Interaction Adsorption

Journal of Molecular Liquids 384 (2023) 122174
Contents lists available at ScienceDirect
Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq
Review
Magnetic adsorbents for removal of pharmaceuticals: A review of

adsorption properties
Tetiana Tatarchuk a, b, *, Liubov Soltys c, Wojciech Macyk a
a
Faculty of Chemistry, Jagiellonian University, ul. Gronostajowa 2, 30-387 Kraków, Poland
b
Educational and Scientific Center of Materials Science and Nanotechnology, Vasyl Stefanyk Precarpathian National University, 76018 Ivano-Frankivsk, Ukraine
c
Department of Chemistry, Vasyl Stefanyk Precarpathian National University, 57 Shevchenko Street, 76018 Ivano-Frankivsk, Ukraine
A R T I C L E I N F O A B S T R A C T
Keywords: The global development of industry and agriculture around the world led to the contamination of various aquatic
Adsorbent environments with pharmaceuticals. Even at low concentrations in water, these pollutants cause significant
Magnetic nanoparticles human health problems, adversely affect the quality of drinking water, and have a detrimental effect on the
Pharmaceuticals
environment. The uncontrolled release of pharmaceuticals into aquatic ecosystems poses a real threat to all life
Adsorption capacity
on Earth and requires effective methods of removal. Adsorption is one of the best and most cost-effective ways to
Environmental pollution
clean wastewater from micropollutants. Magnetic adsorbents attract considerable attention due to their
outstanding magnetic properties, high surface reactivity, chemical stability, and the possibility of their modifi
cation and functionalization. The presence of various functional groups makes it possible to increase the
adsorption efficiency. This article is a comprehensive review of studies on the use of various magnetic nano
particles and composites for the removal of pharmaceuticals from aqueous environments through adsorption.
The main attention is paid to two categories of pharmaceuticals: antibiotics (tetracycline, ciprofloxacin, levo
floxacin, etc.) and nonsteroidal anti-inflammatory drugs (diclofenac, ibuprofen, etc.). The concentration of these
pollutants in the European surface waters is provided. The main modes of interaction between the adsorbent
(functionalized magnetic nanoparticles) and the adsorbate (pharmaceuticals) are discussed. The analyzed drugs
are mainly adsorbed through electrostatic interactions, hydrogen bonds, π-π interaction, surface complexation,
ion-exchange, etc. The effect of various parameters (pH, contact time, temperature, adsorbate concentration,
adsorbent dose) on adsorption efficiency is summarized. The analysis shows that the adsorption behavior
strongly depends on the solution pH, temperature, and the initial concentration of the pollutant. The func
tionalized magnetic nanoparticles have a good potential for pharmaceuticals removal from aqueous media. The
perspectives and problems in magnetic adsorbents applications have been presented.
1. Introduction decomposition by putrefactive bacteria and fungi [2]. During decom

position, organic substances intensively consume dissolved oxygen from
The quality of natural waters is one of the determining factors of water, releasing decomposition products. An excess of organic sub
environmental safety and public health [1]. However, the pharmaceu stances in a reservoir leads first to a violation of the biological balance,
ticals’ entry into water causes the deterioration of aquatic ecosystems. suppression of the biological self-cleaning of the reservoir, and then to a
The pharmaceuticals’ sources are hospital wastewaters, different med change in the type of pond or lake ecosystem [3]. This is why the
ical facilities, and settlements (Fig. 1). These compounds are accumu wastewater must be thoroughly treated by different treatment methods.
lating in bottom sediments, aquatic flora, and fauna, hurting the aquatic The processes that are traditionally used for industrial wastewater
ecosystem and worsening its environmental safety [2]. treatment do not lead to the complete neutralization of toxic compounds
Pharmaceuticals, having entered the reservoir, partially dissolve in contained in the wastewater. Pharmaceuticals, being stable and passing
water and partially sink to the bottom of the reservoir, where organic through several stages of purification, are not completely removed and
biomass of bottom sludge is formed, which is subjected to continuous accumulate in the environment [3]. An excessive concentration of these
* Corresponding author.
E-mail address: [email protected] (T. Tatarchuk).
https://doi.org/10.1016/j.molliq.2023.122174
Received 3 April 2023; Received in revised form 16 May 2023; Accepted 21 May 2023
Available online 25 May 2023
0167-7322/© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
T. Tatarchuk et al. Journal of Molecular Liquids 384 (2023) 122174
compounds in the environment leads to microflora and fauna damage.

