Chemical Thermodynamics and Thermal Analysis 3–4 (2021) 100013

Contents lists available at ScienceDirect

Chemical Thermodynamics and Thermal Analysis

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

Endocrine Disruptors-(estrone and 𝛽-estradiol) removal from water by

Nutshell activated carbon: Kinetic, Isotherms and Thermodynamic studies
Khotha D. Elias 1, Ikechukwu P. Ejidike 1,2,∗, Fanyana M. Mtunzi 1,3, Vusumzi E. Pakade 1
1
Department of Chemistry, Faculty of Applied and Computer Sciences, Vaal University of Technology, Vanderbijlpark, 1911, South Africa
2
Department of Chemical Sciences, Faculty of Science and Science Education, Anchor University, Lagos 100278, Nigeria
3
Institute of Traditional Knowledge and Traditional Medicine, Vaal University of Technology Southern Gauteng Science and Technology Park, Sebokeng, 1983, South
Africa

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

Keywords: A large number of substances in the environment designated as endocrine-disrupting chemicals (EDCs) are
Endocrine Disruptors amongst the most intoxicating compounds found in environmental waters. The removal of two EDCs: estrone
Water (E1 ) and 𝛽-estradiol (E2 ) by activated carbon was examined in an agitated non-flow batch adsorption studies.
Adsorption, Activated Carbon
The macadamia nutshell activated carbon (MAC) was characterized by TGA, FTIR, and SEM. Properties such as
Estrone
contact time, adsorbent dosage, pH, initial steroids concentration, and temperature were examined. Mathematical
𝛽-Estradiol
Thermodynamic models like pseudo-first-order and pseudo-second-order kinetics, thermodynamic, the Freundlich, and Langmuir
isotherms model were used to describe the steroids adsorption phenomenon. From the Langmuir isotherm, max-
imum adsorption capacity was found to be 22.0 mg/g. Thermodynamic factors: ∆G° values of –1.223 to –1.308
kJ/mol, ∆H° = –11.72 kJ/mol, and ∆S° = 37.34 J/mol k of steroids adsorbed onto MAC indicate that the adsorp-
tion was spontaneous, proceeded favourably at lower temperature and exothermic in nature, demonstrating that
physisorption mechanism predominates. The distinctive data and adsorption intensity disclosed that MAC could
be engaged as a substitute for effective adsorbents for the removal of endocrine disruptors-steroids from water.

1. Introduction
Steroid hormones are a class of medications that are prescribed for
diverse human and veterinary purposes. 17𝛽-estradiol is extensively uti-
lized as a human contraceptive pill for the birth regulator, and as a
growth stimulator in feedlot ration of livestock animals [1-3]. Differ-
ent steroid hormones are used in veterinary medications, and as con-
stituents of livestock animal feed, for example, cattle, poultry, and pigs
[4-6]. Essential portions of steroid hormones administered to humans
and animals are not fully metabolized by the body [7]. The excess is
spilled over and passed out as waste, either in the form in which they
are administered or as derivatives of the parent compound [8,9]. Most
of these steroid hormones residues end up in water systems, wastewa-
ter, wastewater treatment plant effluents (WWTPs), fresh surface water,
lakes, and groundwater [4,10,11]. Studies have shown that large con-
centrations of natural and synthetic estrogens coverts male fish to female
fish and also diminish testes size [4,6], disturb propagative fitness [5],
while 𝛽-estradiol (E2 ) possess severe harmful properties on other forms
of marine life [12].
Due to the challenge posed by the presence of steroids and other
pollutants in water, researchers have been working towards develop-
ing low-cost materials that can be used to remove unwanted contam-
inants from water system [13-15]. This has led to the usage of bio-
materials from agricultural waste and nanomaterials for environmen-
tal pollutants [16,17] like organics and dyes [18-20]. An artificial neu-
ral network (ANN) and response surface methodology (RSM) have been
used to model the removal of 4-chlorophenol (4-CP) in a nanoscale zero-
valent iron (nZVI)/persulfate/ water system [16]. Activated carbon (AC)
sorbent produced from acorn shell by loading iron oxide (Fe-AC) have
been used to eliminate methylene blue from aqueous solutions by batch
adsorption efficiency. The maximum adsorption capacity was reported
to be 312.5 and 370.4 mg g−1 for AC and Fe-AC adsorbents at 298 K,
respectively [21]. Magnetization of functionalized multi-walled carbon
nanotubes (FMWCNTs-Fe3 O4 ) was synthesize and characterized for the
removal of ciprofloxacin (CIP) [22]. Zinc oxide nanoparticles loaded
on activated carbon (AC) derived from coffee waste by green synthe-
sis ultrasonic method to form Zn(OH)2 -AC composite have been used
for effective elimination of malachite green (MG) from wastewater by
batch adsorption method [23].
Activated carbons (AC) have been widely adopted in the indus-
trial fields for air, water, and sewage clean up to remove odour in the
air and contaminants in water, taking advantage of their absorptivity
[17,24,25]. Though coal appears to be the most frequently used precur-

