Process Safety and Environmental Protection 186 (2024) 552–565

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Process Safety and Environmental Protection

journal homepage: www.journals.elsevier.com/process-safety-and-environmental-protection

Advanced nano-based adsorbents for purification of pharmaceutical residue

polluted water: A critical review
Manoj Kumar Karuppan Perumal a, Dhivya Gandhi b, Remya Rajan Renuka a, *,
Aranganathan Lakshminarayanan c, Nathiya Thiyagarajulu d, Chinnaperumal Kamaraj e, *
a
Center for Global Health Research, Saveetha Medical College and Hospitals, Saveetha Institute of Medical and Technical Sciences, Chennai, Tamil Nadu 602105, India
b
Centre for Materials Engineering and Regenerative Medicine, Bharath Institute of Higher Education and Research, 173, Agaram Road, Selaiyur, Chennai, Tamil Nadu
600073, India
c
Department of Medical Biotechnology and Integrative Physiology, Institute of Biotechnology, Saveetha School of Engineering, SIMATS, Chennai, Tamil Nadu 602105,
India
d
Department of Life Sciences, Kristu Jayanti College (Autonomous), Bangalore 560077, India
e
Interdisciplinary Institute of Indian System of Medicine (IIISM), Directorate of Research, SRM Institute of Science and Technology (SRMIST), Kattankulathur, Tamil
Nadu 603203, India

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

Keywords: Antibiotics, steroids, and personal care products are examples of pharmaceutical contaminants that pose a
Water remediation serious threat to ecosystems worldwide, even at trace levels that are present in the aquatic environments of more
Nano-adsorbents than 70 countries. Traditional wastewater treatment methods are unable to completely remove these persistent
Pharmaceutical pollutants
pollutants, which leads to problems with secondary contamination. This article evaluates the scientific feasibility
Antibiotics
Mechanism
and practicability of using nano-adsorbents to eliminate pharmaceutical-contaminated water sources. Various
nano-adsorbents with unique properties demonstrated impressive capabilities in the adsorption and removal of
commonly detected pharmaceutical residues. Notably, metal oxide nanoparticles eliminated ibuprofen by 99.3%,
activated carbon removed tetracycline by up to 99.9%, and graphene nanomaterials removed levofloxacin by
99.2%. Novel MXenes, magnetic nanocomposites, and nano-adsorbents based on biopolymers demonstrated
remarkable efficacy, eliminating up to 99.4% ceftriaxone, 99.97% promazine, and 98.89% levofloxacin. A
thorough examination of the influencing factors that control nano-adsorption processes, such as pH, temperature,
contact time, and adsorption isotherm/kinetic models, is discussed in the review. Even though these nano-
adsorbent technologies have a lot of potential, some barriers need to be addressed before they can be fully
implemented for treating pharmaceutical-contaminated water. These include material instability, toxicity con­
cerns, and problems with large-scale production.

1. Introduction antibiotics, steroids, and other complex chemical substances to treat

various diseases globally as shown in Fig. 1. These industries are
According to the UN reports, the world’s population is expanding releasing PCs into the aqueous environment; thereby contaminating the
yearly, reaching 9.7 billion by 2050 (Al-sareji et al., 2023). It’s an ecosystem (Hussain et al., 2023). Therefore, consuming the PCs poses a
alarming situation because many countries have water scarcity and do threat to aquatic life- forms, humans, and living organisms (Hejna et al.,
not have well-developed wastewater management. Each year there is a 2022). There has been a significant increase in the global usage of
significant peak in the release of pollutants especially, pharmaceutical anti-viral and antibiotic drugs (Malik and Mundra, 2022). Following
contaminants (Al-Khadhuri et al., 2023; Moradi et al., 2022). Pharma­ this, the Cauvery River and its waterways in India have been contami­
ceutical contaminants (PCs) are one of the emerging contaminants (EC) nated with antibiotics, anti-hypertensive, anti-inflammatory, and ste­
causing toxic effects on living organisms, even at low concentrations. roids (Balakrishna et al., 2016). The prevalent antibiotics in sewage
These contaminants are non-degradable and can endure in the sludge include fluoroquinolones, sulfonamides, and tetracyclines (Du
ecosystem (Samal et al., 2022). Pharmaceutical industries are producing et al., 2023). Due to their pseudo-persistent nature and detrimental

* Corresponding authors.
E-mail addresses: [email protected] (R.R. Renuka), [email protected] (C. Kamaraj).

https://doi.org/10.1016/j.psep.2024.04.011
Received 8 February 2024; Received in revised form 23 March 2024; Accepted 2 April 2024
Available online 3 April 2024
0957-5820/© 2024 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
M.K.K. Perumal et al. Process Safety and Environmental Protection 186 (2024) 552–565

nanomaterials have when effectively removed drugs from water in

comparison with conventional adsorbents. Hence, this review examines
the performance of various nano-adsorbents and newly developed
next-generation materials in eliminating pharmaceutical pollutants.
Additionally, the greater adsorption capacities of nanomaterials
compared to conventional adsorbents are also explained by a variety of
mechanisms. In conclusion, the review investigates the primary vari­
ables that influence the behaviour of the processes involved in
nano-adsorption. Although nano-adsorbents have demonstrated effec­
tiveness in removing pharmaceuticals up to 99.9% of the time, the re­
view thoroughly discusses the challenges of material instability, toxicity,
and scalability that must be addressed before full implementation on a
large scale.