Another problem is that the growth of resistant bacteria takes place at
low concentrations of pharmaceuticals in the environment [4]. This is
why many researchers are focused on creating enhanced adsorbents for
the removal of pharmaceuticals. During the last few years, research on
the pharmaceuticals removal from wastewater using adsorption has
gained much attention. Nowadays, the number of publications dedi
cated to the adsorption of pharmaceuticals/antibiotics is>5,800 docu
ments in the Scopus database. Fig. 2 shows the number of articles for the
2012–2023 years.
A variety of nanomaterials is used as adsorbents for the extraction of
pharmaceuticals from aquatic environments. A special place among the
adsorbents for wastewater treatment is occupied by “green” adsorbents
due to their low production cost, stability, better physicochemical
properties, and high efficiency in the removal of pharmaceuticals [4].
The “green” biochar and activated charcoal were studied in pharma
ceuticals adsorption by X. Zhu et al. [5]. A “green” synthesis was used by
Magesh et al. [6] in the preparation of zinc oxide biosorbent impreg
Fig. 2. The number of articles on “antibiotics adsorption”, indexed in the
nated with activated carbon for the removal of ciprofloxacin from
Scopus database (as of 03–04-2023).
aqueous solutions. The results showed the achievement of maximum
removal of 99.8% [6]. In the study [7] a biosorbent made from acid-
treated tamarind shells was used to remove ciprofloxacin from water octahedra), inverted (M3+ cations are equally placed on both sites, while
and the removal efficiency was achieved at around 92%. Another M2+ occupies only octahedral sites) and mixed spinels (both types of
“green” ceramic/organic xerogel adsorbent was synthesized by P. Ara cations arbitrarily occupy tetrahedral and octahedral sites, and the
bkhani et al. [8] for the removal of antibiotics from water. Under opti cation distribution can be described as (A1-xBx)[Ax/2B1-x/2]2O4, where x
mized adsorption conditions, the removal efficiency was ca. 99, 99, 98, is the inversion degree. The normal spinel structure is inherent in
and 98% for amoxicillin, tetracycline, cephalexin, and penicillin G, MgAl2O4, ZnFe2O4, FeAl2O4, (Mn, Fe)Al2O4, etc. The inverted spinel
respectively [8]. structure is characteristic of Fe3O4, MgFe2O4, CoFe2O4, γ-Fe2O3, etc.
Among various adsorbents, magnetic oxide nanoparticles play a Important in practical terms are magnetic ferrites with the general for
significant role in environmental restoration [9-11]. In most cases, they mula of MFe2O4, which are usually completely or partially inverted. The
offer a large specific surface area. Iron oxide nanoparticles (maghemite reason is that the Fe3+ ion with five d-electrons, according to the crystal
γ-Fe2O3 or magnetite Fe3O4) and spinel ferrites are the most frequently field theory, has no preference for octahedral positions. Therefore,
studied magnetic nanoparticles [12-14]. Spinels are complex oxides larger divalent ions occupy mainly octahedral positions, while Fe3+ ions
with the general formula AB2O4, where A is Mg2+, Fe2+, Ni2+, Zn2+, are distributed in octahedral and tetrahedral positions leading to the
Mn2+, Be2+, Co2+, and B is Fe3+, Al3+, Cr3+, Mn3+, rarely Ti4+, V3+ [15]. inversion of the structure. It is worth noting that magnetite Fe3O4 is one
The spinel group also includes maghemite (γ-Fe2O3). Spinels are com of the best studied spinel magnetic adsorbents.
pounds with well-developed isomorphisms with a broad variety of A and The methods of synthesis significantly affect the adsorption capacity
B cations [16-18]. According to the cation distribution between the of magnetic adsorbents [19]. S.K. Paswan et al. [20] used the “bottom-
crystallographic positions, the spinel structures are classified as normal up” and “top-down” classification for the synthesis of spinel adsorbents.
(M2+ cations are located in tetrahedral sites, and M3+ cations are in In the “bottom-up” approach, materials are synthesized from smaller
Fig. 1. Ways of environmental pollution by pharmaceuticals.
2
units or molecules, which allows precise control over the size, shape, with silica and loaded with PdNPs demonstrated much higher H2 con
composition, and surface properties of the magnetic adsorbent [20]. sumption compared to palladium NPs alone [24]. In most cases, such
“Top-down” approach involves the synthesis of materials through the magnetic adsorbents can be easily recovered. All magnetic sorbents
decomposition of large structures into smaller particles or components demonstrate increased mechanical strength, high adsorption capacity
[21]. “Bottom-up” methods include the co-precipitation method, sol–gel concerning organic and inorganic pollutants, and high magnetic char
method, hydrothermal, solvothermal, microemulsion, etc. [20-22]. The acteristics, which make it possible to subsequently collect the sorbent
top-down methods include mechanical milling and pulsed laser ablation using permanent or electric magnets.
[21]. In general, the choice of synthesis method will depend on the In this review, we decided to focus in detail on the adsorbents based
desired properties of the magnetic adsorbent, available equipment, cost, on magnetic nanoparticles, which can be used to remove various phar
and scalability of the synthesis method. maceuticals from aquatic environments. In particular, attention is paid
The magnetic properties of ferrospinels are determined by the to two groups of pharmaceuticals – antibiotics and non-steroidal anti-
chemical composition and the distribution of cations within A- and B- inflammatory drugs that are most common and most dangerous for the
sublattices. The different numbers of cations in A- and B-sublattices environment. The physicochemical properties of adsorbents, including
cause different net magnetic moments. Ferrites can be ferrimagnetic or adsorption modes, are described in detail.
antiferromagnetic. This is explained by the fact that the ions that are in
the tetrahedral sites have antiparallel spins to the spins of the ions that 2. Distribution of pharmaceuticals in waters
occupy the octahedral sites. Thus the net magnetic moment is due to the
antiferromagnetic order between the tetrahedral (A) and octahedral (B) Nowadays, >3000 active pharmaceuticals are known, which are
magnetic moments [17]. used for the treatment of various diseases [29]. The most common
Magnetic ferrite nanoparticles are widely used and demonstrate high classes of drugs involve antidepressants, antibiotics, anticonvulsants,
activity in the removal of various types of environmental pollutants: hormones, beta-blockers, and anti-inflammatories. Pharmaceuticals as
metals and non-metals (Hg, Pb, Cr, Cu, U, Ni, As, etc.), dyes (Congo red, pollutants can be detected in soil, ground and surface waters, waste
methylene blue, methyl violet, etc.), pharmaceuticals (tetracycline, water, tap water, and drinking water. They are considered micro
ibuprofen, diclofenac, etc.) and other pollutants. Since the purification pollutants because they are present in the environment at very low
processes are carried out in an aqueous medium, an additional advan concentrations [3]. They are difficult to detect, analyze and remove by
tage of magnetic ferrite nanoparticles, in particular magnetite Fe3O4, are existing wastewater treatment systems [30]. The presence of pharma
magnetic properties that allow its extraction from solution and separa ceuticals in the aquatic environment is a growing concern worldwide.
tion with a magnet after the adsorption. Magnetic nanoparticles can be Drinking water supplied to humans contains a large number of various
used as adsorbents alone, or as a magnetic core for complex composites drugs, including antibiotics, hormones, sedatives, anticonvulsants, and
or a matrix that can be further functionalized (Fig. 3). For example, pain relievers [3]. There are various ways of getting such drugs into the
functionalized magnetic nanoparticles have a big potential also in the water. In particular, when people take medicaments, the body absorbs a
adsorption of gases (hydrogen, H2S, etc.) [23,24]. Fe3O4 NPs coated part of them. Non-absorbed pharmaceuticals (about 70%) are excreted
Fig. 3. (a) Polyethylene glycol-modified Fe3O4 combined with Mg–Al-layered double hydroxides for the removal of methyl orange from water. Reprinted with
permission from [25]. Copyright 2020, American Chemical Society; (b) magnetic graphene oxide/chitin nanocomposites for adsorption of methylene blue and crystal
violet from aqueous solutions separated by the external permanent magnet after the adsorption and its reproducibility. Reprinted with permission from [26].
Copyright 2020, American Chemical Society; (c) UV–vis spectra of Congo red and methylene blue after four removal cycles from tap water using novel core@double-
shell three-layer adsorbent (Fe3O4@SiO2@Zn–TDPAT) [TDPAT = 2,4,6-tris(3,5-dicarboxyl phenylamino)-1,3,5-triazine]. Reprinted with permission from [27].
Copyright 2019, American Chemical Society; (d) activated carbon (AC) modified with metal ferrite CoFe2O4 nanoparticles (AC–CoFe2O4) as a magnetic nano
adsorbent for promazine removal from wastewater. Reprinted with permission from [28]. Copyright 2022, Royal Society of Chemistry. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)
3
naturally, without changing their chemical composition, and are intro interaction decrease very quickly with the increasing distance be
duced to the sewer [2,29]. Wastewater undergoes traditional treatment tween the adsorbent and adsorbate molecules. At the magnetic
and returns to rivers or lakes, the reservoirs of drinking water (Fig. 1). nanocomposite surface, the adsorbate molecule is held by the force
Table 1 shows the distribution of pharmaceuticals in various aquatic field of the surface for some time and then it can be desorbed [45].
environments [31]. Fig. 4 shows the distribution of some representative There is a model of localized adsorption, according to which there
examples of pharmaceuticals in European surface waters (data obtained are adsorption centers at the adsorbent surface, that is, certain areas
from Refs. [32,33]). The municipal sewage treatment system is unable to where stronger adsorption occurs;
completely remove the pharmaceuticals from the water. In addition, it • hydrogen bonds arise due to the electrostatic attraction between the
has been found that adding chlorine and its compounds to water may hydrogen from one molecule and an atom with a high electronega
increase the toxicity of some drugs [2]. tivity from another molecule [45]. Magnetic adsorbents contain a
A wide range of chemical and physical methods can be used to large number of oxygen-containing functional groups at their sur
remove pharmaceuticals, for example, chemical oxidation and biodeg face, such as –OH, –COOH, etc. [46]. These fragments can bind ox
radation (destructive methods), adsorption, liquid extraction, and ygen- or nitrogen-containing groups of pharmaceuticals with the
membrane methods [3]. Adsorption processes are widely used in in formation of hydrogen bonds. The surface hydroxyl groups can be
dustry to remove organic impurities [34], like drugs [28,35-38], per involved in binding various anionic species [47]. For example, the
sonal care products [39], petroleum products [40,41], surfactants [42], C=O and –NH functional groups in the magnetic adsorbent enhance
etc. The term ‘adsorption’ is usually used to describe the attachment of a chemisorption due to the formation of hydrogen bonds with the
molecule from a mobile phase to a solid surface. Adsorption is consid –COOH group in ciprofloxacin [48].
ered one of the most effective methods of drug removal from aquatic • the π-π interaction occurs between aromatic groups of adsorbent and
environments due to its convenience, easiness, and simplicity of adsorbate. The strength of the π-π bond is mostly influenced by the
implementation [30]. The adsorption can be affected by changing such functional groups attached to the benzene ring of the adsorbent [45].
parameters as temperature, concentration, and solution pH [43]. A good Functional groups of pharmaceuticals that have a strong electron-
adsorbent should have a high adsorption capacity for the necessary withdrawing capacity can act as π-acceptors, while, for example,
components. The efficiency of the adsorbent also depends on its pore OH-groups on benzene rings cause the adsorbent to act as a π-donor
size and surface properties [30]. [49];
• surface complexation occurs when the molecules of pharmaceuticals
3. Modes of antibiotics adsorption form complexes with surface functional groups of magnetic adsor
bents [50]. Surface functional groups of adsorbents can contain hy
Understanding, which physicochemical processes taking place at the droxyl, carboxyl, amino, or thiol groups [51]. The formation of
adsorbent surface (magnetic nanoparticles) are crucial for the adsorp complexes may involve the formation of inner-sphere or outer-
tion of adsorbates (pharmaceuticals) is essential to design efficient ad sphere complexes between the pharmaceutical molecule and iron
sorbents. The modes of pharmaceuticals’ adsorption onto magnetic ions coming from the magnetic adsorbent structure [46,52,53].
adsorbents can be governed by electrostatic or non-electrostatic in Inner-sphere complexes are arising when a direct chemical bond
teractions depending on the solution pH and the charge (or at least between the adsorbate (molecule of pharmaceutics) and the adsor
polarity) of the adsorbent and adsorbate. Electrostatic interactions come bent surface is formed. Outer-sphere complexes are formed when the
into play when the adsorbate is protonated or dissociated in an aqueous water molecules or hydroxyl groups are affiliating between the
solution under experimental conditions. Other interactions include van oppositely charged adsorbate (molecule of pharmaceutics) and the
der Waals forces, hydrogen bonds, π-π interactions, etc. [4]. surface of the magnetic adsorbent. The formation of surface com
The main modes of antibiotic adsorption are the following: plexes is influenced by the solution pH, the solution ionic strength,
the concentration of pharmaceuticals in the solution, and the phys
• the electrostatic interaction between the adsorbent surface and the icochemical properties of the adsorbent.
adsorbate can be predicted by the charge of their oppositely charged • hydrophobic interactions occur when non-polar molecules or hy
functional groups [34]. The ionic charge varies depending on the drophobic groups of pharmaceuticals interact with hydrophobic sites
dissociation constants (pKa, pKb), point of zero charge (pHPZC), and on the surface of the magnetic adsorbent. Such hydrophobic inter
solution pH. If the adsorbent surface and adsorbate molecules action is due to the desire of non-polar molecules or groups to
possess the same charge, then adsorption will decrease due to elec minimize their contact with water. Such an adsorption mode is
trostatic repulsion between them [44]. If the charges are opposite, influenced by the concentration of the adsorbate in the solution, the
the electrostatic attraction occurs, and adsorption increases. There density of hydrophobic groups, and the surface area of the adsorbent
fore, the surface charge of the adsorbent and adsorbate is the main [54]. Hydrophobic interactions are observed mostly during the
factor affecting the adsorption efficiency [45]; adsorption of pharmaceuticals, containing both hydrophilic and
• Van der Waals forces are arising between adsorbate molecules and hydrophobic groups in their structure, e.g., ofloxacin, ciprofloxacin,
the adsorbent surface. These relatively small forces of intermolecular norfloxacin, propranolol, clomipramine [55], or when the carbon-
based [55,56] or polysaccharide-based [44] magnetic composites
are used as adsorbents.
Table 1 • ion exchange is observed when the ions that are already attracted to
Distribution of pharmaceuticals in different waters. Reprinted with permission
functional groups of the adsorbent surface can exchange with other
from [31]. Copyright 2018, Elsevier.
ions present in the solution [45]. Magnetic adsorbents can be func
Pharmaceuticals Waters Concentration ranges (μg tionalized with ion-exchange sulfate, carboxylate, or amino groups
mL− 1)
that can attract and exchange ions from wastewater [57]. The
Antibiotics Waste & surface 0.1–1.7 selectivity of ion exchange depends on the specific functional group
water and ionic charge of the magnetic adsorbent, as well as on the con
Wastewater 0.4–1.84
Drinking water 1.7
centration and charge of the ions in the solution [34]. The efficiency
Antiphlogistics/anti- Wastewater 0.05–7.11 of the ion exchange process can be improved by optimizing the pH of
inflammatory the solution, temperature, and contact time of the adsorption. This
Surface water 0.05–7.50 mechanism is especially relevant for ionized antibiotics, which can
Drinking water 1.0–10.0
4
Fig. 4. The distribution of some representative examples of pharmaceuticals in European surface waters (the data obtained from Refs. [32,33]).
be protonated or deprotonated depending on the pH of the solution Fig. 5 shows various types of interactions between magnetic adsor
[34,58]. bents and pharmaceuticals.
• the π-cation interaction involves an adsorption mechanism that can The degree of pharmaceuticals’ adsorption mainly depends on the
occur between aromatic groups of antibiotics (π-electron system of surface charge of magnetic adsorbents, which, in turn, is affected by the
aromatic rings) and positively charged species such as metal ions or pH of the solution. The adsorption can be controlled by measuring the
quaternary ammonium ions, presented on the surface of magnetic point of zero charge (pHPZC) of adsorbents. At pH > pHPZC, the func
adsorbents. The strength of the π-cation interaction depends on the tional groups are deprotonated and the surface of the adsorbent is
pharmaceutical structure, and cationic forms, as well as on the pH negatively charged, so the adsorbent successfully removes cationic ad
and ionic strength of the solution [59]. As an example, the interac sorbates by electrostatic attraction from the aqueous solution. At pH <
tion between the Fe atom of the spinel lattice and the aromatic pHPZC, the protonation of functional groups causes the positive charge of
π-electrons of an antibiotic molecule, for example, tetracycline, can the adsorbent surface, so the adsorbent successfully removes the anionic
be given [60]. adsorbates. Thus, it is possible to change the adsorption capacity of
Fig. 5. Various types of adsorbent-adsorbate interactions at surfaces of magnetic adsorbents.
5
magnetic nanoparticles by changing the solution pH value [61]. For ciprofloxacin removal increases, and at a pH above this point, the
example, as investigated in the work [62], the adsorption capacity of removal process is reduced. Levofloxacin exists in the cationic form at
magnetic graphene oxide adsorbent increases with the pH value pH < 5 and in the anionic form at pH > 8.5. It can be adsorbed by a
increasing and the maximum adsorption was observed at pH 10. The negatively charged adsorbent through the deprotonation of carboxyl
increase in pH led to the deprotonation of –OH and –COOH groups of groups or by a positively charged adsorbent through the protonation of
graphene sheets, making the surface charge more negative [62]. an amino group. The efficiency of levofloxacin removal at low pH is
If pH > pKa, the charge of the pharmaceutical is negative, and if pH lower than at high pH [65].
< pKa the charge of the pharmaceutical is positive. For example, the Usually, the adsorption is improved with increasing temperature,
tetracyclines exist in three forms depending on the solution pH: in the which is associated with an increase in the diffusion rate of dissoluble
cationic form at pH < 3.3, in the zwitterionic form at pH 3.3–7.7, and in molecules. The adsorption process is often endothermic, but it can also
the anionic form at pH > 7.7 [63]. During the adsorption of ciproflox be exothermic for a certain adsorbent, which is associated with weak
acin, the carbonyl group is deprotonated at 5.9 (pKa1), while the amine interactions between the adsorbate and the surface-active groups of the
group is protonated at 8.9 (pKa2) [54]. The removal of ciprofloxacin adsorbent [44]. However, changes in the temperature during the
from aqueous solutions depending on the pH was carried out using adsorption process not only affect the rate of the pharmaceuticals
granular iron hydroxide by M. Asadi-Ghalhari et al. [64]. The pHPZC of diffusion through the outer surface of the adsorbent but also signifi
the granular iron hydroxide is 7.5–8.2, therefore, at a pH below this cantly affect the binding at surface active sites and the equilibrium
range, the surface charge of the adsorbent is positive and the rate of adsorption capacity [66].
Fig. 6. Structures of the most common antibiotics.
6
4. Applications of magnetic nanoparticles for the adsorption of streptomycin [73], cephalexin [111], metronidazole [112], sparfloxacin
antibiotics [86], cefotaxime [71], ceftriaxone [113], chloramphenicol [73], diclo
fenac [114-120], ibuprofen [69,117,120-125], acetylsalicylic acid
The key features of magnetic nanoparticles to be applied in the [124,126], acetaminophen [123,126-129], ketoprofen [106,120,121],
adsorption of pharmaceuticals are the following: high surface concen naproxen [117,120,122], atenolol [93], tamoxifen [130], gemfibrozil
tration of adsorption sites, high specific surface area, high chemical [93,117], etc. For example, P. Yadav et al. [131] synthesized Fe3O4-
stability, adjustable particle size, magnetization, etc. To date, many functionalized MIL101(Fe) chitosan composite beads for the removal of
studies have been conducted to demonstrate the effective use of mag tetracycline, doxycycline, and ciprofloxacin from the aqueous medium
netic oxide nanoparticles as adsorbents for the simple and rapid removal (removal efficiency was over 99%). A. Parashar et al. [132] used mag
of different pharmaceuticals from wastewater: tetracycline [60,62,67- netic iron oxide nanoparticles for effective removal (94.12–99.52%) of
82], minocycline [83,84], ciprofloxacin [44,56,64,85-98], levofloxacin oxcarbazepine from wastewater.
[65,99-104], enrofloxacin [94,105], norfloxacin [94,106,107], amoxi Among more than ten classes of antibiotics, the tetracyclines, fluo
cillin [87,108,109], daptomycin [110], erythromycin [73,87], roquinolones, aminoglycosides, β-lactams, and macrolides pose a
Fig. 7. (a) Chemical structure and (b) ionic species distribution of tetracycline. Reprinted with permission from [135]. Copyright 2018, Springer Nature; effect of pH
on the extraction efficiency of three tetracyclines (OTC – oxytetracycline, TC – tetracycline, CTC – chlortetracycline) by: (c) MGO (MGO dosage = 2 mg, [TCs]0 = 10
mg/L, V = 30 mL, T = 298 K and equilibrium time = 10 h). Reprinted with permission from [75]. Copyright 2019, Elsevier, (d) Fe3O4@SiO2@FeO (V = 10 mL,
[TCs]0 = 0.1 mg L− 1). Reprinted with permission from [77]. Copyright 2017, Elsevier, and (e) mNi@N-GrT (V = 10 mL, [TCs]0 = 5 mg L− 1). Reprinted with
permission from [78]. Copyright 2018, Elsevier; (f) modes of tetracycline adsorption using Fe3O4/clinoptilolite nanocomposite. Reprinted with permission from [80].
Copyright 2022, Elsevier.
7
significant risk to public health and the environment (Fig. 6). Antibiotics according to the Langmuir model, for oxytetracycline, tetracycline, and
of these classes are most widely used both in medicine and in veterinary. chlortetracycline, respectively, while for the corresponding Fe3O4, it was
Therefore, they are the most significant pollutants of surface water. only about 96, 48, and 82 mg/g. The enhanced qmax is because the FeO
Wide use of different antibiotics leads to the faster development of coating can provide additional Fe(II) and numerous adsorption centers
multiresistant pathogenic strains [29]. It is supposed that the increase in [77]. T. Ahamad et al. [79] established that the maximum adsorption
the resistance of pathogenic flora to antibiotics is a serious medical capacity of CDF@MF magnetic nanocomposite, which was fabricated
problem that poses a great danger to human health [29]. using the condensation of the chitosan, formaldehyde, and diphenylurea
in an acidic medium, for tetracyclines is 168 mg/g at room temperature
4.1. Adsorption of tetracyclines and pH = 6. The π-π electron donor–acceptor interactions in aromatic
magnetic adsorbent rings are responsible for enhanced tetracycline
Tetracyclines are one of the most widely used groups of broad- adsorption [79]. Y. Liu et al. [69] synthesized the magnetic genipin-
spectrum bacteriostatic antibiotics. The basis of its chemical structure crosslinked chitosan/GO-SO3H. The maximum adsorption capacity of
is the octahydronaphthacene core [133]. Tetracycline, oxytetracycline, tetracycline increased from 473 to 556 mg/g when the temperature
chlortetracycline, doxycycline, and methacycline are examples of tet increased from 298 to 313 K. B. Yu et al. [62] studied the adsorption
racyclines. Tetracyclines are used in the form of bases or hydrochloride capacity of magnetic graphene oxide towards tetracycline and found it
salts. Tetracyclines are amphoteric compounds with hydroxyl and equal to 473 mg/g. M. Rouhani et al. [80] showed that the maximum
dimethylamine functional groups. They can exist in ionized or non- adsorption capacity of Fe3O4/clinoptilolite nanocomposite was 181 mg/
ionized forms [134] depending on the pH: in the cationic form at pH g, and the efficiency of tetracycline removal was 98.6% at pH = 7–8. The
< 3.3, in zwitterionic form at pH = 3.3–7.7, and in the anionic form at mechanism of adsorption has been explained due to van der Waals forces
pH > 7.7 [63]. The molecular structure of tetracycline (Fig. 7a) has four and the formation of hydrogen bonds between the polar tetracycline
functional groups that can dissociate and it can exhibit five dominant molecules and functional groups at the Fe3O4/clinoptilolite nano
forms in water (Fig. 7b) [135]. These forms exhibit different physico composite surface [80]. Fig. 7f shows the mechanism of tetracycline
chemical and biological properties. adsorption using Fe3O4/clinoptilolite adsorbent [80]. As can be seen the
Many authors study the adsorption capacity of various magnetic hydrogen bonds between H+ from the surface functional groups of the
nanoparticles, which can be used as highly effective adsorbents for the Fe3O4/clinoptilolite nanocomposite and ions, originating from the polar
removal of tetracyclines from wastewater [60,62,67-69,75-82]. In their tetracycline molecule, cause the formation of electrostatic repulsion.
studies, scientists use nanoparticles of magnetic graphene oxide This results in reduced adsorption capacity of magnetic adsorbent under
[62,69,75], goethite [76], Fe3O4 [70,72-74,77,80], NiFe2O4 [71], acidic conditions towards tetracycline molecules [80]. At a neutral pH of
MnFe2O4 [79], etc. J. Miao et al. [75] have shown that the magnetic 7–8, the hydrogen bonds between tetracycline ions and OH groups at the
graphene oxide NPs demonstrate better adsorption of chlortetracycline nanocomposite surface turn into the main driving force for adsorption
in an alkaline medium, while the best adsorption of tetracycline and and leads to the highest removal efficiency [80]. All these results of
oxytetracycline has been observed at pH = 3.3 (Fig. 7c). L. Lian et al. adsorption studies indicate that magnetic oxide nanoparticles and
[77] used the Fe3O4@SiO2@FeO nanocomposite for tetracycline nanocomposites are promising adsorbents for the tetracyclines removal
adsorption and the effect of pH on adsorption capacity was studied from wastewater.
(Fig. 7d). It was shown that the favorable adsorption efficiency was Minocycline is a tetracycline antibiotic used to treat many bacterial
obtained in the pH range of 3 to 9, which may be related to the fact that infections, including pneumonia. L. Lu et al. [84] obtained porous
Fe3O4@SiO2@FeO has a very low ζ-potential at this pH range. The magnetic microspheres of MgFe2O4/γ-Fe2O3 which were investigated as
electrostatic attraction between the negatively charged magnetic sor new effective adsorbents for the minocycline removal from wastewater.
bent surface and tetracycline molecules occurs, so electron-donor groups The maximum adsorption capacity was 201 mg/g. The research results
of tetracycline can easily form stable metal-tetracycline complexes with showed that the adsorption capacity increased with increasing temper
Fe(II) on the sorbent surface [77]. Q. Wang et al. [78] studied tetracy ature, which indicates the endothermic nature of adsorption [84]. In the
cline removal using an ultrathin magnetic nitrogen-doped graphene antibiotic-adsorbent system, the complexes are formed between the
tube with nickel nanoparticles (mNi@N-GrT). It was concluded that the functional groups of the antibiotic and the active centers of the adsor
adsorption efficiency increased with pH increasing from 2 to 4 and did bent, which indicates chemisorption. MgFe2O4/γ-Fe2O3 adsorbents can
not change at pH above 4 (Fig. 7e). Humic acids can enhance the be regenerated with methanol or NaOH solution and easily separated
interaction between tetracycline and goethite at pH < 7 [76]. The from aqueous solution due to their magnetic properties [84].
presence of multivalent heavy metals such as Cu2+ can increase the Table 2 provides an overview of the adsorption parameters for
adsorption of tetracycline on goethite through the formation of inner- various magnetic adsorbents in tetracyclines removal from wastewater.
sphere surface complexes. T. Ahamad et al. [79] synthesized the mag
netic adsorbent using chitosan, diphenylurea, formaldehyde, and mag 4.2. Adsorption of ciprofloxacin
netic nanoparticles MnFe2O4 through the condensation polymerization
route. The tetracyclines adsorption has been tested at pH from 2 to 10. It Ciprofloxacin is an antibiotic of the fluoroquinolone class [136].
was established that the maximum removal efficiency was obtained at Ciprofloxacin exists in three forms in the solution: in the cationic form
pH = 6, which is explained by the electrostatic attraction between the (with a protonated amino group at pH below 5.90 ± 0.15 [137]), in the
adsorbent and tetracycline molecules. The presence of acidic centers anionic form (with a deprotonated carboxylic acid group at pH above
promotes the adsorption of tetracycline, as they can accept or donate 8.89 ± 0.11 [137]) and the zwitterionic form (Fig. 8a) [138]. According
protons depending on the solution pH [79]. A new magnetic adsorbent to [33], the average concentration of ciprofloxacin in the surface waters
genipin-crosslinked chitosan/GO-SO3H (GC/MGO-SO3H) was success of Western Europe is 0.008 μg/L, and the maximum measured concen
fully synthesized by Y. Liu et al. [69]. The maximum adsorption capacity tration is 13.6 μg/L. Many studies have been conducted to find effective
towards tetracycline was obtained at pH = 10, as well as in the study magnetic adsorbents for ciprofloxacin removal from aquatic environ
[62], where magnetic graphene oxide was used as an adsorbent. ments. The analysis of references showed that magnetic nanocomposites
J. Miao et al. [75] synthesized the magnetic graphene oxide NPs and based on Fe3O4 [44,56,85-93,95-97], magnetic biochar [94], granular
investigated that their maximum adsorption capacities towards chlor ferric hydroxide [64], magnetic chitosan grafted graphene oxide nano
tetracycline, oxytetracycline, and tetracycline hydrochloride were 304, composite [98], etc. are most often used.
290, and 141 mg/g, respectively. L. Lian et al. [77] showed that the qmax Fe3O4 nanoparticles are used as adsorbents for the removal of cip
of Fe3O4@SiO2@FeO was calculated to be 178, 129, and 133 mg/g rofloxacin from wastewater [44,85-93,96,97]. S. Rakshit et al. [92]
8
T. Tatarchuk et al.
Table 2
The adsorption parameters of different magnetic adsorbents in tetracyclines removal (PFO – pseudo-first-order kinetic model, PSO – pseudo-second-order kinetic model).
Adsorbent Adsorbate Adsorption Adsorption Optimum parameters Removal References
model capacity (mg/g) pH Contact Temperature Adsorbate Adsorbent efficiency (%)
time (min) (K) concentration (mg/ dose
L)
Magnetic graphene oxide sponge (Fe3O4 + GO) tetracycline PSO, Temkin 473 10 18 h 328 400 5 mg 85 [62]
Magnetic graphene oxide tetracycline PSO, 107 4–5 480 313 50 2 mg N/A [75]
Freundlich
Magnetic graphene oxide chlortetracycline PSO, 162 4–5 480 313 50 2 mg N/A [75]
Freundlich
Magnetic graphene oxide oxytetracycline PSO, 146 4–5 600 313 50 2 mg N/A [75]
Freundlich
γ-cyclodextrin-graphene oxide tetracycline PSO 365 8 30 298 400 1 g/L 91 [67]
γ-cyclodextrin-graphene oxide chlortetracycline PSO 375 8 30 298 400 1 g/L 94 [67]
Zeolite/Fe3O4 oxytetracycline PSO, 83 6 240 298 100 0.1 g 90.6 [68]
Langmuir
Magnetic genipin-crosslinked chitosan/graphene oxide- tetracycline PSO, 556 10 120 313 200 5 mg 85 [69]
SO3H composite Langmuir
Magnetic biochar/Fe3O4 tetracycline PSO, 112 6 60 298 30 20 mg 98.4 [70]
Langmuir
9
NiFe2O4–Covalent organic frameworks -chitosan-tere- tetracycline PSO, 389 8 40 h 293 100 170 mg/L 95 [71]
phthalaldehyde nanocomposites film Freundlich
NH2-Fe3O4/ CuSiW12NP tetracycline PSO, Temkin 192 6.80 24 h 293 250 10 mg 88.6 [72]
Bovine serum albumin/Fe3O4 tetracycline Langmuir 104 N/A 40 N/A 200 0.2 g 92 [73]
Fe3O4@ Polydopamine-SO3H tetracycline PSO, 139 4 1080 298 200 10 mg N/A [74]
Langmuir
Goethite (α-FeOOH) tetracycline PSO N/A 3–10 24 h 298 50 0.02 g N/A [76]
Fe3O4@SiO2@FeO oxytetracycline Langmuir 178 3–9 40 298 50 7.5 mg 91.7 [77]
Fe3O4@SiO2@FeO tetracycline Langmuir 129 3–9 40 298 50 7.5 mg 97.3 [77]
Fe3O4@SiO2@FeO chlortetracycline Langmuir 133 3–9 40 298 50 7.5 mg 93.5 [77]
MnFe2O4 tetracycline PFO, 168 6 60 298 100 0.01 mg 158 [79]
(chitosandiphenylureaformaldehyde resin@MF) Langmuir
Fe3O4/Clinoptilolite tetracycline PFO, 181 7.5 40 323 50 1.5 g/L 98.6 [80]
Freundlich
Iron oxide tetracycline PSO, 0.78 10 360 318 25 30 g/L 97 [81]
Journal of Molecular Liquids 384 (2023) 122174

