Chemical Papers

https://doi.org/10.1007/s11696-021-01637-4

ORIGINAL PAPER

Experimental and modeling study on adsorption of emerging

contaminants onto hyper‑crosslinked cellulose
Sarra Benosmane1 · Meriem Bendjelloul1,2 · El Hadj Elandaloussi2   · Moufida Touhami3 ·
Louis‑Charles de Ménorval4

Received: 3 March 2021 / Accepted: 31 March 2021

© Institute of Chemistry, Slovak Academy of Sciences 2021

Abstract
The primary objective of this study was to synthesize a novel hyper-crosslinked cellulosic adsorbent (CLC) by a straight-
forward one-pot esterification reaction using cellulose and sebacoyl chloride as crosslinker agent. Efficient crosslinking of
cellulose was confirmed by FTIR, CPMAS 13C NMR, elemental analysis, TGA, SEM and BET surface area analysis. The
CLC material with high content of ester groups was employed to remove paracetamol (PCT) and niflumic acid (NFA) from
aqueous solutions in batch adsorption experiments. The mesoporous structure of CLC created upon crosslinking was found
to be a determinant in the adsorption behavior of the drugs. Indeed, PCT and NFA adsorption isotherms onto CLC were
S-shaped and were adjusted by the Gu–Zhu, Frumkin–Fowler–Guggenheim and Hill–de Boer models. From the GZ isotherm
model, the results indicate a cooperative adsorption mechanism leading to the formation of aggregates containing 2.53 and
4.25 molecules of PCT and NFA, respectively. Furthermore, FFG and HdB models reflect that the lateral interactions are
attractive in nature for both drugs. The experimental kinetic data were fitted to the pseudo-second-order and intraparticle
diffusion models, and the obtained parameters were linked to the aggregates arrangement of the drugs.

Keywords  Crosslinked cellulose · Niflumic acid · S-type isotherm · Cooperative adsorption · Adsorption kinetics

Introduction effluents of wastewater treatment plants (WWTPs) and sur-

Over the past decades, the scientific community has become
increasingly concerned about the potential problems related
to water pollution by emerging pollutants (EPs). Among
them, pharmaceuticals and personal care products (PPCPs)
are detected at concentrations of mg/L or below in secondary
* El Hadj Elandaloussi
elhadj.elandaloussi@univ-relizane.dz;
andalou777@yahoo.com
1
Laboratoire de Valorisation des Matériaux, Université
Abdelhamid Ibn Badis, B.P. 227, 27000 Mostaganem,
Algeria
2
Department of Chemistry, Faculty of Sciences
and Technology, Ahmed Zabana University-Relizane,
48000 Relizane, Algeria
3
Modeling and Calculation Methods Laboratory, Moulay
Tahar University, 20000 Saida, Algeria
4
ICG–AIME–UMR 5253, Université Montpellier 2, Place
Eugène Bataillon CC 1502, 34095 Montpellier Cedex 05,
France
face water worldwide (Larsson et al. 2007; Miege et al.
2009; Joss et al. 2006; Sim et al. 2011).
Current research emphasizes on the design and develop-
ment of materials able to remove a large variety of chemicals
from wastewater effluents and natural water compartments.
In this context, adsorption is considered a promising alter-
native as it removes a wide variety of organic and inorganic
compounds and generates less toxic products than many
other remediation methods (Rivera-Utrilla et  al. 2013).
Thus, biological adsorbents, activated carbons, lignocellu-
losic wastes, polymer resins, and other solids have been suc-
cessfully applied for pharmaceutical removal from aqueous
solutions (Escapa et al. 2017; Streit et al. 2021; Nourmo-
radi et al. 2018; Bahamon and Vega 2017; Boudrahem et al.
2017; Ferreira et al. 2015; Thakur et al. 2020; Villaescusa
et al. 2011; Robberson et al. 2006; Menk et al. 2019).
In recent years, biopolymers such as cellulose have been
thoroughly investigated in the removal of pollutants from
water owing to their wide availability, biodegradability, low
cost, low toxicity, regenerability, and lower sludge genera-
tion compared to many other processes (Bhatnagar et al.

