Journal of Environmental Chemical Engineering 3 (2015) 26192630

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Journal of Environmental Chemical Engineering

j o u r n a l h o m e p a g e : w w w . e l s e v i er . c o m / l o c a te / j e c e

Adsorption of aspirin and paracetamol from aqueous solution using Fe/N-

CNT/b-cyclodextrin nanocomopsites synthesized via a benign microwave
assisted method
Keletso Mphahlelea,b, Maurice S. Onyangoa, Sabelo D. Mhlangac,*
a
Department of Chemical and Metallurgical Engineering, Tshwane University of Technology, Private Bag X680, Pretoria 0001, South Africa
b DST/CSIR Nanotechnology Innovation Centre, National Centre for Nanostructured Materials, P.O. Box 395, Pretoria 0001, South Africa

c
Nanotechnology and Water Sustainability Research Unit, College of Science, Engineering and Technology, Florida Science Campus, Johannesburg, 1709 South, Africa

ARTICLE INFO ABSTRACT

Article history: Aspirin and paracetamol are used as drugs by animals and humans but are not totally metabolized inside their bodies and
Received 4 September 2014 Accepted hence they often find way into the raw wastewaters. This study presents kinetic and thermodynamic studies of the sorption and
16 February 2015 Available online 26 removal of aspirin and paracetamol from aqueous solutions using N-CNT/b-CD and Fe/N-CNT/b-CD nanocomposite
February 2015
polymers and the parameters that determine the sorption process. The polymers were prepared via a benign method of
microwave-assisted synthesis of the nanocomposites and characterized using Spectrum 100 Fourier transform infrared
Keywords: spectroscopy (FTIR) and focused ion beam scanning electron microscopy (FIB-SEM). The sorption process for aspirin and
Aspirin paracetamol was described by Freundlich and Langmuir isotherms, respectively. The maximum sorption capacities of aspirin
Paracetamol
and paracetamol onto N-CNTs-b-CD were 71.9 and 41.0 mg g 1 and Fe/N-CNTs-b-CD were 101.0 and 75.2 mg g 1,
b-Cyclodextrins
Nanocomposites respectively, at 298 K. The nanocomposites effectively removed aspirin and paracetamol within 30 min of contact time,
Water treatment suggesting that the materials are effective and economically viable. Furthermore, the sorption kinetics of aspirin and
paracetamol onto the N-CNT/b-CD and Fe/N-CNT/b-CD sorbents well fitted onto the pseudo second order and Elovich
kinetic models, respectively as a minimum SSE was observed. Sorption thermodynamics indicated that the sorption process
was feasible, spontaneous and exothermic in nature.

2015 Published by Elsevier Ltd.

Introduction they can cause aquatic toxicity, development of resistance in pathogenic

Aspirin and paracetamol are important drugs used by humans and animals
[13]. However they are not totally metabolized inside their bodies and they
are excreted through urine or faeces and they enter in wastewaters as
biologically active substances [4]. Further-more, they are discharged during
manufacturing, as well as by discarding of unused or expired drugs [5].
Aspirin and paracetamol are also known as pharmaceutically active
compounds (PACs) [6]. The amounts of PACs found in the environment are
usually very low [7,8]; they are often detected in trace concentrations (ng L 1)
[1,5,9]. Nevertheless, in the long-term, their continuous release poses
potential danger to aquatic and terrestrial organisms. Also, pharmaceuticals
have physiological effects on animals and people also in very low (trace)
concentrations [1]. It has been shown that
* Corresponding author. Tel.: +27 11 471 2104.
E-mail address: mhlangasd@unisa.ac.za (S.D. Mhlanga).
microbes, genotoxicity and endocrine disruption [5].
Water purification technologies based on advanced oxidation processes
(AOP) [1012] or adsorption on appropriate solid materials such as activated
carbon have been evaluated and proposed for the removal of organic
contaminants from the environment, particularly at concentrations lower than
parts-per-million (ppm) [13,14]. The AOPs are costly and energy consuming.
Additionally, total mineralization of contaminants cannot be reached while
toxic products or by-products can arise. Activated carbons have been explored
as sorbents for removal of PACs from waters. They may play a significant
role in the removal of these contaminants, however this still remains to be
confirmed because, compared to the extensive sorption studies on usual
synthetic organic contaminants, the accessibility of sorption data for PACs is
exceptionally limited [15]. Hence, there is a constant need for sorbent
materials that can achieve higher efficiency and better selectivity in the
removal of pharmaceutically active substances, at the present and near future
concentration levels, in a variety of conditions [5]. Low-cost adsorbents
including raw agricultural

