich Linear 0.999 PFO Linear 0.999 (Ali et al., 2016)
Alkaline AC Langmuir Nonlinear 1.000 PSO Nonlinear 1.000 (Ali et al., 2019)
Oxidized AC Langmuir Nonlinear 1.000 PSO Nonlinear 1.000 (Ali et al., 2019)
Basic functionalised AC Langmuir Nonlinear 1.000 PSO Nonlinear 1.000 (Ali et al., 2019)
Hydrophobic functionalised AC Langmuir Nonlinear 1.000 PSO Nonlinear 1.000 (Ali et al., 2019)
Calgon F-400 AC GAB Linear NS PSO Nonlinear 0.998 (Álvarez-Torrellas et al., 2016)
Multi-wall CNT GAB Linear NS PSO Nonlinear 0.996 (Álvarez-Torrellas et al., 2016)
Peachstone acid-AC GAB Linear NS PSO Nonlinear 0.999 (Álvarez-Torrellas et al., 2016)
Rice husk acid-AC GAB Linear NS PSO Nonlinear 0.999 (Álvarez-Torrellas et al., 2016)
Zeolite coated magnetic nanoparticle Freundlich Nonlinear 1.000 PSO Linear 0.999 (Attia and Hu, 2013)
Olive cake AC Langmuir Nonlinear 0.971 PSO Linear 1.000 (Baccar et al., 2012)
Graphene oxide nanoplatelet Langmuir Linear 0.998 PSO Linear 0.999 (Banerjee et al., 2016)
β-cyclodextrin-grafted chitosan Freundlich Linear 0.988 PFO Linear 0.992 (Bany-Aiesh et al., 2015)
Acid-functionalised bean husk Langmuir Linear 0.993 PSO Nonlinear 0.999 (Bello et al., 2019)
Activated coconut husk Langmuir Linear 0.998 PSO Linear 0.999 (Bello et al., 2020)
Bioactive hydroxyapatite nano-rods Sip NS 0.996 Avrami NS 0.998 (Benedini et al., 2019)
O-carboxymethyl-N-laurylchitosan/γ-Fe2O3 Sip Nonlinear 0.972 PSO Nonlinear 0.999 (Chahm and Rodrigues, 2017)
Wood apple biochar Langmuir Linear 0.943 PSO Linear 0.980 (Chakraborty et al., 2018a)
Activated wood apple biochar Langmuir Linear 0.966 PSO Linear 0.958 (Chakraborty et al., 2018a)
Acid activated biochar Freundlich Linear 0.983 PSO Linear 0.998 (Chakraborty et al., 2018b)
Steam activated biochar Freundlich Linear 0.977 PSO Linear 0.997 (Chakraborty et al., 2018b)
Steam activated coconut biochar Langmuir Nonlinear 0.992 PFO Nonlinear 0.983 (Chakraborty et al., 2019)
Acid activated coconut biochar Langmuir Nonlinear 0.996 PFO Nonlinear 0.992 (Chakraborty et al., 2019)
Steam activated date stone biochar Langmuir Linear 0.973 PSO Linear 0.995 (Chakraborty et al., 2020)
Acid activated date stone biochar Langmuir Linear 0.990 PSO Linear 0.997 (Chakraborty et al., 2020)
SWCNTs Polanyi-Manes l Nonlinear 0.999 – – – (Cho et al., 2011)
MWCNTs Polanyi-Manes Nonlinear 0.999 – – – (Cho et al., 2011)
Oxidized MWCNTs Polanyi-Manes Nonlinear 0.999 – – – (Cho et al., 2011)
Lignosulfonate-based sorbent Langmuir Linear 0.996 PSO Linear 0.999 (Ciesielczyk et al., 2019)
AC (F400) Freundlich Nonlinear 0.960 – – – (Delgado et al., 2015)
Activated biochar Freundlich Linear 0.990 PSO Linear 0.999 (Zhang et al., 2020b)
Activated biochar Langmuir Nonlinear 0.969 PSO Linear 0.993 (Dubey et al., 2010)
Modified aluminium mineral Radke–Prausnitz Nonlinear 0.989 PSO Nonlinear 0.938 (Dwivedi et al., 2011)
Pinewood biochar Freundlich Linear 0.816 PSO Linear 0.999 (Essandoh et al., 2015)
AC Sips Nonlinear 0.999 PSO Nonlinear 0.989 (Fröhlich et al., 2018a)
Sonicated AC Sips Nonlinear 0.999 PSO Nonlinear 0.963 (Fröhlich et al., 2018a)
AC Redlich-Peterson Nonlinear 0.999 – – – (Fröhlich et al., 2018b)
Sonicated AC Redlich-Peterson Nonlinear 0.999 – – – (Fröhlich et al., 2018b)
Magnetised AC Sips Nonlinear 0.998 PSO Nonlinear 0.997 (Fröhlich et al., 2019)
Organobentonite Langmuir & Freundlich Nonlinear 0.942–0.987 PSO Linear 0.999 (Ghemit et al., 2019)
TiO2 modified AC Langmuir-Freundlich Nonlinear >0.960 PSO Nonlinear 0.985 (Guedidi et al., 2013)
Activated carbon cloth Langmuir-Freundlich Nonlinear 0.960 Elovich Linear 0.990 (Guedidi et al., 2017)
Microporous AC Langmuir-Freundlich Nonlinear 0.950 – – – (Guedidi et al., 2017)
Hydroxyl amine-functionalised MWCNT Langmuir Linear 0.990 PSO Linear 0.990 (Hanbali et al., 2020)
Hydrazine functionalised MWCNT Langmuir Linear 0.87 PSO Linear 0.990 (Hanbali et al., 2020)
Amino acid-functionalised MWCNT Langmuir Linear 0.94 PSO Linear 0.970 (Hanbali et al., 2020)
Mesoporous carbon Langmuir-Freundlich Nonlinear 0.993 PSO Nonlinear 0.992 (Jedynak et al., 2019)
CO2 activated mesoporous carbon Langmuir-Freundlich Nonlinear 0.990 PSO Nonlinear 0.991 (Jedynak et al., 2019)
Commercial AC Langmuir-Freundlich Nonlinear 0.981 PSO Nonlinear 0.993 (Jedynak et al., 2019)
Commercial MIEX Freundlich Nonlinear 0.982 PSO Nonlinear >0.90 (Jiang et al., 2015)
Synthesised MIEX Langmuir Nonlinear 0.996 PSO Nonlinear >0.90 (Jiang et al., 2015)
Unmodified magnetic biochar Langmuir Nonlinear >0.90 PSO Nonlinear 0.982 (Ai et al., 2020)
Modified magnetic biochar Langmuir Nonlinear >0.90 PFO Nonlinear 0.987 (Ai et al., 2020)
Unmodified polymer Radke-prausnitz Nonlinear 0.972 – – – (Jin and Row, 2005)
Molecular Imprinted Polymer Radke-prausnitz Nonlinear 0.999 – – – (Jin and Row, 2005)
MOFs – – – PSO Linear >0.90 (Jun et al., 2019)
Oxygen pyrolysed biochar Langmuir Linear 0.983 – – – (Jung et al., 2015)
Nitrogen pyrolysed biochar Langmuir Linear 0.991 – – – (Jung et al., 2015)
AC Freundlich Linear 0.978 PSO Linear 0.967 (Kaur et al., 2018)
Modified cellulosic sisal fiber Sip Linear 0.999 PSO Linear 0.999 (Khadir et al., 2020b)
Clay Freundlich Linear 0.980 PSO Linear 0.999 (Khazri et al., 2017)
Modified magnetic nanomaterial Langmuir Linear 0.98 PSO Linear 0.98 (Kollarahithlu and Balakrishnan, 2019)
Unmodified clay mineral – – – PSO Linear >0.99 (Kurczewska et al., 2020)
Functionalised clay Langmuir Linear 0.984 PSO Linear >0.99 (Kurczewska et al., 2020)
Polyamidoamine functionalised clay Langmuir Linear 0.994 PSO Linear >0.99 (Kurczewska et al., 2020)
C3N4/soot Langmuir Linear >0.99 NS NS NS (Liao et al., 2018)
W-biochar Langmuir Nonlinear 0.984 PSO Nonlinear >0.949 (Lin et al., 2017)
MG 1050 Freundlich Nonlinear 0.97 – – – (Luján-Facundo et al., 2019)

(continued on next page)

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S.N. Oba, J.O. Ighalo, C.O. Aniagor et al. Science of the Total Environment 780 (2021) 146608

Table 5 (continued)

Adsorbent Isotherm models Kinetic models

Best fit Type R2 Best fit Type R2 Ref.