13
Vol.:(0123456789)

2015; Hokkanen et al. 2016). Moreover, chemical modi-
fication of cellulose, especially esterification by means of
anhydrides or acid chlorides, is an appealing approach that
allows the synthesis of materials with desired functionalities
designed for a significant enhancement of the adsorption
capacity (Li et al. 2019a, b; Wang 2019; Ji et al. 2019; Zhou
et al. 2015).
To date and to the best of our knowledge, literature relat-
ing functionalized cellulose as adsorbent materials for phar-
maceuticals removal is very scarce. Nonetheless, Selkälä
et al. (2018) have recently reported the use of anionic cel-
lulose nanofibrils for the removal of pharmaceutical salbu-
tamol from aqueous solutions.
Taking into account the abundant surface hydroxyl groups
on cellulose, polyesterification by means of a diacid chloride
could be an effective method to introduce plenty of adsorp-
tion sites on the resulting crosslinked material. We hypothe-
sized that the incorporation of ester sites within the polymer
framework should provide an excellent sorption property
involving weak van der Waals interactions and hydrogen
bonding, especially for nonionic pharmaceutical pollut-
ants. For this study, paracetamol (PCT) and niflumic acid
(NFA) were chosen as model nonsteroidal anti-inflammatory
drugs (NSAIDs) due to their wide use (Coelho et al. 2010).
Because of its relative high solubility and hydrophilicity,
paracetamol (PCT) among other drugs is of recent concern
due to its persistence in the environment which indicates its
incomplete removal by the conventional processes applied
in WWTPs (Petrie et al. 2015; Franca et al. 2016; Xiong and
Hu 2017). Although, niflumic acid (NFA), a widely used
NSAID, is also enlisted among the EPs of possible concern
(Mila et al. 2019; Ibanez et al. 2016; Alygizakis et al. 2016),
it has not been extensively studied so far. Besides, to the
best of our knowledge, there is lack of relevant report on the
removal of niflumic acid through adsorption in the literature,
which limits the comparison of our results to the work of
others. The molecular structures of these pharmaceuticals
along with some of their physicochemical properties are
depicted in Table 1.
Table 1  Molecular structures and properties of selected pharmaceuticals
Compound Molecular structure Molecular weight λmax (nm)
Paracetamol (PCT) H 151.16
N
O
HO
Niflumic acid (NFA) CO2 H 282.22
H 286 (pH 6.8)
F3 C N 288 (Ethanol)
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Chemical Papers
Herein, we developed an efficient and simple one-step
procedure to prepare a highly crosslinked cellulose CLC for
the removal of targeted pharmaceuticals. The CLC material
can be easily synthesized by a simple chemical crosslinking
method since cellulose contains abundant hydroxyl groups
which can be crosslinked with each other by means of seba-
coyl chloride (ClOC–(CH2)8–COCl) as crosslinker agent.
The as-prepared adsorbent material was fully characterized
and evaluated for its sorption capacity of PCT and NFA
drugs. In addition, the surface functional group coverage
along with the morphology and porosity of CLC material
were investigated to identify the sorption mechanism of the
pharmaceuticals removal.
Experimental
Chemicals
Cellulose was kindly provided by a local sugar factory.
The material is used in sugar refining process as filter aid.
Paracetamol (PCT) and niflumic acid (NFA) were kindly
provided by Saidal pharmaceutical group (Oran, Algeria).
All others chemicals were analytical reagent grade and were
used without further purification.
Synthesis of CLC
The crosslinking reaction was carried out using 8.1  g
(50 mmol) of cellulose pre-swollen for 8 h in 150 mL of
dry pyridine. The crosslinking agent (5.98 g of sebacoyl
chloride, 25 mmol) in 10 mL of pyridine was then slowly
added to the slurry cooled in an ice bath. After allowing the
mixture to come to room temperature, it was then heated at
80 °C for 8 h. On cooling, the hypercrosslinked polymer was
collected by filtration and washed with methanol, 0.5 mol/L
HCl in acetone, and again with methanol. The material was
then dried in an electric drying oven at 100 °C for 24 h and
pKa Molecular Size (nm)
(length × height × width)
243 (pH 1.2–10.0) 9.52 (Box and Comer. 1.16 × 0.7 × 0.41
2008)
254 (pH 1.2) 2.26, 4.44 (Box et al. 1.32 × 0.94 × 0.5
2006)
Chemical Papers
passed through a 250-μm sieve to afford 11.27 g of CLC as
an off-white solid.
Characterization techniques
The following characterization methods were used for the
chemical analysis of the CLC sorbent. The Fourier trans-
form infrared (FTIR) spectra were collected using a Nico-
let Avatar 330 Fourier transform IR spectrometer. The 13C
cross-polarization magic angle spinning nuclear magnetic
resonance (CP/MAS NMR) spectra were recorded on a
Bruker 300 (Digital NMR Avance) spectrometer. The N ­ 2
adsorption–desorption experiments at 77 K were carried out
using a Micromeritics Tristar 3000. Prior to the analysis,
CLC sample was first treated to desorption at reduced pres-
sure (< ­10−2 Torr) at 150 °C for 5 h. The specific surface
area (SSA) was calculated using the BET method based on
the adsorption isotherm and pore size, and pore volume val-
ues were calculated using the BJH method on desorption
isotherm branch. The morphology of the crosslinked poly-
mer was examined at high magnification using a HITACHI
S-4800 SEM. High-resolution transmission electron micros-
copy (HR-TEM) image of CLC was collected using a JEM-
3010 (JEOL, Japan). The thermal stability of the samples
was performed using TGA on a NETZSCHSTA 409 PC/PG
simultaneous thermal analyzer at a heating rate of 10 °C/min
under nitrogen atmosphere.
Adsorption experiments
A series of adsorption experiments were conducted by pre-
paring solutions of pharmaceutical compounds in distilled
water or buffer solutions at different initial concentrations
ranging from 0 to 100 mg/L. Stock solution of PCT (100 mg
­L−1) was prepared by dissolving the drug in distilled water
and subsequently diluted to the required concentrations. For
the sparingly water-soluble NFA drug, aqueous solutions of
10–100 mg ­L−1 were prepared by using either 0.1 M HCl
(pH 1.2), buffer solution (pH 1.2) or phosphate buffer (pH
6.8), under vigorous stirring for 4–6 h to ensure complete
dissolution of the drug. When required, PCT solutions of
desired pH values were made by adjustment using 0.1 M
HCl or NaOH solutions. Buffer solution at pH 1.2 was
prepared by mixing 25 mL of 0.2 M sodium chloride with
42.5 mL of 0.2 M of hydrochloric acid. Prior to make up the
volume to 200 mL, the final pH value was adjusted. Buffer at
pH 6.8 was prepared mixing 125 mL of a potassium dibasic
phosphate (0.1 M) with 14 mL sodium hydroxide (0.1 M);
the final pH value was adjusted either with HCl or sodium
hydroxide as required.
The removal of PCT and NFA by CLC sorbent was
investigated in batch experiments by stirring 50 mg of CLC
material with 50 mL of pharmaceuticals solutions in 200-
mL stoppered glass bottles equipped with magnetic stirring
bars. All studies were conducted at room temperature on a
stirring plate adjusted to a 100 rpm stirring rate for 60 min.
The drugs concentrations were measured with a HACH
DR4000U UV–visible spectrophotometer at 243 and 286 nm
for PCT and NFA, respectively. The sorbed amounts of phar-
maceuticals were determined from the difference between
the initial and final concentrations by the following mass
balance equation:
( )
Ci − Ce × V
qe = (1)
w
where qe is the amount (mg g­ −1) of drug sorbed, Ci and Ce
are the initial and equilibrium drug concentrations (mg L ­ −1)
in solution, respectively, V is the adsorbate volume (L) and
w is the sorbent weight (g).
To optimize the variables affecting the drugs adsorption,
the effects of pH were investigated during 60 min at 20 ± 2 °C.
Experiments with each drug were performed to determine the
effect of pH on drug removal. The pH range studied was from
1.2 to 10. The sample mass was 50 mg, and drug concentration
was 30 mg ­L−1 (50 mL) in this series of tests. The maximum
absorption wavelength of PCT was determined as equal to
243 nm. At this wavelength, spectra of PCT were found not to
vary in the pH range (1.2–10.0). For NFA, λmax shifted from
254 nm at pH 1.2–286 nm at pH 6.8. The kinetic measure-
ments were carried out with similar equipment and conditions.
The sorbent mass was 50 mg, and the volume of the drug
solution was 50 mL (30 mg L ­ −1) in this series of tests. The
mixtures were stirred at predetermined intervals of time and
were drawn for drug concentration analysis. Each isotherm
consisted of 10 drugs concentrations varied from 10 to 100 mg
­L−1. The equilibrium concentrations of different combinations
were measured by the spectrophotometer and referenced with
the calibration curves. Drugs saturated CLC that remained
after centrifugation in the adsorption assays (for 100 mg ­L−1
initial drugs concentrations) were used for further desorption
studies. The recovered materials were washed with distilled
water, air-dried, and then suspended in 20 mL of aqueous HCl
solutions (pH 1.2 for NFA and pH 4 for PCT), and thoroughly
stirred during 30 min. Afterward, they were centrifuged for
adsorbate determination in the supernatant. The influence of
temperature on the removal process was studied at three dif-
ferent temperatures (25, 35 and 45 °C) with CLC suspensions
in PCT and NFA solutions (30 mg L ­ −1). The suspensions were
stirred during 60 min, and then the drugs concentrations were
analyzed.
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 Chemical Papers

Modeling of PCT and NFA adsorption OH C-H CH2 C=O C-H C-O C-H

}
----
2848 ----

----
----

----
3456 ----

3040 ----
2930 ----

1710 ----
3348 ----

----
1320

1063
1164

920
1112
Adsorption kinetic and isotherm models

Transmittance (a.u.)
The control mechanism of the adsorption process of PCT
and NFA onto the CLC was evaluated using nonlinear
and linear kinetic equations. Therefore, three widely used
kinetic models including pseudo-first order, pseudo-second
order, and intraparticle diffusion were applied to analyze
the obtained data of adsorption experiments. Additionally,
three adsorption isotherm models, viz. Gu–Zhu, Frum-
kin–Fowler–Guggenheim and Hill–de Boer, have been used
to describe the equilibrium adsorption of pharmaceuticals Cellulose
in the present study. CLC

3500 3000 2500 2000 1500 1000 500

Fitness of kinetic and isotherm models Wavenumbers (cm ) -1

To select the most suitable kinetic and isotherm models, it Fig. 1  FTIR spectra of cellulose and CLC
is necessary to evaluate their validity. Therefore, in this
study, apart from the correlation coefficient (R 2), the
adjusted determination factor ( R2adj ) and the root-mean- Table 2  Elemental analyses of cellulose and crosslinked cellulose

square error (RMSE) were also used as criteria for the good-
ness of fit between the experimental and predicted data.
These functions have been used previously (Babaei et al.
2016; Ciğeroğlu et al. 2021) and are given as:
�
∑n � �2
qi,exp − qi,cal
RMSE =
i=1 (2)
n to the stretching vibration of C=O bonds of ester groups.
( )
) n−1
R2adj = 1 − 1 − R2 (3)
(
n−p
where R2 is the correlation coefficient, qi,calc is each value of
q predicted by the fitted model, qi,exp is each value of q meas-
ured experimentally, n is the number of experiments per-
formed, and p is the number of parameters of the fitted
model. The smaller RMSE value and the R2adj value close to
one suggest the best and the most valid model.
Results and discussion
Characterization of CLC sorbent
The CLC material was analyzed using a series of charac-
terization techniques to confirm the structure of chemical
functional groups resulting from the crosslinking reaction.
Figure 1 shows FTIR spectra of precursor cellulose and
the synthesized crosslinked cellulose material. Compared
to the precursor sample, CLC spectrum showed distinctive
intense absorption band at 1710 ­cm−1, which corresponds
Samples Elemental analysis (wt %)
O/C C O H
Cellulose 1.16 43.24 50.41 6.35
CLC 0.58 59.28 34.75 5.97
The increasing intensities of the symmetric (2848 ­cm−1) and
asymmetric (2930 ­cm−1) ­CH2 stretching vibrations as well
as the increase in the out-of-plane bending vibrations of the
­CH2 (719 ­cm−1) and the in-plane bending vibrations of the
C−H bonds (1469 ­cm−1) also reflect the occurrence of the
esterification reaction between cellulose hydroxyl groups
and sebacoyl chloride. These observations are in agree-
ment with previous work dealing with cellulose esters (Li
et al. 2019a; Jandura et al 2000). Furthermore, the extinc-
tion of the low intensity band at 1640 ­cm−1 is indicative of
a decrease in water content from cellulose precursor after
esterification. On the other hand, the decrease in intensities
of bands at 1112, 1063 and 1032 ­cm−1 originated from the
vibrations of the C−O bonds of alcohols bound to carbon
2, 3 and 6 of cellulose suggested that the esterification is
not selective and that sebacoyl chloride reacts equally easily
with primary and secondary alcohols.
In addition, elemental analyses revealed that the carbon
content of the cellulose precursor was lower than that of
the theoretical values for cellulose, ­C6H10O5, which is indu-
bitably attributed to the water content of the microfibrils.
Moreover, as can be seen in Table 2, the smaller O/C ratio
found for the crosslinked cellulose is attributed to the 8
methylene groups of the coupling agent, resulting in higher