∗
Corresponding Author:
E-mail addresses: iejidike@aul.edu.ng, destinedchild12@gmail.com (I.P. Ejidike).

https://doi.org/10.1016/j.ctta.2021.100013
Received 2 June 2021; Received in revised form 26 August 2021; Accepted 29 August 2021
2667-3126/© 2021 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
K.D. Elias, I.P. Ejidike, F.M. Mtunzi et al.
Figure 1. The chemical structures of estrone (E1 ) and 𝛽-estradiol (E2 )
sor, agricultural waste has shown to be a better choice. Studies have
exemplified the preparation of activated carbon from agricultural waste
including nutshells and other by-products such as coconut shell, almond
shell, apricot and cherry stones, grape seeds, mango shell, nypa fruit-
icans lignin, olive, peach, macadamia nutshell, hazelnut shell, and eu-
calyptus plant parts [17,24,26-28]. As a way of reducing agricultural
by-products, encouraging recycling of waste and econo-social optimiza-
tion envisaging every nation, researchers are synthesizing activated car-
bons as catalyst or adsorbent from agricultural waste sources [24,29-
31]. These class of adsorbents has revealed favourable performance for
the elimination of pollutants from wastewater. Activated carbon elimi-
nates compounds through sorption on both the surface and within the
substrate matrix. The efficacy of activated carbon is prejudiced by sur-
face area, surface pH, porosity, and surface charge [17,25-33]. Bio-based
magnetic activated carbon (Fe3 O4 -AC) was prepared and characterized
for effective adsorption of malachite green (MG) from aqueous solution
[29], while activated and grafted carbon from macadamia nutshell was
utilized for the removal of chlorinated phenols from aqueous solution
[30]. Anionic dye was removed from aqueous solution by palm kernel
fibre as sorbent [31]. Magnetic AC/CeO2 nanocomposite was reported
as effective removal of rhodamine B from aqueous solution. The study
indicated that RhB adsorption by the AC/Fe/Ce magnetic adsorbent has
an endothermic character [32]
Effort towards solving the accumulation problem of pollutants in
soil and water, finding their ways into the farm animal and the human
food chain, identification of robust new procedures of purifying water
at a lesser cost and low energy, while curtailing the use of chemicals
and their impact on the environment [17,21,24,29,30,33,34] is imper-
ative. Owing to the above, we report the use of macadamia nutshell
activated carbon as an effective adsorbent for the removal of endocrine-
disrupting chemicals like estrone (E1 ) and 𝛽-estradiol (E2 ). The acti-
vated carbon material was characterized by Fourier transforms infrared
spectroscopy (FTIR), scanning electron microscopy (SEM), and thermal
gravimetric analysis (TGA). Adsorbent factors such as pH, contact time,
initial steroids concentration, temperature, and adsorbent dosage were
considered. The experimental adsorption data were used to evaluate the
kinetic models like pseudo-first-order (PFO) and pseudo-second-order
(PSO), thermodynamic, the Freundlich, and Langmuir isotherms model.
To the best of our knowledge, no report exists for the removal of steroids
from the aqueous solution using activated carbon from macadamia nut-
shells.
2. Material and methods
2.1. Reagents
All solvents such as estrone and 𝛽-estradiol were delivered by Sigma-
Aldrich (Johannesburg, South Africa). The chemical structures of es-
trone (E1 ) and 𝛽-estradiol (E2 ) are shown in Figure 1. Macadamia nut-
shell activated carbon (MAC) with the surface area of about 1000
m2 /g, was obtained commercially from Filtatech (Johannesburg, South