BM 8 Freundlich Nonlinear 1.00 – – – (Luján-Facundo et al., 2019)

Reused AC Langmuir Nonlinear 0.94 – – – (Luján-Facundo et al., 2019)
Modified CNT Langmuir Linear 0.991 PSO Linear 0.999 (Lung et al., 2020)
Molecular Imprinted polymer Langmuir Linear 0.995 PSO Linear >0.99 (Madikizela and Chimuka, 2016)
Non-imprinted polymer Langmuir Linear 0.999 PSO Linear 0.984 (Madikizela and Chimuka, 2016)
Modified montmorillonite Langmuir Nonlinear 0.953 PSO Nonlinear >0.999 (Malvar et al., 2020)
AC Langmuir Nonlinear – PSO Nonlinear 0.999 (Mansouri et al., 2015)
Modified mica Freundlich Linear 0.994 PSO Linear 0.993 (Martín et al., 2019)
Modified montmorillonite Langmuir Linear >0.998 PSO Linear 0.999 (Martín et al., 2019)
Chemical activated carbon Langmuir Linear >0.99 PSO Linear 0.99 (Mestre et al., 2007)
Chemical + steam activated carbon Langmuir Linear >0.99 PSO Linear >0.99 (Mestre et al., 2007)
Chemically activated cork Langmuir Linear – PSO Linear 0.999 (Mestre et al., 2009)
Steam + chemically activated cork Langmuir Linear – PSO Linear 0.999 (Mestre et al., 2009)
Physically activated PET Langmuir Linear – PSO Linear 0.999 (Mestre et al., 2009)
Physically activated coal Langmuir Linear – PSO Linear 0.999 (Mestre et al., 2009)
Physically activated wood Langmuir Linear – PSO Linear 0.999 (Mestre et al., 2009)
Physically + wet oxidated wood Langmuir Linear – PSO Linear 0.999 (Mestre et al., 2009)
Amine grafted pumice-derived silica aerogel Khan Nonlinear 0.99 – – – (Mohseni-Bandpei et al., 2020)
Chemically modified N-biochar Langmuir Linear >0.99 PSO Linear >0.90 (Mondal et al., 2016b)
Steam activated biochar Langmuir Linear >0.95 PSO Linear >0.90 (Mondal et al., 2016b)
MOFs Langmuir Nonlinear 0.998 – – – (Bhadra et al., 2017)
MOFs Langmuir Nonlinear 0.997 PSO Nonlinear 0.992 (Nguyen et al., 2019)
AC Freundlich Linear 0.990 PSO Linear 0.976 (Nourmoradi et al., 2018)
Chili seed Biochar Langmuir Nonlinear NS – – – (Ocampo-Perez et al., 2019)
Chitosan-modified waste tire rubber Freundlich Linear 0.995 PSO Linear >0.999 (Phasuphan et al., 2019)
Powdered AC (Norit SA Super) Langmuir Linear 0.943 PSO Linear 0.964 (Puszkarewicz et al., 2017)
Powdered AC (Carbopol MB5) Freundlich Linear 0.954 PFO Linear 0.987 (Puszkarewicz et al., 2017)
Functionalised nano-clay Freundlich nonlinear 0.953 PSO Linear 0.962 (Rafati et al., 2018)
Microwave activated bamboo waste Langmuir Linear >0.998 PSO Linear >0.99 (Reza et al., 2014)
Living Phaeodactylum Tricornutum biomass Langmuir Nonlinear 0.880 PSO Nonlinear NS (Santaeufemia et al., 2018)
Dead Phaeodactylum Tricornutum biomass Langmuir nonlinear 0.926 PSO Nonlinear NS (Santaeufemia et al., 2018)
Raw biochar Freundlich Linear 0.969 PFO Linear 0.974 (Show et al., 2020)
Chemically activated biochar Langmuir Linear 0.994 PSO Linear 0.982 (Show et al., 2020)
Microwave irradiated thermally activated shell Redlich-Peterson Nonlinear 0.996 PSO Nonlinear >0.950 (Sivarajasekar et al., 2017)
Microwave irradiated activated Albizialebbeck pods Smith Nonlinear 0.997 Avrami Nonlinear >0.98 (Sivarajasekar et al., 2017)
AC Sips Nonlinear >0.90 PSO Nonlinear >0.99 (Streit et al., 2020)
MOFs (UiO-66) Langmuir Nonlinear 0.964 PSO Nonlinear 0.999 (Sun et al., 2019)
MOFs (UiO-66-NH2) Langmuir Nonlinear 0.994 PSO Nonlinear 0.994 (Sun et al., 2019)
Amberlite resin Langmuir Linear 0.993 PSO Linear 0.998 (Taleb et al., 2017)
Mesoporous MOFs Langmuir NS 0.989 PSO NS >0.999 (Tran et al., 2020)
Functionalised carbonaceous material Freundlich NS 0.968 PSO NS 0.999 (Sekulic et al., 2019)
Mesoporous Carbon – – – PSO NS 0.998 (Ulfa et al., 2019)
Nano Zinc Oxide Temkin Linear 0.997 – – – (Ulfa and Iswanti, 2020)
MIEX Freundlich Linear >0.98 PSO Linear >0.98 (Wang et al., 2015)
Unmodified palm shell AC Freundlich Nonlinear 0.997 – – – (Wong et al., 2015)
Palm shell AC modified with 3.8% Fe Freundlich Nonlinear 0.978 – – – (Wong et al., 2015)
Palm shell AC modified with 7.8% Fe Langmuir Nonlinear 0.993 – – – (Wong et al., 2015)
Palm shell AC modified with 8.6% Fe Langmuir Nonlinear 0.837 – – – (Wong et al., 2015)
Molecularly imprinted membranes – – – PSO Nonlinear 0.995 (Wu et al., 2018c)
Non-imprinted membranes – – – PSO Nonlinear 0.992 (Wu et al., 2018c)
Molecularly imprinted membranes – – – PSO Nonlinear 0.998 (Wu et al., 2018b)
Nanosheets-infiltrated membranes – – – PSO Nonlinear 0.996 (Wu et al., 2018b)
Molecular imprinted polymer – – – PSO Linear >0.99 (Zhou et al., 2013)
Non-imprinted polymer – – – PSO Linear >0.99 (Zhou et al., 2013)
MIEX with polyacrylic matrix Langmuir Nonlinear >0.97 PFO Nonlinear >0.97 (Zhang et al., 2020a)
Modified Organo silica (G16–2-16-SiNSs) Hill Nonlinear 0.9982 PSO Nonlinear >0.99 (Zeng et al., 2018a)
Modified Organo silica (G12–2-12-SiNSs) Hill Nonlinear 0.9862 PSO Nonlinear >0.99 (Zeng et al., 2018b)

GAB = Guggenheim–Anderson–de Boer model.