2. Types of nano-adsorbents for eliminating various antibiotics

Fig. 1. Illustration showing the classification of pharmaceuticals.
Nano-adsorbents are an innovative solution for treating specific
effects even at trace levels, the widespread presence of pharmaceutical pharma pollutants from aquatic biomes. Nano-adsorbents eliminate
contaminants in water bodies across more than 70 countries has become toxic waste from effluent through nanoparticles ranging from 1 to 100
a critical environmental concern. It is now necessary to develop nanometers. They effectively adsorb pollutants with their high surface
advanced remediation techniques because conventional wastewater area and small particle size, Nano-adsorbents have demonstrated their
treatment methods have not been able to eliminate these pharma pol­ effectiveness in removing contaminants from pharmaceuticals. The
lutants (Koul et al., 2022; Zhou et al., 2023a). These substances Nano-adsorbents are broadly classified into carbonaceous nano-
demonstrate a range of concentrations from several nanograms to mi­ material, graphene nano adsorbents, MXenes nano adsorbents, mag­
crograms, specifically including antibiotics, hormones, analgesics, and netic adsorbents, polymeric nano adsorbents, and metal oxide nano­
non-steroidal anti-inflammatory drugs (Chauhan et al., 2023; Zhou particles (Gusain et al., 2020; Priya et al., 2020; Ranjan, 2023) as shown
et al., 2023b). The techniques followed to remove PCs such as antibiotics in Fig. 2.
are biodegradation, adsorption, and persulfate activation. However,
these have limitations such as high equipment investment, manpower, 2.1. Carbonaceous nano-material for pharmaceutical waste
and energy consumption (Wang et al., 2023a). The major problem in PCs
is mixing antibiotics in the water environment. The antibiotics are Carbonaceous nanomaterials are a combination of characteristic
considered as “pseudo-persistent” contaminants; since their introduc­ properties of sp2 hybridized carbon bond, with physical-chemical
tion into ecosystems was detrimentally impacted (Kulik et al., 2023). properties at the nanoscale; exhibit chemical, mechanical, and elec­
Pharmaceuticals use wastewater treatment plants (WWTP) to eliminate trical properties. They include materials such as graphene-based nano­
contaminants from the environment— either by biological or chemical materials, carbon nanotubes (CNTs), activated carbon, fullerenes, etc.
treatment pathways (Eniola et al., 2022). In the 21st century, nano­ Carbon nanotubes (CNs) have the potential to be utilized in various
technology has emerged as one of the most remarkable advancements. areas of wastewater treatment, including adsorption, photocatalysis,
In recent times, the use of nanotech products has been pivotal in giving disinfection, and membrane processes (Raza et al., 2022; Zhang et al.,
alternative solutions, especially in WWTP (Palani et al., 2021). 2022). Cruz-Cruz and his team emphasize carbon-based nanomaterials
Nano-adsorbents are distinct materials with unique properties that can (biochar, carbon nanotubes, activated carbon, and graphene) utilized as
remove pollutants from wastewater. Due to their high surface area, nano adsorbents for adsorbing antibiotics from water (Cruz-Cruz et al.,
chemical reactivity, conductivity, magnetic, and optical properties;
nano-absorbents are widely utilized and considered an alternative
treatment for pharmaceuticals (Ali et al., 2020). There are a numerous
variety of nanoparticles that are the widely used nano-adsorbents (Neha
et al., 2021). These nano-materials can be used to absorb the pharma­
ceuticals, thus preventing them from causing adverse effects on humans,
animals, and plants (Ahmed et al., 2021). There are multiple papers,
which are published on eliminating the pollutants; but only a few arti­
cles have reported on the removal of these compounds by
nano-adsorbents. Nanomaterials/nanoabsorbents possess unique char­
acteristics that distinguish them from conventional adsorbents. These
include their small size and higher surface area/ volume ratios,
permitting greater reactions at the interface between the adsorbent and
pharmaceutical pollutants (Liu et al., 2023). In addition, nanomaterials
are characterized by a range of surface chemical groups that can be
tuned for functionalization or modification purposes including electro­
static forces of attraction, π-π interactions and hydrogen bonding among
others. Such types of interactions play a very important role in the
mechanism behind adsorption by nanoscale materials (Pouramini et al.,
2023). Still, another major advantage of these synthesised materials
over their traditional absorbents is their ability to allow easy penetration
of adsorbed molecules through their porous materials due to unique
phenomena. Thus, these innate characteristics combined with diverse
compositional and structural possibilities are some advantages Fig. 2. Represent the different types of nano adsorbents used to remove
pharmaceutical contaminants.

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2023). (Singh et al., 2022). Graphene oxide (GO), is an oxidizing graphite that
includes single-layered atomic material. This nanomaterial is considered
2.2. Activated Carbon (AC) mitigating for pharmaceutically active a prevalent absorbent or photocatalyst in wastewater treatment because
compounds of its two-dimensional structure with hydrophilic surface groups (Vijaya
Bhaskar Reddy et al., 2019). In a study, Zinc oxide nanoparticles
Activated carbon (AC) is a processed form of carbon derived from (ZnONP) integrated with graphene oxide nanosheets (GONS) were
carbonaceous materials. The AC is commonly used as an adsorbent in prepared to eliminate levofloxacin from pharmaceutical wastewater.
filtration and purification, because of its high carbon content, low ash The highest percentage removal for LEVO was achieved at 99.2% and
content, and significant presence of volatile matter. AC is a prevalent 99.6% respectively. This result was obtained by utilizing a combination
and extensively used conventional adsorbent for wastewater treatment of ZnONP and GONS at a pH level of 9, along with a duration of 120 min
worldwide. In a study, using the adsorption and photodegradation (El-Maraghy et al., 2020). In the conducted investigation involving GO
process; pharmaceutical contaminants, specifically atenolol (AT) and nanoparticles, the process of adsorption of antidiabetic pharmaceuticals
propranolol (PR) were removed using modified activated carbon (Samir (metformin) was executed. The outcomes disclosed that the rate of
et al., 2023). The metal ferrite nanoparticles combined with AC were adsorption quantified at 122.61 mg/g, while the GO specimens
tested to reduce promazine from wastewater (Al-Hetlani et al., 2022). employed during the experiment showcased notable characteristics such
Moreover, heat-treated activated carbon increases the absorption of as a substantial surface area of 187.2 m2/g, pore volume of 0.12 cm3/g,
pharmaceutical aromatic pollutants — salicylic acid and methylparaben and pore width measured at 17.33 nm (Balasubramani et al., 2020). The
by 24 and 34%, respectively (Bernal et al., 2020). The physicochemical most common antibiotics removal by graphene-based nano adsorbent
properties, dispersion forces, p-interactions, and hydrophobic interac­ are listed in Table 1. Ibuprofen, the most common pharmaceutical
tion for carbon-based nanomaterials were studied for the adsorption of pollutant in waterways; is toxic to many living organisms (Jan-Roblero
pharmaceutically active compounds (Ivanković et al., 2021). In an and Cruz-Maya, 2023). The polysulfone nanofiltration membrane was
experiment, eight active pharmaceutical ingredients (APIs) were modified by coating with GO and reduced GO to test against the removal
extracted using ten solvents. Furthermore, the optimized protocol yiel­ of Ibuprofen from water. Furthermore, graphene oxide nanoplatelets
ded extraction recoveries above 70% suggesting its effectiveness in (GONPs) were examined for their ability to eliminate Ibuprofen, and the
evaluating the regenerative properties of carbon sorbents (Oesterle results indicated that it could be a viable treatment option on a larger
et al., 2020). In addition, it has been reported that activated carbon has scale (Banerjee et al., 2016; Hidalgo et al., 2022).
an exclusion quantity of 1340.8 mg/g for tetracycline. Tetracycline,
penicillin, and quinolones were the three pharmaceutical compounds 2.4. Metal oxide nanoparticles (MONPs) for removing PCs
used against activated carbon (Ahmed, 2017). According to Pauletto
et al., the adsorption behaviour changes of pharmaceutical compounds Metal oxide nanoparticles (MONPs) are a broad class of nano­
when treated with AC were examined and compared. Furthermore, AC materials obtained by hydrolyzing metal salts at temperatures below
showed a significant peak in removing the PCs called nimesulide 100◦ C; they are chemically stable without adverse effects. The appli­
(196.32 mg) and paracetamol (58.21 mg) (Pauletto et al., 2021). In cations of MONPs include adsorption, photocatalytic activities, anti­
2017, pharmaceutically active compounds such as carbamazepine, bacterial and antifungal activities, antimicrobial agents, ointments,
clarithromycin, and diclofenac, were eliminated by using AC; showing a lotions, wastewater treatment, and textile industries (Chavali and
removal efficiency of 95%, when implementing a fresh dose of Nikolova, 2019; Pan et al., 2021). The sulfamethoxazole, phenol, and
15–20 mg/L (Eniola et al., 2022). In addition, the AC is investigated to phenol-related pharmaceuticals are predominantly seen in antibiotics in
remove the drugs such as diclofenac, naproxen, and carbamazepine. The aquatic environments. Using iron oxide nanoparticles, zinc oxide
data fit well into the Langmuir equation, and the study found 100% nanoparticles Ferric oxide nanomaterials (FO-NM), and transition metal
removal efficiency of these drugs in wastewater (Stjepanović et al., ions like Fe2+, Cu2+, Mn2+, and Zn2- are developed for the removal of
2023). these contaminants (Adegoke and Stenström, 2019). Rosman et al.
reduced Ag2CO3 to Ag2O on a zinc oxide surface to degrade ibuprofen
from an aqueous environment. Results exhibited the removal percentage
2.3. Graphene-based nano- adsorbent of 99.3% of ibuprofen under visible-light irradiation (Rosman et al.,
2020). The metal oxide-based nano adsorbents for the remediation of
Graphene-based nanomaterials are ranging in thickness from ten pharmaceutical wastewater are listed in Table 2.
nanometres and size from a few to a hundred nanometres. It is made by
exfoliating graphite comprising carbon atoms arranged in a single layer