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carbon content. These results give a clear evidence for the (a) TGA Cellulose DTG Cellulose
occurrence of esterification reaction. 100
TGA CLC DTG CLC
0
The solid-state 13C-NMR spectra of cellulose sample
and synthesized crosslinked cellulose polyester are shown 80

in Fig. 2. The spectrum of unmodified cellulose shows sig-

dW/dt (%/min)
Weight (%)
nals of the six carbon atoms of the glucose unit which were 60

assigned according to the literature (Foston et al. 2011;

40 -5
Larsson et al. 1995), while CLC spectrum shows additional
peaks. One peak at 176 ppm is due to the resonance of
20
carbonyl groups and other peaks at 26–35 ppm, which are
attributed to the 8 methylene carbons of sebacoyl linkers. 0
The thermal stability of the synthesized CLC and its pre- -10
cursor were studied by TGA, the TG curves and their first 0 100 200 300 400 500
derivatives are shown in Fig. 3a. Upon initial heating, the Temperature (°C)
gradual weight loss of both materials (8–10%) proceeded
around 50–60 °C, which is probably due to the loss of physi- (b) 14 Cellulose 320 °C
448 °C

---------------------------
cally adsorbed water from cellulose and CLC. For the lat- CLC
ter material, this weight loss could also be attributed to the 12

----------------------------------------
495 °C

Heat flow(mW mg-1)

evaporation of residual solvent entrapped in the polymer 10
network from the reaction workup. Moreover, the com-
bustion profiles of the samples indicated a higher thermal 8

stability for cellulose than the crosslinked cellulose. After 6

100 °C, thermal analysis showed that cellulose and CLC
exhibit two major weight-loss stages. Cellulose showed its 4
330 °C
maximum rate of weight loss at 312 °C, whereas the effect 2
of crosslinking was apparent for CLC whose maximum rate
of weight loss was displayed at 290 °C. During this stage, 0

the cellulose and CLC were almost completely burnt out 0 100 200 300 400 500

because of the destruction of the crystalline structure and Temperature (°C)

oxidative thermal degradation. The decreased temperature
Fig. 3  a TGA responses of cellulose and CLC at a rate of 10 °C/min,
in nitrogen and their derivatives, b differential scanning calorimetry
analyses of cellulose and CLC

at which the maximum rate of weight loss was observed

Fig. 2  Solid state CPMAS 13C NMR spectra of cellulose and CLC
indicates decreased thermal stability, which may be attrib-
uted to the degradation nature of the chemically modified
cellulose. Thus, increasing the carbon content brought about
a decrease in the decomposition temperature of crosslinked
cellulose material. Therefore, during the thermal degrada-
tion process, sebacoyl linkers could be released at much
lower temperatures. TGA data showed that some residual
materials remained for both samples after heating to the
highest temperature (600 °C). The higher weight residue
of crosslinked cellulose was probably due to the grafted
sebacoyl linkers. Similarly, on the differential scanning
calorimetry analysis (Fig. 3b), a lighter exothermic release
at about 50 °C was observed for CLC, which corresponds
to the elimination of either adsorbed water and or residual
solvent entrapped in the polymer network. A second exo-
thermic peak was observed at 320 °C for CLC. Thus, it is
very likely that the polymeric network of CLC undergoes
a partial fusion during the thermal decomposition, unlike

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pure cellulose. Likewise, the exothermic peak of cellulose

observed at 330 °C was found after chemical functionali-
zation. The last exothermic peak observed at 495 °C cor-
responds to the onset of decomposition of the crosslinked
cellulose and the formation of residual char.
The morphology of the crosslinked cellulose was
assessed by scanning electron microscopy (SEM). A highly
porous structure consisting of aggregated fibrils assembled
into an interconnected structure forming a continuous three-
dimensional network (Fig. 4a, b). The images also show
pores of various sizes and many larger open cavities. The
images show irregularly distributed pores of different sizes
and shapes bound together in a three-dimensional network.
The random orientation of the pores within the polymer net-
work suggests that growth defects occur due to steric crowd-
ing within the sebacoyl linkers (Bendjelloul et al. 2017).
As shown in Fig. 4c, the TEM micrograph confirms the
Fig. 5  N2 adsorption–desorption isotherms curves measured at 77 K
mesoporous structure of CLC polymer. for CLC and Barret, Joyner, and Halenda (BJH) pore size distribution
To further confirming the inner architecture of the (inset)
crosslinked cellulose, nitrogen adsorption–desorption iso-
therms were carried out to quantify the surface area (SBET).
As shown in Fig. 5, a classical type IV isotherm with type CLC surface can be either positively or negatively charged.
H2 hysteresis is observed, suggesting the presence of PCT as a weak electrolyte (­ pKa ~ 9.52) is not dissociated
mesopores within the synthesized CLC material. below pH 9.52; therefore, the steady adsorption rate cannot
A Brunauer–Emmett–Teller (BET) surface area (SBET) of be related to electrostatic interactions between the CLC sur-
148 ­m2 ­g−1 and a pore volume of 0.70 c­ m3·g−1 are obtained face and PCT molecules. Besides, the crosslinked polymer is
for CLC. The Barret, Joyner, and Halenda (BJH) pore size nonionic and mainly composed of ester and hydroxyl polar
distribution is shown in Fig. 5 (inset). A sharp peak around groups which could play a dominant role in adsorption by
27 nm is observed, strongly suggesting the presence of abun- weak van der Waals interactions and/or hydrogen bonding
dant mesopores in the CLC structure. between these groups’ sites on surface of the adsorbent and
PCT molecules.
Effect of pH On the other hand, the sorption rate of PCT and NFA
onto CLC was investigated at pH 1.2 and 6.8 in buffer
The influence of the solution pH of PCT on adsorp- solutions. As can be seen in Fig. 6b, the results clearly
tion capacity of CLC was investigated within a wide pH indicate that the sorption efficiency for PCT is neither
range (2–10). As shown in Fig. 6a, the experimental data altered nor influenced by the presence of other cations
show clearly that the solution pH has nearly no effect on (e.g., ­Na +, ­K +). The same trend was observed for the
the amount of PCT sorbed onto CLC. The p­ Hpzc of CLC, ampholyte NFA drug where at pH 1.2, NFA is protonated
measured by the pH drift method according to the proce- (the ­pKa of the basic form is ~ 2.26) and the CLC surface
dure described by Bakatula et al. (2018), was found to be is also positively charged. Likewise, at pH 6.8, both NFA
3.12 (Fig. 6c). Under these conditions (pH range 2–10), the molecules ­( pK a ~ 4.44 for the acid form) and the CLC

(a) (b) (c)

100 nm
3.00 um 600 nm

Fig. 4  SEM and TEM images of CLC

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80 80 Adsorption isotherms
(a) PCT (b) NFA
PCT
The sorption capacity of CLC material bearing weakly
60 60 acidic ester functional groups was investigated using par-
acetamol and niflumic acid as model pharmaceutical
% Removal