http://dx.doi.org/10.1016/j.jece.2015.02.018 2213-
3437/ 2015 Published by Elsevier Ltd.
2620 K. Mphahlele et al. / Journal of Environmental Chemical Engineering 3 (2015) 26192630
solid wastes and waste materials from forest industries such as maize cob,
palm-fruit bunch particles, bagasse pith, sawdust, papaya seeds, and hazelnut
shells have been used successfully as alternative to high cost commercial
activated carbon [16,17].
Cyclodextrins (CDs) are starch based nanostructured materials known to
form hostguest complexes with hydrophobic compounds in water [18,19].
This phenomenon led to the idea that insolubilized CDs may act as a good
adsorbent ofaspirin and paracetamol [20]. Due to their solubility in water
[21], CDs cannot be used directly for separation; one has to make them
insoluble. Insoluble CDs polymers have been shown to be recyclable
adsorbent which selectively bind to organics in water [2224]. However, its
solubilityin watermakes it inconvenient touseas an adsorbent,therefore, CD
polymers wereco-polymerized with carbon nanotubes (CNTs) [15]. When
CNTs (15%) were co-polymerized with CD polymers the recyclability
improved significantly, losing only 10% of the polymer mass over twenty five
cycles, compared to 50% loss over nine cycles for the native CDs polymers
[25].
CDs and CD/CNT composite polymers have been used by several
investigators to remove environmental pollutants such as organics [26,27], but
little is known about the adsorption properties of the polymers for aspirin and
paracetamol [28]. In order to fine-tune CNT properties, CNTs can be doped
with nitrogen. Modification of the crystalline nanotube properties by
controllably placing deficiency or unknown atoms (heteroatoms) brings along
incredible technological implications [29,30]. CNTs with nitrogen wall
doping are attractive because of the deficiency and rugosityof the outerwalls.
This isa way to improve the tube covalent chemistry, which once
functionalized can serve to anchor groups or particles that are useful for
further functionalization routes [29,31,32]. Clearillustrations are the current
works on platinum particle immobilization envisaging tailored materials with
high catalytic surface. Bundles of doped C-SWNT could be though for similar
application [29].
Zero valent iron (Fe) is known for its reductive properties and the sorption
capabilities for removing heavy metals by turning them into less soluble
forms [33,34] through changes in their oxidation state and/or by adsorption
[35]. Concerns over the discharge of these NPs into the environment led to
this study where bimetallic NPs of Ag and Fe were anchored on nitrogen
doped carbon nanotubes (N-CNTs) in order to immobilize and reduce their
environmental mobility. CNTs and nanofibres are ideal supports for
immobilizing NPs as shown by recent studies which indicate that these NPs
do not leach into solution when used during water treatment [24,36].
The objective of this study was to investigate the sorption mechanisms
and thermodynamics of aspirin and paracetamol from aqueous solution using
N-CNTs and Fe/N-CNTs co-polymer-ized with b-CDs. The metal
nanoparticles were dispersed on N-CNTs by a microwave polyol method. The
effect of time, initial aspirin and paracetamol concentration, pH, the sorption
kinetic, equilibrium and thermodynamic parameters at various temper-atures
and concentrations were investigated. The accuracy and consistency in
parameters prediction is also evaluated using an error function and by
considering both linear and non-linear adsorption models.
Methods
Materials
All solvents and chemicals used in this study were purchased from
SigmaAldrich (USA) and were used as received without further purification.
The pharmaceutical and personal care products (PPCPs) used as target
adsorbate in the present study is aspirin ( 99% purity) and paracetamol ( 97%
purity). Their solutions were prepared with distilled water. Reagent grade
chemicals such as sodium hydroxide (NaOH), 65% nitric acid (HNO 3) were
used for adjusting pH. N,N-dimethylformamide (DMF) (99% purity), toluene
diisocyanate (TDI) (98% purity) were used to co-polymerize b-CDs and N-
CNTs.
Preparation of N-CNT/b-CD and Fe/N-CNT/b-CD nanocomposite
polymers
N-CNTs were synthesized using a CVD method we have used previously
[24]. All the N-CNTs used in this study were multiwalled. Fe-CNTs were
prepared using an efficient microwave assisted polyol method [24]. The
preparation of N-CNTs and Fe/N-CNTs co-polymerized with b-CD was as
follows: 2 g of b-CD was dried and dissolved in 18 mL of N,N-
dimethylformamide (DMF) with constant magnetic stirring (i.e. 80 rpm). This
solution was then added to a solution containing 1% of N-CNTs and metal/N-
CNTs previously suspended and sonicated in 2 mL DMF for 10 min. The
mixture of b-CD and metal/N-CNTs was heated to 70 C followed by dropwise
addition of a bi-functional linker, toluene 2,4-diisocyanate (2 mL). This mixture
was stirred under inert atmosphere for 24 h. The formed polymer was precipitated
and washed with acetone and dried under vacuum over night at ambient
temperature.
Batch adsorption equilibrium studies
Batch equilibrium adsorption experiments were carried out using the
bottle-point method. A stock solution of aspirin and paracetamol (1000 mg L
1) was prepared and was subsequently diluted to the required initial
concentrations. Adsorption capacity of the sorbents towards aspirin and
paracetamol was determined by contacting a constant mass (0.05 g) of sorbent
with a fixed volume (50 mL) in sealed plastic bottles of initial concentrations
ranging from 10 to 100 (mg L 1) of aspirin and paracetamol solution. The
bottles were agitated in an isothermal water-bath shaker for 24 h until
equilibrium was reached.
Calibration curves for aspirin and paracetamol were prepared by recording
the absorbance values for a range of known concentrations of aspirin and
paracetamol solution and the maximum absorbance was determined ( lmax =
300.3 nm and lmax = 241 nm, respectively). The concentration of aspirin and
paracetamol in aqueous solution was then determined at lmax = 300.3 nm and lmax
= 241 nm, respectively; using double beam UV visible spectrophotometer (UV
VIS) (Lambda 7505, PerkinElmer). The amount of aspirin and paracetamol
adsorbed onto sorbent, qe (mg g 1), was calculated by the following equation:
q Co CeV 1
e m
where Co and Ce are the initial and equilibrium concentrations of aspirin and
paracetamol solution (mg L 1), respectively. V is the total volume of the dye
solution in litres, and m is the mass of sorbent used in grams.
In order to investigate the adsorption isotherm, two equilibri-um
isotherms were analysed: the Langmuir and Freundlich models were used to
describe the relationship between the sorbed amount of aspirin and
paracetamol and its equilibrium concentration in solution. The Langmuir
isotherm represented by Eq. (2) [37].
Qmax bL Ce
q e 1 b L Ce 2
The linearized Langmuir isotherm is expressed below; Eq. (3):
Ce 1 Ce
b Q Q
qe L max max 3
where Ce is the supernatant concentration after the equilibrium of the system
(mg L 1), bL the Langmuir affinity constant (L mg 1),
 K. Mphahlele et al. / Journal of Environmental Chemical Engineering 3 (2015) 26192630 2621