Freundlich
Mn–Zn ferrite/biochar (MZF-BC) tetracycline PSO, 142 3 240 N/A 50 10 mg 62 [82]
Freundlich
Magnetic-ordered mesoporous carbon materials minocycline PFO, Sips 193 8 10 293 1 1 mg N/A [83]
MgFe2O4/γ-Fe2O3 minocycline PSO, 119 N/A 48 h 298 100 25 mg N/A [84]
Langmuir
Fig. 8. (a) Distribution of ciprofloxacin forms as a function of pH. Reprinted with permission from [138]. Copyright 2015, Elsevier; (b) schematic illustration of the
ciprofloxacin adsorption mechanism at different pH using chitosan nanocomposite (Fe-CS NC) supported by Fe3O4. Reprinted with permission from [44]. Copyright
2019, Elsevier.
evaluated the adsorption of ciprofloxacin on magnetic Fe3O4(s) nano ciprofloxacin and the adsorbent at neutral pH can be another dominant
particles, which were obtained as a secondary corrosion product of iron mechanism of the adsorption process [44]. H. Mao et al. [89] investi
nanoparticles. It was concluded that the adsorption of ciprofloxacin gated the adsorption capacity of magnetic Fe3O4-RM-NPs for the effec
increased from 45% at pH = 3.44 to 80% at pH = 5.97. The results of in tive removal of ciprofloxacin from aqueous media. The highest removal
situ ATR-FTIR showed that coordination of ciprofloxacin on the rate of ciprofloxacin was achieved at pH = 6. This is explained by the
magnetite surface with the involvement of functional carboxyl groups fact that when the solution pH is below 5.9, the ciprofloxacin exists in
occurs [92]. H. Rasoulzadeh et al. [44] used chitosan nanocomposite the cationic form due to the protonation of the secondary amine on the
(Fe-CS) supported by Fe3O4 for the removal of ciprofloxacin from piperazine group. When the solution pH is in the range of 6.1 to 8.7, the
aqueous solutions. The maximum removal efficiency and maximum ciprofloxacin exists in a zwitterionic form. At a pH higher than 8.89,
adsorption capacity were 68% and 142 mg/g, respectively [44]. Fig. 8b ciprofloxacin is available in the anionic form [89]. The results of the
shows the mechanism of ciprofloxacin adsorption using Fe-CS at above studies show that Fe3O4 nanoparticles have great potential for the
different pH. As shown in Fig. 8b, the charge of functional groups de effective removal of ciprofloxacin from wastewater.
pends on the solution pH. At pH < 5.9 and pH > 8.9, the same signs of Table 3 provides an overview of the adsorption parameters of various
surface charge of Fe-CS and CIP molecules caused electrostatic repulsion magnetic adsorbents for the removal of ciprofloxacin from wastewater.
and reduced adsorption efficiency. However, at pH within the range of
5.9–8.9, the electrostatic attraction was responsible for the adsorption
process. 4.3. Adsorption of other antibiotics
Hydrophobic interactions between zwitterionic species of
Levofloxacin is a broad-spectrum antibiotic from the group of
10
fluoroquinolones. Levofloxacin is active against gram-positive and

References
gram-negative pathogens, including strains resistant to penicillins,
cephalosporins, and/or aminoglycosides. The levofloxacin molecule
[44]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[91]
[93]
[94]
[64]
[96]
[97]
[97]
[98]
exhibits two dissociation constant values (pKa1 = 6.02 and pKa2 = 8.15)
and can be present in the cationic form (at pH < 6.02), in the zwitter
Removal efficiency
ionic form (at 6.02 < pH < 8.15) or in the anionic form (pH > 8.5)
(Fig. 9a) [65].
Various magnetic adsorbents are used for levofloxacin removal from
water: Fe3O4@SiO2 [99], Fe3O4–gINPs [104], NiFe2O4/biochar com
95.6
N/A
N/A
N/A
N/A
posites [101], biochar/MgFe2O4 [103], Ag3PO4/rGO/CoFe2O4 [102],
(%)
68
57
82
61
98
95
87
42
90
86
72
magnetic carbon nanocomposite [100], etc. M.H. Al-Jabari et al. [99]
studied the adsorption of levofloxacin at the surface of Fe3O4 and
Fe3O4@SiO2 nanoparticles. The maximum adsorption capacity of levo
Adsorbent
135 mg/L
1.39 g/L
1.4 g/L
2.5 g/L
1.5 g/L
floxacin at the magnetic adsorbent ranged from 6.09 to 6.85 mg/g. The
10 mg
0.02 g
0.02 g
2 g/L
3 g/L
1 mg
1 mg
1 mg
5 mg
5 mg
0.1 g
dose
best removal efficiency was observed at pH 6.5 and achieved 80.2%.

This is associated with the existence of levofloxacin in the neutral/
zwitterion forms. The removal efficiency decreased with a decrease or
The concentration of adsorbate
increase in pH, which is related to the electrostatic repulsion of the same

type of charges [99]. A. Ullah et al. [100] prepared a magnetic carbon
nanocomposite from pineapple biomass and showed that its maximum
adsorption towards levofloxacin was observed at pH = 7 and achieved
20.75 mg/g, which is associated with the cation exchange and a higher
number of adsorption centers. Z. Xu et al. [101] used a manganese
(mg/L)
ferrite-modified biochar to remove levofloxacin. Hydrogen bonds in

6.05
160
40
15
10
10
50
15
15
10
10
10
20
fluence the adsorption process. It was shown that oxygen-containing

8
functional groups of the adsorbent can bind through the –OH and
C=O groups of the levofloxacin molecule forming hydrogen bonds. Also,
Temperature
The adsorption parameters of different magnetic adsorbents in ciprofloxacin removal (PSO – pseudo-second-order kinetic model).
the presence of –OH and –COOH groups on the biochar surface

contributed to the π-π and n-π electron-donor–acceptor interaction,
N/A
N/A
298
298
298
298
303
298
298
298
303
298
298
333
333
298
(K)
increasing the adsorption efficiency [101]. B. Yao et al. [103] also used
biochar in levofloxacin adsorption studies. The maximum adsorption
Optimum parameters
capacity was 115 mg/g. The adsorption modes proposed by the authors
Contact time
are shown in Fig. 9b. As can be seen from Fig. 9b, the surface functional
groups C=C, O–C=O, and M− O were involved in levofloxacin removal.
(min)
72 h
24 h
27.5
N/A
300
120
210
720
480
180
150
150
480
In addition, the adsorption was enhanced by π-π electron-

80
40
60
donor–acceptor interactions and H-bonds. The iron and magnesium

6.5
7.5
pH
N/
atoms act as active adsorption centers, promoting levofloxacin adsorp

12
10
A
8
6
3
7
6
8
7
7
5
tion [103].
Enrofloxacin is a fluoroquinolone antibiotic. The structure of
Adsorption capacity
enrofloxacin contains the dissociating groups –COOH and –NHn, which

indicates that enrofloxacin can exist in different forms depending on the
solution pH (Fig. 9c) [139]. G. Peng et al. [105] studied the modes of
enrofloxacin adsorption using Fe3O4/magnetic montmorillonite nano
(mg/g)
3.76
N/A
143
283
181
102
111
283
composite. The maximum adsorption capacity of 163 mg/g was ach

24
90
12
90
54
39
39
45
ieved. Good adsorption properties were associated with electrostatic

PSO, Langmuir
PSO, Langmuir
PSO, Langmuir
PSO, Langmuir
PSO, Langmuir
PSO, Langmuir
PSO, Langmuir
PSO, Langmuir
interaction.
Models of best
R. Li et al. [140] synthesized a composite of manganese oxide based

Freundlich
Freundlich
Freundlich
Freundlich
Freundlich
Quadratic
Langmuir
on magnetic biochar and untreated biochar for enrofloxacin removal.

PSO,
PSO,
PSO,
PSO,
N/A
The maximum adsorption capacity of the magnetic nanocomposite was

fit
7.19 mg/g. The adsorption capacity decreased with solution pH

K2xMnxSn3-xS6 (x = 0.5 – 0.95) (KMS-1)/L-Cysteine/Fe3O4
Magnetic chitosan grafted graphene oxide nanocomposite
increasing (between 3.0 and 10.0) and with increasing ionic strength
Fe3O4/graphene oxide/citrus peel-derived magnetic bio-
(0.001–0.1 M). Z. Gordi et al. [141] synthesized an adsorbent based on a

mixture of magnetically functionalized graphene oxide and MOF for
Magnetic alginate–Fe3O4 hydrogel fiber capable
enrofloxacin removal. The maximum adsorption capacity was 345 mg/

Levulinic acid (LA)-coated magnetic Fe3O4
g. As the solution pH increased to 7.5, the efficiency of enrofloxacin

Humic acid (HA)-coated magnetic Fe3O4
removal increased, and above pH = 7.5, it decreased (pKa values of

Fe3O4-coated polymer clay composite
carboxyl and amine groups are 5.88 and 7.74, respectively). The main
Fe3O4-imprinted chitosan (Fe-CS)
Fe3O4/activated carbon/chitosan
adsorption mode was the electrostatic interaction. M. Zahoor et al. [142]

Fe3O4–MoO3-Activated Carbon
Humic acid/magnetic biochar
used magnetic carbon nanocomposites to remove enrofloxacin from

Granular ferric hydroxide
Fe3O4-RM(red mud)-NPs
industrial wastewater. The maximum adsorption efficiency was

observed at pH 6–8. The pH value affects the surface charge of the
nanocomposite
magnetic adsorbent and the dissociated form of enrofloxacin in the so

Fe3O4–MoO3
lution: the surfaces of the adsorbent and adsorbate have the same charge
(mGOCP)
Adsorbent
signs under acidic or alkaline conditions and electrostatic repulsion

Fe3O4/C
Table 3
Fe3O4
forces hinder the adsorption capacity.