% Removal
compounds. Figure 7a shows the experimental adsorption
40 40 isotherms of PCT and NFA drugs from aqueous solutions
onto CLC polymer. Typical S-shaped curves, according to
Giles’ classification, are obtained. The initial parts of the
20 20 S curves show a slight increase in adsorption capacities at
low concentrations. However, as the concentration of drugs
in the liquid phase increased (up to 40 mg L ­ −1), adsorption
0 0
0 2 4 6 8 10 1,2 6,8
occurred more readily and the isotherms are characterized by
pH pH a very favorable shape, indicating a greater affinity of CLC
for the drugs molecules. This behavior is characteristic of
cooperative adsorption resulting in a favorable association
(c) between adsorbed molecules at the surface of the adsorbent
0,8
(Torrellas et al. 2015; Gómez et al. 2007).
First, it is noteworthy to state that the Langmuir and Fre-
undlich models did not fit adequately the experimental data
∆pH = pHi -pHf

0,4
since these models do not take into account of the adsorb-
ate–adsorbate lateral interaction. The experimental data
were analyzed with the three parameters Gu–Zhu isotherm
0,0
2 4 6 8 10
model which is a combination of Langmuir and Freundlich
pHi isotherms used for various types of S-shaped adsorption
pHPZC= 3.12
isotherms. The GZ model is expressed by Eqs. (4) and (5):
-0,4
n
Ce g
qe = q∞ KGZ n (non - linear form) (4)
Fig. 6  a Effect of pH on the sorption of PCT. b Effect of pH on sorp-
1 + KGZ Ce g
tion of PCT and NFA in buffer solutions at pH 1.2 and 6.8. Condi-
tions: initial drug concentration of 30 mg/L, adsorbent dose of 1 g/L, [ ]
qe
and reaction time of 60 min. c Determination of pHpzc of CLC by the ln = ng ln Ce + ln KGZ (linear form) (5)
pH drift method q∞ − qe

where qe (mg ­g−1) is the amount of drug adsorbed per gram

surface are negatively charged. These results confirm that
electrostatic interactions are unlikely to prevail between
the CLC surface and drugs molecules under these sorption
conditions. Therefore, we hypothesize that hydrogen bond-
ing between oxygen sites onto the adsorbent and adsorbate
may possibly play a dominant role in the adsorption pro-
cess. In fact, PCT and NFA molecules possess amide and
amine functional groups (N–H) that are potentially capable
of interacting with oxygen atoms at the CLC surface via
hydrogen bonding.
The above results suggest that the solution pH and the
ionic strength have nearly no effect on the drugs removal.
Thus, for the subsequent adsorption experiments, PCT
solutions (having pH values around 6.8 units) were pre-
pared without pH adjustment, whereas NFA solutions
were prepared in phosphate buffer (pH 6.8). This could be
advantageous for wastewater treatment applications since
the pH of typical municipal wastewaters is in the range of
6 to 8 units.
of adsorbent, q∞ (mg ­g−1) is the maximum sorption capac-
ity per gram of adsorbent, Ce (mg L ­ −1) is the equilibrium
concentration of drug in solution, KGZ is the model constant,
and ng is the adsorption order.
The adsorption data for PCT and NFA drugs onto CLC
were analyzed by a regression analysis to fit the GZ isotherm
model. Since q∞ can be obtained from the adsorption iso-
therms plateaus (experimental qmax), the correlation of data
with the linear expression of GZ equation gave a straight line
over the whole concentration range as shown in Fig. 7b. The
values of the constants ng and KGZ obtained from the slopes
and intercepts of the plots are given in Table 3. The model
perfectly describes the adsorption isotherms with very high
R2adj and relatively low values of RMSE. Consequently, the
adsorption isotherms of PCT and NFA onto CLC can be ade-
quately described by the GZ isotherm model. On the other
hand, the average aggregation number ng was found to be 2.53
and 4.25 for PCT and NFA, respectively. The standard free

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(a) (b)
40
3,0

30 1,5

ln[qe/(q8-qe)]
qe (mg g-1)

20 0,0

-1,5
10
NFA
NFA PCT
PCT -3,0 Linear Gu-Zhu
0
0 10 20 30 40 50 60 70 -10,5 -10,0 -9,5 -9,0 -8,5 -8,0
-1
Ce (mg L ) ln Ce
(c) (d) -7

10 -8

θ)
θ]-[θ/(1-θ -9
θ)]
ln[θ/Ce(1-θ

9 -10
θ)/θ
ln[Ce(1-θ

-11

8 NFA -12 NFA

PCT PCT
Linear Frumkin-Fowler-Guggenheim Linear Hill-de Boer
-13
0,1 0,2 0,3 0,4 0,5 0,6 0,1 0,2 0,3 0,4 0,5 0,6
θ θ

Fig. 7  a Adsorption isotherms of PCT and NFA for CLC; Conditions: pH 6.8, initial sorbate concentration of 0–100 mg/L, adsorbent dose of
1 g/L, and contact time of 60 min. b–d Linear Gu and Zhu, FFG and HdB plots for PCT and NFA drugs removal by CLC

energy of aggregation (ΔG0) for 1 mol of pharmaceuticals was where KF is the model constant, a is the interaction param-
calculated( from)KGZ values (Table 3) by using the equation, eter, 𝜃 = qe ∕qm is the surface coverage, K1 is the model con-
ΔG0 = − 1∕ng RT ln KGZ , where ng is the number of mono- stant (L ­mol−1), K2 is the energetic constant of the interac-
mers in the pharmaceuticals aggregates. tion between adsorbed molecules (KJ m ­ ol−1), R is the gas
The adsorption of PCT and NFA onto CLC can also be constant (kJ ­mol−1 ­K−1), and T is the temperature (K).
described using Frumkin–Fowler–Guggenheim (FFG) and The plots of the Frumkin–Fowler–Guggenheim (Fig. 7c)
Hill–de Boer (HdB) isotherm models. These models also and Hill–de Boer (Fig. 7d) equations were carried out tak-
take into account lateral interaction between adsorbed mole- ing into account values of surface coverage, θ < 0.6. The
cules on the adsorbent surface. The linear forms of FFG and models fit well the data and straight lines were obtained
HdB models are expressed by Eqs. (6) and (7), respectively: with high correlation coefficients indicating that lateral
[( )( )] interaction between adsorbed species is significant for the
𝜃 1 adsorption of PCT and NFA. From Table 3, the positive
ln = ln KF + 2a𝜃 (linear form) (6)
(1 − 𝜃 Ce values obtained for parameter a (1.592 and 1.705 for PCT
and NFA, respectively) indicate a cooperative adsorption
mechanism and reflect that the lateral interactions are attrac-
[ ]
Ce (1 − 𝜃 𝜃 K
ln − = − ln K1 − 2 𝜃 (linear form) tive in nature for both drugs. PCT shows relatively weaker
𝜃 1−𝜃 RT
(7) lateral interaction than NFA. The calculated negative values

13
Chemical Papers

Table 3  Adsorption parameters for PCT and NFA sorption onto CLC Table 4  Comparison of PCTsorption capacities with other adsorbent
Isotherm Model PCT NFA Adsorbent qm (mg ­g−1) References

Gu–Zhu Rice husk ash 7.65 Thakur et al. (2020)