Table 1
List of commonly used antibiotics and their elimination using graphene-based nano adsorbents.
S. Name of Nano adsorbent Namo of the pollutant Removal results Adsorbent isotherm/kinetic model Reference
No.

1 rGO/nZVI doxycycline 94.6% pseudo-second-order (Abdelfatah et al., 2022)

2 hydroxyethylcellulose HEC-GO Tetracycline 95% pseudo-first-order, pseudo-second-order, (SefidSiahbandi et al.,
Elovich models 2023)
3 GO Azithromycin 98.8% Freundlich isotherm model (Upoma et al., 2022)
4 GO cephalexin 80% Pseudo-second-order kinetic and (Hatami Solukluei et al.,
Langmuir isotherm models. 2023)
5 β-cyclodextrin/dopamine hydrochloride- sulfamethoxazole, 144 mg⋅g− 1 and pseudo-second-order kinetic model, (Yu et al., 2022)
graphene oxide, CD-DGO sulfadiazine 152 mg⋅g− 1 Langmuir adsorption isotherm
6 GO- nanosheets. ibuprofen 99.01% Freundlich model (Nekooei et al., 2023)
7 κ-car-g-PAAm@Fe3O4-GO ciprofloxacin 1146.467 mg/g pseudo-second-order (Hassanzadeh-Afruzi et al.,
2023)
8 Fe3O4/GO cephalexin 97.69% - (Alishiri et al., 2023)
9 GO paracetamol 76.6 pseudo-first and pseudo-second order, (Osobamiro and Oladipo,
Langmuir and Freundlich isotherms 2022)
10 CuO-rGO amoxicillin 80% pseudo-second-order kinetic equations (Rajapaksha et al., 2022)

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Table 2 that include, hydrophilicity, large surface area and adsorption capability
Metal oxide-based nano adsorbents for the remediation of pharmaceutical (Khan et al., 2023). Due to these unique characteristics, they find ap­
wastewater. plications in a wide range of fields including energy storage composites,
S. Pharmaceutical Metal Efficient Reference water purification, and gas sensors (Ayodhya, 2023). Under visible light
No. Contaminant oxide nano degradation radiation, graphitic carbon nitride and Ti3C2 MXene were studied to
adsorbents percentage mitigate pharmaceutical pollutants—cefixime. The results showed
1 Ibuprofen BiOBr/ 100 (Thiruppathi excellent activity and these proved efficient when used three times,
Fe3O4@SiO2 et al., 2018) without losing its photocatalytic performance (Kumar et al., 2022). In a
2 Diclofenac Fe3O4/Bi2S3/ 93.81 & (Li et al.,
study, CuFe2O4/MXene (CFO/Ti3C2) nano adsorbent was used for
Ibuprofen BiOBr 96.78 2019)
3 Naproxen ZnFe2O4@TiO2/ 80.73 (Ahmadpour visible light-assisted photocatalytic degradation of sulfamethazine.
Cu et al., 2020) Therefore, the mitigation percentage of sulfamethazine reached about
4 Nitrofurantoin TiO2, P25 100 (Szabó-Bárdos 60%. Furthermore, it was observed that SMZ molecules became adsor­
et al., 2020) bed or targeted by the active material throughout the entire photo­
5 Tetracycline ZnO/SO2 90 (Lwin et al.,
hydrochloride 2019)
catalytic process (Zhang et al., 2021). Kadid et al. discovered
6 Paracetamol CuO 64.52 (Akpomie and ZnO/TiO2-nanorod MXene nano photocatalyst under simulated sunlight
Conradie, the excluded the pharmaceutical ceftriaxone— evaluated removal effi­
2023) ciency of 99.4% (Abbas et al., 2022).
7 Ceftriaxone CuS QDs/ ZnO 100 (Mohammed
Similarly, MXene incorporated with novel Zn/Ti layered double
et al., 2022)
8 Ciprofloxacin TiO2/SnO2 92.8% (Pascariu hydroxide was fabricated by grzegórska et al. This nano-adsorbent de­
et al., 2023) grades acetaminophen & and ibuprofen with an efficiency percentage of
9 Tetracycline and (SDS)/BiOBr 85% & 95% (Liu et al., 100 & 99.7 in the presence of O2− (Grzegórska et al., 2022). Shahzad
ciprofloxacin 2020a) et al. discovered a heterostructure TiO2/Ti3C2Tx (MXene) for mitigating
10 Tetracycline Fe3O4/BiVO4/ 87.37 (Xu et al.,
the antiepileptic drug carbamazepine. They investigated adsorption/­
CdS 2021)
11 amoxicillin ZnO@SiO2 90% (Pham et al., photocatalytic degradation by comparing ultraviolet light and natural
2022) solar light with pH ranging from 3.0 to 5.0. The result determined that
12 sulfonamides ZnO/ 98.5% (Khongkla the ultraviolet light was higher than the natural solar light for removing
Fe3O4@SiO2- et al., 2023)
carbamazepine (Shahzad et al., 2018). A novel nano adsorbent, PVP
NH2/MIP/
alginate encapsulated with MXene coated on a PET surface has shown the highest
photo-degradation of 99.71% for tetracycline (TC) antibiotic (Talreja
et al., 2023). MXene-based nano adsorbents are utilized as alternatives
2.5. MXene-based nano adsorbent for water treatment applications. There are certain limitations such as
scaling up fabrication, long-term stability, and recycling. MXenes pre­
MXenes are a type of nanomaterials that are two-dimensional (2D) in sent an exciting possibility as low-cost and environmentally benign
nature and are produced from transition metal carbides, nitrides, or adsorbents for the purification of water polluted with pharmaceutical
carbonitrides (Fig. 3). These nanomaterials possess distinct properties residues (Tawalbeh et al., 2023).