and Qmax is the maximum adsorption capacity of the material (mg g 1). Integrating this for the boundary conditions t = 0 to t = t and q t = 0 to qt =
qt, Eq. (7) maybe rearranged for linearized data plotting as shown in Eq. (8):
The Freundlich isotherm represented by Eq. (4) [38].
qe KF C1e=n 4 k1
The linearized Freundlich isotherm is expressed below; Eq. (5):
t
logqe qt log qe 2:303 8
1
where k1 is the rate constant of first order sorption (L min 1), qe is the amount
ln qe ln KF nln Ce 5 of solute at equilibrium (mg g 1), and qt is the amount of solute sorbed on the
where KF is Freundlich constant (L g 1) and n is the heterogeneity factor. The surface of the sorbent at any time t (mg g 1).
KF value is related to the adsorption capacity; while 1/n value is related to the The pseudo-second order kinetic rate equation is expressed as
adsorption intensity. The magnitude of exponent (n) gives an indication of the [16]:
favourability and capacity of the adsorbent/adsorbate system. Where the value
of (n) is greater than unity represents favourable adsorption [39]. dqt 2

The effect of pH on aspirin and paracetamol removal was studied over a dt k2qe qt 9
pH range 212. pH was adjusted by the addition of NaOH or HCl solution. Integrating this for the boundary conditions t = 0 to t = t and
The 50 mL bottles with an initial concentration of 50 mg L 1 were qt = 0 to qt = qt, Eq. (9) maybe rearranged for linearized data plotting as
subsequently capped and agitated in a thermostatic shaker at 150 strokes per shown in Eq. (10):
minute (spm) for 24 h. The concentration of the contaminants in solution after t 1 t
equilibri-um adsorption was measured using a UVVIS spectrophotometer.
The equilibrium sorption capacity was calculated from Eq. (1). q 2 q
k2 qe e
t 10
where is the rate constant of second order sorption (g mg 1 min 1), is the
Sorption isotherm data were generated by contacting 0.05 g of sorbent
with aspirin and paracetamol containing aqueous solution with a fixed volume amount of solute at equilibrium (mg g 1), and is the amount of solute sorbed
(50 mL) in sealed plastic bottles of initial concentrations ranging from 10 to on the surface of the sorbent at any time t (mg g 1).
100 (mg L 1). The bottles were then placed in a thermostatic shaker and The Elovich model equation is generally expressed as [23]:
shaken for 24 h at 298, 308 and 318 K. The shaking speed was set at 150 spm;
at the end of the experiment samples were filtered and the filtrate was dqt
measured by UVVIS. The equilibrium sorption capacity was calculated from dt a exp bqt 11
Eq. (1).
where a is the initial adsorption rate (mg g 1 min 1), b is the desorption
constant (g mg 1) during any one experiment. To simplify the Elovich
Batch adsorption kinetics equation, Chien and Clayton assumed abt t and by applying the boundary
condition qt = 0 at t = 0 and qt = qt at t = t. Eq. (11) becomes:
The effect of contact time, mass and initial concentration of aspirin and
paracetamol on the sorption kinetics was studied at a room temperature. First, ln ab 1ln t
q 12
the experiments were carried out in a 1 L batch reactor with initial aspirin and
paracetamol concentration of 50 mg L 1, where the initial masses of the
t b b
sorbent was varied (i.e. 0.5, 0.7 and 1 g). The reactor was stirred with an where a and b are the constants.
overhead stirrer operated at 200 rpm. At predetermined time intervals, 5 mL
sample were taken from the reactor, filtered through a syringe filter and Error analysis
residual aspirin and paracetamol concentration was measured by UVVIS
spectrophotometer. By performingappropriatematerialbalance, the quantity of Linear regressions are frequently used to determine the best fitting
aspirin and paracetamol adsorbed at the selected time intervals was relationship, quantifying the distribution of adsorbates, mathematically
determined and used for kinetic analysis. In subse-quent experiments, the analysing the adsorption systems and verifying the consistency and theoretical
effect of contact time and initial concentra-tion (i.e. 50, 75 and 100 mg L 1) assumptions of both isotherm and kinetic models [37]. On the other hand,
non-linear methods minimization of predefined error functions. Sum of
was also investigated as described above; the sorbent mass was fixed at 1 g.
The amount of aspirin and paracetamol sorbed at any time was calculated by: squares of error (SSE) is the most widely used error function, at higher end of
the liquid-phase concentration ranges, the magnitude and squares of the errors
tend to increase, illustrating a better fit for the isotherm parameters derivation
[37], thus it was used in this study. SSE equation is represented in Eq. (13):
q Co Ct V 6