q∞ ­104 (mol ­g−1) 2.031a 1.442a Grape stalk 2.18 Villaescusa et al. (2011)
ng 2.53 4.25 Champignon stalks 338.1 Menk et al. (2019)
KGZ 2.78 × ­1010 1.27 × ­1018 Shiitake stalks 34.2 Menk et al. (2019)
−ΔG0(KJ ­mol−1) 19.49 19.71 Beverage sludge AC 145.4 Streit et al. (2021)
RMSE 0.174 0.196 Babassu coconut AC 71.39 Ferreira et al. (2015)
R2adj 0.990 0.979 Dende coconut AC 70.62 Ferreira et al. (2015)
Frumkin–Fowler–Guggenheim Oak acorn AC 45.45 Nourmoradi et al. (2018)
K ­(10−3) 2.835 3.102 Cotton cloth wastes AC 105 Boudrahem et al. (2017)
a 1.592 1.705 CLC 30.7 This work
−ΔG0ads(KJ ­mol−1) 19.49 19.71
RMSE 0.038 0.074
R2adj 0.992 0.975 2004; Baccar et al. 2012). The sorption studies were carried
Hill de Boer out at pH 6.8, a pH at which the surface of CLC sorbent is
K1 ­(10−3) (L ­mol−1) 2.08 2.44 negatively charged ­(pHpzc = 3.12). As discussed in “Effect of
K2 (KJ ­mol−1) 14.44 14.32 pH” section, the sorption data indicate that neither the solu-
RMSE 0.063 0.040 tion pH nor the ionic strength have a substantial effect on the
R2adj 0.994 0.996 drugs removal. Furthermore, our results demonstrated that
a
electrostatic interactions is unlikely to prevail between the
 Experimental qmax determined from the adsorption isotherms pla-
CLC surface and the molecules of paracetamol (­ pKa ~ 9.5),
teaus
which is not dissociated at this pH. On the other hand, seeing
the ­pKa value it was predictable that ampholyte NFA mol-
of ΔG0ads (− 19.49 and − 19.71 kJ ­mol−1), for PCT and NFA, ecules would be the least adsorbed due to the highest electro-
respectively, indicate the spontaneity and are in agreement static repulsive interactions between the deprotonated form
with physical adsorption process for both drugs (Cheminski and the negatively charged surface of the adsorbent. Besides,
et al. 2019; El-Aila et al. 2016). As can be seen in Table 3, the presence of a strong electron-withdrawing group such
similar trend is observed when the Hill-de Boer equation is as trifluoromethyl in the chemical structure of NFA would
used. The parameter K2, known as the interaction energy, is certainly favor aggregation of the drug molecules (4.2 mono-
positive for both PCT and NFA, indicating that the drugs mers), thus resulting in a low NFA uptake. The number of
exhibit attractive adsorbate–adsorbate interaction. On the monomers in the pharmaceuticals aggregates appeared to be
other hand, for both FFG and HdB models, the NFA adsorp- decisive in drugs uptake as lower number (n ~ 2.5) for par-
tion constant is slightly higher than those obtained for PCT, acetamol provided the higher qmax (206 ppm ­g−1) compared
which denotes the relatively better affinity of CLC for NFA. to that of niflumic acid (145 ppm ­g−1), with n ~ 4.2. This
To sum up, these results strongly suggest that the adsorption denotes that PCT has easy access to diffuse in all available
of PCT and NFA drugs onto CLC is cooperative, leading to sorption sites on the surface of the hyper-crosslinked cel-
a one-step formation of aggregates containing n molecules lulose adsorbent.
of drugs. Table 4 depicts some PCT sorption capacities
reported in the literature with other adsorbents. Maximum Thermodynamic parameters
adsorption capacity provides information on how efficient is
an adsorbent when compared to others. Although qm was not The removal of PCT and NFA by CLC sorbent was stud-
obtained under the same experimental conditions, one can ied in the temperature range (298–318 K) to determine the
realize that the efficiency obtained with CLC material is sig- thermodynamic parameters, and the results are summarized
nificantly lower if compared with activated carbons. On the in Table 5. The drugs uptake decreased by increasing the
other hand, it can also be said that the adsorption capacity temperature, indicating an exothermic process. The thermo-
of CLC is more or less better than those of other adsorbents. dynamic parameters ΔG0 , ΔH 0 , and ΔS0 were calculated by
It is well established that parameters such as molecular using the following equation (Zhu et al. 2010):
size, water solubility, pKa, and the nature of the substituents
ΔG0 ΔS0 ΔH 0
are among the factors that mainly affect the adsorption pro- log K = − = − (8)
RT R RT
cess of aromatic hydrocarbons molecules (Moreno-Castilla

13

Table 5  Thermodynamic parameters for PCT and NFA sorption onto
CLC
ΔH0 (KJ m
­ ol–1) ΔS0 (J ­K–1 ­mol–1) ΔG0 (KJ ­mol–1)
298 K 308 K 318 K
PCT –24.76 –20.46 –18.67 –18.45 –18.25
NFA –21.13 8.30 –23.60 –23.69 –23.77
where T is the temperature (K), R is the ideal gas constant
(8.314 J ­mol−1 ­K−1), and K is the equilibrium constant (L
­mg−1).
The vant’Hoff plot of ln K versus 1/T gave straight lines.
The calculated slope and intercept from the plot were used to
determine ΔH 0 and ΔS0 , respectively (Table 5). The negative
value of ΔG0 (− 23.77 to − 18.25 kJ·mol−1) at each tempera-
ture implies a favorable and spontaneous adsorption process
and confirms the affinity of CLC material for PCT and NFA
drugs. These values are in accordance with those found ear-
lier with GZ and FFG models (“Adsorption isotherms” sec-
tion). In good agreement with the FFG and HdB models, the
affinity of CLC adsorbent towards NFA is again confirmed
by the positive value of ΔS0 , which indicates an increase in
the degree of freedom of the adsorbed NFA molecules and
also suggests the increased randomness at the solid/solution
interface with some structural changes in the adsorbate and
the adsorbent. The negative values of Δ H 0 indicate that the
adsorption is exothermic and also suggest that the sorption
process is a physical adsorption.
Kinetics of PCT and NFA removal by CLC
The effect of contact time on the removal of drugs by CLC
is shown in Fig. 8a. The results revealed that the initial con-
centration decreased rapidly with time, indicating the avail-
ability of plenty of readily accessible sorption sites. The
process was uniform which suggests strong interactions
between pharmaceuticals and the crosslinked cellulose.
Maximum PCT was sequestered from the solution within
30 min of contact time while for NFA, the equilibrium point
was reached only after 50 min. After that, the concentration
of pharmaceuticals in the liquid phase remained nearly con-
stant. This was due to the less active sites being available
on CLC surface at the end of the sorption process. Sixty
minutes proved to be enough to reach adsorption equilibrium
for both PCT and NFA drugs.
The experimental data were fitted to the Lagergren model,
but the linearity of log(qe − qt) versus t plots is seen only for
the initial adsorption period, in the region where rapid
adsorption took place (0–25 min for PCT and 0–35 min for
NFA), and thereafter it deviates from theory. In addition, the
calculated adsorption capacity values (qe, cal) from Lager-
gren model are not in agreement with the experimental ones
13
Chemical Papers
(qe, exp). On the other hand, the experimental data were well
fitted to the pseudo-second-order model. The plots of t/qt
versus t (Fig. 8b) gave excellent results with connection to
the criteria of R2adj and RMSE (Table 6), which confirm the
applicability of the pseudo-second-order equation. In full
agreement with the experimental data, the value of the
pseudo-second-order rate constant (KS) is also more than
three times greater for the adsorption of PCT than that of
NFA. The half-life time (t1/2) and the initial rate of adsorp-
tion (h) parameters estimated according to the equations
t1∕2 = 1∕KS qe and h = KS q2e (Ho 2006; Tsai et al. 2006),
where qe is the total amount adsorbed, have revealed that the
elapsed time for half of the PCT adsorption (1.15  min)
increased by fourfold (4.71 min) for the adsorption of NFA.
The same trend is noticed as the initial rates of adsorption
were found to be 15.98 and 3.48 mg ­g−1 ­min−1 for PCT and
NFA, respectively.
Thus, in summary, it can be deduced that even though the
mean diameter of the drugs molecules (1.16 and 1.35 nm for
PCT and NFA, respectively) is of the same order of magni-
tude, the sorption of aggregates containing ~ 4.25 NFA mol-
ecules caused a deceleration in its removal rate compared to
PCT which forms lower aggregates (n ~ 2.5). Although most
of the pores in CLC are in the size range of 27 nm, which are
large enough to fully support the different arrangements of
both PCT and NFA aggregates, the adsorbent showed how-
ever better sorption efficiency towards PCT. This could be
explained by the fact that the NFA molecules might just be
clustered on the side of the pores while the PCT molecules
are spread out inside the pores of the CLC adsorbent.
Analysis of intraparticle diffusivity mechanisms
Sorption processes of the drugs onto functionalized CLC
material have been further examined by intraparticle diffu-
sion model. Figure 8c shows the plots of the Weber–Morris
equation for the experimental data of the drugs sorption.
The plot for NFA adsorption gives a straight line over the
whole sorption period suggesting that the sorption process
is controlled by intraparticle diffusion. However, deviation
of the plot from the origin suggests the contribution from
film diffusion process (Ru-Ling et al. 2003), whereas for
PCT, the data exhibit two linear plots indicating the simul-
taneous occurrence of two adsorption stages. The first
straight portion illustrates external pore diffusion and the
second which is attributed to the final equilibrium stage,
and where internal pore diffusion may possibly occur (Val-
derrama et al. 2007). The slopes of the intraparticle diffu-
sion plots give the value of kid and extrapolation of the plots
back to the y-axis gives the intercepts, which provide the
measure of the boundary layer thickness. The order of sorp-
tion rate for PCT was in the first stage (kid1) higher than the
Chemical Papers