NS = Not specified.

energy of a process via the Arrhenius equation can also be achieved using
kinetic models (Podder and Majumder, 2019). The kinetic model of best
fit obtained from the reviewed IBP adsorption papers is presented in
Table 5. It could be observed that IBP adsorption onto various adsorbents
was generally best-fitted to the pseudo-second-order (PSO) model, ex-
cept in very few studies (Table 5). It is however worrisome that despite
the availability of numerous computer software for nonlinear data fittings
(Lima et al., 2020) and the bias associated with the nonlinear model
linearisation (Aniagor and Menkiti, 2018), some researchers still opted
for the linear regression modelling approach as shown in Table 5.
With PSO as the best fit model, an adsorbate-to-adsorbent electron
transfer is presumed as the obvious characteristics of such an adsorption
system. Furthermore, the emergence of linear PSO equation as the best
fit in most of the reviewed literature may be erroneous and problematic,
as only one out of all the PSO linearised equations has found successful
application in solid-liquid adsorption system (Lima et al., 2020). There-
fore, this singular version of PSO linear equation is assumed to adjust
practicably to all the reported kinetic results (Lima et al., 2020). As a re-
sult, many researchers have usually concluded that the experimental
data of adsorption kinetics were well described by the PSO model as
shown in Table 5. However, to some extent, such a conclusion is incor-
rect because of certain modelling errors. Furthermore, as already stated
in Section 6.1, the comparison between models with different ordinate
is deemed erroneous, hence the need for the use of nonlinear fitting

12
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al.
regression. The linear and nonlinear equation for the PSO model is
expressed as Eqs. (6) & (7), respectively (Lima et al., 2020).
t 1 1 some hydration sheath by ions could account for ΔH° > 0 in adsorption.
¼ þ t ð6Þ
qt k2 ðqe2 Þ2 qe2
K 2 q2e t
qe ¼ ð7Þ
1 þ K 2 qe t
7. Thermodynamics modelling
Thermodynamics of adsorption give insights into energetic changes
resulting from the interactions between targeted pollutants and adsor-
bents. The changes are investigated as a function of temperature and
measurable thermodynamic variables – Gibbs free energy (ΔG°), en-
thalpy (ΔH°), and entropy (ΔS°) (Bello et al., 2019). Respectively, the
parameters refer to the spontaneity, energy transfer, and degree of dis-
orderliness of the process and jointly define its features (Saha and
Chowdhury, 2011). Eqs. (8)-(10) are mathematical representations of
these parameters obtained from classical Van't Hoff expression and
the values of adsorption equilibrium constant Keq (Bonilla-Petriciolet
et al., 2019):
ΔG ¼ −RT ln K eq ð8Þ
ΔG ¼ ðΔH  −TΔS Þ ð9Þ
ΔS ΔH 
ln K eq ¼ − ð10Þ
R RT
where R = universal gas constant, T is the temperature in Kelvin. Keq
is estimated from the experimental results of adsorption isotherms at
different temperatures. If ΔG° < 0, then the adsorption process is always
feasible and spontaneous, while if ΔG° > 0 then it is non-spontaneous
and unfavourable. Positive ΔH° denotes that the adsorption is endother-
mic whereas it is exothermic in the case of negative ΔH°. Lastly, positive
ΔS° denotes an increase in disorderliness resulting in more adsorption
activity while a decrease in such activity is characterised with ΔS° < 0
(Ghosal and Gupta, 2017).
From Table 6, the sorptive removal of IBP by biochar from organic
precursors (Chakraborty et al., 2018a; Zhang et al., 2020b; Mondal
et al., 2016a; Chakraborty et al., 2018b; Chakraborty et al., 2019;
Chakraborty et al., 2020; Show et al., 2020); AC (Guedidi et al., 2013;
Ali et al., 2019; Bello et al., 2020; Bello et al., 2019; Ali et al., 2016;
Sivarajasekar et al., 2017; Sivarajasekar et al., 2018); resins (Taleb
et al., 2017); inorganic materials (Malvar et al., 2020; Fröhlich et al.,
2019; Van Tran et al., 2019; Khazri et al., 2017); carbon- and
magnetic-based adsorbents (Hanbali et al., 2020; Lung et al., 2020; Ali
et al., 2016) was thermodynamically favourable as seen in the negative
ΔG° values obtained at the studied temperatures. The feasibility could
be attributed to the abundance of active sites which were well-
engineered and suitable for adsorption; hence, the spontaneity of the
process using the aforementioned adsorbents. However, the non-
spontaneity of IBP adsorptive removal occurred with magnetic chitosan
nanocomposite (Chahm and Rodrigues, 2017) and AC from oak acorn
(Nourmoradi et al., 2018) due to the obtained positive ΔG° values.
This implies that IBP adsorption on such materials would occur under
an external influence/force; obviously, such situation is unfavourable
and denotes random feasibility (Ahmadi et al., 2019).
The sign convention and magnitude of change in enthalpy depict the
nature and type of adsorption, respectively. Table 6 showed the exo-
thermic nature (i.e. ΔH° < 0) of IBP adsorption by biochars from organic
precursors (Chakraborty et al., 2018a; Chakraborty et al., 2018b;
Chakraborty et al., 2019; Chakraborty et al., 2020; Show et al., 2020),
magnetic chitosan (Chahm and Rodrigues, 2017), modified organo-
13
Science of the Total Environment 780 (2021) 146608
silica (Zeng et al., 2018a), ACs (Reza et al., 2014; Sivarajasekar et al.,
2018), but was predominantly endothermic (i.e. ΔH° > 0) for most ad-
sorbents. Anastopoulos and Kyzas (2016) suggested that the release of
This is because the energy consumed by dehydration in most situations
is greater than the exothermicity of ions adsorbed on the surface of the
material. Adsorption can be divided into two categories, physisorption
and chemisorption when it comes to the magnitude of change in en-
thalpy. Physisorption is characterised by reversibility and weak bonding
(mostly Van der Waal forces) and has ΔH° values between 2.1 and 20.9
KJ/mol (Saha and Chowdhury, 2011). Patel (2019) suggested that for
this adsorption, the adsorbate molecules are not bound to a particle-
side on the adsorbent surface, hence, their free movement around it. Ad-
sorbents wherein physisorption was predominant include iron nano-
composite (Ali et al., 2016), AC from date palm (Ali et al., 2019),
natural clay (Khazri et al., 2017), functionalized clay (Kurczewska
et al., 2020), biochar from biomass (Chakraborty et al., 2019;
Chakraborty et al., 2020). For chemisorption, ΔH° values range between
80 and 200 KJ/mol and it is predominantly characterised by strong elec-
trostatic forces which establish chemical bonds between adsorbate and
adsorbent. Based on the ΔH° values in Table 6, chemisorption was the
case for functionalised agricultural wastes (Bello et al., 2020; Bello
et al., 2019), GO nanoplatelets (Banerjee et al., 2016), modified cellu-
losic sisal fiber (Khadir et al., 2020b) to mention but a few.
The change in entropy (ΔS°) is a reflection of two important aspects
– the affinity of the adsorbent towards the adsorbate species and the de-
gree of disorderliness within the system (Al-Ghouti and Da'ana, 2020).
These features could be understood from the sign convention of this pa-
rameter. Findings from reviewed works of literature (Table 6) showed
that there is more affinity between IBP and modified natural adsorbents
– biochar; ACs (Guedidi et al., 2017; Fröhlich et al., 2019; Guedidi et al.,
2013; Wong et al., 2015; Ali et al., 2019); activated biomasses (Reza
et al., 2014; Bello et al., 2020; Sivarajasekar et al., 2017) than synthetic
(Malvar et al., 2020; Kurczewska et al., 2020; Khazri et al., 2017) and
other specialized adsorbents (Hanbali et al., 2020; Taleb et al., 2017;
Jun et al., 2019). This could be due to the development of a highly po-
rous surface impacted by activation which aids structural adjustments
on the loaded matrices of these materials, hence, more freedom is
accorded to IBP ions to adsorb on available sites (Saha and
Chowdhury, 2011). With ΔS° < 0, findings showed that reduced IBP ad-
sorption occurred on biochar (Chakraborty et al., 2018a; Mondal et al.,
2016a; Chakraborty et al., 2018b; Chakraborty et al., 2019;
Chakraborty et al., 2020; Mondal et al., 2016b); modified organo-silica
(Zeng et al., 2018a); activated biomass (Reza et al., 2014). This could
be as a result of significant IBP species which remain in the bulk liquid
phase when freed from the solid phase, hence, there is reduced adsorp-
tion activity. For ΔS° > 0, there exists more randomness at the solid/so-
lution interface, as well as structural adjustments in the adsorbate and
adsorbent (Saha and Chowdhury, 2011). Apart from materials that ex-
hibited reduced IBP adsorption (as seen from negative ΔS° values listed
in Table 6), most adsorbents showed increased disorderliness. This
could be due to the increase in translational entropy as a molecule of
IBP is displaced by numerous water molecules, hence, energetic distor-
tions among the adsorbate species (Hiew et al., 2019).
Based on the energetic analysis seen thermodynamic values pre-
sented in Table 6, it can be surmised that IBP adsorption is largely spon-
taneous, with heat absorbed from the surrounding and with high
disorderliness for most adsorbents.
8. Desorption and reusability
Desorption, which is the reverse of adsorption, is essential for adsor-
bent regeneration as a way of keeping treatment costs down, reducing
wastes, and increasing the chances of recovering pore sites (Lu et al.,
2020; Daneshvar et al., 2017). This results in the development of high-
efficient recovery processes in effluent treatment involving sturdy and
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al. Science of the Total Environment 780 (2021) 146608