t m
where Co and Ct are the initial and concentrations at anytime of aspirin and q e
q
paracetamol solution (mg L 1), respectively. V is the total volume of the
2
n q ;exp e;cal
SSE X 13
aspirin and paracetamol solution (l), and m is the mass of sorbent used (g). N
i1
In order to investigate the adsorption characteristics of aspirin and
paracetamol on sorbents N-CNT/b-CD and Fe/N-CNT/b-CD, the pseudo first Results
order, pseudo second order and Elovich kinetic models were used to test the
adsorption dynamics in this work.
Characterization of the composite materials
The Lagergren pseudo-first order kinetic rate expression [40,41] is given
as:
Focused ion beam scanning electron microscopy (FIB-SEM)
dqt The surface morphologies of the nanocomposite materials before and after
dt k1qe qt 7 sorption of aspirin are shown in Fig. 1. The images
2622 K. Mphahlele et al. / Journal of Environmental Chemical Engineering 3 (2015) 26192630

Fig. 1. FIB SEM images of Fe/N-CNT/b-CD nanocomposite polymers (a) before and (b) after adsorption of aspirin. Similar morphologies were observed with paracetamol.

were obtained by FIB-SEM, AUIGA1 CrossBeam workstation from Carl
Zeiss in order to assess morphological changes in the sorbent surfaces
following sorption of the contaminant. Before sorption (Fig. 1a), the sorbent
exhibits a cave-like, irregular and uneven surface morphology; the roughness
of the surface should be considered as a factor providing an increase in the
surface area. In addition, these pores decrease diffusional resistance and make
easy for mass transfer because of high internal surface area [42,43]. The
surfaces of sorbent after sorption (Fig. 1b) showed that the pores and surfaces
of sorbent were covered by the sorbate and became smoother. After sorption,
the pores were packed with sorbate. The micrograph showed that the sorbate
possessed densely and homogeneously adhered to the surface of the sorbent,
as a result of either natural entrapment in to the porous nanocomposite, due to
physical sorption by electrostatic forces or to covalent binding between the
cellular sorbent and the sorbate [44].
FTIR analysis
FTIR spectroscopy was also used to study the nanocomposite polymers
before and after adsorption (Fig. 2). The bands in Fig. 2a correspond to O H
(3200 cm 1), C H (2938 cm 1), CO (1714 cm 1) and C O (1200 cm 1 and
1000 cm 1) functional groups found on acid functionalized N-CNTs and
cyclodextrins. The absence of an isocyanate peak confirmed that
polymerization between monomer and the linker did occur [45,46]. After
adsorption (Fig. 2b), a disappearance of peaks C O (1200 cm 1 and 1000 cm
1) and C H (2938 cm 1) was observed. New bands were observed i.e. CC
band at1600 cm 1 and 1500 cm 1. These changes indicated the possible
involvement of those functional groups on the surface of the sorbent during
sorption of aspirin.
UVVIS analysis
Fig. 3 shows the UVVis absorbance before and after adsorption of
aspirin and paracetamol from water using Fe/N-CNT/b-CD

Fig. 2. FTIR spectrum of Fe/N-CNT/b-CD nanocomposite polymers (a) before and (b) after adsorption of aspirin.
 K. Mphahlele et al. / Journal of Environmental Chemical Engineering 3 (2015) 26192630 2623

Fig. 3. UVvis spectra showing the amounts of (a) aspirin and (b) paracetamol before and after sorption using Fe/N-CNTs/b-CD at 298 K.

nanocomposite polymers. It was observed that after sorption of aspirin and
paracetamol the absorbance decreased significantly confirming that aspirin
and paracetamol has been removed from aqueous solution. The quantitative
analysis revealed that the sorption of aspirin was 100% and of paracetamol
63% on Fe/N-CNT/ b-CD at 298 K. The N-CNT/b-CD nanocomposite polymers
were less effective at removing the compounds in water (see Fig. 3).
Batch equilibrium studies
Effect of pH
The effect of pH on the sorption of aspirin and paracetamol was studied
by varying the initial pH from 2 to 12 for the sorbents N-CNT/b-CD and
Fe/N-CNT/b-CD. The sorption of aspirin sorption significantly changed over
the pH value of 26 and became constant from pH 6 to 12 (Fig. 4a). The
highest sorption of aspirin was recorded at pH 2, which was 40.0 and 45.4 mg
g 1 for N-CNT/ b-CD and Fe/N-CNT/b-CD, respectively. As the pH of the
aspirin solution was increased, a proportional decrease in sorption was observed
due to the successive deprotonation of positive charged
groups on the sorbent and electrostatic repulsion between negatively charged
sites on the sorbent and aspirin. There was competition between OH (at high
pH) and aspirin for positively charged sorption sites [47,48].
The effect of pH on the sorption capacity of paracetamol onto N-CNT/b-
CD and Fe/N-CNT/b-CD is presented in Fig. 4(b). A slight change on the
sorption of paracetamol over the pH value of 610 was observed. This was
attributed to available OH ions in the solution, which consequently increases
the sorption of paraceta-mol [49]. However, from pH 10 to 12 a slight
decrease in the sorption of paracetamol was observed because the effect of pH
on the sorption of paracetamol from aqueous solution was minimal; pH 7 was
selected for subsequent experiments as this would minimize cost in pH
adjustment. Similar observation was reported by Villaescusa et al. where
paracetamol sorption onto cork bark, yohimbe bark and grape stalk sorbents
was not depended on pH [4]; since there was minimal change in the sorption
capacity it is clear that electrostatic interactions are not responsible for
paracetamol sorption onto N-CNTs/b-CD and Fe/N-CNT/b-CD sorbents.
Furthermore, it was also observed that the sorption