(a) (b)
4
20

3
15

t/qt (min mg g-1)

qt (mg g-1)

10 2

5 NFA 1
PCT
PSO NFA
PFO PCT
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60 70
Time (min.) Time (min)
(c) (d)
20 5

15
3
qt(mg g-1)

Bt

10
1

NFA NFA
0 PCT
PCT
5
1 2 3 4 5 6 7 8 0 10 20 30 40 50

Time 0.5
(min )0.5
Time (min)

Fig. 8  a Adsorption kinetics of PCT and NFA onto CLC; Conditions: ond-order kinetic model. c Intraparticle diffusion plots for the adsorp-
initial drug concentration of 30  mg/L, adsorption dose of 1  g/L, pH tion of PCT and NFA onto CLC. d B(t) versus t plots of PCT and
6.8, contact time of 60 min. b Kinetic data fitted with the pseudo-sec- NFA adsorption onto CLC of bead size 180–250 μm

Table 6  Kinetic data of paracetamol and niflumic acid adsorption second (kid2) with values of 1.68 and 0.30 mg ­g−1 ­min−1/2,
onto CLC fitted to the pseudo-second order and the pseudo-first order respectively. As mentioned before, NFA sorption proceeded
Adsorption kinetic models Non linear Linear merely in a single step and provided a sorption rate value
PCT NFA PCT NFA of 0.96 mg ­g−1 ­min−1/2. Therefore, at the beginning of the
sorption process whether for PCT or NFA, the drugs are
Pseudo-second-order
sorbed by the external pores available on the surface of the
qe (mg ­g−1) 19.21 15.91 18.63 16.70
exterior structure of CLC adsorbent so the sorption rates
KS (g mg ­min−1) 0.029 0.020 0.047 0.013
were very high. When the saturation of these sites is reached,
RMSE 0.051 0.166 0.009 0.060
and taking into account the molecular size along with the
R2adj 0.999 0.999 0.999 0.996
aggregates arrangement of the drugs, only PCT molecules
Pseudo-first-order (smaller size) migrate to the inner tridimensional network
qe (mg ­g−1) 17.95 14.55 9.99 5.81 and diffuse in the internal surface pores and then are sorbed
Kf ­(min−1) 0.289 0.195 0.171 0.043 at the internal surface of the crosslinked polymer. The dif-
RMSE 0.118 0.286 0.045 0.028 fusion resistance increased gradually as PCT molecules dif-
R2adj 0.996 0.998 0.990 0.968 fuse in the inner pores, thus resulting in a decrease in the

13
 Chemical Papers

diffusion rate until the equilibrium is reached. Therefore, ln (1 − F) = −kfd t (10)

the discrepancy between kid1 and kid2values is attributed to
the sorption stages of the external and internal surfaces. In
summary, these results demonstrate that the sorption process
of PCT and NFA which are featured by faster rate kid1 is
undoubtedly controlled by intraparticle diffusion and to a
lesser extent by film diffusion.
The sorption data were further analyzed by the kinetic
expression for particle diffusion written as:
∞ 2
qt 6 ∑ e−n Bt
F= =1− 2
q∞ 𝜋 n=1 n2
where F is the fractional attainment of equilibrium; B is a
constant ( B = 𝜋 2 Di ∕r2 ), where Di is the effective diffusion
coefficient and r is the radius of the particle assuming that
all the adsorbent particles are uniform spheres.
From the experimental F values, the corresponding Bt
values were obtained from Reichenberg’s table and were
then plotted against the experimental values of t. As shown
in Fig. 8d, the Bt versus t plot for NFA gave a relatively good
straight line over the whole range but does not pass through
the origin, indicating that the rate-controlling process may
possibly be film diffusion. However, the prevalence of intra-
particle diffusion in the NFA adsorption process is quite
feasible given the intercept value (0.429) of the plot which
passes close to the origin. As previously expected for PCT,
the plot did indeed provide a good straight line passing
through the origin, thus indicating that particle diffusion is
the rate controlling step. The R2adj coefficients and RMSE
values indicate a good fit for both drugs. The values of effec-
tive diffusion coefficients (Di) were calculated from the slope
(B value) and are reported in Table 7. The average radius of
where F = qt/qe, is the fractional attainment of equilibrium
and kfd is the film diffusion rate constant.
A linear plot of ln(1 − F) versus t passing through the
origin suggests that the adsorption kinetics is controlled by
diffusion through liquid film surrounding the solid adsor-
bent. Although good straight lines could be obtained for the
film diffusion model, they do not pass through the origin,
however (Fig. 9).
The results of the linear regression analysis for PCT and
(9)
NFA drugs are summarized in Table 7. The intercept values
for both PCT (0.598) and NFA (0.903) are higher than zero,
which suggest that the process is not exclusively controlled
by film diffusion and that the process may be impeded by the
aggregation of drugs. Furthermore, the liquid film diffusion
rate constant (kfd) values show that PCT (0.17) adsorption
was faster than that of NFA (0.049) which can also be related
to the number of aggregates of these drugs. In summary, the
global adsorption rate of PCT and NFA onto CLC seemed
to be controlled by intraparticle diffusion simultaneously in
external and internal pores of the hyper-crosslinked cellu-
lose adsorbent. It appears also that the low number of drugs
aggregates promotes the diffusion and migration of PCT
molecules into the internal surface pores of CLC. This was
5
4
3
ln(1-F)

the particle was estimated to be 0.0115 cm as the CLC par-

ticles were in 210–250 μm size range. The calculated Di
2
coefficients of the drugs molecules involved in the sorption
process overlap with those reported in the literature for
organic compounds sorbed by macroporous and hyper- 1 NFA
PCT
crosslinked polymeric sorbents (Valderrama et al. 2007;
Linear liquid film diffusion model
Azanova and Hradil 1999).
0
0 5 10 15 20 25 30 35 40 45
Liquid film diffusion model Time (min)

If liquid film diffusion controls the rate of sorption, the fol-

Fig. 9  Linear liquid film diffusion plots for the sorption of PCT and
lowing expression [49] can be used: NFA onto CLC

Table 7  Kinetic data of Intraparticle diffusion model Liquid film diffusion model

paracetamol and niflumic acid
−1 2 −1
adsorption onto CLC fitted kid (mg A (mg g­ ) RMSE R2adj Di ­(m ­s ) kfd Intercept RMSE R2adj
to the intraparticle diffusion ­g−1 ­min−1/2)
models
PCT 1.68 10.61 0.308 0.953 2.25 ­10−14 0.598 0.171 0.103 0.990
NFA 0.96 8.89 0.200 0.980 6.27 ­10−15 0.903 0.049 0.117 0.950