Table 6
Summary of thermodynamics modelling for IBP.

Adsorbent Thermodynamic parameters Ref.

Temp (K) ΔG° (kJ/mol) ΔH° (kJ/mol) ΔS° (J/mol.K)

Iron nanocomposite 298 −10.24 −2.710 24.20 (Ali et al., 2016)

AC from date palm leaves 298 −4.810 18.18 77.16 (Ali et al., 2019)
Oxidized AC 298 −6.100 22.19 94.92 (Ali et al., 2019)
Surface functionalised AC-1 298 −0.660 21.20 73.37 (Ali et al., 2019)
Surface functionalised AC-2 298 −2.690 15.58 61.31 (Ali et al., 2019)
Functionalised bean husks 303 −26.68 96.23 109,111 (Bello et al., 2019)
Wood apple biochar (raw) 298 −5.537 −156.2 −508.8 (Chakraborty et al., 2018a)
Wood apple steam activated biochar 298 −7.614 −156.5 −512.3 (Chakraborty et al., 2018a)
GO nano-platelets 293 −3282 233.9 90.70 (Banerjee et al., 2016)
Magnetic-chitosan 293 0.290 −11.20 −39.00 (Chahm and Rodrigues, 2017)
Activated coconut husk 303 −22.634 106.63 274.0 (Bello et al., 2020)
Sugarcane bagasse biochar (steam activated) 298 −0.374 −89.84 −298.0 (Chakraborty et al., 2018b)
Sugarcane bagasse biochar (chemically activated) 298 −0.215 −69.12 −232.0 (Chakraborty et al., 2018b)
AC cloth 298 −5.800 45.00 170.4 (Guedidi et al., 2017)
Chemically modified AC cloth 298 −1.000 60.20 205.4 (Guedidi et al., 2017)
Thermally modified AC cloth 298 −6.700 11.60 61.60 (Guedidi et al., 2017)
Granulated AC 298 −1.100 74.60 254,100 (Guedidi et al., 2013)
Chemically modified granulated AC 298 −7.300 8.100 51,600 (Guedidi et al., 2013)
Thermally modified granulated AC 298 −4.500 31.90 122,200 (Guedidi et al., 2013)
Mesoporous silver-aluminium material 308 −0.046 2.659 10.07 (Dwivedi et al., 2011)
AC from mugwort 308 −3.297 57.46 198.2 (Dubey et al., 2010)
Date stone biochar (physically activated) 298 −3.710 −12.42 −306.0 (Chakraborty et al., 2020)
Date stone biochar (chemically activated) 298 −2.520 −6.190 −135.0 (Chakraborty et al., 2020)
Coconut shell biochar (physically activated) 298 −0.259 −3.610 −146.0 (Chakraborty et al., 2019)
Coconut shell biochar (chemically activated) 298 −0.458 −3.920 −135.0 (Chakraborty et al., 2019)
Biochar from Alternanthera philoxeroides 293 −23.53 −4.720 63.20 (Zhang et al., 2020b)
Hydroxylamine functionalized m-MWCNT 298 −1.200 2.450 12.40 (Hanbali et al., 2020)
Cystine functionalized m-MWCNT 298 −7.860 123.7 441.6 (Hanbali et al., 2020)
Hydrazine functionalized m-MWCNT 298 −1.940 48.09 167.9 (Hanbali et al., 2020)
Biochar from mung bean husk 298 −10.93 −42.13 −104.7 (Mondal et al., 2016a)
Chemically modified Parthenium hysterophorus biochar 303 −3.735 −50.81 −158.2 (Mondal et al., 2016b)
Carbon nitride/soot 288 −6.570 3.760 35.89 (Liao et al., 2018)
Modified cellulosic sisal fiber 298 −17.98 227.5 152.3 (Khadir et al., 2020b)
Activated Aegle marmelos correa fruit shell 293 −45.21 0.678 156.6 (Sivarajasekar et al., 2017)
AC from Albizialebbeck seed pods 293 −52.81 −0.718 216.2 (Sivarajasekar et al., 2018)
Biochar from tamarind seed (raw) 298 −2.310 −65.52 −0.211 (Show et al., 2020)
Biochar from tamarind seed (chemically activated) 298 −6.010 −113.5 −0.363 (Show et al., 2020)
Amberlite resin (for IBP in water) 298 −8.040 21.59 99.85 (Taleb et al., 2017)
Amberlite resin (for IBP in ethanol) 298 −7.980 27.09 117.1 (Taleb et al., 2017)
Mesoporous carbon from MOF 298 −51.60 −23.40 94.50 (Van Tran et al., 2019)
Molecularly imprinted polymers (MIP) 298 −9.617 4.667 39.39 (Zhou et al., 2013)
Non-imprinted polymers (NIP) 298 −5.304 9.228 48.76 (Zhou et al., 2013)
Silk sericin 300 −133.5 19.33 151,377 (Verma and Subbiah, 2017)
AC from magnetised palm-shell 298 −1.690 6.350 21.61 (Wong et al., 2015)
NiFe2O4/activated carbon magnetic composite 298 −34.18 20.27 180.0 (Fröhlich et al., 2019)
AC 298 −8.200 19.20 91.00 (Fröhlich et al., 2018a)
Sonicated AC 298 −9.700 25.30 117.0 (Fröhlich et al., 2018a)
Activated bamboo waste 303 −5.890 −21.20 −50.05 (Reza et al., 2014)
AC from oak acorn 298 0.850 24.85 80.50 (Nourmoradi et al., 2018)
Modified montmorillonite 308 −10.10 −26.40 119.9 (Malvar et al., 2020)
CNT nanocomposite 293 −26.34 18.15 181.9 (Lung et al., 2020)
MOF – – 5.230 60.00 (Jun et al., 2019)
Natural clay 293 −0.007 10.50 30.00 (Khazri et al., 2017)
Amino functionalized clay mineral 298 −2.490 2.490 20.96 (Kurczewska et al., 2020)
Polyamidoamine functionalized clay mineral 298 −3.240 3.310 22.03 (Kurczewska et al., 2020)
Modified organo-silica nanosheets 298 −0.960 −5.570 −15.47 (Zeng et al., 2018a)
Microporous activated carbon 298 −7.060 −4.060 10.04 (Guedidi et al., 2020a)