Norfloxacin is a synthetic antibiotic belonging to the class of
11
Fig. 9. (a) The cationic, anionic, and zwitterionic forms of levofloxacin at different pH. Reprinted with permission from [65]. Copyright 2021, Elsevier; (b) the
possible adsorption modes of levofloxacin at biochar/MgFe2O4 magnetic composite. Reprinted with permission from [103]. Copyright 2021, Elsevier; (c) the formula
of enrofloxacin (the dissociation may occur through the few pathways: path 1 is the cleavage of the C2–C5 bond, path 2 is the N7–C8 bond, path 3 is the F9–C10
bond, path 4 is the C11–N12 bond, and path 5 is the N12–C13 bond). Reprinted with permission from [139]. Copyright 2018, Springer Nature; (d) the molecular
structure of norfloxacin and its ionic forms as a function of pH. Reprinted with permission from [143]. Copyright 2012, Elsevier.
fluoroquinolones. The dissociation constants pKa of norfloxacin are 6.22 –COOH, –OH [144]. It has three different acid dissociation constants:
and 8.51. The cationic, zwitterionic, and anionic forms are shown in pKa1 = 2.68 (carboxyl group), pKa2 = 7.49 (amino group), and pKa3 =
Fig. 9d [143]. According to [33] the average concentration of nor 9.63 (phenolic group) [145]. Therefore, amoxicillin can exist in an
floxacin in surface waters of Western Europe is 0.009 μg/L, and the aqueous solution in four different forms (Amox+, Amox, Amox− , and
maximum measured concentration is 1.15 μg/L. Nowadays, the possi Amox2− ) depending on the solution pH (Fig. 10a) [145]. M. Pooresmaeil
bility of norfloxacin removal from wastewater is extensively studied, et al. [108] synthesized a magnetic nanocomposite Fe3O4@Cd-MOF@CS
because it has a very harmful impact on the environment and human for removing amoxicillin from wastewater. Fig. 10b shows the proposed
health. Much attention has been paid to the synthesis of new magnetic modes of amoxicillin adsorption at the synthesized magnetic adsorbent.
adsorbents [94,106,107], which would effectively remove norfloxacin Fe3O4@Cd-MOF@CS has several types of functional groups that can
from the aqueous environment. G. Peng et al. [106] synthesized a participate in the adsorption of amoxicillin. Chitosan contains numerous
nitrogen-modified reduced graphene oxide incorporated into Fe3O4 hydroxyl and amine functional groups that can bind to the antibiotic
magnetic nanoparticles (N-RGO/Fe3O4) as an adsorbent for norfloxacin through electrostatic attraction and hydrogen bonding. The Fe3O4@Cd-
removal. It was concluded that the maximum adsorption capacity was MOF composite contains a large number of aromatic rings, which pro
158 mg/g. The mode of adsorption can be explained by the fact that vide the possibility of contaminant capture inside the cavities and, thus,
norfloxacin has two proton-binding centers (carboxyl and piperazinyl additionally contribute to adsorption [108].
groups) and they can exist in different forms depending on the solution Daptomycin is an antibacterial drug of the cyclic lipopeptides class
pH. The cationic form is the dominant type at pH < 6, so the adsorption [146]. It has six ionizable residues [147], including three aspartic acids
of norfloxacin is unfavorable in acidic solution due to electrostatic (Asp-3, Asp-7, and Asp-9), one methylglutamic acid (mGlu-12), one
repulsion. When pH increases, the surface of the nanoadsorbent and the aliphatic amine (Orn-6), and one aromatic amine (Kyn-13) (Fig. 10c)
norfloxacin molecule gains opposite charges, so the adsorption increases [148]. It has four acidic groups (pKa of 1.3, 3.8, 4.1, and 4.4) and two
[106]. M.M. Gaho et al. [107] synthesized the magnetic polymers – basic groups (pKa of 1.3 and 10.7), resulting in a total molecular charge
cross-linked Fe3O4 coated with oleic acid using methacrylic acid, of − 3 at neutral pH (the basic residue with a pKa of 1.3 is not dissociated
ethylene glycoldimethacrylate, and 2,2-azobisisobutyronitrile. They at neutral pH) [148]. T. Ai et al. [110] studied the adsorption of dap
showed high efficiency in norfloxacin removal from wastewater. The tomycin at two magnetic ultrafine wood-based materials WSBC/Fe3O4
maximum adsorption capacity at 35 ◦ C was 42 mg/g. The van der Waals (willow sawdust) and PSBC/Fe3O4 (pine sawdust). The maximum
forces and hydrogen bonds are mostly responsible for the adsorption of adsorption capacity of daptomycin on WSBC/Fe3O4 and PSBC/Fe3O4
norfloxacin [107]. was 217 and 213 mg/g, respectively. The study of the adsorption
Amoxicillin is a broad-spectrum β-lactam antibiotic. Amoxicillin has mechanism indicates three stages of the adsorption process. The first
amphoteric properties due to three main functional groups: –NH2, step is the diffusion of daptomycin to the material surface, the second
12
Fig. 10. (a) Different forms of amoxicillin and pKa values. Reprinted with permission from [145]. Copyright 2016, Elsevier; (b) the proposed modes of amoxicillin
binding by the Fe3O4@Cd-MOF@CS composite. Reprinted with permission from [108]. Copyright 2021, Elsevier; (c) the structure of daptomycin (acidic groups are
surrounded by solid line circles, and basic groups are surrounded by dashed line circles: Asp – aspartic acid, mGlu – methylglutamic acid, Orn – ornithine, Kyn –
kynurenine). Reprinted with permission from [148]. Copyright 2020, Springer Nature.
one involves penetration of the molecule into the porous structure of the Europe is 0.020 μg/L, and the maximum measured concentration is
adsorbent, where finally the equilibrium between adsorbed and non- 18.74 μg/L [33]. Therefore, the problem of purifying wastewater and
adsorbed daptomycin is reached [110]. drinking water from this pharmaceutical attracts particular attention.
Table 4 provides an overview of the adsorption parameters for One of the methods of diclofenac removal from the aqueous environ
various magnetic adsorbents in different antibiotics removal from ment is the use of adsorbents based on magnetic oxide nanoparticles
wastewater. [114-116].
Magnetic hybrid adsorbents Fe3O4@SiO2/SiHTCC consisting of
5. Applications of magnetic nanoparticles for the adsorption of magnetite cores encapsulated in a silicon mesh containing quaternary
non-steroidal drugs chitosan were synthesized [114]. The ability of nanoparticles to adsorb
diclofenac was evaluated in the pH range of 5–8 with a contact time of 5
Nonsteroidal anti-inflammatory drugs are a class of drugs that pro h. The highest removal was achieved at pH = 6, which is associated with
vide analgesic and antipyretic (antipyretic) effects and, when used in the anionic form of diclofenac (–COO–). The maximum adsorption ca
higher doses, can cause anti-inflammatory effects. The most famous pacity was 240 mg/g. The mode of diclofenac adsorption is shown in
representatives are diclofenac, ibuprofen, acetaminophen, ketoprofen, Fig. 12a. The electrostatic interactions between the anionic form of the
naproxen, acetylsalicylic acid (Fig. 11). drug and the –N+(CH3)3 groups of Fe3O4@SiO2/SiHTCC particles is the
main driving force of the adsorption process [114].
5.1. Adsorption of diclofenac J.M.N. dos Santos et al. [115] used the ZnFe2O4/chitosan magnetic
adsorbent capable of reducing the initial concentration of diclofenac
Diclofenac is used as a sodium salt. Diclofenac has poor biode from 50 to 12 mg/L within 20 min, at the initial pH of 4 and adsorbent
gradability and low adsorbability. Diclofenac is widely used throughout dose of 0.2 g/L. It was associated with the ability of the amino groups of
the world and it is found in environmental waters. It was found that the chitosan to protonation in an acidic medium. The maximum adsorption
average concentration of diclofenac in the surface waters of Western capacity was 188 mg/g [115]. X.X. Liang et al. [116] synthesized a
13
Table 4
Adsorption parameters of different magnetic adsorbents for other antibiotics (PFO – pseudo-first-order kinetic model, PSO – pseudo-second-order kinetic model).
Adsorbent Adsorbate Models of Adsorption Optimal parameters Removal References
best fit capacity pH Contact Temperature Antibiotic Adsorbent efficiency
(mg/g) time (K) concentration dose (%)
(min) (mg/L)
Fe3O4 levofloxacin PSO, 6.8 6.5 240 298 20 100 mg 80.2 [99]
Langmuir
Magnetic carbon levofloxacin PSO, 21 7 60 298 40 0.04 g N/A [100]
nanocomposite Langmuir
NiFe2O4/biochar levofloxacin PSO, 172 6 60 h 298 40 10 mg N/A [101]
composites Langmuir
Biochar/MgFe2O4 levofloxacin PSO, 115 5 240 298 100 0.3 g/L N/A [103]
Freundlich
Fe3O4–green iron NPs levofloxacin PSO, 22.5 7 24 h 298 4 100 mg/L 86 [104]
Freundlich
Humic acid/magnetic enrofloxacin PSO, 4.03 10 480 298 10 2 g/L 85 [94]
biochar Langmuir
Fe3O4/magnetic enrofloxacin PSO, 163 6.85 60 298 30 0.1 g/L 90 [105]
montmorillonite Langmuir
Humic acid/magnetic norfloxacin PSO, 3.94 10 480 298 10 2 g/L 90 [94]
biochar Langmuir
Nitrogen-doped norfloxacin PSO, 158 10 210 298 20 100 mg/L 61.2 [106]
reduced graphene Langmuir
oxide/Fe3O4
nanocomposite
Magnetic molecularly norfloxacin PFO, 42.3 6 30 308 30 1.5 mg 95 [107]
imprinted polymers Langmuir
Fe3O4/activated amoxicillin PSO, 526 N/A 120 298 60 1 mg 72 [87]
carbon/chitosan Langmuir
Magnetic cadmium- amoxicillin PSO, 103 8 240 298 200 50 mg 75 [108]
based MOFs Langmuir
modified with
chitosan
(Fe3O4@Cd-
MOF@CS)
Magnetically amoxicillin PSO, 14.10 5 90 293 10 5 mg 84 [109]
modified graphene Langmuir,
nanoplatelets Temkin
Willow sawdust daptomycin PSO, 217 4 240 298 25 0.025 g N/A [110]
biochar/Fe3O4 Freundlich 213
Pine sawdust
biochar/Fe3O4
Bovine serum erythromycin Langmuir 145 N/A 60 N/A 200 0.2 g 99 [73]
albumin/Fe3O4
Fe3O4/activated erythromycin PSO, 179 N/A 120 298 60 1 mg 54 [87]
carbon/chitosan Langmuir
Bovine serum streptomycin Langmuir 69 N/A 60 N/A 200 0.2 g 81.5 [73]
albumin/Fe3O4
Amine-coated streptomycin PSO, 49 5 15 298 12 10 mg 70 [123]
magnetic Langmuir
nanocomposite
NiFe2O4@SiO2
Magnetic Fe3O4 NPs cephalexin PSO, 25 7 120 293 40 0.6 g/L 93 [111]
coated zeolite Langmuir
Fe3O4-chitosan (CTS- metronidazole PSO, 97 3 90 318 10 2 g/L 99 [112]
MNPs) Freundlich
Fe3O4/graphene sparfloxacin PSO, 502 6 72 h 298 360 0.02 g N/A [86]
oxide/citrus peel- Freundlich
derived magnetic
bio-nanocomposite
NiFe2O4– Covalent cefotaxime PSO, 309 4 40 h 293 100 170 mg/L 95 [71]
organic frameworks Freundlich
-chitosan-tere-
phthalaldehyde
nanocomposites
film
Activated carbon ceftriaxone PSO, 29 3.14 90 298 10 1.99 g/L 97 [113]
modified with Langmuir
magnetic Fe3O4 NPs
Bovine serum chloramphenicol Langmuir 148 N/A 50 N/A 200 0.2 g 96.4 [73]
albumin/Fe3O4
magnetic composite based on amino-functional chitosan and Fe3O4 electrostatic interactions between the negative surface charge of
(ACS@Fe3O4) for diclofenac removal from water. The maximum ACS@Fe3O4 and the negatively charged anionic form of diclofenac
adsorption capacity was 470 mg/g. It was shown that the amount of [116]. T.M. Salem Attia et al. [117] used zeolite-coated magnetic
adsorbed diclofenac decreased with increasing pH due to repulsive nanoparticles (γ-Fe2O3-zeolite) to remove diclofenac. Fast and high
14
Fig. 11. Formulas of the common non-steroidal anti-inflammatory drugs.
Fig. 12. (a) Schematic illustration of the mode of diclofenac adsorption at Fe3O4@SiO2/SiHTCC particles. Reprinted with permission from [114]. Copyright 2018,
Elsevier; (b) distribution of neutral and ionic forms of ibuprofen at various pH. Reprinted with permission from [150]. Copyright 2020, The Author(s); (c) proposed
mechanism of removal of ibuprofen by the rape straw biomass fiber and biochar/Fe3O4 /cyclodextrin adsorbent. Reprinted with permission from [125]. Copyright
2021, Elsevier.
15
adsorption of diclofenac is mainly explained by the presence of NH– and acetylsalicylic acid removal occurs at pH = 4–8 due to the electrostatic
OH-groups in the diclofenac structure, so the adsorbent can adsorb a interaction between the positively charged adsorbent surface and the
large amount of the drug (95%) in a very short time (10 min) (at negatively charged adsorbate with carboxylate anions. E.A. Moacă et al.
adsorbent dose 1 g/L and diclofenac concentration of 0.1 mg/L) [117]. [126] used a magnetite-core active charcoal-shell matrix, Fe3O4@C, to
Table 5 provides an overview of the adsorption parameters for various remove acetylsalicylic acid from aqueous solutions. The maximum
magnetic adsorbents for diclofenac removal from wastewater. adsorption capacity of 234 mg/g was achieved. The magnetic matrix
demonstrates two benefits: the easy magnetic separation from the liquid
5.2. Adsorption of ibuprofen medium and the highly porous structure necessary for effective
adsorption.
Ibuprofen is a derivative of phenylpropionic acid, which causes anti- Acetaminophen is a widely used analgesic. The average concen
inflammatory, analgesic, and antipyretic effects [149]. Fig. 12b shows tration of acetaminophen in surface waters of Western Europe is 0.046
the distribution of neutral and ionic forms of ibuprofen at various pH μg/L, and the maximum measured concentration is 230 μg/L [33]. S. C.
[150]. According to [33], the average concentration of ibuprofen in the Kollarahithlu et al. [123] used the amine-functionalized super
surface waters of Western Europe is 0.097 μg/L, and the maximum paramagnetic silica nanocomposite for acetaminophen adsorption.
measured concentration is 303 μg/L. Magnetic nanoparticles coated Amino groups (–NH2), which are present in the NiFe2O4@SiO2@ami
with zeolite (γ-Fe2O3-zeolite) were synthesized by T.M. Salem Attia et al. nopropyltrimethoxysilane adsorbent, are easily protonated (–NH+ 3 ) and
[117]. Zeolites are minerals with molecular-sized pores that can absorb promote adsorption in an acidic medium (at pH from 4 to 6) through
and reliably retain various contaminants [151]. The ibuprofen removal electrostatic interaction. This is explained by the formation of hydrogen
efficiency was>95% within 10 min at an adsorbent dose of 1 g/L and bonds between the –OH group of acetaminophen and –NH+ 3 of the
ibuprofen concentration of 0.1 mg/L [117]. A.C. Fröhlich et al. [121] adsorbent [123]. R. Natarajan et al. [129] synthesized rhamnolipid-
obtained NiFe2O4/activated carbon magnetic composite used for the based chitosan magnetic nanosorbents for the removal of acetamino
ibuprofen adsorption. It was found that the adsorption was favorable phen from aqueous solutions. The study showed the maximum removal
under acidic conditions at 328 K. The maximum adsorption capacity was of acetaminophen of 96.7%, the adsorption capacity was 96.3 mg/g at
261 mg/g. Y. Liu et al. [69] synthesized the magnetic genipin- 60 min contact time, pH = 5, and temperature of 303 K.
crosslinked chitosan/graphene oxide-SO3H (GC/MGO-SO3H) as an Ketoprofen and naproxen are synthetic drugs that originate from
adsorbent for ibuprofen removal. The maximum adsorption capacity propionic acid (according to their chemical structure) and belong to the
increased from 113 to 138 mg/g at a temperature increased from 298 to group of non-steroidal anti-inflammatory drugs. The average concen
313 K.G. Wu et al. [125] synthesized a magnetic rape straw biomass tration of naproxen in the surface waters of Western Europe is 0.057 μg/
fiber/β-Cyclodextrin/Fe3O4, which is a promising adsorbent for L, and the maximum measured concentration is 12.3 μg/L [33]. L. A. Al-
ibuprofen removal from wastewater (Fig. 12c). The mechanism of Khateeb et al. [120] synthesized Fe3O4@graphene nanoplatelets nano
ibuprofen removal encompasses the formation of hydrogen bonds and composite for the removal of ketoprofen from wastewater. The adsorp
electrostatic interactions. The synthesized adsorbent contains a large tion capacity at a temperature of 296 K was 8.76 mg/g. The study
number of oxygen-containing groups (OH, C=O) on its surface, which showed that the π-π interaction is involved in the adsorption process
can bind with ibuprofen through hydrogen bonds [125]. Table 6 pro between the π-electrons of the aromatic nanocomposite and the benzene
vides an overview of the adsorption parameters of various magnetic rings of ketoprofen. Hydrogen bonds can also participate in adsorption
adsorbents for the removal of ibuprofen from wastewater. through the interaction between the hydroxyl and carboxyl groups of
the adsorbent and the carboxylic, nitrogen, and carbonyl groups of the
5.3. Adsorption of other non-steroidal anti-inflammatory drugs adsorbate [120]. A. C. Fröhlich et al. [121] synthesized a NiFe2O4/
activated carbon magnetic composite for the ketoprofen removal from
Acetylsalicylic acid belongs to the group of non-steroidal anti-in an aqueous medium. The ketoprofen adsorption was favorable in acidic
flammatory drugs with analgesic, antipyretic, and anti-inflammatory media at 328 K. The maximum adsorption capacity was 98 mg/g. L. A.
properties. The average concentration of acetylsalicylic acid in the Al-Khateeb et al. [120] used Fe3O4@graphene nanoplatelets nano
surface waters of Western Europe is 0.002 μg/L, and the maximum composite for the removal of naproxen from wastewater. The adsorption
measured concentration is 0.36 μg/L [33]. A.S. Liyanage et al. [124] capacity at a temperature of 296 K was 10.6 mg/g.
synthesized the magnetic Fe3O4/Douglas fir biochar adsorbents for Table 7 provides an overview of the adsorption parameters of various
acetylsalicylic acid removal from wastewater. The highest magnetic adsorbents for nonsteroidal anti-inflammatory drugs removal
Table 5
Adsorption parameters of different magnetic adsorbents for diclofenac removal (PSO – pseudo-second-order kinetic model).
Adsorbent Adsorption Adsorption Optimum parameters Removal References
models capacity (mg/ pH Contact Temperature Concentration Adsorbent efficiency
g) time (min) (K) (mg/L) dose (%)
Fe3O4@SiO2/SiHTCC (N-(2- Langmuir 240 6 300 298 40 10 mg 60 [114]

hydroxypropyl)-3-
trimethylammonium chitosan
chloride)
ZnFe2O4/chitosan PSO 188 4 20 298 50 0.2 g/L 75 [115]
Amino-functional chitosan@Fe3O4 PSO, 469 4.5 60 303 1000 10 mg 91 [116]
Langmuir
Magnetic nanoparticles coated with PSO, N/A 2 300 303 0.1 1 g/L 99.6 [117]
zeolite Freundlich
Cetyltrimethyl ammonium N/A 36 9 5 N/A 0.5 10 mg 75 [118]
bromide-coated Fe3O4@decanoic
acid
Magnetic polydopamine-chitosan PSO N/A 7 400 298 2 25 mg/mL 71 [119]
modified adsorbent
Fe3O4@graphene nanoplatelets PSO 17 8 20 323 20 10 mg 81 [120]
nanocomposite
16
Table 6
Adsorption parameters of different magnetic adsorbents for ibuprofen removal (PSO – pseudo-second-order kinetic model).
Adsorbent Adsorption Adsorption Optimum parameters Removal References
models capacity (mg/g) pH Contact Temperature Concentration Adsorbent efficiency (%)
time (min) (K) (mg/L) dose
Magnetic genipin-crosslinked PSO, 138 6 120 308 10 5 mg 85 [69]