Africa), and utilized without additional purification. All dilutions and
standard preparations were achieved using Ultra-pure water collected
2
Chemical Thermodynamics and Thermal Analysis 3–4 (2021) 100013
from Siemens LaboStar equipment (Warrendale, Pennsylvania, USA).
Accurately weighed (grams) of estrone or 𝛽-estradiol were added each to
a pre-cleaned 1000 mL volumetric flask, dissolved with a little amount of
ultra-pure water, shaken very well and then made to the mark and stored
for analysis. pH of the solutions were measured using ADWA AD111
OPR pH meter (Szeged, Hungary).
2.2. Characterization of Macadamia nutshell activated carbon (MAC)
The infrared spectrum was obtained with a Shimadzu Spectrum FT-
IR spectrometer 8300 series (Kyoto, Japan), ranging from 4000 to 400
cm−1 for surface functional group changes detection. The morphological
evaluation of macadamia nutshell activated carbon (MAC) was evaluated
using an electron Hitachi S-5200 scanning electron microscope (Tokyo,
Japan). Centrifugation was achieved using CL10 Centrifuge ThermoSci-
entific (Johannesburg, South Africa). Thermogravimetric analysis (TGA)
was executed with a Shimadzu DTG-60H simultaneous DTA-TG appara-
tus (Kyoto, Japan) under a nitrogen atmosphere with a heating system
rate of about 5°C/ min stretching from 0°C to 900°C. Batch adsorptions
of the selected steroids onto the adsorbent was performed using a Mul-
tichannel agitator MS-53 M model Jeio Tech (Seoul, Korea).
2.3. Evaluation by batch adsorption method
The adsorption studies were performed in a batch manner using
multi-stirrer in a sequence of Erlenmeyer flasks of 50 mL capacity shel-
tered to prevent contamination. The effect of time, temperature, concen-
tration, and solution pH were studied. An equal quantity of absorbent
was added separately into each discrete flask, and the other parameters
time, temperature, concentration, and pH were set different, and the
flasks were agitated. The tests were performed using 50.0 mL of estrone
or 𝛽-estradiol solutions namely: pH values (2, 4, 6, 7, 8, 10), contact
times (10, 30, 90, 180, 360 min); adsorbent dosage (0.1, 0.4, 1, 1.2, 1.6
g/L), temperature (20, 25, 30, 35°C), and initial steroids concentration
(1, 2, 6, 8, 10 mg/L), respectively. 0.1 mg adsorbent positioned in a
sequence of 50.0 mL conical flask at pH 7 and 300 rpm for 120 min
was utilized for sorption equilibrium studies was performed using. The
experiments were carried out in replicate (n = 3), and the blanks also
performed. After prescribed parameters, the solutions were centrifuged,
and the concentrations of steroids in the supernatant examined using
the HPLC Agilent. The adsorption capacity for steroids (estrone or 𝛽-
estradiol) uptake, 𝑞𝑒 (mg/g) and the amount removed was determined
as follow Eqs. 1 and (2):
( )
𝐶𝑜 − 𝐶𝑒 𝑉
𝑞𝑒 = (1)
𝑀
( )
𝐶𝑜 − 𝐶𝑒 100
%𝑅= (2)
𝐶𝑜
Co initial concentration of steroids (mg/L)
Ce concentration of steroids (mg/L)
V solution volume (L)
M amount of the adsorbent used (g)
3. Results and Discussion
3.1. Characterization of activated carbon by Fourier transform infrared
(FT-IR)
The functional and reactive groups present at the surface of
macadamia activated carbon, which supports adsorption activities
(Figure 2) was qualitatively and quantitatively studied using FTIR spec-
tra collected. The sorption capacity of the prepared activated carbon is
influenced by porosity and the chemical reactivity of functional groups
present at the surface. A disproportion between forces present at the
K.D. Elias, I.P. Ejidike, F.M. Mtunzi et al. Chemical Thermodynamics and Thermal Analysis 3–4 (2021) 100013