2.6. Transition metal dichalcogenide/g-c3n4-based nano-adsorbents

Other transition metal dichalcogenides besides MXenes exhibit po­

tential as pharmaceutical removal nano adsorbents. For example,
graphitic carbon nitride (g-C3N4) mixed with molybdenum disulfide
(MoS2). These heterostructure nanomaterials effectively use the unique
characteristics of polymeric g-C3N4 and 2D MoS2 to facilitate photo­
catalytic degradation pathways and the adsorption of pharmaceutical
pollutants (Biswal et al., 2021). In addition, under visible light irradia­
tion, MoS2/g-C3N4 nanocomposites have demonstrated excellent po­
tential for removing antibiotics such as ciprofloxacin and tetracycline
from water (Selvamani et al., 2021). MoS2 encourages charge separation
and the production of reactive oxidative species, such as superoxide and
hydroxyl radicals, to break down the drugs that have been adsorbed,
while g-C3N4 serves as a photosensitizer to visible light (Liu et al.,
2020b). Similarly, the antibiotics carbamazepine and sulfamethoxazole
have been photo catalytically degraded using WS2/g-C3N4 (Mafa et al.,
2019). Comparing these transition metal dichalcogenide/g-C3N4
nanocomposites to their components, they have synergistic benefits
that improve adsorption and photocatalysis, such as tuneable band gaps,
high surface areas, and distinctive heterostructure interfaces (Chen
et al., 2023; Shi et al., 2018).

2.7. Polymeric nano adsorbents

Polymeric nano adsorbents are nanomaterials with repetitively

branched molecules employed for mitigating heavy metals organic
pollutants and pharmaceutical contaminants. The critical characteristics
Fig. 3. MXenes and MXene-based materials for removal of pharmaceutical include mechanical features, regeneration under mild conditions, sur­
compounds from wastewater. face chemical framework, eco-friendly, and strong mechanical strength.

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some of the polymeric nano adsorbents include - Polyaniline (PANI), with iron oxide nanoparticles employing chemical activation and py­
Polypyrrole (Ppy), Polythiophene (PTh), Polyacrylamides, and Cellulose rolysis. These nano-adsorbents provide magnetic separability, but they
acetate (Pan et al., 2019; Siahkamari et al., 2017). In a study, a thin film have disadvantages as well. These include expensive synthesis, poor
of nano-adsorbent was designed to absorb montmorillonite and modi­ aqueous dispersibility, difficulties scaling up production, performance
fied montmorillonite onto a polysulfone membrane. The results indicate dependence on environmental factors, and rapid loss of adsorption ac­
the successful elimination of PCs especially ibuprofen, amoxicillin, and tivity upon reuse because of surface fouling and magnetic core leaching
cephalexin in addition, the cephalexin exhibited the lowest hydropho­ over time (Mudhoo and Sillanpää, 2021).
bicity and had a rejection rate of 94.05% (Medhat Bojnourd and Pak­ The Magnetic activated carbon is incorporated into ferromagnetic
izeh, 2018). Using isotherm models, the nano-clay composite as metal oxide nanoparticles and powder-activated carbon is utilized for
adsorbent was tested to remove ibuprofen under different adsorption the removal of pharmaceutical waste such as amoxicillin, carbamaze­
conditions. The results suggested that the maximum removal efficacy for pine, and diclofenac. The results exhibited the removal efficiency per­
ibuprofen was 95.2%. Ibuprofen was removed using 1 g of adsorbent, at centage was 61% and 84% (Rocha et al., 2021). Similarly, magnetically
a concentration of 10 mg L− 1, for 120 min with a pH of 6 (Rafati et al., activated carbon-Fe3O4 nano adsorbent was tested for mitigating the
2018). antibiotics from wastewater. A phenothiazine antipsychotic drug (pro­
An experiment was conducted in which clay nanocomposites were mazine) was used in the study. The results showed an efficiency rate of
used to adsorption metronidazole and ibuprofen into water. Two types 99.97% for eliminating the promazine from the waterways (D’Cruz
of ceramic nanocomposites have been developed: nZVI-clay and AC. The et al., 2020). Magnetic nanocomposite P (St-b-AAc)/Fe3O4 designed as
activated carbon-nZVI-clay with 20% activated carbon removed 87.11% nano adsorbent for removing ciprofloxacin from water streams. The
of metronidazole and 87.1% of ibuprofen, showing effective adsorption results indicate that the highest removal efficiency was 97.5%, with a
isotherm and kinetic behaviour (Azizpourian et al., 2023). Chitosan is a concentration of 5 mg/L, dosage of 2 mg/L, and contact time of
natural polymer used as a nano adsorbent to mitigate pharmaceutical 37.5 min. The absorption isotherms—Langmuir isotherm and
waste from aquatic environments. This biopolymer consists of linear second-order kinetic equation are considered ideal for the adsorption
polysaccharides, composed of randomly distributed β-(1→4)-linked processes (Mohammadi et al., 2020). In order to remove carbamazepine
D-glucosamine, and the second most abundant polysaccharide in the (CBZ) from wastewater, a magnetic nanocomposite known as poly­
world; is derived from the shells of crustaceans (Kumari et al., 2023). pyrrole-chitosan-Fe3O4 (PPy-CS-Fe3O4 MNC) was utilized. This method
Various types of chitosan-based nano adsorbents for removing the PCs demonstrated an efficiency rate of approximately 94.5% within a
are listed in Table 3. The hydrogel composed of 1% chitosan, 40% 25-minute timeframe, as per the Langmuir isotherm model (Nezhadali
PEG4000, and 4% xanthan gum was found to exhibit considerable ef­ et al., 2021). The magnetic metal-ceramic nanocomposites as nano ad­
ficacy in removing diclofenac sodium from water. Remarkably, at a sorbents were tested to remove sulfanilamide (SA) from water. Zeolite A
dosage of 200 mg, the hydrogel demonstrated a maximum adsorption and a natural clinoptilolite were the materials tested against SA. Addi­
capacity of 172.41 mg/g within 350 min (Chelu et al., 2023). tionally, the study indicates that the pH factor exerted an influence on
the removal of SA and has discerned two potential mechanisms of SA
adsorption, predicated on the interplay of polar and hydrophobic in­
2.8. Magnetic adsorbents for mitigating pharmaceutical waste teractions (Sannino et al., 2022).

One of the most promising methods for eliminating pharmaceutical 3. Mechanistic insights into adsorption and adsorption
waste was by incorporating nanoparticles with magnetic materials behaviour
(Siddiqui et al., 2023). Other transition metal dichalcogenides of the
magnetic nano-adsorbents enable easy recovery and separation after Adsorptive materials are substances that adhere to molecules on
use, promoting reuse and reducing waste. These adsorbents combine their surface. These materials are prevalent used for removing antibi­
active ingredients such as metal oxides, polymers, biological com­ otics from water and soil. The adsorption of antibiotics on adsorbents
pounds, activated carbon, and other magnetic materials like iron, nickel, can be elucidated through diverse mechanisms, encompassing electro­
cobalt, chromium, and manganese (Barozzi et al., 2022). Their sizes static interaction, hydrophobic interaction, hydrogen bonds, and π-π
range from 5 to 100 nanometers and are found naturally or artificially. interactions, as visually depicted in Fig. 4. The process of adsorption can
After the adsorption process is completed, the magnetic core allows the occur either in a single step or in combination with several steps,
manipulation and extraction of the nano-adsorbents from the solution including (a) the passage of the solute in the bulk, (b) the dispersion of
using an external magnetic field. Similarly, the AC was incorporated