chitosan/graphene oxide- Langmuir
SO3H composite
Magnetic nanoparticles coated PSO, N/A 2 300 303 0.1 1 g/L 99 [117]
with zeolite Freundlich
Fe3O4@graphene nanoplatelets PSO 9.24 8 20 323 20 10 mg 41 [120]
nanocomposite
NiFe2O4/activated carbon PSO, Sips 261 2 240 328 0–100 0.5 g/L 86.5 [121]
Amine-coated magnetic PSO, 59 7 15 298 12 10 mg 97 [123]
nanocomposite Langmuir
NiFe2O4@SiO2
Fe3O4/Douglas fir biochar Langmuir 40 8 5 308 100 2.5 g/L 90 [124]
Rape straw biomass fiber/ PSO, 48 6 60 308 100 50 mg 90.3 [125]
β-Cyclodextrin/Fe3O4 Freundlich
from wastewater. the main advantages of magnetically susceptible adsorbents, compared

to ordinary (nonmagnetic) ones, is the possibility of controlling them by
6. Perspectives an external magnetic field. A magnetic field can penetrate various ma
terials, including glass and polymers. Therefore, magnetic separation, as
Research aimed at creating composite adsorbents with magnetic a non-contact and non-destructive technology, allows the removal of the
properties for water treatment is becoming more and more popular. The used adsorbent, preventing water re-contamination with pharmaceuti
use of modification and functionalization of the surface of magnetic cals or other adsorbates. The effectiveness of magnetic separation is not
adsorbents allows creating the samples with unique properties. One of affected by temperature, pH, or the concentration of the adsorbate in the
Table 7
Adsorption parameters of different magnetic adsorbents for non-steroidal anti-inflammatory drugs (PSO – pseudo-second-order kinetic model).
Adsorbent Adsorbate Adsorption Adsorption Optimum parameters Removal References
models capacity pH Contact Temperature Concentration Adsorbent efficiency
(mg/g) time (K) (mg/L) dose (%)
(min)
Fe3O4/Douglas fir acetylsalicylic Langmuir 150 8 5 308 100 2.5 g/L 70 [124]
biochar acid
Fe3O4@C Matrix acetylsalicylic PSO, Freundlich 234 3 100 298 100 2 g/L 86 [126]
acid
Amine-coated acetaminophen PSO, Langmuir 58 6 15 298 12 10 mg 94 [123]
magnetic
nanocomposite
NiFe2O4@SiO2
Magnetite acetaminophen PSO, Langmuir 133 7 5 298 400 0.5 mg/L 75 [127]
nanoparticles
modified
β-cyclodextrin
Polymer Coupled
Magnetic acetaminophen PSO, Langmuir 311 5 30 303 150 1 g/L 97.4 [128]
mesoporous silica
microspheres
Magnetic NPs acetaminophen PSO, Langmuir 96 5 60 303 60 20 mg 96.7 [129]
coated with
rhamnolipids
(Rh-cMNP)
Fe3O4@C Matrix acetaminophen PSO, 142 3 60 298 50 2 g/L 97 [126]
(paracetamol) Redlich–Peterson
Nitrogen-doped ketoprofen PSO, Langmuir 468 7 210 298 20 100 mg/L N/A [106]
reduced graphene
oxide/Fe3O4
nanocomposite
Fe3O4@graphene ketoprofen PSO 12.2 8 20 323 20 10 mg 53.8 [120]
nanoplatelets
nanocomposite
NiFe2O4/activated ketoprofen PSO, Sips 98 2 240 328 0–100 0.5 g/L 86.5 [121]
carbon
Magnetic NPs naproxen PSO, Freundlich N/A 2 300 303 0.1 1 g/L 99.8 [117]
coated with
zeolite
Fe3O4@graphene naproxen PSO 13.1 8 20 323 20 10 mg 60.3 [120]
nanoplatelets
nanocomposite
17
solution. Thus, magnetically controlled adsorbents can be used for the adsorption will be electrostatic attraction and complex formation.
adsorption of heavy metals, and dyes, as well as for the purification of Simultaneous removal of several pharmaceuticals from the solution can
pharmaceutical effluents from antibiotics, drugs, etc. The use of such occur at different conditions (e.g., higher or lower pH or temperature)
materials makes it possible to replace the mechanical separation stage, compared to separate removal of the same pharmaceuticals. In-situ
which is one of the most labor- and energy-consuming stages of this experimental methods, as well as artificial intelligence and quantum
process. However, the development of the ideal treatment technology chemical modeling, should be used for a deeper understanding of
should be done in such a way that it could easily integrate with existing adsorption modes. Thus, extensive studies on the possibilities of real
treatment facilities and should be a cost-effective and profitable process. applications in water and wastewater treatment are crucial for the
Traditional adsorbents after their use in wastewater treatment create further development of prospective magnetic adsorbents.
sludge, thus leading to secondary pollution. Instead, magnetic adsor
bents do not cause this problem. 7. Conclusions
Water purification with magnetic nanoparticles is a rather complex
procedure that presents some demands, in particular: low concentration The purpose of this review was to show the state of research on the
of pollutants must be treated; extremely low concentration limits should removal of some most popular pharmaceuticals from an aqueous envi
be achieved after the process; nanoparticles cannot remain in purified ronment and to provide some suggestions for the enhancing adsorption
water [152]. In addition, the magnetism of nanoparticles leads to a effectiveness of magnetic adsorbents. Since pharmaceuticals have a
noticeable aggregation of particles and, consequently, a decrease in significant toxic effect on the environment, and a detrimental effect on
adsorption capacity, which complicates their reuse. Most of the analyzed flora and fauna, therefore, the purification of wastewater from phar
studies were conducted using laboratory equipment, so more attention maceuticals gains higher and higher priority among researchers around
should be put to solve several problems such as analysis of the magnetic the world. Adsorption is considered the most common method of
nanoparticles’ productivity when they are used on an industrial scale; pharmaceuticals removal from water. This review presents the modes of
studying the process of continuous pharmaceuticals removal; investi adsorption of pharmaceuticals (in particular, antibiotics and non-
gation of the magnetic nanoparticles’ toxicity after several cycles; the steroidal anti-inflammatory drugs) from aqueous environments using
disposal of magnetic nanoparticles; assessment of the life cycle of various adsorbers with magnetic functionality. According to the analysis
magnetic nanoparticles; studying the impact of magnetic nanoparticles of articles, the high adsorption capacity of magnetic nanoparticles
on the environment [153]. makes them prospective for large-scale use. The advantages of magnetic
Adsorbents with magnetic properties are attractive not only because adsorbents encompass the possibility of separation from the aqueous
they are easily extracted from the treatment medium, but also due to the medium using a magnetic field, the use of cheap precursors for synthesis,
possibility of modulating the physicochemical characteristics of the the high stability of these materials in water, the possibility of reuse,
adsorbent in the presence of an external magnetic field, created by both biocompatibility, simple synthesis methods, and the possibility of sur
permanent magnet or electromagnetic field. In the second case, an face functionalization. Scientists from all over the world published a lot
additional effect of heating the magnetic adsorbent appears, which may of works on the removal of pharmaceuticals, such as tetracycline, cip
enhance the adsorption of pollutants molecules. The applied magnetic rofloxacin, levofloxacin, diclofenac, and ibuprofen. Among the magnetic
field can cause changes in both the structure of the adsorbents (the so- adsorbents, Fe3O4-based nanoparticles are most often examined. The
called “magnetic memory effect”) and adsorbed molecules. Adsorbates structures of magnetite or ferrites can be tuned with various cations,
can change their dipole moment in the presence of a magnetic sorbent, making it possible to increase the adsorption capacity, increase the
thus causing additional agglomeration and stronger retention by the amount of surface adsorption active sites and at the same time not to
adsorbent surface. This phenomenon requires further research. reduce significantly the magnetization of the adsorbent, which is
The regeneration of the magnetic adsorbents is an important aspect important for separating the used adsorbent from the solution. The
of their utilization and also should be taken into account. The regener adsorption capacity of magnetic adsorbents ranges from tens to hun
ation depends on the type of magnetic adsorbent and the nature of the dreds of mg/g. It can be increased in few times by creating composite
adsorbed pollutant. Regeneration involves removing contaminants from magnetic adsorbents based on biochar, layered hydroxides, MOFs/COFs,
the surface of the adsorbent so that it can be reused. There are several graphene oxide, etc. The disadvantage of magnetic nano-adsorbents is
methods of regeneration of magnetic adsorbents: thermal, chemical, their tendency to agglomeration, which can be simply resolved using
biological, and magnetic. Thermal regeneration involves the heating of coating/functionalization by different agents (amino acids, surfactants,
the adsorbent at a high temperature to remove adsorbed impurities. silica, polymers (polyaniline, polystyrene, polypyrrole, etc.)). It is
During the chemical regeneration, the adsorbent is treated with chem shown that the adsorption mode strongly depends on pH, temperature,
icals (e.g., HCl [44], CH3OH [79], CH3OH + NaOH [84], CH3OH + adsorbent dose, and adsorbate concentration. We have discussed the
CH3COOH [94]), which desorb the impurities. During biological correlations between molecular structures of pharmaceuticals and their
regeneration, the microorganisms destroy or remove pollutants onto the existence in cationic, anionic, and zwitterionic forms depending on the
adsorbent surface. Another type of regeneration involves the use of a pH of the aqueous solution. Analysis of the literature showed that the
magnetic field to increase the mobility of adsorbed pollutants and modes of pharmaceuticals adsorption on magnetic nanoadsorbents are
enhance their desorption from the adsorbent surface [116]. After the mainly based on hydrophobic and electrostatic interactions, π-π inter
regeneration, the adsorbent should be thoroughly rinsed to remove any action, surface complexations, ion exchange, as well as hydrogen bonds.
remaining contaminants or regeneration agents. Therefore, proper This points to very limited possibilities to control the selectivity of the
regeneration and cleaning procedures are important to improve the processes, e.g., aimed at the removal of only pharmaceuticals from
performance of the magnetic adsorbent during repeated use [154]. water. Based on all these data, it is possible to assert the effective use of
Simultaneous adsorption of co-existing pharmaceuticals and selec magnetic adsorbents for the removal of pharmaceuticals from aqueous
tivity of the adsorbents to specific pharmaceuticals are other important environments.
issues and challenges for the future development of the discussed tech
nology [155]. The adsorption of co-existing pollutants should be per
formed by properly functionalized magnetic adsorbents to ensure the Declaration of Competing Interest
involvement of several types of adsorption modes [156,157]. The
functional groups create new adsorption centers and can selectively/ The authors declare that they have no known competing financial
simultaneously adsorb different types of pharmaceuticals from the so interests or personal relationships that could have appeared to influence
lution [124]. It is expected that the main modes of simultaneous the work reported in this paper.
18
Data availability [19] K.K. Kefeni, B.B. Mamba, T.A.M. Msagati, Application of spinel ferrite
nanoparticles in water and wastewater treatment: A review, Sep. Purif. Technol.
188 (2017) 399–422, https://doi.org/10.1016/J.SEPPUR.2017.07.015.
No data was used for the research described in the article. [20] S.K. Paswan, P. Kumar, R.K. Singh, S.K. Shukla, L. Kumar, Spinel ferrite magnetic
nanoparticles, Pollut. Water Manag., Wiley, in, 2021, pp. 273–305.
Acknowledgment [21] K.K. Kefeni, T.A.M. Msagati, B.B. Mamba, Ferrite nanoparticles: Synthesis,
characterisation and applications in electronic device, Mater. Sci. Eng. B. 215
(2017) 37–55, https://doi.org/10.1016/J.MSEB.2016.11.002.
Tetiana Tatarchuk would like to acknowledge the support given by [22] T. Tatarchuk, M. Bououdina, J. Judith Vijaya, L. John Kennedy, Spinel ferrite
the National Science Centre (Poland) (project 2022/01/3/ST5/00136). nanoparticles: Synthesis, crystal structure, properties, and perspective
applications, in: O. Fesenko, L. Yatsenko (Eds.), Nanophysics, Nanomater.
Interface Stud. Appl. NANO 2016, Springer Proc. Phys., Springer, Cham, 2017,
References pp. 305–325, https://doi.org/10.1007/978-3-319-56422-7_22.
[23] J. Wu, D. Gao, T. Sun, J. Bi, Y. Zhao, Z. Ning, G. Fan, Z. Xie, Highly selective gas
[1] V. Vinayagam S. Murugan R. Kumaresan M. Narayanan M. Sillanpää D. Viet N Vo sensing properties of partially inversed spinel zinc ferrite towards H2S, Sensors
O.S. Kushwaha P. Jenis P. Potdar S. Gadiya Sustainable adsorbents for the Actuators B Chem. 235 (2016) 258–262, https://doi.org/10.1016/j.
removal of pharmaceuticals from wastewater: A review Chemosphere. 300 2022 snb.2016.05.083.
10.1016/j.chemosphere.2022.134597. [24] K.C. Shrivastava, A.K. Pandey, S. Banerjee, A.K. Debnath, S.S. Meena, A.
[2] Y. Zhao, C. Zhang, Z. Yang, Y. Yang, N. Huang, J.E. Arku, G. Mao, Y. Wang, P. Srivastava, V. Sudarsan, Hydrogen adsorption and interactions in self-reducing
Global trends and prospects in the removal of pharmaceuticals and personal care shell hosted palladium nanoparticles on magnetite support, Int. J. Hydrogen
products: A bibliometric analysis, J. Water Process Eng. 41 (2021) 102004, Energy. 47 (2022) 34128–34138, https://doi.org/10.1016/j.
https://doi.org/10.1016/j.jwpe.2021.102004. ijhydene.2022.07.267.
[3] A.K. Priya, L. Gnanasekaran, S. Rajendran, J. Qin, Y. Vasseghian, Occurrences [25] S. Natarajan, V. Anitha, G.P. Gajula, V. Thiagarajan, Synthesis and
and removal of pharmaceutical and personal care products from aquatic systems characterization of magnetic superadsorbent Fe3O4-peg-mg-al-ldh
using advanced treatment- A review, Environ. Res. 204 (2022) 112298, https:// nanocomposites for ultrahigh removal of organic dyes, ACS Omega 5 (2020)
doi.org/10.1016/j.envres.2021.112298. 3181–3193, https://doi.org/10.1021/acsomega.9b03153.
[4] A.H. Khan, N.A. Khan, M. Zubair, M. Azfar Shaida, M.S. Manzar, A. Abutaleb, [26] D. Gautam, S. Hooda, Magnetic graphene oxide/chitin nanocomposites for
M. Naushad, J. Iqbal, Sustainable green nanoadsorbents for remediation of efficient adsorption of methylene blue and crystal violet from aqueous solutions,
pharmaceuticals from water and wastewater: A critical review, Environ. Res. 204 J. Chem. Eng. Data. 65 (2020) 4052–4062, https://doi.org/10.1021/acs.
(2022) 112243, https://doi.org/10.1016/j.envres.2021.112243. jced.0c00350.
[5] X. Zhu, M. He, Y. Sun, Z. Xu, Z. Wan, D. Hou, D.S. Alessi, D.C.W. Tsang, Insights [27] R. Wo, Q.-L. Li, C. Zhu, Y. Zhang, G. Qiao, K. Lei, P. Du, W. Jiang, Preparation and
into the adsorption of pharmaceuticals and personal care products (PPCPs) on characterization of functionalized metal-organic frameworks with core/shell
biochar and activated carbon with the aid of machine learning, J. Hazard. Mater. magnetic particles (Fe3O4@SiO2@MOFs) for removal of congo red and
423 (2022) 127060, https://doi.org/10.1016/j.jhazmat.2021.127060. methylene blue from water solution, J. Chem. Eng. Data. 64 (2019) 2455–2463,
[6] N. Magesh, A.A. Renita, R. Siva, N. Harirajan, A. Santhosh, Adsorption behavior https://doi.org/10.1021/acs.jced.8b01251.
of fluoroquinolone(ciprofloxacin) using zinc oxide impregnated activated carbon [28] E. Al-Hetlani, B. D’Cruz, M.O. Amin, M. Madkour, An effective magnetic
prepared from jack fruit peel: Kinetics and isotherm studies, Chemosphere 290 nanoadsorbent based on a carbonaceous/spinel ferrite nanocomposite for the
(2022) 133227, https://doi.org/10.1016/j.chemosphere.2021.133227. removal of pharmaceutical pollutants from wastewater, Environ. Sci. Water Res.
[7] M. N., A. Renita A., S. Kumar P., S. Abraham L., Adsorption of ciprofloxacin from Technol. 8 (2022) 998–1010, https://doi.org/10.1039/D1EW00495F.
aqueous solution using surface improved tamarind shell as an economical and [29] L. Shearer, S. Pap, S.W. Gibb, Removal of pharmaceuticals from wastewater: A
effective adsorbent, Int. J. Phytoremediation. 24 (3) (2022) 224–234. review of adsorptive approaches, modelling and mechanisms for metformin and
[8] P. Arabkhani, A. Asfaram, The potential application of bio-based ceramic/organic macrolides, J. Environ. Chem. Eng. 10 (2022) 108106, https://doi.org/10.1016/
xerogel derived from the plant sources: A new green adsorbent for removal of j.jece.2022.108106.
antibiotics from pharmaceutical wastewater, J. Hazard. Mater. 429 (2022) [30] A. Kujawska, U. Kiełkowska, A. Atisha, E. Yanful, W. Kujawski, Comparative
128289, https://doi.org/10.1016/j.jhazmat.2022.128289. analysis of separation methods used for the elimination of pharmaceuticals and
[9] A. Lakshmanan, P. Surendran, S. Sakthy Priya, K. Balakrishnan, P. Geetha, personal care products (PPCPs) from water – A critical review, Sep. Purif.
P. Rameshkumar, T.A. Hegde, G. Vinitha, K. Kannan, Investigations on structural, Technol. 290 (2022), https://doi.org/10.1016/j.seppur.2022.120797.
optical, dielectric, electronic polarizability, Z-scan and antibacterial properties of [31] A.A. Basheer, New generation nano-adsorbents for the removal of emerging
Ni/Zn/Fe2O4 nanoparticles fabricated by microwave-assisted combustion contaminants in water, J. Mol. Liq. 261 (2018) 583–593, https://doi.org/
method, J. Photochem. Photobiol. A Chem. 402 (2020) 112794, https://doi.org/ 10.1016/J.MOLLIQ.2018.04.021.
10.1016/j.jphotochem.2020.112794. [32] W.J. L., B.A.B. A., K.D. W., L.K.M. Y., L.R.W. S., G.-M. Cristóbal, A.A. D., M. Julie,
[10] S.K. Lakkaboyana, K. Soontarapa, Vinaykumar, R.K. Marella, K. Kannan, M. Marc, M.R. A., B.-M. Alejandra, C.-S. Aida, C. Anja, C. Pedro, R. Macarena, G.