Fig. 4. Effect of pH on adsorptive removal of (a) aspirin and (b) paracetamol using N-CNTs/b-CD and Fe/N-CNT/b-CD nanocomposite polymers.
2624 K. Mphahlele et al. / Journal of Environmental Chemical Engineering 3 (2015) 26192630

Fig. 5. Effect of temperature on the sorption of aspirin onto N-CNT/b-CD (a) non-linear fitting of Freundlich isotherm, (b) Langmuir isotherm and (c) Freundlich isotherm respectively (shaking speed
= 150 spm, sorbent dose 0.05 g/50 mL; pH 2.4)..

capacity of Fe/N-CNT/b-CD nanocomposites (35.0 mg g 1) was higher than
the sorbent capacity of N-CNTs/b-CD (34.0 mg g 1); due to the presence of
nanoparticles of Fe on the surface of N-CNTs enhanced the sorption capacity
of the sorbent. CDs are starch based nanostructured materials known to form
hostguest complexes with hydrophobic compounds in water [18,19].
Hydrophobic interactions are more effective at higher molecular weights, as
in that case there are more possible interaction points. This explains why
paracetamol, which a relatively small molecule, shows the lowest adsorption
[50] compared to aspirin.
Effect of temperature on equilibrium isotherms
The effect of temperature on sorption capacity of the nano-composite was
investigated in the temperature ranges of 298318 K. The interaction between
the sorbents (N-CNT/b-CD and Fe/N-CNT/b-CD) and aspirin and
paracetamol are presented in the form of equilibrium data shown in Figs. 5, 6,
7 and 8 . The data show that sorption capacity of aspirin and paracetamol is
insensitive to temperature. In Figs. 5 and 6, the sorption of aspirin on N-
CNT/b-CD and Fe/N-CNT/b-CD is shown. The equilibrium curves rise
sharply in the initial stages indicating that there are

Fig. 6. Effect of temperature on the sorption of aspirin onto Fe/N-CNT/b-CD (a) non-linear fitting of Freundlich isotherm, (b) Langmuir isotherm and (c) Freundlich isotherm respectively (shaking
speed = 150 spm, sorbent dose 0.05 g/50 mL; pH 2.4).
 K. Mphahlele et al. / Journal of Environmental Chemical Engineering 3 (2015) 26192630 2625

Fig. 7. Effect of temperature on the sorption of paracetamol onto N-CNT/b-CD (a) non-linear fitting of Freundlich isotherm, (b) Langmuir isotherm and (c) Freundlich isotherm respectively (shaking
speed = 150 spm, sorbent dose 0.05 g/50 mL; pH 7.0)..

plenty of readily accessible sites for adsorption (Figs. 5a and 6a). The
asymptotic plateau is reached indicating that the sorbents are saturated at this
level. An L-type graph according to the Giles classification is observed. In
this type of isotherm, the initial portion provides information about the
availability of the active sites to the sorbate and an asymptotic plateau
observed. This shows the ratio between the concentration of paracetamol
remaining in solution and adsorbed onto N-CNT/b-CD and Fe/ N-CNT/b-CD
decreases when the paracetamol concentration
increases, providing a concave curve [51]. The initial curvature indicates that
large amounts of aspirin and paracetamol are adsorbed at lower
concentrations as more active sites of N-CNT/ b-CD and Fe/N-CNT/b-CD are
available. As the concentration increased the aspirin and paracetamol molecules
could not find vacant sites. The sorption capacity for sorbents Fe/N-CNT/b-CD
was higher when compared to the sorption capacity of N-CNT/ b-CD, which was
indicative of the strong interaction between aspirin, paracetamol and nanoparticles
on the sorbents.