efficient adsorbents (Lee and Lee, 2016). Important parameters consid-
ered in desorption and reusability studies include eluent type, number
of cycle and removal efficiency, and collectively they denote adsorbent
strength. The summary of IBP desorption, adsorbent removal efficiency,
and reusability is presented in Table 7. Some of the eluents utilised in
IBP desorption and adsorbent regeneration include organic compounds
– acetone (Van Tran et al., 2019; Jun et al., 2019), methanol (Essandoh
et al., 2015; Chakraborty et al., 2018a; Reza et al., 2014; Chakraborty
et al., 2018b; Chakraborty et al., 2019; Chakraborty et al., 2020; Show
et al., 2020; Chakraborty and Halder, 2020; Mestre et al., 2011), ethanol
(Ghemit et al., 2019; Liao et al., 2018; Chahm and Rodrigues, 2017); in-
organic compounds – HCl (Lung et al., 2020; Zeng et al., 2018a; Bello
et al., 2019; Ali et al., 2016), NaCl (Zhang et al., 2020a), NaOH (Hanbali
et al., 2020; Álvarez-Torrellas et al., 2016); distilled water
(Moulahcene et al., 2016) and binary solutions (Bhadra et al., 2017;
Kollarahithlu and Balakrishnan, 2019; Wu et al., 2018c). On the premise
that desorption is a reverse of adsorption, Bello et al. (2019) pointed out
that the type of desorbing eluent could serve as an indicator of the
mechanism of adsorption. For instance, if the eluent is water, the ad-
sorption is by weak bonds. If the solution is acidic or alkaline, ion ex-
change is used. If organic acids will desorb the pollutant, then, the
adsorbate is bound onto the adsorbent by chemical bonds.
Organic solvents were the most preferred eluents for desorption due
to the high solubility of IBP in such compounds (Kollarahithlu and
Balakrishnan, 2019). Alcohols, as eluents, have significant effects on ad-
sorbent stability as they enhance intramolecular interactions and can

14
 Table 7
Summary of desorption and reusability for IBP.

Adsorbent Elution Removal efficiency Removal efficiency at Removal equilibrium Removal equilibrium Number Ref.
agent at 1st cycle (%) the nth cycle (%) concentrations at 1st cycle (mg/g) concentrations at nth cycle (mg/g) of cycles

Iron nanocomposite HCl 85.00 92.00 – – 8 (Ali et al., 2016)

AC from date palm leaves – – – >40 >20 2 (Ali et al., 2019)
Oxidized AC – – – 50 >45 2 (Ali et al., 2019)
Surface functionalised AC-1 – – – 20 <10 2 (Ali et al., 2019)
Surface functionalised AC-2 – – – >30 >10 2 (Ali et al., 2019)
Functionalised bean husks HCl 88.75 94.68 – – 4 (Bello et al., 2019)
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al.

Wood apple biochar (raw) Methanol 74.00 61.00 – – 4 (Chakraborty et al., 2018a)
Wood apple steam activated biochar Methanol 81.00 69.00 – – 4 (Chakraborty et al., 2018a)
Graphene oxide nano-platelets – 98.17 95.91 – – 10 (Banerjee et al., 2016)
Magnetic-chitosan Ethanol – – 35 30 6 (Chahm and Rodrigues, 2017)
Biochar from sugarcane bagasse (steam Methanol >75 67.42 – – 4 (Chakraborty et al., 2018b)
activated)
Biochar from sugarcane bagasse Methanol 90.00 78.47 – – 4 (Chakraborty et al., 2018b)
(chemically activated)
Date stone biochar (physically activated) Methanol 92.43 69.54 – – 5 (Chakraborty et al., 2020)
Date stone biochar (chemically activated) Methanol 85.26 61.89 – – 5 (Chakraborty et al., 2020)
Coconut shell biochar (physically activated) Methanol 70.18 57.13 – – 4 (Chakraborty et al., 2019)
Coconut shell biochar (chemically Methanol 74.31 60.21 – – 4 (Chakraborty et al., 2019)
activated)
Hydroxyl-amine functionalized m-MWCNT NaOH 61.50 56.00 – – 3 (Hanbali et al., 2020)
Cystine functionalised m-MWCNT NaOH 98.00 92.30 – – 3 (Hanbali et al., 2020)
Hydrazine functionalised m-MWCNT NaOH 93.00 87.00 – – 3 (Hanbali et al., 2020)
Carbon nitride/soot Ethanol 99.70 97.1 – – 5 (Liao et al., 2018)
Modified cellulosic sisal fiber – 95.00 >76 – – 5 (Khadir et al., 2020b)
Activated Aegle marmelos correa fruit shell Acetic acid 60.00 <50 – – 9 (Sivarajasekar et al., 2017)