Figure 2. FT-IR-spectra of macadamia nutshell activated carbon

surface as compared to the force within the body is created by reac-

tivity, thereby, leading to molecular adsorption by van der Waals force
[17]. To have an understanding of the adsorption capacity of the pro-
duced macadamia activated carbon, information on the surface func-
tional groups were studied. The spectrum of macadamia activated car-
bon around the region 3328 cm−1 specifies the presence of the hydroxyl
stretching vibration: 𝜈(–OH) group (Figure 1) [20,21,33,35]. The methy-
lene groups were detected by the symmetric/ asymmetric vibrational
𝜈(–CH3 /–CH2 ) stretching at wavenumbers within the regions 2947 –
2800 cm−1 [17]. The aldehyde group of 𝜈(–O–CH3 ) was found around
2863 cm−1 and 2851 cm−1 . Strong bands at 1716 cm−1 indicate 𝜈(–C–
O–) stretching of carboxyl or carbonyl groups and 1496 – 1293 cm−1
signposts the occurrence of 𝜈(–C-C–) stretch ring aromatics [21,33].
Aliphatic 𝜈(–C–O–C–) groups are revealed by bands around 1385 – 1380
cm−1 . The bands from 1200 to 1000 cm−1 designates the fingerprint re- Figure 3. Scanning electron microscopy micrograph of macadamia nutshell ac-
gion of the aliphatic 𝜈(–C–H–) bending [21,35]. Aldehyde (–C–H–O–) tivated carbon
and stretching of benzene ring were detected by the peaks around re-
gions 851 and 761 cm−1, respectively [17,35].

3.2. Surface morphology of macadamia nutshell activated carbon
The surface physical morphology of the macadamia nutshell ac-
tivated carbon was characterized via scanning electron microscopy
(SEM), and the micrograph shown in Figure 3. The SEM image re-
vealed that the macadamia activated carbon consists of flaky long fold-
like structure with visible porosity in the materials. The analysis of the
sample showed that the structural backbone was not significantly trans-
formed since they retained their flakiness, signifying that the handling
was not disproportionately severe towards destroying the texture of the
material. The penetrable exterior of the produced activated carbon is
critical for fascinating in adsorbate molecules or particles during the
adsorption trials [21,33]. A closer look at the material surface, it was ob-
served that the pores were lengthened confirming that macadamia nut-
shell activated carbon maintained the structure of lignocellulose-based
plant resources demonstrating that the activation procedure eliminated
more of the non-carbonaceous materials [16,17,25].
3.3. Thermal gravimetric analysis of the macadamia nutshell activated
carbon
Activated carbon of Macadamia nutshell TGA/DTA data were
achieved at a heating system rate of 5°C/min under nitrogen atmosphere
(atm) with a temperature range of 0°C to 900°C. The percentage weight
loss against the temperature of the obtained data was plotted to have
insight about the stability, characteristics of the various fragments or
molecules, decomposition patterns, the oxidized carbons obtained af-
ter decomposition [21,30,33]. The temperature effect on the percent
weight loss of the macadamia nutshell activated carbon is displayed
in Figure 4. Thermal degradation of the activated carbon can be char-
acterized into four consecutive individual stages, specifically moisture
evolution, the putrefaction of hemicelluloses, cellulose and the lignin’s
[17,23]. Figure 4 exhibits the weight loss curve from 30 to 900 °C. The
weight loss at the start (< 150 °C) was most probable owed to the loss
of moisture in macadamia activated carbon. The quantity of adsorbed
water in plant material is a degree of the hydrophilic constituents in
the structure. The hemicellulose hydroxyl groups associated with wa-
ter molecules via hydrogen bonding could be responsible for the higher
water content [36]. The weight loss was observed around 150 – 482
°C due to the loss of unstable substances, including CO2 , CH4 , SO2 ,
CO2 , and RCHO- [30.33,37]. After that, a slight reduction in weight
loss was observed around 483 – 926 °C. At this stage, the principal com-
pounds: hemicelluloses, cellulose, and fractional lignin, were a loss from
macadamia activated carbon. Lastly, the weight loss was gradually de-
creased after 925 °C. It is typically related to the phase structure stability
when compared to the starting material [30,38].