Fig. 8. Effect of temperature on the sorption of paracetamol onto Fe/N-CNT/b-CD (a) non-linear fitting of Freundlich isotherm, (b) Langmuir isotherm and (c) Freundlich isotherm respectively
(shaking speed = 150 spm, sorbent dose 0.05 g/50 mL; pH 7)..
2626 K. Mphahlele et al. / Journal of Environmental Chemical Engineering 3 (2015) 26192630

Table 1
Langmuir and Freundlich isotherm parameters at three temperatures for sorption of aspirin using N-CNT/b-CD and Fe/N-CNT/b-CD nanocomposite polymers.
b K
Temperature Qmax (mg g 1) L R2 SSE F n R2 SSEa
1
(K) (L g ) (mg1 1/n l1/n/g)
N-CNT/b-CD
298 71.94 0.211 0.993 0.0239 2.87 2.1 0.998 0.0013
308 71.43 0.192 0.992 0.0681 1.49 2.6 0.999 0.0032
318 71.42 0.173 0.990 0.0222 0.73 1.59 0.999 0.0036

Fe/N-CNT/b-CD
298 101 0.142 1.000 0.0020 15 2 0.943 0.0006
308 104 0.120 0.998 0.0030 12 2 0.915 0.0017
318 105 0.100 0.994 0.0005 10 1 0.880 0.0000
a
Values represent minimum sum of square error (SSE).

Solidliquid equilibrium can be easily described by sorption isotherms.
The Langmuir and Freundlich models were fitted to the experimental data.
Straight lines were obtained by plotting Ce/qe versus Ce for the Langmuir
isotherm and ln Ce versus ln qe for the Freundlich isotherm, for the adsorption
of aspirin and paracetamol onto N-CNT/b-CD and Fe/N-CNT/b-CD. The
values of Qmax, bL, KF, n and R2 are reported in Tables 1 and 2 for aspirin
and paracetamol, respectively. It was observed that the experimental data
fitted both Langmuir and Freundlich models with the correlation coefficients
R2 > 0.95, therefore error function such as SSE was used to verify which
model fitted the experimental data best.
Linear regression (listed in Table S1) was the most commonly used
method to obtain the parameters involved in the kinetic expression and also in
predicting the best-fit kinetic expression. The linear method presumes that the
scatter of points around the trend line follows a Gaussian distribution and the
error distribu-tion is the same at every value of X [52,53]. But this is seldom
true or practically unfeasible with kinetics (as most of the sorption isotherms
and kinetics are non-linear due to different mecha-nisms) as the error
distribution gets distorted after transforming data to a linearized form. Though
the error distribution for each experimental data point may be approximately
invariable over a variety of measurement, when linearized to different form
the error distribution linked with each data point becomes reliant on its
magnitude [52]. This has correlated to the use of non-linearized models in
conjunction with number of error analysis technique
A direct evaluation of the sorption capacities of several sorbent materials
cannot be objective due to the different synthesis parameters [54].
Nevertheless, in order to understand a first sense about the sorption diversity
of the materials used in the present study, some examples are presented in
Supplementary documents (i.e. Table S2 with appropriate references) [54
58]. Sotele et al. investigated the removal of four pharmaceutical compounds
(i.e. atenolol, caffeine, diclofenac and isoproturon) using activated carbon.
The equilibrium sorption capacities for atenolol, caffeine, diclofenac and
isoproturon were 130, 270, 280 and 180 mg g 1 on activated carbon,
respectively [55]. Though, high equilibrium capacity was observed, a gradual
uptake of these compounds on activated carbon and the establishment of
equilibrium was 3 days for caffeine and 14 days for diclofenac [55]. Bui and
Choi investigated the sorption of five pharmaceutical compounds including
carbamazepine, clofibric, diclofenac, ibuprofen and ketoprofen on
mesoporous silica SBA-15. The optimum pH for sorption was found to be
acidic for the all these compounds; as pH was increased, sorption decreased
[57]. This was similar to our pH studies for aspirin sorption. The sorption
capacities observed by Bui and Choi were however extremely low and ranged
between 0.07 and 0.41 mg g 1 [57]. Since, each material presents its own
advantages like surface characteristics and disadvantages such as synthesis
cost, it is understandable that a direct comparison of sorbent performance on
the sorption of pharmaceutical is difficult

[37]. The non-linear regression has been performed by using the curve fitting
technique with Microsoft Excel (i.e. Figs. 5a, 6a, 7a and 8a) at 298 K. A
comparison of SSE for the two isotherms is listed in Tables 1 and 2. The
Freundlich isotherm was suitable for the experimental data compared to
Langmuir isotherm for sorption of aspirin. The Freundlich isotherm showed
good correlation coefficients and minimum SSE compared to Langmuir
isotherm for the sorption of aspirin onto N-CNT/b-CD and Fe/N-CNT/b-CD,
while the Langmuir isotherm showed good correlation coefficients and
minimum SSE compared to Freundlich isotherm for the sorption of
paracetamol onto N-CNT/b-CD and Fe/N-CNT/b-CD.
[54]. Nevertheless, this study showed that sorption process can be considered
an efficient treatment for the removal of emerging compounds from water.
Both sorbents showed a good equilibrium capacity and, furthermore, since the
sorption is a physical process, it does not imply by-products formation, which
could be more toxic than the parent compounds.
At this equilibrium condition the rates of adsorption and desorption are
equal and the net loading on the sorbate cannot increase further. It becomes
essential either to regenerate the sorbent or to dispose it off. In certain
applications it may be more inexpensive to discard the sorbent after use.
Disposal would be preferred when the sorbent is of low cost, is very hard to