Preparation of novel chitosan polymeric nanocomposite as an efficient material Chris, C. Magdalena, M. Monique, L. Thais, P. Vahagn, P. Yekaterina, M.C. S., M.
for the removal of Acid Blue 25 from aqueous environment, Int. J. Biol. C. J., H. Thilo, K. Tapos, I. Volga, G.-O. Jessica, T.J. L., G.D.F. Francisco, R.M.T.
Macromol. 168 (2021) 760–768. P., D. Victorien, G. Gildas, T. Oumar, B.J. M., K.L. E., W. Michelle, W. Donald, N.
[11] A. Sathiya Priya, D. Geetha, K. Karthik, M. Rajamoorthy, Investigations on the Romaric, P. Jaime, Y. Guang-Guo, C. Chang-Er, P. Martha, M.-L. Jina, O. Jean-
enhanced photocatalytic activity of (Ag, La) substituted nickel cobaltite spinels, Paul, P. John, I.S. A., W. Penelope, E.-S. Silvia, U.-K. Nikolina, M. Milena, F.-K.
Solid State Sci. 98 (2019) 105992, https://doi.org/10.1016/j. Despo, I.-T. Lida, B. Vladimíra, V. Jan, C.-B. María, K.B. A., G. Jeanne, C. Arnaud,
solidstatesciences.2019.105992. G. Peter, K. Ilia, S. Sven, L. Gerasimos, H.H. P., M. Molly, S. Thatikonda, L.
[12] M. Hashim, S.E. Shirsath, S.S. Meena, M.L. Mane, S. Kumar, P. Bhatt, R. Kumar, N. Manisha, N. Anindrya, S. Adee, P. Nima, A. Ali, A. Omar, G.S. S., P. Francesco, C.
K. Prasad, S.K. Alla, J. Shah, R.K. Kotnala, K.A. Mohammed, E. Şentürk, Benny, T. Tom, Y.K. Marcellin, A. Bakhyt, B. Raikhan, O. Lydia, M.J. K., C. Peter,
Alimuddin, manganese ferrite prepared using reverse micelle process: Structural N. Victor, B.N. T., S. Sheck, A.A. Zaharin, L.L. Juen, N. Mahamoudane, T.S. T., O.
and magnetic properties characterization, J. Alloys Compd. 642 (2015) 70–77, Rik, O. Olatayo, A. Muhammad, I. Muhammad, A. Ziad, O. Aaron, M.-S.J. Manuel,
https://doi.org/10.1016/j.jallcom.2015.04.085. C. María, de la C. Heidi, N. Ian, C. Fabio, G.A. Brima, K.B. M., C.-F. Vesna, G.
[13] L. Soltys, O. Olkhovyy, T. Tatarchuk, M. Naushad, Green synthesis of metal and Mitja, T. Melusi, C. Kyungho, K. Habyeong, L.J.L. Celestino, R. Andreu, A.
metal oxide nanoparticles: Principles of green chemistry and raw materials, Priyanie, S. Anna, H. Gisela, Z.A. K., K.A. C., J. Jheng-Jie, K. Rebecca, T. Madaka,
Magnetochemistry. 7 (2021), https://doi.org/10.3390/ T. Ulas, O.T. T., L.J. B., V. Yuliya, V. Yuriy, H. Horacio, P.-P. Andrés, S.D. B., F.
magnetochemistry7110145. Maritza, G. David, T. Charles, Pharmaceutical pollution of the world’s rivers,
[14] C. Srinivas, E. Ranjith Kumar, B.V. Tirupanyam, S. Singh Meena, P. Bhatt, C. Proc. Natl. Acad. Sci. 119 (2022) e2113947119., https://doi.org/10.1
L. Prajapat, T.V. Chandrasekhar Rao, D.L. Sastry, Study of magnetic behavior in 073/pnas.2113947119.
co-precipitated Ni–Zn ferrite nanoparticles and their potential use for gas sensor [33] T. aus der Beek, F.A. Weber, A. Bergmann, S. Hickmann, I. Ebert, A. Hein,
applications, J. Magn. Magn. Mater. 502 (2020) 166534, https://doi.org/ A. Küster, Pharmaceuticals in the environment-Global occurrences and
10.1016/j.jmmm.2020.166534. perspectives, Environ. Toxicol. Chem. 35 (2016) 823–835, https://doi.org/
[15] N.K. Prasad, D. Panda, S. Singh, M.D. Mukadam, S.M. Yusuf, D. Bahadur, 10.1002/etc.3339.
Biocompatible suspension of nanosized γ-Fe2O3 synthesized by novel methods, [34] R. Natarajan, K. Saikia, S.K. Ponnusamy, A.K. Rathankumar, D.S. Rajendran,
J. Appl. Phys. 97 (2005) 10Q903, https://doi.org/10.1063/1.1849056. S. Venkataraman, D.B. Tannani, V. Arvind, T. Somanna, K. Banerjee,
[16] S.K. Shaw, J. Kailashiya, A. Gangwar, S.K. Alla, S.K. Gupta, C.L. Prajapat, S. N. Mohideen, V.K. Vaidyanathan, Understanding the factors affecting adsorption
S. Meena, D. Dash, P. Maiti, N.K. Prasad, γ-Fe2O3 nanoflowers as efficient of pharmaceuticals on different adsorbents – A critical literature update,
magnetic hyperthermia and photothermal agent, Appl. Surf. Sci. 560 (2021) Chemosphere 287 (2022) 131958, https://doi.org/10.1016/j.
150025, https://doi.org/10.1016/j.apsusc.2021.150025. chemosphere.2021.131958.
[17] D.H.K. Reddy, Y.-S. Yun, Spinel ferrite magnetic adsorbents: Alternative future [35] V. Springer, E. Pecini, M. Avena, Magnetic nickel ferrite nanoparticles for
materials for water purification? Coord. Chem. Rev. 315 (2016) 90–111. removal of dipyrone from aqueous solutions, J. Environ. Chem. Eng. 4 (2016)
[18] A. Mitra, B. Barick, J. Mohapatra, H. Sharma, S.S. Meena, M. Aslam, Large 3882–3890, https://doi.org/10.1016/j.jece.2016.08.026.
tunneling magnetoresistance in octahedral Fe 3 O 4 nanoparticles, AIP Adv. 6 [36] V. Springer, L. Barreiros, M. Avena, M.A. Segundo, Nickel ferrite nanoparticles for
(2016) 055007, https://doi.org/10.1063/1.4948798. removal of polar pharmaceuticals from water samples with multi-purpose
19
features, Adsorption 24 (2018) 431–441, https://doi.org/10.1007/s10450-018- [60] C.P. Okoli, E.B. Naidoo, A.E. Ofomaja, Role of synthesis process variables on
9953-2. magnetic functionality, thermal stability, and tetracycline adsorption by magnetic
[37] P.A. Ajibade, E.C. Nnadozie, Ketoprofen and benzophenone adsorption on starch nanocomposite, Environ. Nanotechnology, Monit. Manag. 9 (2018)
manganese ferrite biochar magnetic nanocomposite from aqueous solution, 141–153, https://doi.org/10.1016/j.enmm.2018.02.001.
Environ. Chem. Ecotoxicol. 4 (2022) 140–147, https://doi.org/10.1016/j. [61] Z. Fallah, E.N. Zare, M. Ghomi, F. Ahmadijokani, M. Amini, M. Tajbakhsh,
enceco.2022.03.001. M. Arjmand, G. Sharma, H. Ali, A. Ahmad, P. Makvandi, E. Lichtfouse,
[38] D. Wu, J. Yao, G. Lu, F. Liu, C. Zhou, P. Zhang, M. Nkoom, Adsorptive removal of M. Sillanpää, R.S. Varma, Toxicity and remediation of pharmaceuticals and
aqueous bezafibrate by magnetic ferrite modified carbon nanotubes, RSC Adv. 7 pesticides using metal oxides and carbon nanomaterials, Chemosphere 275
(2017) 39594–39603, https://doi.org/10.1039/C7RA07260K. (2021), https://doi.org/10.1016/j.chemosphere.2021.130055.
[39] A. Morone, P. Mulay, S.P. Kamble, Removal of pharmaceutical and personal care [62] B. Yu, Y. Bai, Z. Ming, H. Yang, L. Chen, X. Hu, S. Feng, S.T. Yang, Adsorption
products from wastewater using advanced materials, Elsevier Inc. (2019), behaviors of tetracycline on magnetic graphene oxide sponge, Mater. Chem. Phys.
https://doi.org/10.1016/B978-0-12-816189-0.00008-1. 198 (2017) 283–290, https://doi.org/10.1016/j.matchemphys.2017.05.042.
[40] I.A. Amar, S. Faraj, M. Abdulqadir, I. Abdalsamed, F. Altohami, M. Samba, Oil [63] G. Gopal, S.A. Alex, N. Chandrasekaran, A. Mukherjee, A review on tetracycline
Spill Removal from Water Surfaces using Zinc Ferrite Magnetic Nanoparticles as A removal from aqueous systems by advanced treatment techniques, RSC Adv. 10
Sorbent Material, Iraqi J. Sci. (2021) 718–728, https://doi.org/10.24996/ (2020) 27081–27095, https://doi.org/10.1039/D0RA04264A.
ijs.2021.62.3.2. [64] M. Asadi-ghalhari, A. Kishipour, R. Mostafaloo, Ciprofloxacin removal from
[41] X. Ding, R. Wang, X. Zhang, Y. Zhang, S. Deng, F. Shen, X. Zhang, H. Xiao, aqueous solutions by granular ferric hydroxide : Modeling and optimization,
L. Wang, A new magnetic expanded graphite for removal of oil leakage, Mar. J. Trace Elem. Miner. 2 (2022) 100007, https://doi.org/10.1016/j.
Pollut. Bull. 81 (2014) 185–190, https://doi.org/10.1016/j. jtemin.2022.100007.
marpolbul.2014.01.056. [65] L. Saya, V. Malik, D. Gautam, G. Gambhir, W.R. Balendra, S.H. Singh,
[42] X. Cao, M. Lin, H. Wei, H. Yu, L. Li, Effect of the modification of magnetic A comprehensive review on recent advances toward sequestration of levofloxacin
graphene oxide with ionic liquid on the adsorption of nonionic surfactant antibiotic from wastewater, Sci. Total Environ. 813 (2022) 152529, https://doi.
NP10EO, Environ. Sci. Pollut. Res. 28 (2021) 58629–58639, https://doi.org/ org/10.1016/j.scitotenv.2021.152529.
10.1007/s11356-021-14784-8. [66] K. Fang, L. Deng, J. Yin, T. Yang, J. Li, W. He, Recent advances in starch-based
[43] I. Ihsanullah, M.T. Khan, M. Zubair, M. Bilal, M. Sajid, Removal of magnetic adsorbents for the removal of contaminants from wastewater: A review,
pharmaceuticals from water using sewage sludge-derived biochar: A review, Int. J. Biol. Macromol. 218 (2022) 909–929, https://doi.org/10.1016/j.
Chemosphere 289 (2022) 133196, https://doi.org/10.1016/j. ijbiomac.2022.07.175.
chemosphere.2021.133196. [67] Z.A. ALOthman, N. AlMasoud, X.Y. Mbianda, I. Ali, Synthesis and
[44] H. Rasoulzadeh, A. Mohseni-Bandpei, M. Hosseini, M. Safari, Mechanistic characterization of γ-cyclodextrin-graphene oxide nanocomposite: Sorption,
investigation of ciprofloxacin recovery by magnetite–imprinted chitosan kinetics, thermodynamics and simulation studies of tetracycline and
nanocomposite: Isotherm, kinetic, thermodynamic and reusability studies, Int. J. chlortetracycline antibiotics removal in water, J. Mol. Liq. 345 (2022) 116993,
Biol. Macromol. 133 (2019) 712–721, https://doi.org/10.1016/j. https://doi.org/10.1016/j.molliq.2021.116993.
ijbiomac.2019.04.139. [68] G. Başkan, Ü. Açıkel, M. Levent, Investigation of adsorption properties of
[45] J. Nie, D. Zhi, Y. Zhou, Magnetic biochar-based composites for removal of oxytetracycline hydrochloride on magnetic zeolite/Fe3O4 particles, Adv. Powder
recalcitrant pollutants in water, in, Sorbents Mater. Control. Environ. Pollut., Technol. 33 (2022), https://doi.org/10.1016/j.apt.2022.103600.
Elsevier (2021) 163–187, https://doi.org/10.1016/B978-0-12-820042-1.00015- [69] Y. Liu, R. Liu, M. Li, F. Yu, C. He, Removal of pharmaceuticals by novel magnetic
8. genipin-crosslinked chitosan/graphene oxide-SO3H composite, Carbohydr.
[46] S.J. Olusegun, T.G.F. Souza, G.d.O. Souza, M. Osial, N.D.S. Mohallem, V.S. Polym. 220 (2019) 141–148, https://doi.org/10.1016/j.carbpol.2019.05.060.
T. Ciminelli, P. Krysinski, Iron-based materials for the adsorption and [70] D. Shan, S. Deng, T. Zhao, B. Wang, Y. Wang, J. Huang, G. Yu, J. Winglee, M.
photocatalytic degradation of pharmaceutical drugs: A comprehensive review of R. Wiesner, Preparation of ultrafine magnetic biochar and activated carbon for
the mechanism pathway, J. Water Process Eng. 51 (2023) 103457. pharmaceutical adsorption and subsequent degradation by ball milling,
[47] D. Mangla, A. Annu, S.I. Sharma, Critical review on adsorptive removal of J. Hazard. Mater. 305 (2016) 156–163, https://doi.org/10.1016/j.
antibiotics: Present situation, challenges and future perspective, J. Hazard. Mater. jhazmat.2015.11.047.
425 (2022) 127946, https://doi.org/10.1016/j.jhazmat.2021.127946. [71] Z. Li, Y. Liu, S. Zou, C. Lu, H. Bai, H. Mu, J. Duan, Removal and adsorption
[48] Y. Tang, Q. Chen, W. Li, X. Xie, W. Zhang, X. Zhang, H. Chai, Y. Huang, mechanism of tetracycline and cefotaxime contaminants in water by NiFe2O4-
Engineering magnetic N-doped porous carbon with super-high ciprofloxacin COF-chitosan-terephthalaldehyde nanocomposites film, Chem. Eng. J. 382 (2020)
adsorption capacity and wide pH adaptability, J. Hazard. Mater. 388 (2020) 123008, https://doi.org/10.1016/j.cej.2019.123008.
122059, https://doi.org/10.1016/j.jhazmat.2020.122059. [72] J. Ou, M. Mei, X. Xu, Magnetic adsorbent constructed from the loading of amino
[49] F. Bu, W. Huang, M. Xian, X. Zhang, F. Liang, X. Liu, X. Sun, D. Feng, Magnetic functionalized Fe3O4 on coordination complex modified polyoxometalates
carboxyl-functionalized covalent organic frameworks for adsorption of nanoparticle and its tetracycline adsorption removal property study, J. Solid State
quinolones with high capacities, fast kinetics and easy regeneration, J. Clean. Chem. 238 (2016) 182–188, https://doi.org/10.1016/j.jssc.2016.03.021.
Prod. 336 (2022) 130485, https://doi.org/10.1016/j.jclepro.2022.130485. [73] B. Zhang, H. Zhang, X. Li, X. Lei, C. Li, D. Yin, X. Fan, Q. Zhang, Synthesis of BSA/
[50] X. Bao, Z. Qiang, W. Ling, J.-H. Chang, Sonohydrothermal synthesis of MFe2O4 Fe3O4 magnetic composite microspheres for adsorption of antibiotics, Mater. Sci.
magnetic nanoparticles for adsorptive removal of tetracyclines from water, Sep. Eng. C. 33 (2013) 4401–4408, https://doi.org/10.1016/j.msec.2013.06.038.
Purif. Technol. 117 (2013) 104–110, https://doi.org/10.1016/j. [74] Y. Li, X. Lin, C. Zhang, Q. Zhuang, W. Dong, Polydopamine magnetic
seppur.2013.03.046. microspheres grafted with sulfonic acid groups for efficient adsorption of
[51] X. Yang, Y. Wan, Y. Zheng, F. He, Z. Yu, J. Huang, H. Wang, Y.S. Ok, Y. Jiang, tetracycline, Colloids Surfaces A Physicochem. Eng. Asp. 628 (2021) 127263,
B. Gao, Surface functional groups of carbon-based adsorbents and their roles in https://doi.org/10.1016/j.colsurfa.2021.127263.
the removal of heavy metals from aqueous solutions: A critical review, Chem. [75] J. Miao, F. Wang, Y. Chen, Y. Zhu, Y. Zhou, S. Zhang, The adsorption performance
Eng. J. 366 (2019) 608–621, https://doi.org/10.1016/j.cej.2019.02.119. of tetracyclines on magnetic graphene oxide: A novel antibiotics absorbent, Appl.
[52] X. Hu, Y. Zhao, H. Wang, X. Tan, Y. Yang, Y. Liu, Efficient mbly, Int. J. Environ. Surf. Sci. 475 (2019) 549–558, https://doi.org/10.1016/J.APSUSC.2019.01.036.
Res. Public Health. 14 (2017) 1495, https://doi.org/10.3390/ijerph14121495. [76] Y. Zhao, J. Geng, X. Wang, X. Gu, S. Gao, Adsorption of tetracycline onto goethite
[53] L. Lu, M. Liu, Y. Chen, Y. Luo, Effective removal of tetracycline antibiotics from in the presence of metal cations and humic substances, J. Colloid Interface Sci.
wastewater using practically applicable iron(III)-loaded cellulose nanofibres, 361 (2011) 247–251, https://doi.org/10.1016/j.jcis.2011.05.051.
R. Soc. Open Sci. 8 (2021) 210336, https://doi.org/10.1098/rsos.210336. [77] L. Lian, J. Lv, X. Wang, D. Lou, Magnetic solid–phase extraction of tetracyclines
[54] C.A. Igwegbe, S.N. Oba, C.O. Aniagor, A.G. Adeniyi, J.O. Ighalo, Adsorption of using ferrous oxide coated magnetic silica microspheres from water samples,
ciprofloxacin from water: A comprehensive review, J. Ind. Eng. Chem. 93 (2021) J. Chromatogr. A. 1534 (2018) 1–9, https://doi.org/10.1016/j.
57–77, https://doi.org/10.1016/j.jiec.2020.09.023. chroma.2017.12.041.
[55] F. Feizi, F. Reguyal, N. Antoniou, A. Zabaniotou, A.K. Sarmah, Environmental [78] Q. Wang, L. Zhang, Fabricated ultrathin magnetic nitrogen doped graphene tube
remediation in circular economy: End of life tyre magnetic pyrochars for as efficient and recyclable adsorbent for highly sensitive simultaneous
adsorptive removal of pharmaceuticals from aqueous solution, Sci. Total Environ. determination of three tetracyclines residues in milk samples, J. Chromatogr. A.
739 (2020) 139855, https://doi.org/10.1016/j.scitotenv.2020.139855. 1568 (2018) 1–7, https://doi.org/10.1016/j.chroma.2018.07.012.
[56] S. Shi, Y. Fan, Y. Huang, Facile low temperature hydrothermal synthesis of [79] T. Ahamad, Ruksana, A.A. Chaudhary, M.u. Naushad, S.M. Alshehri, Alshehri,
magnetic mesoporous carbon nanocomposite for adsorption removal of Fabrication of MnFe 2 O 4 nanoparticles embedded chitosan-
ciprofloxacin antibiotics, Ind. Eng. Chem. Res. 52 (2013) 2604–2612, https://doi. diphenylureaformaldehyde resin for the removal of tetracycline from aqueous
org/10.1021/ie303036e. solution, Int. J. Biol. Macromol. 134 (2019) 180–188.
[57] V. Phouthavong, R. Yan, S. Nijpanich, T. Hagio, R. Ichino, L. Kong, L. Li, Magnetic [80] M. Rouhani, S.D. Ashrafi, K. Taghavi, M.N. Joubani, J. Jaafari, Evaluation of
adsorbents for wastewater treatment: advancements in their synthesis methods, tetracycline removal by adsorption method using magnetic iron oxide
Materials (Basel). 15 (2022) 1053, https://doi.org/10.3390/ma15031053. nanoparticles (Fe3O4) and clinoptilolite from aqueous solutions, J. Mol. Liq. 356
[58] T. Wang, X. Pan, W. Ben, J. Wang, P. Hou, Z. Qiang, Adsorptive removal of (2022) 119040, https://doi.org/10.1016/j.molliq.2022.119040.
antibiotics from water using magnetic ion exchange resin, J. Environ. Sci. 52 [81] K. Sun, F. Cheng, Y. Liu, Y. Hua, Y. Zhang, Microwave-assisted iron oxide process
(2017) 111–117, https://doi.org/10.1016/j.jes.2016.03.017. for efficient removal of tetracycline, J. Environ. Manage. 307 (2022) 114600,
[59] Y. Gao, Y. Li, L. Zhang, H. Huang, J. Hu, S.M. Shah, X. Su, Adsorption and https://doi.org/10.1016/j.jenvman.2022.114600.
removal of tetracycline antibiotics from aqueous solution by graphene oxide, [82] Z.-T. Hu, X.-F. Wang, S. Xiang, Y. Ding, D.-Y. Zhao, M. Hu, Z. Pan, S. Varjani, J.-
J. Colloid Interface Sci. 368 (2012) 540–546, https://doi.org/10.1016/j. W.-C. Wong, J. Zhao, Self-cleaning MnZn ferrite/biochar adsorbents for effective
jcis.2011.11.015.
20
removal of tetracycline, Sci. Total Environ. (2022) 157202, https://doi.org/ [105] G. Peng, T. Li, B. Ai, S. Yang, J. Fu, Q. He, G. Yu, S. Deng, Highly efficient removal
10.1016/j.scitotenv.2022.157202. of enrofloxacin by magnetic montmorillonite via adsorption and persulfate
[83] X. Hu, L. Jia, J. Cheng, Z. Sun, Magnetic ordered mesoporous carbon materials for oxidation, Chem. Eng. J. 360 (2019) 1119–1127, https://doi.org/10.1016/j.
adsorption of minocycline from aqueous solution: Preparation, characterization cej.2018.10.190.
and adsorption mechanism, J. Hazard. Mater. 362 (2019) 1–8, https://doi.org/ [106] G. Peng, M. Zhang, S. Deng, D. Shan, Q. He, G. Yu, Adsorption and catalytic
10.1016/j.jhazmat.2018.09.003. oxidation of pharmaceuticals by nitrogen-doped reduced graphene oxide/Fe3O4
[84] L. Lu, J. Li, J. Yu, P. Song, D.H.L. Ng, A hierarchically porous MgFe<inf>2</ nanocomposite, Chem. Eng. J. 341 (2018) 361–370, https://doi.org/10.1016/j.
inf>O<inf>4</inf>/γ-Fe<inf>2</inf>O<inf>3</inf> magnetic microspheres cej.2018.02.064.
for efficient removals of dye and pharmaceutical from water, Chem. Eng. J. 283 [107] M.M. Gaho, G.Z. Memon, J. ur R. Memon, J.B. Arain, A.J. Arain, A. Shah, M.
(2016) 524–534, https://doi.org/10.1016/j.cej.2015.07.081. Q. Samejo, Synthesis of novel magnetic molecularly imprinted polymers by solid-
[85] C.C. Lin, C.Y. Lee, Adsorption of ciprofloxacin in water using Fe3O4 nanoparticles phase extraction method for removal of norfloxacin, Chinese, J. Anal. Chem. 50
formed at low temperature and high reactant concentrations in a rotating packed (2022), https://doi.org/10.1016/j.cjac.2022.100079.