15
Biochar from tamarind seed (raw) Methanol 70.31 62.54 – – 4 (Show et al., 2020)
Biochar from tamarind seed (chemically Methanol 89.31 79.88 – – 4 (Show et al., 2020)
activated)
Mesoporous carbon Acetone – – 88.5 73.4 5 (Van Tran et al., 2019)
Powdered AC from magnetised palm-shell (Wong et al., 2015)
Palm shell AC modified with 3.8% Fe – – – 122 70 6 (Wong et al., 2015)
Palm shell AC modified with 8.6% Fe – – – 112 86 6 (Wong et al., 2015)
Activated bamboo waste Methanol 96.87 (negligible) 2 (Reza et al., 2014)
CNT nanocomposite HCl 85.60 80.00 5 (Lung et al., 2020)
MOF Acetone 72.00 70.00 70 68 4 (Jun et al., 2019)
Modified organo-silica HCl – – 47.68 39.09 3 (Zeng et al., 2018a)
Organo-bentonites Ethanol >95 >50 4 (Ghemit et al., 2019)
Biochar from pinewood Methanol 10 8 4 (Essandoh et al., 2015)
Modified spherical AC – 30 14.7 7 (Xu and An, 2016)
Activated carbon (AC-F400) NaOH – 42.20 – – 2 (Álvarez-Torrellas et al., 2016)
AC from peach stone NaOH – 54.70 – – 2 (Álvarez-Torrellas et al., 2016)
AC from rice husk NaOH – 70.40 – – 2 (Álvarez-Torrellas et al., 2016)
Zirconium alginate beads Methanol 87.37 37.59 5 (Chakraborty and Halder, 2020)
MIEX 0.0175 0.0171 7 (Wang et al., 2015)
Modified organic-coated magnetic Water + 82.00 80.00 – – 3 (Kollarahithlu and Balakrishnan, 2019)
nanocomposite acetone
Modified polyacrylic polymer NaCl – – 0.0412 0.039 10 (Zhang et al., 2020a)
Modified molecularly imprinted Methanol + – – 22.02 21.03 5 (Wu et al., 2018c)
nanocomposite membrane acetic acid
AC from sisal waste Methanol – – >80 – – (Mestre et al., 2011)
Biosorbent from Phaeodactylum tricornutum – 58 >40 3.4 2.8 6 (Santaeufemia et al., 2018)
MOF-based porous carbon Water + >262.5 >225 4 (Bhadra et al., 2017)
acetone
Cyclodextrin polymers Water 65.00 65.00 10 (Moulahcene et al., 2016)
Science of the Total Environment 780 (2021) 146608
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al.
easily be removed from the surfaces using water (Essandoh et al., 2015).
It was suggested that covalent bonding formed by loaded carbon ni-
tride/soot and ethanol resulted in the near-perfect removal efficiency
(99.1% and 97% for the 1st and 5th cycles respectively) (Liao et al.,
2018). This buttresses the excellent recyclability and capability of the
adsorbent, thus making it potentially a suitable choice for industrial
applications.
The desorption of IBP molecules with inorganic eluents (HCl, NaCl,
NaOH) had significant effects due to exchanges between the adsorbate
species and ions (H+, Na+, and OH−). The use of HCl had positive effects
on iron nanocomposite (Ali et al., 2016) and functionalized bean husk
(Bello et al., 2019) at the end of the 8th and 4th cycles, respectively.
The positive effects could be attributed to the creation of additional
pores on the adsorbents, hence, increased removal efficiencies at the
end of the adsorption-desorption cycles. Moreover, leaching of adsor-
bate from pore sites with a corresponding increase in removal efficiency
could be induced by the presence of metallic ions in the solution. For
CNT nanocomposite (Lung et al., 2020), a slight decrease was obtained
after 5 cycles due to the protonation of H+ ions to IBP and resulting in
the formation of conjugate acid. The use of aqueous NaOH as eluent
had notable decreasing effects on the desorption of IBP from functional-
ized multiwall carbon nanotubes (Hanbali et al., 2020). This decrease
could be attributed to electrostatic repulsion as there exist negative
charges on adsorbent (acquired from its functionalization with the
amino group) and a hydroxyl group. Consequently, a reduction in re-
moval efficiency of IBP from the surfaces of the three functionalized ad-
sorbents and adsorption-desorption cycle is imminent.
As a solvent, water remains a poor eluent in IBP desorption either
when used solely or as a binary mixture. This is as there were no
changes in removal efficiency recorded for cyclodextrin polymers
(Moulahcene et al., 2016) after ten cycles while for modified organic-
coated nanocomposite (Kollarahithlu and Balakrishnan, 2019), an insig-
nificant change in removal efficiency was recorded at the end of three
cycles. This could be attributed to the insolubility of IBP in water that
makes it nearly impossible for molecules of the adsorbate to be
dislodged from loaded surfaces.
The reusability of wood apple biochar and its steam-activated vari-
ant were tested over 4 adsorption-desorption cycles using methanol
as eluent (Chakraborty et al., 2018a). Results showed that 74% and
81% of IBP were desorbed from the materials with 61% and 69% of
their initial capacities retained at the end of the 4th cycle, respectively.
The retained capacities showed the economic viability of the adsorbent
for the elimination of pharmaceutical compounds from the aqueous so-
lution by adsorption. For carbon nitride/soot composite, its removal ef-
ficiency of IBP molecules in aqueous solutions using ethanol was near
perfect (99.7%) after the first cycle and significantly high (97.1%) at
the end of the fifth cycle (Liao et al., 2018). It was suggested that since
IBP has an aromatic group, the adsorption mechanism is a π-π interac-
tion that facilitates electron transfer/acceptance and equally contributes
to robust adsorption activity. The excellent recyclability of the adsor-
bent is due to almost no loss in removal efficiencies over five adsorp-
tion/regeneration cycles.
Table 7 summarises the results of desorption and reusability. Based
on the results, it is clear that higher removal efficiency of adsorbed IBP
on synthetic adsorbents could be induced by metallic ions while chela-
tion by the carboxylic group in organic acids creates more sites on nat-
ural and semi-synthetic adsorbents.
9. Competitive adsorption studies
The degree to which a target adsorbate is removed from aqueous
matrices amidst co-pollutants depends primarily on ionisation and sur-
face charges on the adsorbent (Bui and Choi, 2010). In aqueous-phase
equilibrium studies, removal of organic pollutants can be influenced
by ionic strength due to the coexistence of inorganic salts in solution
with the pollutant. Also, the presence of organic co-pollutants such as
16
Science of the Total Environment 780 (2021) 146608
anti-steroidal drugs (diclofenac, naproxen), natural organic matter
(bovine serum albumin (BSA), humic acid (HA), fulvic acid (FA), gallic
acid (GA), tannic acid (TA)) which are commonly found on surface wa-
ters can inhibit removal of IBP in binary systems. Varying ionic strengths
could create synergistic effects such as weakening of electrostatic inter-
action, clustering of adsorbents, which invariably will interrupt adsorp-
tion phenomena (Jun et al., 2019) just as organic matter could cause
blockage of adsorbent pores (Behera et al., 2012) and fouling on adsor-
bents (Zhang et al., 2020a).
IBP adsorption onto biochar obtained from various sources such as
wood apple shell (Chakraborty et al., 2018a), chili seeds (Ocampo-
Perez et al., 2019), and wood chips (Jung et al., 2015) was impeded by
the presence of co-solutes such as diclofenac, and electrolyte ions (K+,
Mg2+, Cl¯, Ca2+). This disruption could be due to cloud effects by virtue
of differences in molecular structures of the organic co-solutes (Jung
et al., 2015), or electrostatic repulsion between IBP and inorganic con-
stituents (Lin et al., 2017) resulting in the competition for available
sites. In addition, the formation of hydrogen bonds with organic acids,
such as carbonates, could result in the neutralization of surface charges
as IBP forms complexes with these acids.
Ordinarily, an increase in ionic strength bears effects on the adsorp-
tion of target organic pollutant amidst co-pollutants. However, this sit-
uation could produce two counteracting effects that are too weak
thereby becoming insignificant to adsorption (Sun et al., 2019). A
study showed that decline in the concentration of inorganic salt
(NaCl) enhances particle aggregation as more Na+ ions migrate onto
adsorbent active sites and this reduces IBP sorption (Van Tran et al.,
2019). The findings of Phasuphan et al. (2019) suggested secondary
functional groups could enhance electrostatic interaction and selectivity
within a mixture of anti-inflammatory drugs and chitosan-modified ad-
sorbent. This functional group, binds to the modifier via H-bonds,
resulting in the preferential dissociation of IBP and selectivity with com-
peting solutes. in a study, involving magnetic anion resin, noted that
1.0 mmol L−1 of Cl¯ ion caused about 63.5%, 56.9% and 48.8% reduction
in three anion exchange resins while for SO2− 4 ions, the figures were
93%, 91.9% and 91.8% respectively. The study observed that while both
ions could inhibit the adsorption of IBP onto the surface of the sorbent,
the influence of SO2− 4 ions are more due to the larger amount of
negative charge on its surface. Hence, this creates non-electrostatic in-
teraction between adsorbent surface and sorbate.
The impact of NOM significantly decreased IBP adsorption on silica,
findings from Bui and Choi (2010) showed. The decrease could be at-
tributed to hydrophobic interaction and covalent bonding (H-bonds)
which the pharmaceutical forms with NOM that confines it on the
adsorbent's surface and consequently decreases its adsorption. Further-
more, polyelectrolytic behaviour of NOMs and net negative charges cre-
ate coulombic forces that cause pore blockage and constricting effect for
negatively charged IBP, hence, it undergoes electrostatic repulsion with
these coexisting organic pollutants (Delgado et al., 2015).
In conclusion, the ability of adsorption and affinity of adsorbents in
the course of IBP removal are simultaneously affected by the presence
of many micro-pollutants and ionic strength of the solution (Ghemit
et al., 2019). It is essential to understand these properties in adsorption
technology since they produce effects such as salting-out/electrostatic
screening and aggregation at sorbent-sorbate interfaces. The summary
of the competitive adsorption of IBP with various co-pollutants is
shown in Table 8.
10. Column adsorption studies
This is an experimental investigation that considers the dynamics of
adsorption in predicting practical features such as adsorbent capacity.
Column adsorption is undertaken to ensure continuous contact be-
tween pollutant and sorbent in large-scale treatment of aqueous solu-
tions. This is because the technique can efficiently accommodate
higher pollution loads while still ensure that the adsorbate is constantly
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al. Science of the Total Environment 780 (2021) 146608

Table 8
Summary of competitive adsorption of IBP with various co-pollutants.