3
K.D. Elias, I.P. Ejidike, F.M. Mtunzi et al.
Figure 4. Thermogravimetric analysis (TGA) of macadamia activated carbon
showing weight loss
Figure 5. Effect of pH on adsorption of estrone and 𝛽–estradiol unto macadamia
activated carbon, experimental conditions: pH 2 to 10, dosage 0.1 g, temp. 25°C,
time 120 min, solution volume 25 mL.
3.4. Effect of selected parameters on the steroids adsorption onto
macadamia activated carbon
Adsorption investigations were performed in batch mode using
multi-stirrer in a series of Erlenmeyer flasks of 50 mL capacity covered
to avoid adulteration. The effect of time, temperature, adsorbent mass,
concentration, and solution pH were investigated. Adsorption isotherms
were obtained by fitting the data collected during the impact of concen-
tration study into Langmuir and Freundlich isotherm.
3.4.1. Effects of pH
The pH effects on the sorption of estrone (E1 ) and 𝛽-estradiol (E2 )
were examined at varying pH values of 2, 4, 6, 7, 8 and 10. At the
same time, all other investigational variables were kept constant (2
mg/L, adsorbent dose 0.1 g, temperature 25°C). The effect of pH on
E1 and E2 sorption are exemplified in Figure 5. It was observed that
the pH values showed a substantial impact on the adsorption proce-
dure. The percentage effectiveness was higher in the acidic and neutral
pH ranges, and the lowest pH ranges in the alkaline medium, exhibit-
ing effect the surface charges of the activated carbon. The percentage
of E1 and E2 adsorbed was observed at lower and neutral pH (4, 6,
and 7). The number of steroids adsorbed was found to be maximum at
pH = 7 for both E1 and E2 are neutral and occur in non-ionic molecu-
lar form; hence, they were readily adsorbed onto the activated carbon
[25]. At higher pH of 8 and 10, the surface carbon constituent part be-
comes negatively charged, thereby reducing the adsorption procedure
by electrostatic repulsion [18,25,32]. It has been established that an up-
4
Chemical Thermodynamics and Thermal Analysis 3–4 (2021) 100013
Figure 6. Effect of adsorbent dosage on estrone (E1 ) and 𝛽-estradiol (E2 ) re-
moval by macadamia activated carbon, experimental conditions: dosage 0.1 to
1.6 g, pH 7, temp. 25°C, time 120 min, solution volume 25 mL.
surge in hydroxyl ions at higher pH values, it brings about the produc-
tion of aqua-complexes leading to the competition of ions available for
the carbonyl sites [16,39], thus reducing the adsorption capabilities of
the activated carbon (Figure 5). Adsorption of pharmaceutical products
onto activated carbon surface materials might occur via multi-layered
exchange of dispersal and electrostatic interactions existing amongst the
steroid ions and adsorbent (MAC) surface [30,33]. These interactions
might occur through the formation of the hydrogen bond, deposition
of the electron donor-acceptor compounds at the carbon surface, and
𝜋-𝜋 dispersal exchange existing between the delocalized electrons and
aromatic spheres of the estrone (E1 ) and 𝛽-estradiol (E2 ) [18,33,39].
3.4.2. Effect of adsorbent dosage
At constant steroids concentration of 2 mg/L, different amounts of
macadamia activated carbon (0.1, 0.2, 0.4, 1, 1.2, 1.6 g/L) were added
to steroids solutions (50 mL) to study the adsorbent dosage effect on es-
trone (E1 ) and 𝛽-estradiol (E2 ) sorption. Results in Figure 6 shows that
the adsorption measurements in the first stage increased rapidly with
adsorbent dosage increase, then increased slowly until equilibrium was
reached with further increase in the adsorbent dose [37-40]. It was ob-
served that at 1.0 g of the adsorbent dose, the % removal of 𝛽-estradiol
(E2 ) reached about 83%, while about 3% more reaching 85% depict the