Table 3
Various types of Chitosan-based nano adsorbents for mitigating PCs.
S. Pharmaceutical contaminants Nano adsorbents Models of adsorption isotherm Efficiency Reference
No. percentage

1 Levofloxacin & ceftriaxone Nbent-ntio2-chit Langmuir, freundlich and Temkin 90.2% & 93.5% (Mahmoud et al.,
2020)
2 Furosemide Chitosan films Pseudo-second-order kinetic model 100% (Rizzi et al., 2020)
3 Diclofenac Chitosan grafted adsorbents Langmuir-freundlich 100% (Tzereme et al.,
2019)
4 Tetracycline Mnfe2o4 nanoparticles Pseudo-first-order model 157.97% (Ahamad et al.,
embedded in chitosan 2019)
5 Rifampicin Chitosan Langmuir, freundlich, Dubinin-Radushkevich (DR) 66.91% (Shahrin et al.,
and Temkin isotherm models, 2023)
6 Diclofenac Chitosan films Pseudo-second order kinetic model 90% (Rizzi et al., 2019)
7 ibuprofen, Polymeric chitosan Freundlich isotherm model. 70.0% (Phasuphan et al.,
2019)
8 Ibuprofen Hybrid chitosan with polymer Freundlich isotherm and pseudo-second-order 79.41% (Stachowiak et al.,
hydrogel beads kinetic models 2023)
9 Diclofenac (dcf), ibuprofen (ibp), Magnetic chitosan/activated Langmuir and Freundlich isotherms 96.4%, 98.8%, (Mojiri et al., 2019)
and naproxen (npx) biochar (cmcab). 95.2%

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Fig. 4. Illustrates the mechanism behind the nanoscale adsorption.

the adsorbate as a film, (c) the diffusion of the adsorbate through the 2020). The research findings showcased that the SA/TA hydrogel dis­
pores, and (d) the interaction between the adsorbate and the adsorbent played superior and more consistent capacity to capture CQ when
(Pourhakkak et al., 2021). The electrostatic attraction, π-π interaction, compared to its predecessor, the SA hydrogel. Remarkably, the SA/TA
and hydrogen bonding, other mechanisms such as van der Waals forces hydrogel achieved a maximum CQ adsorption capacity of 0.699 mmol/g
and hydrophobic interactions, contribute to the adsorption of antibiotics at a pH value of 9.0, with the optimal SA to TA ratio being 1:1 (SA/TA2).
onto adsorbent materials (Eniola et al., 2019). The adsorption of ionic The experimental outcomes suggested that the adsorption mechanisms
compounds plays a significant role in these interactions. Carbon nano­ of CQ by the SA/TA hydrogel encompassed various interactions, notably
tubes (CNTs) are carbon-based materials that perform sublime in anti­ chelation, electrostatic interactions, π-π electron donor-acceptor inter­
biotic adsorption through electrostatic interactions. The adsorption of action, and hydrogen bonding (Tao et al., 2023).
sulfonamide drug molecules on carbon nanotubes has been determined Hydrophobic interaction refers to interaction between water and
as physical adsorption, which exhibits higher adsorption energy in hydrophores which are nonpolar molecules that have low water solu­
aqueous environments. However, the adsorption energies experience a bility. This interaction is also known as the hydrophobic effect (Wang
significant reduction in acid-base environments, indicating the et al., 2023b). Hydrophobic interactions promote the adsorption process
requirement of an appropriate pH range for achieving optimal adsorp­ of nano adsorbents. Interaction occurs between the hydrophobic surface
tion (Wu et al., 2023). of the nano adsorbents and the hydrophobic regions of ciprofloxacin
Based on adjustments to the ionic strength, electrostatic interactions (CIP) molecules, enabling the adsorption of the antibiotics onto the
were found to be neutral and could not be increased or diminished. In an surface of adsorbents. In a study, activated biochar was used to eliminate
experiment, biochar called PHC (Peanut Husk Charcoal) was tested to CIP from wastewater using adsorption dynamics. The results suggested
remove tetracycline (TET) and amoxicillin (AMX), from water. The PHC that the efficiency percentage of CIP removal was 89.94% (Hamadeen
was incorporated with CTAB to enhance its adsorption properties. PHC- and Elkhatib, 2022).
CTAB showed maximum adsorption capacities of 272 mg/g for tetra­ Hydrogen bonding, a specific type of intermolecular force (IMF) that
cycline and 305 mg/g for amoxicillin. Hence, the adsorption process for occurs between molecules. Hydrogen bonds are classified into three
tetracycline mainly occurred through physisorption, which is a physical types: weak, moderate, and strong. Weak hydrogen bonds have less
interaction between the adsorbent and the adsorbate. In the same interaction energies. Moderate hydrogen bonds have interaction en­
context, the process of adsorption of amoxicillin occurs through chem­ ergies of about 2–15 kcal/mol. Strong hydrogen bonds have more
isorption. Chemisorption refers to a chemical reaction that takes place interaction energies. Hydrogen bonding promotes the adsorption of
between the adsorbent and the adsorbate (Egbedina et al., 2023). various substances by nano adsorbents. For instance, metal-organic
Another significant technique is the interaction between electron framework-based materials utilize hydrogen bonding contributes to
donor and acceptor through π-π bonding, also known as electron donor- the adsorption of hazardous organics in the liquid phase (Ahmed et al.,
acceptor interactions (EDA). The existence of amino or fluorine groups 2022). Hydrogen bonds also induce the adsorption processes of carbon
in oxytetracycline-like antibiotics enhances their ability to act as nanotubes and graphene oxide. In this case, these bonds form between
powerful π-acceptors. These functional groups function as strong elec­ the benzene ring present on the adsorbent’s surface and organic com­
tron donors. The unshared pair of electrons forms a robust association pounds that possess oxygen-containing functional groups (Petit et al.,
with the π electrons of the benzene structure, leading to a vigorous 2017).
network with positively charged sites on CNTs (Joshi et al., 2023;
Oyekunle et al., 2023; Qu et al., 2023). In a scientific investigation, a
newly developed hydrogel consisting of sodium alginate (SA) and tannic 3.1. Adsorption isotherms
acid (TA), denoted as SA/TA, was examined as a potential adsorbent for
the removal of chloroquine phosphate (CQ) from water (Yang et al., The amount of adsorbate adsorbed on an adsorbent and the con­
centration of adsorbate in solution relate to adsorption isotherms, when