bed with co-precipitation, Mater. Chem. Phys. 240 (2020) 122049, https://doi. [108] M. Pooresmaeil, H. Namazi, Chitosan coated Fe3O4@Cd-MOF microspheres as an
org/10.1016/j.matchemphys.2019.122049. effective adsorbent for the removal of the amoxicillin from aqueous solution, Int.
[86] Y. Zhou, S. Cao, C. Xi, X. Li, L. Zhang, G. Wang, Z. Chen, A novel Fe3O4/graphene J. Biol. Macromol. 191 (2021) 108–117, https://doi.org/10.1016/j.
oxide/citrus peel-derived bio-char based nanocomposite with enhanced ijbiomac.2021.09.071.
adsorption affinity and sensitivity of ciprofloxacin and sparfloxacin, Bioresour. [109] Ö. Kerkez-Kuyumcu, Ş.S. Bayazit, M.A. Salam, Antibiotic amoxicillin removal
Technol. 292 (2019) 121951, https://doi.org/10.1016/j.biortech.2019.121951. from aqueous solution using magnetically modified graphene nanoplatelets,
[87] S.T. Danalıoğlu, Ş.S. Bayazit, Ö. Kerkez Kuyumcu, M.A. Salam, Efficient removal J. Ind. Eng. Chem. 36 (2016) 198–205, https://doi.org/10.1016/j.
of antibiotics by a novel magnetic adsorbent: Magnetic activated carbon/chitosan jiec.2016.01.040.
(MACC) nanocomposite, J. Mol. Liq. 240 (2017) 589–596, https://doi.org/ [110] T. Ai, X. Jiang, Q. Liu, L. Lv, H. Wu, Daptomycin adsorption on magnetic ultra-
10.1016/j.molliq.2017.05.131. fine wood-based biochars from water: Kinetics, isotherms, and mechanism
[88] A. Konwar, A. Gogoi, D. Chowdhury, Magnetic alginate–Fe 3 O 4 hydrogel fiber studies, Bioresour. Technol. 273 (2019) 8–15, https://doi.org/10.1016/j.
capable of ciprofloxacin hydrochloride adsorption/separation in aqueous biortech.2018.10.039.
solution, RSC Adv. 5 (2015) 81573–81582, https://doi.org/10.1039/ [111] A. Mohseni-Bandpi, T.J. Al-Musawi, E. Ghahramani, M. Zarrabi, S. Mohebi, S.
C5RA16404D. A. Vahed, Improvement of zeolite adsorption capacity for cephalexin by coating
[89] H. Mao, S. Wang, J.Y. Lin, Z. Wang, J. Ren, Modification of a magnetic carbon with magnetic Fe3O4 nanoparticles, J. Mol. Liq. 218 (2016) 615–624, https://
composite for ciprofloxacin adsorption, J. Environ. Sci. (China) 49 (2016) doi.org/10.1016/j.molliq.2016.02.092.
179–188, https://doi.org/10.1016/j.jes.2016.05.048. [112] E. Asgari, A. Sheikhmohammadi, J. Yeganeh, Application of the Fe3O4-chitosan
[90] Y.X. Wang, K. Gupta, J.R. Li, B. Yuan, J.C.E. Yang, M.L. Fu, Novel chalcogenide nano-adsorbent for the adsorption of metronidazole from wastewater:
based magnetic adsorbent KMS-1/L-Cystein/Fe3O4 for the facile removal of Optimization, kinetic, thermodynamic and equilibrium studies, Int. J. Biol.
ciprofloxacin from aqueous solution, Colloids Surfaces A Physicochem. Eng. Asp. Macromol. 164 (2020) 694–706, https://doi.org/10.1016/j.
538 (2018) 378–386, https://doi.org/10.1016/j.colsurfa.2017.11.016. ijbiomac.2020.07.188.
[91] S.T. Danalıoğlu, Ş.S. Bayazit, Ö. Kerkez, B.G. Alhogbi, M. Abdel Salam, Removal [113] M. Yegane Badi, A. Azari, H. Pasalari, A. Esrafili, M. Farzadkia, Modification of
of ciprofloxacin from aqueous solution using humic acid- and levulinic acid- activated carbon with magnetic Fe3O4 nanoparticle composite for removal of
coated Fe3O4 nanoparticles, Chem. Eng. Res. Des. 123 (2017) 259–267, https:// ceftriaxone from aquatic solutions, J. Mol. Liq. 261 (2018) 146–154, https://doi.
doi.org/10.1016/j.cherd.2017.05.018. org/10.1016/j.molliq.2018.04.019.
[92] S. Rakshit, D. Sarkar, E.J. Elzinga, P. Punamiya, R. Datta, Mechanisms of [114] S.F. Soares, T. Fernandes, M. Sacramento, T. Trindade, A.L. Daniel-da-Silva,
ciprofloxacin removal by nano-sized magnetite, J. Hazard. Mater. 246–247 Magnetic quaternary chitosan hybrid nanoparticles for the efficient uptake of
(2013) 221–226, https://doi.org/10.1016/j.jhazmat.2012.12.032. diclofenac from water, Carbohydr. Polym. 203 (2019) 35–44, https://doi.org/
[93] V. Arya, L. Philip, Adsorption of pharmaceuticals in water using Fe 3 O 4 coated 10.1016/j.carbpol.2018.09.030.
polymer clay composite, Microporous Mesoporous Mater. 232 (2016) 273–280, [115] J.M.N. dos Santos, C.R. Pereira, E.L. Foletto, G.L. Dotto, Alternative synthesis for
https://doi.org/10.1016/j.micromeso.2016.06.033. ZnFe 2 O 4 /chitosan magnetic particles to remove diclofenac from water by
[94] J. Zhao, G. Liang, X. Zhang, X. Cai, R. Li, X. Xie, Z. Wang, Coating magnetic adsorption, Int. J. Biol. Macromol. 131 (2019) 301–308, https://doi.org/
biochar with humic acid for high efficient removal of fluoroquinolone antibiotics 10.1016/j.ijbiomac.2019.03.079.
in water, Sci. Total Environ. 688 (2019) 1205–1215, https://doi.org/10.1016/j. [116] X.X. Liang, A.M. Omer, Z.-H. Hu, Y. Wang, D.i. Yu, X.-K. Ouyang, Efficient
scitotenv.2019.06.287. adsorption of diclofenac sodium from aqueous solutions using magnetic amine-
[95] A.K. Al-Buriahi, M.M. Al-shaibani, R.M.S.R. Mohamed, A.A. Al-Gheethi, functionalized chitosan, Chemosphere 217 (2019) 270–278.
A. Sharma, N. Ismail, Ciprofloxacin removal from non-clinical environment: A [117] T.M. Salem Attia, X.L. Hu, D.Q. Yin, Synthesized magnetic nanoparticles coated
critical review of current methods and future trend prospects, J. Water Process zeolite for the adsorption of pharmaceutical compounds from aqueous solution
Eng. 47 (2022) 102725, https://doi.org/10.1016/j.jwpe.2022.102725. using batch and column studies, Chemosphere 93 (2013) 2076–2085, https://doi.
[96] S. Aydin, M.E. Aydin, F. Beduk, A. Ulvi, Removal of antibiotics from aqueous org/10.1016/j.chemosphere.2013.07.046.
solution by using magnetic Fe3O4/red mud-nanoparticles, Sci. Total Environ. 670 [118] A.A. Asgharinezhad, N. Mollazadeh, H. Ebrahimzadeh, F. Mirbabaei, N. Shekari,
(2019) 539–546, https://doi.org/10.1016/j.scitotenv.2019.03.205. Magnetic nanoparticles based dispersive micro-solid-phase extraction as a novel
[97] M.E. Mahmoud, S.R. Saad, A.M. El-Ghanam, R.H.A. Mohamed, Developed technique for coextraction of acidic and basic drugs from biological fluids and
magnetic Fe3O4–MoO3-AC nanocomposite for effective removal of ciprofloxacin waste water, J. Chromatogr. A. 1338 (2014) 1–8, https://doi.org/10.1016/j.
from water, Mater. Chem. Phys. 257 (2021) 123454, https://doi.org/10.1016/j. chroma.2014.02.027.
matchemphys.2020.123454. [119] M. Sun, Q. Sun, C. Zhao, Y. Huang, J. Jiang, W. Ding, H. Zheng, Degradation of
[98] F. Wang, B. Yang, H. Wang, Q. Song, F. Tan, Y. Cao, Removal of ciprofloxacin diclofenac sodium with low concentration from aqueous milieu through
from aqueous solution by a magnetic chitosan grafted graphene oxide composite, polydopamine-chitosan modified magnetic adsorbent-assisted photo-Fenton
J. Mol. Liq. 222 (2016) 188–194, https://doi.org/10.1016/j.molliq.2016.07.037. process, Sep. Purif. Technol. 289 (2022) 120771, https://doi.org/10.1016/j.
[99] M.H. Al-Jabari, S. Sulaiman, S. Ali, R. Barakat, A. Mubarak, S.A. Khan, seppur.2022.120771.
Adsorption study of levofloxacin on reusable magnetic nanoparticles: Kinetics [120] L.A. Al-Khateeb, W. Hakami, M. Abdel Salam, J.A. Sanari, R. El-Shaheny, M. El-
and antibacterial activity, J. Mol. Liq. 291 (2019) 111249, https://doi.org/ Maghrabey, Solid phase-fabrication of magnetically separable Fe3O4@graphene
10.1016/j.molliq.2019.111249. nanoplatelets nanocomposite for efficient removal of NSAIDs from wastewater.
[100] A. Ullah, M. Zahoor, S. Alam, R. Ullah, A.S. Alqahtani, H.M. Mahmood, Perception of adsorption kinetics, thermodynamics, and extra-thermodynamics,
Separation of levofloxacin from industry effluents using novel magnetic Anal. Chim. Acta. (2022) 340158, https://doi.org/10.1016/j.aca.2022.340158.
nanocomposite and membranes hybrid processes, Biomed Res. Int. 2019 (2019), [121] A.C. Fröhlich, E.L. Foletto, G.L. Dotto, Preparation and characterization of NiFe 2
https://doi.org/10.1155/2019/5276841. O 4 /activated carbon composite as potential magnetic adsorbent for removal of
[101] Z. Xu, Y. Xiang, H. Zhou, J. Yang, Y. He, Z. Zhu, Y. Zhou, Manganese ferrite ibuprofen and ketoprofen pharmaceuticals from aqueous solutions, J. Clean.
modified biochar from vinasse for enhanced adsorption of levofloxacin: Effects Prod. 229 (2019) 828–837, https://doi.org/10.1016/j.jclepro.2019.05.037.
and mechanisms, Environ. Pollut. 272 (2021) 115968, https://doi.org/10.1016/j. [122] P.W. Seo, B.N. Bhadra, I. Ahmed, N.A. Khan, S.H. Jhung, Adsorptive removal of
envpol.2020.115968. pharmaceuticals and personal care products from water with functionalized
[102] Z. Hu, M. Ge, C. Guo, Efficient removal of levofloxacin from different water metal-organic frameworks: remarkable adsorbents with hydrogen-bonding
matrices via simultaneous adsorption and photocatalysis using a magnetic abilities, Sci. Rep. 6 (2016) 1–11, https://doi.org/10.1038/srep34462.
Ag3PO4/rGO/CoFe2O4 catalyst, Chemosphere 268 (2021) 128834, https://doi. [123] S. Chandrashekar Kollarahithlu, R.M. Balakrishnan, Adsorption of
org/10.1016/j.chemosphere.2020.128834. pharmaceuticals pollutants, Ibuprofen, Acetaminophen, and Streptomycin from
[103] B. Yao, Z. Luo, S. Du, J. Yang, D. Zhi, Y. Zhou, Sustainable biochar/MgFe2O4 the aqueous phase using amine functionalized superparamagnetic silica
adsorbent for levofloxacin removal: Adsorption performances and mechanisms, nanocomposite, J. Clean. Prod. 294 (2021) 126155, https://doi.org/10.1016/j.
Bioresour. Technol. 340 (2021) 125698, https://doi.org/10.1016/j. jclepro.2021.126155.
biortech.2021.125698. [124] A.S. Liyanage, S. Canaday, C.U. Pittman, T. Mlsna, Rapid remediation of
[104] S. Altaf, R. Zafar, W.Q. Zaman, S. Ahmad, K. Yaqoob, A. Syed, A.J. Khan, M. Bilal, pharmaceuticals from wastewater using magnetic Fe3O4/Douglas fir biochar
M. Arshad, Removal of levofloxacin from aqueous solution by green synthesized adsorbents, Chemosphere 258 (2020) 127336, https://doi.org/10.1016/j.
magnetite (Fe3O4) nanoparticles using Moringa olifera: Kinetics and reaction chemosphere.2020.127336.
mechanism analysis, Ecotoxicol. Environ. Saf. 226 (2021) 112826, https://doi. [125] G. Wu, Q. Liu, J. Wang, S. Xia, H. Wu, J. Zong, J. Han, W. Xing, Facile fabrication
org/10.1016/j.ecoenv.2021.112826. of rape straw biomass fiber/β-CD/Fe3O4 as adsorbent for effective removal of
21
ibuprofen, Ind. Crops Prod. 173 (2021) 114150, https://doi.org/10.1016/j. frameworks employing D-optimal mixture design, water environ, Res. 92 (2020)
indcrop.2021.114150. 1935–1947, https://doi.org/10.1002/wer.1346.
[126] E.A. Moacǎ, C.V. Mihali, I.G. Macaşoi, R. Racoviceanu, C. Şoica, C.A. Dehelean, [142] M. Zahoor, A. Ullah, S. Alam, Removal of enrofloxacin from water through
C. Pǎcurariu, S. Florescu, Fe3O4@C matrix with tailorable adsorption capacities magnetic nanocomposites prepared from pineapple waste biomass, Surf. Eng.
for paracetamol and acetylsalicylic acid: Synthesis, characterization, and kinetic Appl. Electrochem. 55 (2019) 536–547, https://doi.org/10.3103/
modeling, Molecules 24 (2019), https://doi.org/10.3390/molecules24091727. S1068375519050156.
[127] Y. Shi, Y. Zhang, Y. Cui, J. Shi, X. Meng, J. Zhang, H. He, Magnetite nanoparticles [143] M. Sui, Y. Zhou, L. Sheng, B. Duan, Adsorption of norfloxacin in aqueous solution
modified β-cyclodextrin PolymerCoupled with KMnO4 oxidation for adsorption by Mg–Al layered double hydroxides with variable metal composition and
and degradation of acetaminophen, Carbohydr. Polym. 222 (2019) 114972, interlayer anions, Chem. Eng. J. 210 (2012) 451–460, https://doi.org/10.1016/j.
https://doi.org/10.1016/j.carbpol.2019.114972. cej.2012.09.026.
[128] R. Natarajan, S. Venkataraman, D.S. Rajendran, B. Tamilselvam, H. Zaveri, [144] I. Anastopoulos, I. Pashalidis, A.G. Orfanos, I.D. Manariotis, T. Tatarchuk,
N. Jeyachandran, H. Prashar, V.K. Vaidyanathan, Adsorption performance of L. Sellaoui, A. Bonilla-Petriciolet, A. Mittal, A. Núñez-Delgado, Removal of
magnetic mesoporous silica microsphere support toward the remediation of caffeine, nicotine and amoxicillin from (waste)waters by various adsorbents. A
acetaminophen from aqueous solution, J. Water Process Eng. 48 (2022) 102835, review, J. Environ. Manage. 261 (2020), https://doi.org/10.1016/j.
https://doi.org/10.1016/j.jwpe.2022.102835. jenvman.2020.110236.
[129] R. Natarajan, M. Anil Kumar, V.K. Vaidyanathan, Synthesis and characterization [145] C. Homsirikamol, N. Sunsandee, U. Pancharoen, K. Nootong, Synergistic
of rhamnolipid based chitosan magnetic nanosorbents for the removal of extraction of amoxicillin from aqueous solution by using binary mixtures of
acetaminophen from aqueous solution, Chemosphere 288 (2022) 132532, Aliquat 336, D2EHPA and TBP, Sep. Purif. Technol. 162 (2016) 30–36, https://
https://doi.org/10.1016/j.chemosphere.2021.132532. doi.org/10.1016/j.seppur.2016.02.003.
[130] M. Ghoochian, H.A. Panahi, S. Sobhanardakani, L. Taghavi, A.H. Hassani, [146] K. Cave, I. Gould, Daptomycin, Compr. Pharmacol., Elsevier, in, 2022,
Synthesis and application of Fe3O4/SiO2/thermosensitive/PAMAM-CS pp. 106–122.
nanoparticles as a novel adsorbent for removal of tamoxifen from water samples, [147] J. Qiu, L. Yu, L.E. Kirsch, Estimated pKa values for specific amino acid residues in
Microchem. J. 145 (2019) 1231–1240, https://doi.org/10.1016/j. daptomycin, J. Pharm. Sci. 100 (2011) 4225–4233, https://doi.org/10.1002/
microc.2018.12.004. jps.22608.
[131] P. Yadav, A. Yadav, P.K. Labhasetwar, Sustainable adsorptive removal of [148] N. Gregoire, A. Chauzy, J. Buyck, B. Rammaert, W. Couet, S. Marchand, Clinical
antibiotics from aqueous streams using Fe3O4-functionalized MIL101(Fe) pharmacokinetics of daptomycin, Clin. Pharmacokinet. 60 (2021) 271–281,
chitosan composite beads, Environ. Sci. Pollut. Res. 29 (2022) 37204–37217, https://doi.org/10.1007/s40262-020-00968-x.
https://doi.org/10.1007/s11356-021-18385-3. [149] S.N. Oba, J.O. Ighalo, C.O. Aniagor, C.A. Igwegbe, Removal of ibuprofen from
[132] A. Parashar, S. Sikarwar, R. Jain, Removal of pharmaceuticals from wastewater aqueous media by adsorption: A comprehensive review, Sci. Total Environ. 780
using magnetic iron oxide nanoparticles (IOPs), Int. J. Environ. Anal. Chem. 102 (2021) 146608, https://doi.org/10.1016/j.scitotenv.2021.146608.
(2022) 117–133, https://doi.org/10.1080/03067319.2020.1716977. [150] G. Zhang, S. Li, C. Shuang, Y. Mu, A. Li, L. Tan, The effect of incorporating
[133] S. Gaur, A.M. Bal, T. Morgannwg, R.G. Hospital, R.C. Taf, Tetracyclines 7 (2022) inorganic materials into quaternized polyacrylic polymer on its mechanical
136–153, https://doi.org/10.1016/B978-0-12-820472-6.00185-7. strength and adsorption behaviour for ibuprofen removal, Sci. Rep. 10 (2020)
[134] A. Rusu, E.L. Buta, The development of third-generation tetracycline antibiotics 5188, https://doi.org/10.1038/s41598-020-62153-1.
and new perspectives, Pharmaceutics. 13 (2021) 2085, https://doi.org/10.3390/ [151] L.M. Soltys, I.F. Mironyuk, T.R. Tatarchuk, V.I. Tsinurchyn, Zeolite-based
pharmaceutics13122085. composites as slow release fertilizers (review), Phys. Chem. Solid State. 21 (2020)
[135] L. Ge, Q. Dong, C. Halsall, C.E.L. Chen, J. Li, D. Wang, P. Zhang, Z. Yao, Aqueous 89–104, https://doi.org/10.15330/pcss.21.1.89-104.
multivariate phototransformation kinetics of dissociated tetracycline: [152] C. Martinez-Boubeta, K. Simeonidis, Magnetic nanoparticles for water
implications for the photochemical fate in surface waters, Environ. Sci. Pollut. purification, Nanoscale Mater. Water Purif., Elsevier, in, 2019, pp. 521–552.
Res. 25 (2018) 15726–15732, https://doi.org/10.1007/s11356-018-1765-0. [153] P.R. Yaashikaa, P.S. Kumar, Fabrication and characterization of magnetic
[136] D. Sparkes, D.A. Enoch, C. Microbiology, I. Diseases, Quinolones 7 (2022) nanomaterials for the removal of toxic pollutants from water environment: A
240–254, https://doi.org/10.1016/B978-0-12-820472-6.00171-7. review, Chemosphere 303 (2022) 135067, https://doi.org/10.1016/j.
[137] D.A. Palacio, B.L. Rivas, B.F. Urbano, Ultrafiltration membranes with three water- chemosphere.2022.135067.
soluble polyelectrolyte copolymers to remove ciprofloxacin from aqueous [154] Y. Zhang, Z. Jiao, Y. Hu, S. Lv, H. Fan, Y. Zeng, J. Hu, M. Wang, Removal of
systems, Chem. Eng. J. 351 (2018) 85–93, https://doi.org/10.1016/j. tetracycline and oxytetracycline from water by magnetic Fe3O4@graphene,
cej.2018.06.099. Environ. Sci. Pollut. Res. 24 (2017) 2987–2995, https://doi.org/10.1007/s11356-
[138] M.E. Roca Jalil, M. Baschini, K. Sapag, Influence of pH and antibiotic solubility on 016-7964-7.
the removal of ciprofloxacin from aqueous media using montmorillonite, Appl. [155] P.S. Pauletto, S.F. Lütke, G.L. Dotto, N.P.G. Salau, Adsorption mechanisms of
Clay Sci. 114 (2015) 69–76, https://doi.org/10.1016/j.clay.2015.05.010. single and simultaneous removal of pharmaceutical compounds onto activated
[139] S. Wang, Z. Wang, C. Hao, W.J.G.M. Peijnenburg, DFT/TDDFT insights into carbon: Isotherm and thermodynamic modeling, J. Mol. Liq. 336 (2021) 116203,
effects of dissociation and metal complexation on photochemical behavior of https://doi.org/10.1016/j.molliq.2021.116203.
enrofloxacin in water, Environ. Sci. Pollut. Res. 25 (2018) 30609–30616, https:// [156] S. Uebele, T. Goetz, M. Ulbricht, T. Schiestel, Mixed-matrix membrane adsorbers
doi.org/10.1007/s11356-018-3032-9. for the simultaneous removal of different pharmaceutical micropollutants from
[140] R. Li, Z. Wang, X. Zhao, X. Li, X. Xie, Magnetic biochar-based manganese oxide water, ACS Appl. Polym. Mater. 4 (2022) 1705–1716, https://doi.org/10.1021/
composite for enhanced fluoroquinolone antibiotic removal from water, Environ. acsapm.1c01546.
Sci. Pollut. Res. 25 (2018) 31136–31148, https://doi.org/10.1007/s11356-018- [157] M. Zhai, B. Fu, Y. Zhai, W. Wang, A. Maroney, A.A. Keller, H. Wang, J.-
3064-1. M. Chovelon, Simultaneous removal of pharmaceuticals and heavy metals from
[141] Z. Gordi, M. Ghorbani, M. Ahmadian Khakhiyani, Adsorptive removal of aqueous phase via adsorptive strategy: A critical review, Water Res. 236 (2023)
enrofloxacin with magnetic functionalized graphene oxide@ metal–organic 119924, https://doi.org/10.1016/j.watres.2023.119924.
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Journal of Molecular Liquids 384 (2023) 122174