13
Chemical Papers
cross-checked by desorption assays of the drugs saturated
CLC. Thus, NFA was entirely recovered by vigorous stir-
ring with pH 1.2 aqueous solution for 30 min, while 90% of
adsorbed PCT was recovered after the first wash with pH 4
aqueous solution, reaching complete recovery only after a
subsequent wash.
Conclusions
The presented work extends the applicability of a novel
crosslinked cellulose adsorbent to investigate adsorption
processes of pharmaceuticals in aqueous media. Based on
the equilibrium adsorption studies, it was found that the sur-
face interaction of paracetamol and niflumic acid drugs can
be well described by the GZ, FFG and HdB models, indicat-
ing that lateral interactions is dominant for the adsorption
of these species onto the CLC surface. Both drugs exhibit
attractive lateral interactions and their sorption onto CLC
are cooperative, leading to the formation of aggregates of
n monomers. The lesser n value is the better for the drugs
uptake, so paracetamol shows a higher uptake unlike nif-
lumic acid, which presents higher n. Likewise, the global
adsorption rate of NFA is decelerated as a result of its higher
number of monomers aggregates. Regardless the huge size
of the pores in the crosslinked cellulose, it appears again
that n equally controls the intraparticle diffusion step so that
NFA molecules are clustered on the side of the pores, while
the PCT molecules are spread out inside the pores of the
CLC adsorbent. This was further confirmed by desorption
tests where the NFA molecules were totally recovered from
the first wash while PCT required two successive washes
for full recovery.
References
Alygizakis NA, Gago-Ferrero P, Borova VL, Pavlidou A, Hatzianestis
I, Thomaidis NS (2016) Occurrence and spatial distribution of
158 pharmaceuticals, drugs of abuse and related metabolites in
offshore seawater. Sci Total Environ 541:1097–1105. https://​doi.​
org/​10.​1016/j.​scito​tenv.​2015.​09.​145
Azanova VV, Hradil J (1999) Sorption properties of macroporous and
hypercrosslinked copolymers. React Funct Polym 41:163–175.
https://​doi.​org/​10.​1016/​S1381-​5148(99)​00029-2
Babaei AA, Alavi SN, Akbarifar M, Ahmadi K, Esfahani AR, Kaka-
vandi B (2016) Experimental and modeling study on adsorption of
cationic methylene blue dye onto mesoporous biochars prepared
from agrowaste. Desalin Water Treat 57:27199–27212. https://d​ oi.​
org/​10.​1080/​19443​994.​2016.​11637​36
Baccar R, Sarrà M, Bouzid J, Feki M, Blánquez P (2012) Removal of
pharmaceutical compounds by activated carbon prepared from
agricultural by-product. Chem Eng J 211–212:310–317. https://​
doi.​org/​10.​1016/j.​cej.​2012.​09.​099
Bahamon D, Vega LF (2017) Pharmaceutical removal from water efflu-
ents by adsorption on activated carbons: a monte carlo simulation
study. Langmuir 33:11146–11155. https://​doi.​org/​10.​1021/​acs.​
langm​uir.​7b019​67
Bakatula EN, Richard D, Neculita CM, Zagury GJ (2018) Deter-
mination of point of zero charge of natural organic materials.
Environ Sci Pollut Res 25:7823–7833. https://​doi.​org/​10.​1007/​
s11356-​017-​1115-7
Bendjelloul M, Elandaloussi EH, de Ménorval LC, Bentouami A
(2017) Quaternized triethanolamine-sebacoyl moieties in highly
branched polymer architecture as a host for the entrapment of acid
dyes in aqueous solutions. J Water Reuse Desalin 7:53–65. https://​
doi.​org/​10.​2166/​wrd.​2016.​191
Bhatnagar A, Sillanpää M, Witek-Krowiak A (2015) Agricultural waste
peels as versatile biomass for water purification—a review. Chem
Eng J 270:244–271. https://​doi.​org/​10.​1016/j.​cej.​2015.​01.​135
Boudrahem N, Delpeux-Ouldriane S, Khenniche L, Boudrahem F,
Aissani-Benissad F, Gineys M (2017) Single and mixture adsorp-
tion of clofibric acid, tetracycline and paracetamol onto activated
carbon developed from cotton cloth residue. Process Saf Environ
Prot 111:544–559. https://​doi.​org/​10.​1016/j.​psep.​2017.​08.​025
Box KJ, Comer JEA (2008) Using measured pKa, LogP and solubility
to investigate supersaturation and predict BCS class. Curr Drug
Metab 9:869–878. https://​doi.​org/​10.​2174/​13892​00087​86485​155
Box KJ, Völgyi G, Baka E, Stuart M, Takács-Novák K, Comer JEA
(2006) Equilibrium versus kinetic measurements of aqueous solu-
bility, and the ability of compounds to supersaturate in solution—
a validation study. J Pharm Sci 95:1298–1307. https://​doi.​org/​10.​
1002/​jps.​20613
Cheminski T, de Figueiredo NT, Silva PM, Guimarães CH, Prediger P
(2019) Insertion of phenyl ethyleneglycol units on graphene oxide
as stabilizers and its application for surfactant removal. J Environ
Chem Eng 7:102976. https://​doi.​org/​10.​1016/j.​jece.​2019.​102976
Ciğeroğlu Z, Küçükyıldız G, Erim B, Alp E (2021) Easy preparation of
magnetic nanoparticles-rGO-chitosan composite beads: optimiza-
tion study on cefixime removal based on RSM and ANN by using
Genetic Algorithm Approach. J Mol Struct 1224:129182. https://​
doi.​org/​10.​1016/j.​molst​ruc.​2020.​129182
Coelho AD, Sans C, Esplugas S, Dezotti M (2010) Ozonation of
NSAID: a biodegradability and toxicity study. Ozone Sci Eng
32:91–98. https://​doi.​org/​10.​1080/​01919​51090​35081​62
El-Aila HJ, Elsousy KM, Hartany KA (2016) Kinetics, equilibrium,
and isotherm of the adsorption of cyanide by MDFSD. Arab J
Chem 9:S198–S203. https://d​ oi.o​ rg/1​ 0.1​ 016/j.a​ rabjc.2​ 011.0​ 3.0​ 02
Escapa C, Coimbra RN, Paniagua S, García AI, Otero M (2017) Par-
acetamol and salicylic acid removal from contaminated water by
microalgae. J Environ Manage 203:799–806. https://​doi.​org/​10.​
1016/j.​jenvm​an.​2016.​06.​051
Ferreira RC, de Lima HHC, Candido AA, Couto Junior OM, Arroyo
PA, de Carvalho KQ, Gauze GF, Barros MASD (2015) Adsorp-
tion of paracetamol using activated carbon of dende and babassu
coconut mesocarp. Int J Biol Biomol Agric Food Biotechnol Eng
9:575–580
Foston MB, Hubbell CA, Ragauskas AJ (2011) Cellulose isolation
methodology for NMR analysis of cellulose ultrastructure. Materi-
als 4:1985–2002. https://​doi.​org/​10.​3390/​ma411​1985
Franca MD, Santos LM, Silva TA, Borges KA, Silva VM, Patrocinio
AOT, Trovo AG, Machado AEH (2016) Efficient mineralization of
paracetamol using the nanocomposite ­TiO2/Zn(II) phthalocyanine
as photocatalyst. J Braz Chem Soc 27:1094–1102. https://​doi.​org/​
10.​5935/​0103-​5053.​20160​007
Gómez V, Larrechi MS, Callao MP (2007) Kinetic and adsorption
study of acid dye removal using activated carbon. Chemosphere
69:1151–1158. https://​doi.​org/​10.​1016/j.​chemo​sphere.​2007.​03.​
076
Ho YS (2006) Review of second-order models for adsorption systems.
J Hazard Mater B136:681–689. https://​doi.​org/​10.​1016/j.​jhazm​
at.​2005.​12.​043
13