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M.K.K. Perumal et al. Process Safety and Environmental Protection 186 (2024) 552–565

equilibrium reaches a constant temperature. Thermodynamic calcula­ investigated the adsorption of azithromycin (AZM) using activated
tions determine the affinity, surface properties, and adsorption mecha­ porous carbon prepared from a plant called Azolla filiculoides (AF). The
nism. The rate of adsorption onto nano adsorbents is influenced by results indicated that Freundlich isotherm is found to be the best fit for
factors such as temperature, contact time, and pH. The efficiency of describing the adsorption isotherm. Similarly, the calculations from
nanoparticles for the adsorption of pharmaceutical compounds is second-order pseudo kinetics indicate that the adsorption process is
calculated by various isotherm models. The amount of substance that relatively fast. The efficiency percentage for removing AZM was 98% in
adheres to a surface data must fit the adsorption isotherm equations. 75 min, at 303 and 333 K, respectively (Balarak et al., 2021). A recent
Langmuir and Freundlich equations are widely used adsorption iso­ report on AC derived from rice and coffee husk removed acetaminophen
therms, while other adsorption equations include the Temkin, modified in urine. The results suggested a homogeneous adsorption process in
Dubinin-Radushkevich, and multisite Langmuir equations (Kinniburgh, which the Redlich-Peterson isotherm provided the best fit (Par­
1986; Wang and Guo, 2020). These are used to emphasize the adsorp­ edes-Laverde et al., 2019).
tion of toxic pharmaceutical pollutants (Adedeji and Jahan, 2023; Blaga The study focused on the use of acid-AC derived from Prosopis juli­
et al., 2022; Debnath and Das, 2023). Langmuir isotherm and Freundlich flora wood (PPJ) for mitigating antibiotics, specifically ciprofloxacin
models were used to determine the adsorption of solutes on solid sur­ and amoxicillin from wastewater. PPJ adsorption capacity was deter­
faces. According to Al-Sareji et al (Al-sareji et al., 2023)., the Freundlich mined to be 250 mg/g for CIP and 714.29 mg/g for AMX. The collected
model does not adequately fit the drugs’ adsorption data; the correlation data was successfully fitted into the Langmuir isotherm model and the
coefficients for amoxicillin, diclofenac, and ciprofloxacin range from pseudo-second-order model. In summary, PPJ demonstrated effective­
0.992 to 0.996. This implies that the drug molecules may have assem­ ness in the removal of AMX (Chandrasekaran et al., 2020). The various
bled into a monolayer on the MPPs’ surface. For amoxicillin and cip­ types of equilibrium isotherms involved in calculating the amount of
rofloxacin, the sorption capacity (qm) was determined to be between absorption are mentioned in Tables 2 and 3. Yang et al. emphasized
598.80 and 704.22 mg/g, respectively (Fig. 5 A&B). bamboo-based magnetic activated carbon for reducing sulfadiazine from
In the case of monolayer adsorption in homogeneous sites, this ap­ wastewater. Their applications and adsorption mechanisms are also
plies. The Freundlich adsorption isotherm model has been used to discussed in this study (Yang et al., 2023). According to studies by Rosli
illustrate the relationship between the volume of gas adsorbed on a solid et al (Rosli et al., 2021). and Al-Khateeb et al (Al-Khateeb et al., 2017).,
surface and its pressure. For multiple adsorption in heterogeneous lo­ Fig. 6 demonstrates the effective removal of pharmaceuticals from water
cations Freundlich isotherm suites are used (Guo and Wang, 2019). The using graphene nanoplatelets (GNP) as adsorption/desorption isotherm
Freundlich adsorption isotherms are calculated by qe =KFC1/n e and the type IV. An H3-type hysteresis loop confirms that aggregates (loose as­
Langmuir equation semblages) of platelet-like particles formed slit-shaped mesopores (Sing,
1985). As stated by Mukhopadhyay et al (Mukhopadhyay et al., 2020).,
Qm KL Ce
qe = (1) the intermediate flat zone in the isotherm represents the formation of
1 + KL Cee
monolayers in the lower pressure region of the graph, which are fol­
The Eq. (1) considers the variables KF, KL, n, and Qm. KF represents lowed by multilayers (Rosli et al., 2021).
the Freundlich constant, which indicates the adsorption capacity. KL
refers to the Langmuir adsorption equilibrium constant, which de­ 3.2. Adsorption kinetics
termines the adsorption energy and the affinity between the adsorbate
and the adsorbent. The n represents the constant that represents the Adsorption kinetics denotes a line or a curve that explains the rate at
strength of adsorption, while Qm represents the maximum adsorption which the solute is either released or retained from the aqueous envi­
capacity. The Langmuir isotherm assumes that the adsorption sites are ronment. It also calculates the amount of time taken by the solute in the
evenly distributed throughout the entire surface area of the adsorbent. solid-liquid interface. Adsorption kinetics involves two primary pro­
This suggests that the adsorbate molecules are only adsorbed on these cesses, physisorption (physical) and chemisorption (chemical). It per­
sites, with each site capable of accommodating only one particle. The forms a critically important function in the bonding of particles onto the
adsorbent surface typically holds multiple sites with varying adsorption surface of a substance, whereas the latter entails the movement of par­
energies. The Freundlich isotherm assumes that adsorption occurs on a ticles into a distinct material. Various models regarding kinetics have
non-uniform surface, in contrast to the Langmuir isotherm. The study been put forth for the process of adsorption, including the Pseudo-First-

Fig. 5. Langmuir (A) and Freundlich (B) isotherm models fittings.

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M.K.K. Perumal et al. Process Safety and Environmental Protection 186 (2024) 552–565

Fig. 6. N2 adsorption/desorption isotherms for GNP (a) C750, (b) C300, (c) M15 and (d) M5 (Rosli et al., 2021).

Order (PSO), Modified Pseudo-First-Order, Pseudo-Second-Order, onto the adsorbent is due to physisorption. Fig. 7, despite the adsorption
Pseudo-Third-Order, and Avrami’s fractional order models (Tran et al., kinetics of paracetamol by commercial activated carbon fitted by the
2021). PSO model (Tran, 2023). Conversely, the PSO model considers chemi­
The PSO assumes that the primary limitation of particle adsorption sorption as the rate-limiting mechanism for the process. The

Fig. 7. Adsorption kinetics of paracetamol by commercial activated carbon fitted by the PSO model (Tran, 2023).

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M.K.K. Perumal et al. Process Safety and Environmental Protection 186 (2024) 552–565