Adsorbent Competing species Maximum change with competing species Ref.

Wood apple biochar (raw) Diclofenac >68% IBP removal after 24 h (Chakraborty et al., 2018a)
Wood apple steam activated Diclofenac >75% IBP removal after 20 h (Chakraborty et al., 2018a)
biochar
Mesoporous carbon from MOF Na+ Slight decline in the amount of IBP adsorbed (Van Tran et al., 2019)
MIP Ketoprofen, naproxen and aspirin – (Zhou et al., 2013)
AC from oak acorn Ca2+ Slight reduction (10.2%) in IBP sorption by the AC. (Nourmoradi et al., 2018)
MOF Organic matter (HA) Anionic HA significantly affected the capacity of the adsorbent for (Jun et al., 2019)
Inorganic ions (Na+, Ca2+, Cl¯, SO42−) IBP sorption.
Divalent ions (Ca2+, SO2−4 ) suppressed electrostatic interactions.
Modified organo-silica Na+, Ca2+ Ca2+ significantly affected IBP adsorption more than Na+ due to (Zeng et al., 2018a)
stronger electrostatic interactions at the adsorption sites.
Organo-bentonite Diclofenac >57% decrease in the affinity of the adsorbent for IBP. (Ghemit et al., 2019)
MIEX Cl¯, SO24¯ >40% decrease in capacity of the sorbent by Cl¯ ion. (Wang et al., 2015)
Significant inhibition (>90% reduction) in sorption capacity of
the resin by SO42¯ ion.
Modified polyacrylic polymer Inorganic salt ions (Cl¯, SO2−
4 ); Organic 64% decrease caused by Cl¯ ion. (Zhang et al., 2020a)
constituents (HA, TA, GA) 76% decrease in sorption capacity caused by SO2− 4 .
HA – insignificant effect.
< 50% decrease by TA & GA (TA – 20% decrease; GA – 48%
decrease).
Modified MIP membranes Ketoprofen – (Wu et al., 2018c)
Silica Anions (NO3¯, HCO3¯, SO42¯, PO43¯). No observable effects caused by anions. Increase in ionic strength (Bui and Choi, 2010)
Divalent cations (Ca2+, Mg2+). and the presence of divalent cations, trivalent cations, and NOM
Trivalent cations (Al3+, Fe3+). did significantly impact the adsorption of pharmaceuticals.
Natural organic matter (NOM) on surface
waters (HA, FA)
Biochar from chili seeds Cl¯ ions Increase in Cl¯ ions neutralised the positive charges on the surface (Ocampo-Perez et al., 2019)
of the biochar
Activated biochars Diclofenac 58% reduction on N-biochar (Jung et al., 2015)
62% reduction for O-biochar
Activated biochars Naproxen 20% reduction onto N-biochar (Jung et al., 2015)
18% reduction onto O-biochar
Biochar Inorganic ions (Na+, Ca2+, Mg2+, K+, Cl¯, Ca2+ (43% increase), SO2− 4 (16% increase), Mg
2+
(2% increase), (Lin et al., 2017)
SO2−
4 ); Organic contaminants (humic acid, K
+
(1% increase).
bovine serum albumin) HA (41% decrease), BSA (8% decrease)
MOFs Naproxen 43.7% decrease (Sun et al., 2019)
MOFs Inorganic salts Insignificant (Sun et al., 2019)
Modified waste tire Diclofenac and naproxen Diclofenac impacted significantly on IBP adsorption. (Phasuphan et al., 2019)
Commercial AC Natural organic matter (HA) HA caused pore blockage on adsorbents' surfaces; significantly (Delgado et al., 2015)
affected IBP adsorption.
AC and clay minerals Inorganic salt (NaCl); Natural organic Inorganic salt (Behera et al., 2012)
(kaolinite and matter (HA) 37% decrease on AC;
montmorillonite), goethite >18% increase on kaolinite;
77% increase on montmorillonite; >200% increase on goethite.
HA
39.18–4.13% decrease on AC.
2.5–4.35% increase on kaolinite.
4.3–5.6% increase on montmorillonite.
1.74–5.86% increase on goethite
+ 2+ 2
MIEX Na , Ca , Cl¯ and SO4¯ The existence of SO24¯ had detrimental effect than Cl¯ on the (Jiang et al., 2015)
solubility of the IBP.
BiOCl microspheres Cl¯, SO24¯, NO3¯, HPO24¯ Cl¯, SO24¯ & HPO24¯ significantly affected the adsorbent. NO3¯ was (Li et al., 2017)
insignificant.

in contact with fresh adsorbent (Patel, 2019). Here, several analytical
models (Clark, Thomas, Yoon-Nelson, etc.) are adopted to measure the
effects of process parameters (bed height, influent concentration,
flowrate, breakthrough point, etc.) on adsorbent efficiency.
Chakraborty and Halder (2020) investigated the sorption capability of
zirconium allied alginate beads for IBP removal from synthetic waste-
water in a fixed bed column (Table 9). Analyses of results showed that
the efficiency of adsorption was predicted by three models – Bed
Depth Service Time (BDST), Thomas, and Yoon-Nelson. BDST proposed
better adsorption is achieved (by the adsorbent) with increase in bed
height, while Thomas and Yoon-Nelson predicts flowrate and influent
concentration.
Four models – BDST, Clark, Thomas, and Yoon-Nelson – satisfactorily
predicted the dynamic behaviour of the column and performance of
nano-adsorbent clay for IBP uptake (Rafati et al., 2019). The results
showed that adsorption capacity increased as concentrations and bed
depth increased, but decreased as the flow rate increased. Furthermore,
the goodness of fit obtained by the four models confirmed the effects of
external mass transfer resistance on breakthrough curves. Error analysis
showed no difference in values and confirmed the validity of these
models to the dynamic behaviour of the adsorbent through a fixed-
bed column system (Ahmed and Hameed, 2018). The findings of
Dubey et al. (2014) on column adsorption of IBP by raspberry mesopo-
rous carbon showed that adsorption capacity decreases with an increase
in volumetric flowrate as predicted by the Thomas model. However, this
could be accelerated by the nature of the sorbate (which is a weak acid)
and the surface property of the adsorbent.
In conclusion, a comparative look at values of adsorption capacities
calculated from a batch experiment (Table 3) and column studies
(Table 9) show that the latter remain lesser due to higher mass transfer
resistance within micropores, hence the rate-limiting step is intra-
particle diffusion. This point is corroborated by 239.8 mg/g and
22.70 mg/g obtained Álvarez-Torrellas et al. (2016) as adsorption capac-
ities of AC from rice husk from batch and column studies, respectively.