Table 2
Langmuir and Freundlich isotherm parameters at three temperatures for sorbents N-CNTs-b-CD and Fe/N-CNTs-b-CD of sorption of paracetamol.
Q
Temperature max bL R2 SSEa KF n R2 SSEa
(K) (mg g 1) (L g 1) (mg1 1/n l1/n/g)
N-CNTs-b-CD
298 41 0.357 0.978 0.0002 0.670 0.700 0.980 0.0018
308 40 0.313 0.998 0.0002 0.216 0.586 0.967 0.0016
318 39 0.275 0.998 0.0002 0.051 0.466 0.948 0.0017

Fe/N-CNTs-b-CD
298 75.18 0.029 0.918 0.0002 2 1 1.000 0.0019
308 78.12 0.024 0.911 0.0001 2 1 1.000 0.0008
318 71.30 0.021 0.920 0.0002 2 1 1.000 0.0002
a
Values represent minimum sum of square error (SSE).
 K. Mphahlele et al. / Journal of Environmental Chemical Engineering 3 (2015) 26192630
regenerate, and the non-sorbed constituent is the desired product of very high
value. In the majority of applications, the disposal of sorbents as waste is not
a cost-effective option [59]; consequently desorption and regenerations
studies are recommended.
Adsorption kinetics
Effect of initial concentration
The time profiles for the sorption of aspirin and paracetamol are present in
Figs. 9 and 10, respectively. The sorption equilibria were achieved in
approximately 30 min.. Equilibrium time is one of the important parameters
for economical treatment of wastewater. The equilibrium sorption capacity
increased from 33.44 to 71.43 mg g 1 and 32.15 to 69.93 mg g 1 when initial
aspirin concentration was increased from 50 to 100 mg L 1 and sorption onto
N-CNT/b-CD and Fe/N-CNT/b-CD, respectively. A similar pattern was
observed for paracetamol where the equilibrium sorption capacity increased
from 18.18 to 40.16 mg g 1 and 18.05 to 39.68 mg g 1 when the initial
paracetamol concentration was increased from 50 to 100 mg L 1 onto N-
CNT/b-CD and Fe/N-CNT/ b-CD, respectively. This suggests that the initial
concentration plays an important role in the sorption of aspirin onto Fe/N-CNT/ b-
CD.
The uptake of aspirin and paracetamol and the kinetics using linearized
pseudo first order, pseudo second order and Elovich model at different initial
concentrations of both aspirin and paracetamol onto Fe/N-CNT/b-CD are also
presented in Figs. 9 and 10. It is evident that the kinetic modelling of the
aspirin and
Fig. 9. The influence of contact time on the sorption capacity of aspirin for different concentrations onto Fe/N-CNT/b-CD, the experimental data are fitted on (a) pseudo first order, (b) pseudo second
order, (c) Elovich and (d) non-linear pseudo second order kinetic model. At 298 K, sorbent dose 1 g/1000 mL, pH 2.4.
2627
paracetamol sorption onto N-CNTs-b-CD and Fe/N-CNTs-b-CD sorbents
well fitted the pseudo second order model with the correlation coefficients
higher than 0.95 for all the systems studied. The rate k 2 for aspirin and
paracetamol decreased with an increase in concentration, suggesting that the
sorption capacity decreased due to less available sorption sites [60].
However, it has been reported that transformations of non-linear equations
to linear forms implicitly alter their error structure in the measurement of
model parameters [61]. Hence, non-linear statistic SSE and linear coefficient
R2 were used to determine the model that best fitted the experimental data for
aspirin and paracetamol as shown in Figs. 9(d) and 10(d), respectively. The
pseudo second order showed the highest correlation coefficient as it fitted the
experimental data for aspirin and moreover it also yielded a minimum SSE
(i.e. Table 3) compared to the pseudo first order model and Elovich kinetic
model. While paracetamol experimental data were best fitted by the Elovich
kinetic model compared to the pseudo first order model and pseudo second
model; because it yielded a minimum SSE (i.e. Table S3).
Sorption thermodynamics
Thermodynamic considerations of a sorption procedure are essential to
conclude whether the procedure is spontaneous or not. Gibbss free energy
change, DG , is the essential measure of spontaneity [62]. Reaction occur
spontaneously at a given temperature if DG is a negative value. The
thermodynamic
2628 K. Mphahlele et al. / Journal of Environmental Chemical Engineering 3 (2015) 26192630

Fig. 10. The influence of contact time on the sorption capacity of paracetamol for different concentrations onto Fe/N-CNT/b-CD, the experimental data are fitted on (a) pseudo first order.

parameters of Gibbs free energy change, DG , enthalpy change, DH , and process. A plot of ln KL against 1 T 1 should yield a straight line with the
entropy change, DS , for the adsorption processes are calculated using the intercept ofDS /RT and a slope of DH /R [63]. The thermody-namic
equation below: parameters are given in Table S4 and Table 4, which were calculated using
Eqs. (14) and (15). The negative values of the Gibbs free energy change
confirms the feasibility of the process and indicates the spontaneous nature of
DG RT ln Ka 14 sorption of aspirin and paracetamol at all the temperatures of all the sorbents
and studied. For the sorption of aspirin the values of DG increased from 2.99 to
1.37 kJ mol 1 and 5.25 to 5.08 kJ mol 1 with N-CNTs-b-CD and Fe/N-CNTs-
DG DH TDS 15
b-CD, respectively. The negative values of DH 27.13 kJ mol 1 and 10.61 kJ
where R is universal gas constant (8.314 J mol 1 K 1) and T is the absolute
temperature in K. mol 1 for aspirin sorption onto N-CNTs-b-CD and Fe/N-CNTs-b-CD,
respectively, indicates that the sorption process was exothermic.
A positive value of enthalpy change indicates that the process is
endothermic, while a negative value indicates an exothermic

Table 3
Pseudo first order, pseudo second order and Elovich kinetic models parameters at 298 K for sorption of aspirin on sorbents N-CNT/b-CD and Fe/N-CNT/b-CD for concentration 50, 75 and 100 mg L
1
. Sorbent dose = 1 g/1000 mL solution.