pseudo-second order, for the most followed and prevalent model leads to an improvement in adsorption capacity (Fanourakis et al., 2020;
because of its ability to accurately depict numerous adsorption systems Khadir et al., 2020; Patel et al., 2022). A range of nano adsorbents were
(Ezzati, 2020; Revellame et al., 2020). Ninwiwek et al. studied the employed in the elimination of non-steroidal anti-inflammatory drugs
removal of sulfamethoxazole from an aqueous environment using a (NSAIDs) such as Ibuprofen (Ibu), Naproxen (Nab), and Diclofenac
silica-magnetic GO nanocomposite. They used the pseudo-second-order (Dic). Through the utilization of copper nanoparticles (Cu NPs) as a nano
model to analyse the adsorption kinetics (Ninwiwek et al., 2019). Nas­ adsorbent, significant removal percentages of these NSAIDs were ach­
seh et al. investigated the adsorption of metronidazole using a FeNi3/­ ieved. Specifically, removal rates of 74.4%, 86.9%, and 91.4% were
SiO2/CuS magnetic nanocomposite. They used the pseudo-second-order observed for Ibu, Nab, and Dic respectively. This successful removal
model and other kinetic studies to calculate an efficiency percentage of process occurred at a temperature of 298 K and a pH level of 4.5 (Husein
85.26 for metronidazole removal (Nasseh et al., 2019). et al., 2019). Meanwhile, the maximum removal efficiency (100%) was
recorded by the second-order model, for mitigating metronidazole
3.3. Surface modification (MTZ) by using Fe3O4-chitosan nano-adsorbent (CTS-MNPs).
This research examined at pH 3.0, dosage of 2 g L− 1, and a contact
The materials used as nano adsorbents have innate limitations; the time of 90 min was efficient to remove MTZ (Asgari et al., 2020). Hy­
predominant of them have low adsorption capacities. Hence, the pure or droxyapatite and chitosan nano-composite are used as nano adsorbents
naked form of nanomaterials is inadequate to perform better as Nano for the effective removal of norfloxacin. Using isotherm and kinetic
adsorbent. To overcome this limitation functionalization or surface studies, it was observed that the maximum adsorption efficiency of 92%.
modification is introduced to associate with nanoparticles, in order to This was achieved at a dosage of 0.5 g/L and a pH level of 7.0 (Nayak
the advantages of these adsorbents over conventional ones. Nano­ et al., 2022). The porous graphene nanomaterials were tested against
particle surface modification involves the modification and processing pharmaceutical contaminants such as ibuprofen, carbamazepine, cip­
of the surface of nanoparticles through physical and chemical processing rofloxacin, diclofenac, and atenolol. The results indicated that there was
methods. This facilitates the control of internal stress and the amplifi­ a successful removal of pharmaceutical contaminants with a removal
cation of the repulsive force among the nanoparticles (Manyangadze efficiency of 99% (Khalil et al., 2020). Ibuprofen drug, which is pre­
et al., 2020). According to Samsami team developed a thin-film nano­ dominantly found in flora and fauna—is removed by an iron nano
composite incorporated with an osmosis membrane; with a combination adsorbent. The study suggested using the nano adsorbent at pH- 7 for the
of metal-organic frameworks and a thin-film nanocomposite material. effective removal of Ibuprofen (Ali et al., 2016). Xiang et al. discussed
This innovation was used to remove the antibiotic - doxycycline from the activated carbon used to remove various antibiotics from the water
water. The metal-organic framework was made up of aluminium (Al) streams. The detailed review also mentions the mechanism and influ­
atoms and was surface-modified to MOF-TFN FO. By utilizing this encing factors (pH, temperature, and ionic strength) involved in miti­
technique, the physicochemical characteristics of the membranes such gating the antibiotics (Xiang et al., 2019). Magnetic graphene oxide
as their morphology and hydrophilicity were analysed. The results (MGO) was fabricated to remove the antibiotics—tetracycline hydro­
indicate that the modified membrane had a high flux recovery ratio of chloride (TC) and oxytetracycline. At a pH range of 3.3, MGO has shown
96.67%, and was effective in removing the doxycycline (Samsami et al., a positive effect in absorbing TC and OTC (Miao et al., 2019). Li et al (Li
2022). et al., 2020). discovered manganese dioxide nanoparticles (BC/MnO2)
The study investigated Fe3O4 magnetic nanoparticles (MNPs) were loaded onto biochar from the rice husk. It is prepared to reduce the
composed of iron oxide (Fe3O4), which were modified on their surface antibiotics: TC and doxycycline (DC). In conclusion, the concentration of
through a process of coating with a chemical substance known as 3-ami­ ions present in the nano adsorbent has greatly influenced the removal of
nopropyltriethoxysilane (APS) in conjunction with copolymers consist­ TC and DC by BC/MnO2 (Li et al., 2020). Similarly, magnetic graphene
ing of acrylic acid and crotonic acid. Additionally, this research aimed to oxide (NDMGO) was utilized to reduce TC from the water. The results
comprehend the mechanism by which the MNPs adsorb metal ions, thus showed adsorption capacity of TC increased rapidly to the concentration
entailing an examination of adsorption isotherms, kinetics, and ther­ of ions, thus, increasing the adsorption capacity (Li et al., 2017). Nano
modynamics. The findings reported a significant maximum adsorption adsorbent was synthesized by using pomegranate peel for effective
capacity of the MNPs at a pH level of 5.5, leading to their convenient removal of cefixime antibiotic from waterways. Studying parameters
reusability as an adsorbent (Ge et al., 2012). A novel discovery by such as temperature pH, adsorbent dosage, and contact storage were
lysozyme-modified nano-silica (LMNS), a biomaterial for reducing lev­ also examined. At pH 2–11, the nano-absorbent was efficient in
ofloxacin (LFX) in aqueous environments. The optimal situation for removing the cefixime from the aqueous environment (Esmaeili Bid­
adsorption of lysozyme on nano-silica were a solution pH of 10, a con­ hendi et al., 2020). As demonstrated by Fig. 8, immobilised laccase on
tact time of 120 min, a nano-silica dosage of 10 mg/mL, and the pres­ activated carbon made from pomegranate peels (MPPs) effectively
ence of 1 mM KCl (potassium chloride). This condition enabled removes pharmaceutical pollutants from water and wastewater. At
lysozyme to attach to the surface of nano-silica particles and proved the dosages of 0.1, 0.2, and 0.4 g/L adsorbent, the pHpzc values of MPPs
removal efficiency of LFX from 51.51% to 80.63% (Vu et al., 2023). As a were 5.9, 5.4, and 6.1, respectively. The pHpzc shows that the MPPs have
result, surface modification of nanoparticles has been a significant tool a negative surface charge at pH values more than 5.8 and a positive
to improve adsorption capacity, adsorption efficiency, dispensability, surface charge at pH values less than 5.8 (the average value for three
and stability. dosages), indicating that acidic groups predominate on the surface of the
MPPs. The pH generally drifted towards the point of zero charge (PZC)
4. Factors influencing the nano absorbent for effective removal of MPP doses (Al-sareji et al., 2023) when the adsorbent dosage was
of PCs raised (Kosmulski, 2009).

4.1. Effect of pH 4.2. Effect of temperature

The chief constituents involved in the process of adsorption - Van der The variations in the temperature have greatly impacted the affinity
Waals forces and electrostatic affinity. In addition, they are also influ­ of antibiotics to the adsorbent surface; as increase in solution tempera­
enced by other factors such as temperature, pH, pollutant concentration, ture, the adsorption capacity of the adsorbents also maximizes. The
particle size, and physiochemical properties. The surface groups present presence of active site expansion increases the removal efficiency and
on the adsorbent and the pollutant charge are altered by the level of pH. adsorption capacity. Meanwhile, increasing temperature promotes the
Furthermore, during endothermic reactions, the rise in temperature removal of antibiotics. For instance, Fe3O4 nanoparticles synthesized