17
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al.
Table 9
Summary of column adsorption for IBP.
Adsorbent Best-fit model Colum parameters
Bed height
(cm)
Activated carbon (AC-F400) – –
AC from peach stone – –
AC from rice husk – –
Zirconium allied alginate Yoon-Nelson, Thomas 20
beads
Nano-clay composite Bed-depth service time 1.5
(BDST), Clark, Thomas,
Yoon-Nelson
Nano-porous AC – –
Commercial granular AC – 10
(MG 1050)
Commercial powder AC – 10
(BM8)
Reused powder AC – 10
Magnetic coated zeolite – 15
Mesoporous carbon from Thomas 3 3
Raspberry
11. Adsorption modelling by computational strategies
Several researchers have employed a variety of molecular simulation
techniques, computational strategies and in silico platforms for the in-
vestigation of various aspects of IBP uptake from aqueous media.
Grand canonical Monte Carlo simulation has been employed to investi-
gate IBP uptake on activated carbon (Bahamon et al., 2017). It was ob-
served that reducing the surface functionality of the activated carbons
favoured IBP uptake because there is less competition with water mol-
ecules. A similar investigation has also been conducted by Bahamon
and Vega (2017) albeit for comparison of the adsorptive performance
of activated carbon for different pharmaceutical compounds (IBP inclu-
sive). Classical molecular dynamics and density functional theory (DFT)
were two computation strategies employed by Hadad et al. (2011) to
investigate the adsorption of IBP unto fullerene. The study revealed a
two-layer adsorption of the adsorbate onto the adsorbent at 300 K.
This observation of two-layer adsorption was also complemented by
the statistical physics modelling of Li et al. (2019) albeit for modified
sepiolite.
Molecular modelling was used to interpret the binding energy be-
tween IBP and activated biochar (Jung et al., 2015). The molecular
models for the adsorbate and adsorbent were developed using
dispersion-corrected density functional theory while the computation
was done by SMD continuum solvation model. A binding energy of
about 14 kcal/mol was observed for IBP uptake in a singular system
and this value reduced in the competitive system (Jung et al., 2015).
3D numerical simulation was used by Ocampo-Perez et al. (2019) to in-
vestigate the external mass fluxes that control the adsorptive rate of IBP
uptake onto biochar from chili seeds. The study predicted the diffusivity
and revealed that intra-particle mass fluxes were greater along the
shorter axis of the biochar. Based on the DFT modelling of IBP uptake
unto MOFs (Sun et al., 2019), it was observed that π-π interaction, hy-
drogen bonding, Lewis acid/base complexing, and anion-π interaction
were involved in the interaction between adsorbent and adsorbate.
Computational studies have also been reported for IBP uptake onto
single-walled CNT (Parlak and Alver, 2019), silica (Delle Piane et al.,
2014; Tielens et al., 2017), activated carbon (Sellaoui et al., 2015;
Sellaoui et al., 2016a; Sellaoui et al., 2016b; Sellaoui et al., 2016c) and
macroporous resins (Tao et al., 2020).
12. Knowledge gap and future perspectives
Based on this review of literature several gaps in knowledge are
herein discussed. Though a vast amount of literature has recently been
Science of the Total Environment 780 (2021) 146608
Adsorption capacity Ref.
(mg/g)
Vol. flowrate Inlet concentration
(mL/min) (mg/L)
2.0 10 115.1 (Álvarez-Torrellas et al., 2016)
2.0 10 55.00 (Álvarez-Torrellas et al., 2016)
2.0 10 22.70 (Álvarez-Torrellas et al., 2016)
2.0 30 23.33 (Chakraborty and Halder, 2020)
6.0 3 3.780 (Rafati et al., 2019)
4.0 100 – (Mansouri et al., 2015)
166.67 1.5 – (Luján-Facundo et al., 2019)
166.67 1.5 – (Luján-Facundo et al., 2019)
166.67 1.5 – (Luján-Facundo et al., 2019)
25 0.1 99.62% (RE) (Attia and Hu, 2013)
10 48.576 (Dubey et al., 2014)
published on the uptake of IBP by adsorption, some grey areas still
exist that calls for attention by researchers. The continuous contacting
mode considered is fixed-bed column. Studies on other contact modes
such as fluidised bed, moving bed, pulsed bed are necessary to ascertain
adsorbent performance due to the vast application of such modes to
separation technology on industrial scale. The disposal of used adsor-
bent is seldom discussed in literature. The used adsorbents after the up-
take of IBP needs to be properly disposed of else the goal of the process
will be defeated as pollutants will be released once again to the environ-
ment. It is encouraged that researchers evaluate ways to dispose these
adsorbents besides the conventional incineration technique. A similar
lack of disposal studies has also been observed for metronidazole
(Ighalo et al., 2020a) and ciprofloxacin (Igwegbe et al., 2020c).
The improvement of IBP adsorption process has been investigated
by combining the adsorption process with photocatalysis (Di et al.,
2017; Gu et al., 2019; Lin et al., 2019) and sonication (Tao et al., 2020;
Ondarts et al., 2018). The incorporation of other processes such as
electrocoagulation (Al-Qodah et al., 2020), advanced oxidation pro-
cesses (Michael et al., 2013), and biological systems (Pilli et al., 2020)
in a hybrid setup with adsorption technology improves efficiency. Hy-
brid systems are the future of separation technology as such, it is perti-
nent to conduct studies on the removal of IBP from wastewater using
such systems. In the future, researchers would explore more innovative
process improvement techniques for the uptake of IBP. Enhancing func-
tionalities such as pollutant recognition via molecular imprinting tech-
nology needs to be explored for the selective adsorption of IBP from
aqueous environment (Guan et al., 2020). This technique has added ad-
vantage of adsorbent recyclability which obliterates the need for a new
adsorbent for each process (Kollarahithlu and Balakrishnan, 2019).
13. Conclusion
In this paper, the empirical findings on the adsorption of IBP from
aqueous media were reviewed. An overview of mitigation strategies re-
vealed that adsorption is comparatively simple, easy to run, low cost
and yields higher performance. From the review, it was observed that
carbon-based adsorbents are the best class of adsorbent for the uptake
of IBP. The highest reported maximum adsorption capacity (qmax) for
IBP was 496.1 mg/g by SWCNTs. The mechanism of uptake depends
on the adsorbent type and the nature of the solution chemistry. How-
ever, the more regularly observed mechanisms are hydrophobic inter-
actions, π – π stacking, hydrogen bonds, electrostatic interactions and
dipole-dipole interaction. IBP uptake was best fit to a wide variety of iso-
therm models but was well suited to the pseudo-second order kinetics
18
S.N. Oba, J.O. Ighalo, C.O. Aniagor et al.
model. This suggests that uptake was affected both by IBP initial concen-
tration and availability of pores on the adsorbent. Also, it reveals chem-
isorption as an important mechanism in IBP uptake. The
thermodynamics of IBP uptake depends majorly on the nature of the ad-
sorbent. IBP was observed to be readily desorbed from the solid phase
with an appropriate choice of the eluent. The ability of adsorption and
affinity of adsorbents in the course of IBP removal are simultaneously af-
fected by the presence of many micro-pollutants and ionic strength of
the solution. Several studies have also employed various computation
strategies for the removal of IBP which were also discussed by the
study. Knowledge gaps were observed in used adsorbent disposal and
process improvement. Looking to the future, it is speculated that inter-
est would increase not just in traditional research and publishing but in
scale-up, industrial applications and practical utilisation of the research
findings. This would help transfer this vast body of work into actual sus-
tainable water resource management, pollutant risk mitigation and en-
vironmental protection.
Funding
There was no external funding available for this work.
Compliance with ethical standards
This article does not contain any studies involving human or animal
subjects.
CRediT authorship contribution statement
Stephen N. Oba, Conceptualisation; Writing - original draft; Writing -
review & editing; Validation; Visualisation.
Joshua O. Ighalo, Conceptualisation; Data curation; Writing - original
draft; Writing - review & editing; Supervision; Visualisation.
Chukwunonso O. Aniagor, Conceptualisation; Writing - original draft;
Writing - review & editing; Validation; Visualisation.
Chinenye Adaobi Igwegbe, Conceptualisation; Writing - original draft;
Writing - review & editing; Validation; Visualisation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
The authors wish to acknowledge the efforts of the authors who
have worked on IBP adsorption over the years.
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