extraction of estrone (E1 ). Thus 1.0 g/L of activated carbon was con-
sidered as the optimum dose and utilized in further experiments. The
preliminary increase in adsorption with adsorbent dose could be owing
to a strong driving force with an increase in adsorbent dose, leading to a
proportionate rise in adsorption resulting from higher adsorptive usage
of adsorbent [17]. The increase in % removal of E1 and E2 with the rise
in the amount of activated carbon up to 1.0 g could be accredited to the
upsurge in both the surface area and the adsorption sites available for
the removal of estrone and 𝛽-estradiol [24,29,40]. However, the adsorp-
tion rate was not enhancing effectively concerning the adsorbent dose
increasing from 1.0 to 1.6 g/L. This inference may be responsible for the
increase in the overlapping or aggregation of adsorbent sites at a high
dose [37,39].
3.4.3. Effect of contact time
The quantity of estrone (E1 ) and 𝛽-estradiol (E2 ) adsorbed onto the
macadamia activated carbon was observed as steroid solution function
at various shaking times (10 - 360 min) at 25°C and pH 7 to inves-
tigate the contact time effect on the adsorption process. An activated
carbon dosage of 0.1 g was added to 50 mL of 2 mg/L steroids solution.
Figure 7 indicated that the adsorption of estrone and 𝛽-estradiol onto
macadamia activated carbon (MAC) increased with increasing contact
K.D. Elias, I.P. Ejidike, F.M. Mtunzi et al.
Figure 7. Effect of contact time on estrone (E1 ) and 𝛽-estradiol (E2 ) removal
by macadamia activated carbon, experimental conditions: time 10 to 360 min,
pH 7, dosage 0.1 g, temp. 25°C, solution volume 25 mL.
Figure 8. Effect of initial steroids concentration on estrone (E1 ) and 𝛽-estradiol
(E2 ) removal by macadamia activated carbon, experimental conditions: concen-
tration 1 to 2 ppm, time 120 min, pH 7, dosage 0.1 g, temp. 25°C, solution
volume 25 mL.
time. Moreover, the sorption was very rapid in the first 25 min; hence
the % removal reaching 60% for estrone (E1 ) and 58% for 𝛽-estradiol
(E2 ). The adsorption of E1 and E2 increased progressively during the
following 45 min until equilibrium is reached at about 90 min. The ob-
tained results presented that the uptake of steroids by the activated car-
bon be contingent on contact time. The rapid adsorption of estrone (E1 )
and 𝛽-estradiol (E2 ) during the preliminary stages (25 min) might result
from the obtainability of the exposed surface and energetic sites on the
macadamia activated carbon (MAC) surface [21,25,30,33]. The satura-
tion point was stretched at 90 min. The quantity of steroids adsorbed at
the equilibrium time replicates the maximum adsorption capacity of the
adsorbent even at the advanced stages between 100 and 360 min. These
observations may be subject to the time required for the steroids to en-
counter the border layer effect, then diffuse to the surface of activated
carbon and lastly diffuse into the permeable structure of the adsorbent
[25,39-40].
3.4.4. Effect of concentration
The impact of initial estrone (E1 ) and 𝛽-estradiol (E2 ) concentration
was examined by shaking known amounts of MAC adsorbents in varying
levels of steroids in the range 1 to 2 mg/L. At the same time, other pa-
rameters like temperature, pH, and time were set constant. The adsorp-
tion data for the steroids uptake against different initial concentrations
are represented in Figure 8, displaying an increased value from 0.1 ppm
up until 1.0 ppm. The amount of estrone and 𝛽-estradiol adsorbed (%)
5
Chemical Thermodynamics and Thermal Analysis 3–4 (2021) 100013
Figure 9. Effect of temperature on estrone (E1 ) and 𝛽-estradiol (E2 ) removal by
macadamia activated carbon, experimental conditions: temperature 15 to 40 ˚C,