Hokkanen S, Bhatnagar A, Sillanpää M (2016) A review on modifica-
tion methods to cellulose-based adsorbents to improve adsorption
capacity. Water Res 91:156–173. https://​doi.​org/​10.​1016/j.​watres.​
2016.​01.​008
Ibanez M, Borova V, Boix C, Aalizadeh R, Bade R, Thomaidis NS, Her-
nandez F (2016) UHPLC-QTOF MS screening of pharmaceuticals and
their metabolites in treated wastewater samples from Athens. J Hazard
Mater 323:26–35. https://​doi.​org/​10.​1016/j.​jhazm​at.​2016.​03.​078
Jandura P, Kokta BV, Riedl B (2000) Fibrous long-chain organic acid
cellulose esters and their characterization by diffuse reflectance
FTIR spectroscopy, solid-state CP/MAS 13C-NMR, and X-ray dif-
fraction. J Appl Polym Sci 78:1354–1365. https://​doi.​org/​10.​1002/​
1097-​4628(20001​114)​78:7%​3c135​4::​AID-​APP60%​3e3.0.​CO;2-V
Ji H, Xiang Z, Qi H, Han T, Pranovich A, Song T (2019) Strategy towards
one-step preparation of carboxylic cellulose nanocrystals and nanofi-
brils with high yield, carboxylation and highly stable dispersibility
using innocuous citric acid. Green Chem 21:1956–1964. https://​doi.​
org/​10.​1039/​C8GC0​3493A
Joss A, Zabczynski S, Göbel A, Hoffmann B, Löffler D, McArdell CS,
Ternes TA, Thomsen A, Siegrist H (2006) Biological degradation
of pharmaceuticals in municipal wastewater treatment: Proposing a
classification scheme. Water Res 40:1686–1696. https://​doi.​org/​10.​
1016/j.​watres.​2006.​02.​014
Larsson PT, Westermark U, Iversen T (1995) Determination of the cel-
lulose Iα allomorph content in a tunicate cellulose by CP/MAS 13C-
NMR spectroscopy. Carbohydr Res 278:339–343. https://​doi.​org/​10.​
1016/​0008-​6215(95)​00248-0
Larsson DGJ, de Pedro C, Paxeus N (2007) Effluent from drug manufac-
tures contains extremely high levels of pharmaceuticals. J Hazard
Mater 148:751–755. https://​doi.​org/​10.​1016/j.​jhazm​at.​2007.​07.​008
Li B, Pan Y, Zhang Q, Huang Z, Liu J, Xiao H (2019a) Porous cellulose
beads reconstituted from ionic liquid for adsorption of heavy metal
ions from aqueous solutions. Cellulose 26:9163–9178. https://​doi.​
org/​10.​1007/​s10570-​019-​02687-4
Li Y, Xiao H, Pan Y, Zhang M, Jin Y (2019b) Thermal and pH dual-
responsive cellulose microfilament spheres for dye removal in single
and binary systems. J Hazard Mater 377:88–97. https://​doi.​org/​10.​
1016/j.​jhazm​at.​2019.​05.​033
Menk JJ, Nascimento AIS, Leite FG, Oliveira RA, Jozala AF, Oliveira
JM Jr, Chaud MV, Grotto D (2019) Biosorption of pharmaceuti-
cal products by mushroom stem waste. Chemosphere 237:124515.
https://​doi.​org/​10.​1016/j.​chemo​sphere.​2019.​124515
Miege C, Choubert JM, Ribeiro L, Eusebe M, Coquery M (2009) Fate
of pharmaceuticals and personal care products in wastewater treat-
ment plants-conception of a database and first results. Envir Pollut
157:1721–1726. https://​doi.​org/​10.​1016/j.​envpol.​2008.​11.​045
Mila E, Nika MC, Thomaidis NS (2019) Identification of first and sec-
ond generation ozonation transformation products of niflumic acid
by LC-QToF-MS. J Hazard Mater 365:804–812. https://​doi.​org/​10.​
1016/j.​jhazm​at.​2018.​11.​046
Moreno-Castilla C (2004) Adsorption of organic molecules from aqueous
solutions on carbon materials. Carbon 42:83–94. https://​doi.​org/​10.​
1016/j.​carbon.​2003.​09.​022
Nourmoradi H, Moghadam KF, Jafari A, Kamarehie B (2018) Removal
of acetaminophen and ibuprofen from aqueous solutions by acti-
vated carbon derived from Quercus Brantii (Oak) acorn as a low-
cost biosorbent. J Environ Chem Eng 6:6807–6815. https://​doi.​org/​
10.​1016/j.​jece.​2018.​10.​047
Petrie B, Barden R, Kasprzyk-Hordern B (2015) A review on emerging
contaminants in wastewaters and the environment: current knowledge,
understudied areas and recommendations for future monitoring. Water
Res 72:3–27. https://​doi.​org/​10.​1016/j.​watres.​2014.​08.​053
Rivera-Utrilla J, Sánchez-Polo M, Ferro-García MÁ, Prados-Joya G,
Ocampo-Pérez R (2013) Pharmaceuticals as emerging contaminants
and their removal from water. A review. Chemosphere 93:1268–
1287. https://​doi.​org/​10.​1016/j.​chemo​sphere.​2013.​07.​059
13
Chemical Papers
Robberson KA, Waghe AB, Sabatini DA, Butler EC (2006) Adsorption
of the quinolone antibiotic nalidixic acid onto anion-exchange and
neutral polymers. Chemosphere 63:934–941. https://​doi.​org/​10.​
1016/j.​chemo​sphere.​2005.​09.​047
Ru-Ling T, Feng-Chin W, Ruey-Shin J (2003) Liquid-phase adsorption of
dyes and phenols using pinewood-based activated carbons. Carbon
41:487–495. https://​doi.​org/​10.​1016/​S0008-​6223(02)​00367-6
Selkälä T, Suopajärvi T, Sirviö JA, Luukkonen T, Lorite GS, Kalliola S,
Sillanpää M, Liimatainen H (2018) Rapid uptake of pharmaceutical
salbutamol from aqueous solutions with anionic cellulose nanofi-
brils: the importance of pH and colloidal stability in the interaction
with ionizable pollutants. Chem Eng J 350:378–385. https://​doi.​org/​
10.​1016/j.​cej.​2018.​05.​163
Sim WJ, Lee JW, Lee ES, Shin SK, Hwang SR, Oh JE (2011) Occurrence
and distribution of pharmaceuticals in wastewater from households,
livestock farms, hospitals and pharmaceutical manufactures. Che-
mosphere 82:179–186. https://​doi.​org/​10.​1016/j.​chemo​sphere.​2010.​
10.​026
Streit AFM, Collazzo GC, Druzian SP, Verdi RS, Foletto EL, Oliveira
LFS, Dotto GL (2021) Adsorption of ibuprofen, ketoprofen, and
paracetamol onto activated carbon prepared from effluent treatment
plant sludge of the beverage industry. Chemosphere 262:128322.
https://​doi.​org/​10.​1016/j.​chemo​sphere.​2020.​128322
Thakur A, Sharma N, Mann A (2020) Removal of ofloxacin hydrochlo-
ride and paracetamol from aqueous solutions: binary mixtures and
competitive adsorption. Mater Today Proc 28:1514–1519. https://​
doi.​org/​10.​1016/j.​matpr.​2020.​04.​833
Torrellas SA, Lovera RG, Escalona N, Sepúlveda C, Sotelo JL, García
J (2015) Chemical-activated carbons from peach stones for the
adsorption of emerging contaminants in aqueous solutions. Chem
Eng J 279:788–798. https://​doi.​org/​10.​1016/j.​cej.​2015.​05.​104
Tsai WT, Lai CW, Su TY (2006) Adsorption of bisphenol-A from
aqueous solution onto minerals and carbon adsorbents. J Haz Mat
B134:169–175. https://​doi.​org/​10.​1016/j.​jhazm​at.​2005.​10.​055
Valderrama C, Gamisans X, de las Heras FX, Cortina JL, Farrán A (2007)
Kinetics of polycyclic aromatic hydrocarbons removal using hyper-
cross-linked polymeric sorbents Macronet Hypersol MN200. React
Funct Polym 67:1515–1529. https://​doi.​org/​10.​1016/j.​react​funct​
polym.​2007.​07.​020
Villaescusa I, Fiol N, Poch J, Bianchi A, Bazzicalupi C (2011) Mecha-
nism of paracetamol removal by vegetable wastes: The contribu-
tion of π–π interactions, hydrogen bonding and hydrophobic effect.
Desalination 270:135–142. https://​doi.​org/​10.​1016/j.​desal.​2010.​11.​
037
Wang D (2019) A critical review of cellulose-based nanomaterials for
water purification in industrial processes. Cellulose 26:687–701.
https://​doi.​org/​10.​1007/​s10570-​018-​2143-2
Xiong P, Hu J (2017) Decomposition of acetaminophen (Ace) using
­TiO2/UVA/LED system. Catal Today 282:48–56. https://​doi.​org/​
10.​1016/j.​cattod.​2016.​03.​015
Zhou Y, Min Y, Qiao H, Huang Q, Wang E, Ma T (2015) Improved
removal of malachite green from aqueous solution using chemically
modified cellulose by anhydride. Int J Biol Macromol 74:271–277.
https://​doi.​org/​10.​1016/j.​ijbio​mac.​2014.​12.​020
Zhu HY, Jiang R, Xiao L, Zeng GM (2010) Preparation, characteriza-
tion, adsorption kinetics and thermodynamics of novel magnetic
chitosan enwrapping nanosized γ-Fe2O3 and multi-walled carbon
nanotubes with enhanced adsorption properties for methyl orange.
Bioresour Technol 101:5063–5069. https://​doi.​org/​10.​1016/j.​biort​
ech.​2010.​01.​107
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