Contents lists available at ScienceDirect

Journal of Molecular Liquids

Magnetic adsorbents for removal of pharmaceuticals: A review of

1. Introduction decomposition by putrefactive bacteria and fungi [2]. During decom­

compounds in the environment leads to microflora and fauna damage.

Fig. 1. Ways of environmental pollution by pharmaceuticals.

Fig. 5. Various types of adsorbent-adsorbate interactions at surfaces of magnetic adsorbents.

Fig. 6. Structures of the most common antibiotics.

Journal of Molecular Liquids 384 (2023) 122174

fluoroquinolones. Levofloxacin is active against gram-positive and

best removal efficiency was observed at pH 6.5 and achieved 80.2%.

increase in pH, which is related to the electrostatic repulsion of the same

ferrite-modified biochar to remove levofloxacin. Hydrogen bonds in­

fluence the adsorption process. It was shown that oxygen-containing

the presence of –OH and –COOH groups on the biochar surface

In addition, the adsorption was enhanced by π-π electron-

donor–acceptor interactions and H-bonds. The iron and magnesium

atoms act as active adsorption centers, promoting levofloxacin adsorp­

enrofloxacin contains the dissociating groups –COOH and –NHn, which

composite. The maximum adsorption capacity of 163 mg/g was ach­

ieved. Good adsorption properties were associated with electrostatic

R. Li et al. [140] synthesized a composite of manganese oxide based

on magnetic biochar and untreated biochar for enrofloxacin removal.

The maximum adsorption capacity of the magnetic nanocomposite was

7.19 mg/g. The adsorption capacity decreased with solution pH

Magnetic chitosan grafted graphene oxide nanocomposite

(0.001–0.1 M). Z. Gordi et al. [141] synthesized an adsorbent based on a

enrofloxacin removal. The maximum adsorption capacity was 345 mg/

g. As the solution pH increased to 7.5, the efficiency of enrofloxacin

removal increased, and above pH = 7.5, it decreased (pKa values of

adsorption mode was the electrostatic interaction. M. Zahoor et al. [142]

used magnetic carbon nanocomposites to remove enrofloxacin from

industrial wastewater. The maximum adsorption efficiency was

magnetic adsorbent and the dissociated form of enrofloxacin in the so­

signs under acidic or alkaline conditions and electrostatic repulsion

forces hinder the adsorption capacity.

Fig. 11. Formulas of the common non-steroidal anti-inflammatory drugs.

Fe3O4@SiO2/SiHTCC (N-(2- Langmuir 240 6 300 298 40 10 mg 60 [114]

Magnetic genipin-crosslinked PSO, 138 6 120 308 10 5 mg 85 [69]

from wastewater. the main advantages of magnetically susceptible adsorbents, compared

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1. Introduction decomposition by putrefactive bacteria and fungi [2]. During decom

ferrite-modified biochar to remove levofloxacin. Hydrogen bonds in

atoms act as active adsorption centers, promoting levofloxacin adsorp

composite. The maximum adsorption capacity of 163 mg/g was ach

magnetic adsorbent and the dissociated form of enrofloxacin in the so