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M.K.K. Perumal et al. Process Safety and Environmental Protection 186 (2024) 552–565

the percentages reached were 96.55% and 98.89% respectively

(El-Maraghy et al., 2023).
Similarly, using parameters pH 2–10 and contact time of 10 min, the
elimination of cefixime from wastewater using nZVI copper slag as a
nano adsorbent has been achieved by 98.71%. In addition, the results
show that it has an efficiency rate of 90% for removing cefixime when
used with nZVI slag and copper after six cycles of reuse (Moridi et al.,
2023). The nano adsorbent has been recently developed to absorb cip­
rofloxacin from water by utilizing magnetic nanoparticles. Extensive
research has been conducted to analyze the various factors which in­
fluence the absorption process. The optimal conditions and precise
mathematical model for predicting ciprofloxacin absorption were
developed by methodologies - Response Surface Methodology (RSM)
and Central Composite Design (CCD) (Birniwa et al., 2022). These
experimental approaches revealed that the synthesized adsorbent
exhibited a remarkable level of adsorption efficiency. The adsorption
process followed a quadratic model and Langmuir isotherm, and an
impressive recovery rate of approximately 80% at a contact time of
45 min was achieved after five cycles (Ghadami et al., 2024).
Fig. 8. pHpzc of different modified pomegranate peels (MPPs) dosages (Al-sareji
et al., 2023).
5. Conclusion
from Excoecaria cochinchinensis extract are used as nano adsorbents for
In conclusion, the review discussed the potential of different nano-
removing rifampicin from an aqueous environment. The Fe3O4 nano
adsorbents for removing pharmaceutical pollutants from water bodies.
adsorbent at a temperature of 303 K achieved the maximum adsorption
The most effective nano-adsorbents include carbonaceous materials,
capacity reaching 98.4% (Cai et al., 2019). AC magnetized by iron (III)
metal oxides, MXenes, magnetic nanocomposites, and polymeric nano­
oxide magnetic nanoparticles (PAC@Fe3O4-MN) are synthesized for
materials. Particularly, graphene-based nano-adsorbents have shown
reducing the CIP. The Results indicated that the PAC@Fe3O4-MN
high removal efficiencies of antibiotics such as levofloxacin with 99.2%
showed outstanding adsorption capacity at a pH of 7.0 with a contact
and ibuprofen with 99.9%. Similarly, MXenes can remove up to 99.4%
time of 60 min and a temperature of 298 K dosages for removing the CIP
of ceftriaxone. However, despite significant progress, some of these
(Al-Musawi et al., 2021). Roy et al. discussed a comprehensive overview
technologies still face some major challenges that limit their utility.
of various nano-structured photocatalysts, their strategies, and the
These challenges include their inability to be used at a commercial scale,
different parameters involved in removing the anti-biotics affecting the
toxicity, and high material instability. This study suggests that future
aqueous environment (Roy et al., 2021). Copper oxide nanoparticles
investigations should focus on eco-friendly synthesis, novel hybrid or
(CuONPs) and nano-zero-valent iron (nZVI) were employed to mitigate
composite nanomaterials, and overcoming the limitations of existing
the presence of levofloxacin in wastewater. The optimal conditions for
nano-adsorbents. Developing more effective and cost-effective nano-
achieving the highest levofloxacin removal capacity were found to be a
adsorbent technologies for removing pharmacologically active phar­
temperature of 35 ◦ C, a pH of 7.0, and a contact time of 120 min when
maceutical contaminants from water sources is also feasible as nano­
utilizing CuONPs. It should be noted that the removal efficiency of
material design and synthesis continue to advance in recent times.
levofloxacin was found to be influenced by temperature, with a
maximum absorption efficiency percentage of 89% observed at 25 ◦ C
and a 91% absorption efficiency at 35 ◦ C (Hamad and El-Sesy, 2023). Funding

This study did not receive any financial support or funding from
4.3. Influence of Contact time to remove PCs external sources.

The impact of Contact time is important in adsorption studies, as CRediT authorship contribution statement
contact time is a key parameter that determines the extent to which
adsorption occurs. It provides important information regarding the Manoj Kumar Karuppan Perumal: Writing – original draft, Data
adsorption kinetics of adsorbent given a particular starting dose for an curation, Formal analysis, Methodology, Visualization, Validation.
adsorbent. Initially, as contact time increases, the rate of adsorption also Dhivya Gandhi: Data curation, Formal analysis, Resources, Software,
increases, but eventually levels off and becomes almost constant. This Writing – review & editing. Remya Rajan Renuka: Conceptualization,
phenomenon occurs because the molecules tend to aggregate with Methodology, Project administration, Resources, Supervision, Valida­
prolonged contact time, making it more difficult for them to penetrate tion, Visualization, Writing – review & editing. Aranganathan Laksh­
deeper into the structure of the adsorbent at higher energy sites. The minarayanan: Formal analysis, Investigation, Resources, Software,
adsorption property is heavily influenced by the time necessary to reach Validation, Visualization, Writing – review & editing. Nathiya Thiya­
equilibrium between the adsorbent and the adsorbate. When the length garajulu: Data curation, Formal analysis, Resources, Software, Valida­
of contact between the adsorbent and the adsorbate increases, removal tion, Visualization, Writing – review & editing. Chinnaperumal
efficiency and adsorption capacity are continuously increased (Priya Kamaraj: Conceptualization, Formal analysis, Investigation, Resources,
et al., 2020; Rajapaksha et al., 2022; Wahyuhadi et al., 2023). For Supervision, Validation, Visualization, Writing – original draft.
instance, magnetite pectin nanoparticles are used to remove levo­
floxacin from wastewater. The results showed that at pH 4, with a
contact time of 4 h, an optimum adsorption capacity for the eliminated Declaration of Competing Interest
PCs from an aqueous environment using MPNP was obtained. The
optimal adsorption range of pH 7 with a contact period of 12 h has been The authors declare that there are no known competing financial
demonstrated when MSNP is used. The concentrations used were interests or personal relationships that could have appeared to influence
10 µg/mL for the drug and 16 g/L for the nanoparticles. For adsorption, the work reported in this paper.

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M.K.K. Perumal et al. Process Safety and Environmental Protection 186 (2024) 552–565

Acknowledgements using immobilized laccase on activated carbon derived from pomegranate peels. Sci.
Rep. 13, 11933 https://doi.org/10.1038/s41598-023-38821-3.
Asgari, E., Sheikhmohammadi, A., Yeganeh, J., 2020. Application of the Fe3O4-chitosan
The authors of this article would like to acknowledge the technical nano-adsorbent for the adsorption of metronidazole from wastewater: Optimization,
support provided by Center for Global Health Research, Saveetha kinetic, thermodynamic and equilibrium studies. Int. J. Biol. Macromol. 164,
Medical College and Hospitals, Saveetha Institute of Medical and 694–706. https://doi.org/10.1016/j.ijbiomac.2020.07.188.
Ayodhya, D., 2023. A review of recent progress in 2D MXenes: Synthesis, properties, and
Technical Sciences, Chennai-602105, Tamil Nadu, India. & Interdisci­ applications. Diam. Relat. Mater. 132, 109634 https://doi.org/10.1016/j.
plinary Institute of Indian System of Medicine (IIISM), Directorate of diamond.2022.109634.
Research, SRM Institute of Science and Technology (SRMIST), Azizpourian, M., Kouchakzadeh, G., Derikvand, Z., 2023. Removal of pharmaceutical
compounds from aqueous solution by clay-based synthesized adsorbents: adsorption
Kattankulathur-603203, Tamil Nadu, India. kinetics and isotherms studies. Chem. Pap. 77, 4245–4264. https://doi.org/
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