Pseudo-first-order kinetic model Pseudo-second-order kinetic model Elovich kinetic model

1 1 1 1 1
Co (ppm) qe,exp (mg g ) K1 (1 min ) qe,cal (mg g ) R2 SSE K2 (g mg min ) qe,cal (mg g ) R2 SSE a (mg g min 1) b R2 SEE
N-CNT/b-CD
50 32.670 0.122 38.020 0.960 0.0018 0.004 33.44 0.995 0.0002 29.600 0.051 0.970 0.0004
75 52.450 0.136 54.950 0.950 0.0011 0.076 52.36 0.999 0.0005 18.220 0.068 0.980 0.0013
100 72.390 0.129 63.100 0.980 0.0002 0.009 71.43 0.999 0.0002 8.400 0.100 0.980 0.0009

Fe/N-CNT/b-CD
50 30.8 0.11 34.48 0.982 0.0006 0.0027 32.15 0.986 0.0003 6.94 0.11 0.97 0.0923
75 50.8 0.10 33.56 0.814 0.0003 0.0064 50.76 0.999 0.0000 17.08 0.08 0.98 0.0012
100 70.7 0.16 69.79 0.767 0.0011 0.0078 69.93 0.999 0.0003 29.53 0.06 0.98 0.0023
 K. Mphahlele et al. / Journal of Environmental Chemical Engineering 3 (2015) 26192630
Table 4
Thermodynamic parameters for the sorption of paracetamol at different temperatures for
adsorbents N-CNT/b-CD and Fe/N-CNT/b-CD.
Sorbent DH (kJ mol 1) DS (J mol K 1) DG (kJ mol 1)
298 K 308 K
N-CNTs-b-CD 4.56 10.76 1.36 1.25
Fe/N-CNTs-b-CD 6.71 17.98 1.35 1.16
Similarly, the same trends were observed for the sorption of paracetamol,
(i.e. Table 4). For the sorption of paracetamol the values of DG increased
from 1.36 to 1.14 kJ mol 1, 1.35 kJ mol 1 to 0.99 kJ mol 1, for sorption onto
N-CNTs-b-CD and Fe/N-CNTs-b-CD, respectively. The negative values of
DH indicate that the sorption process was exothermic. The negative values of
DS indicated the decreased randomness at the solid-solute interface during
adsorption; while the positive value of DS suggest increased randomness at
the solid-solute interface during adsorption process. Negative values of DG
for both aspirin and paracetamol sorption onto N-CNT/b-CD and Fe/N-
CNT/b-CD sorbents were obtained indicates the feasibility and spontaneity of
the sorption process.
Conclusion
Greener N-CNT-b-CD and Fe/N-CNT-b-CD nanocomposite polymers
were successfully prepared using an efficient process that involved dispersion
of the Fe nanoparticles onto N-doped CNTs. The results showed that the
sorption capacities of aspirin and paracetamol onto N-CNT-b-CD sorbent
were lower than those of Fe/N-CNT-b-CD due to the presence of Fe NPs in
the nanocomposites. The Freundlich isotherm model fitted the equilibrium
data best for aspirin for both linear and non-linear sorption models; because
the Freundlich isotherm showed high correlation coefficients (R2) and a
minimum SSE for the sorption of aspirin onto all the sorbents at temperatures
298, 308 and 318 K and the maximum sorption capacities of aspirin increased
from 71.94 to 101.00 mg g 1, onto N-CNT-b-CD and Fe/N-CNT-b-CD,
respectively, at 298 K. The opposite was observed for paracetamol, Langmuir
isotherm model fitted the equilibrium data best for both linear and non-linear
sorption models. The Langmuir isotherm showed high correlation coefficients
(R2) and a minimum SSE for the sorption of paracetamol onto all the sorbents
in this study at temperatures 298, 308 and 318 K, and the monolayer sorption
capacities of paracetamol increased from 41.00 mg g 1 to 75.15 mg g 1 at 298
K, onto N-CNT-b-CD and Fe/N-CNT-b-CD, respectively. Furthermore, the
sorption kinetics of aspirin onto the N-CNT-bCD and Fe/N-CNT/b-CD
sorbents well fitted onto the pseudo second order model, as a minimum SSE
was observed compared to pseudo first order and Elovich models. The
paracetamol experimental data was best fitted by the Elovich kinetic model
compared to the pseudo first order and pseudo second models; because it
yielded a minimum SSE.
Acknowledgments
The authors thank the South African National Research Foundation
(NRF), Tshwane University of Technology (TUT) and the Council for
Science and Industrial Research (CSIR), Pretoria, South Africa for financial
support.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the online
version, at http://dx.doi.org/10.1016/j.jece.2015.02.018.
2629
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