time 120 min, pH 7, dosage 0.1 g, temp. 25°C, solution volume 25 mL.
enhanced with a rise in the preliminary concentration. The calculations
revealed that almost 85% of estrone and 82% of 𝛽-estradiol removal
was achieved at low levels (0.1–1.0 mg/L). Once the concentration was
increased further from 1.0 to 1.6 mg/L, the percentage removal of E1
and E2 reduced to about 76-77 % (Figure 8), while adsorption ability
rises with an increase in concentration. With the rise in the initial level,
the mass transfer driving force increases, thereby resulting in a higher
estrone (E1 ) and 𝛽-estradiol (E2 ) adsorption.
At low concentrations, the available active sites on the adsorbent
to the initial steroids concentration ratio is higher; consequently, the
removal of steroids becomes independent of the introductory level. At
high concentrations, the proportion of the available active sites on the
adsorbent to the initial steroid concentration is low [25-30]. The de-
crease in sorption of estrone (E1 ) and 𝛽-estradiol (E2 ) at high concen-
tration can be ascribed to the saturation of active binding sites, leav-
ing steroids unabsorbed in solution [16,25,30,40]. Nevertheless, with
increasing initial concentration leading to the increase in the steroids
uptake by the macadamia activated carbon (MAC), this phenomenon
could be attributed to the electrostatic interactions increase, that is the
physical adsorption relative to covalent interactions [18,21,29,30].
3.4.5. Effect of temperature
The temperature effect on the sorption of estrone (E1 ) and 𝛽-estradiol
(E2 ) by macadamia activated carbon (MAC) was estimated within the
temperatures (15, 20, 25, 30, 35 and 40°C). In contrast, all other pa-
rameters temperature, pH, and time were set constant (Figure 9). The
plot shows that % adsorption by the activated carbon at variable tem-
peratures with optimal sorption of 65% for estrone (E1 ) and 64.5% for
𝛽-estradiol (E2 ) taking place at low temperature (15–20 °C). This is be-
cause room temperature is suitable for the binding of steroids on the
surface of the adsorbent. Figure 9 presents that a further rise in tem-
perature prompted an adsorption reduction. The equilibrium sorption
decreases from 65 to 58 %, with an increase in temperature. These ob-
servations could be due to the propensity of steroids molecules to seep-
age from the solid phase to bulk phase with an upsurge in temperature
of the solution [21,30]. Also, an increase in the solubility of the steroids
concerning temperature increase results in a more potent contact force
between steroids and the solvent than its effect between steroids and
macadamia activated carbon [17,30,41]. The extent of adsorption varies
inversely as the temperature that is lower the temperature, higher is the
adsorption, and vice versa. Consequently, temperature rise could also
lead to current intermolecular hydrogen bonding breaking between es-
trone (E1 ) and 𝛽-estradiol (E2 ) and activated carbon, which is signifi-
cant participation in the adsorption process [21,29,39,41]. During high
K.D. Elias, I.P. Ejidike, F.M. Mtunzi et al. Chemical Thermodynamics and Thermal Analysis 3–4 (2021) 100013

Table 1
Pseudo-first and second-order kinetic parameters for sorption of steroids onto adsorbent (MAC)

Analyte Equation K1 R2 K2
(1/min) (g mg−1 min−1 )
estrone (E1 ) Y = 0.0151x+0.8122 0.0151 0.9872 0.00930
𝛽-estradiol (E2 ) Y = 0.0153x+0.9291 0.0153 0.9916 0.00584

temperature, the kinetic energy of adsorbate does support binding with

the surface active sites available on the activated carbon shells. This be-
haviour pattern could be ascribed to the weakening of the contact forces
between the activated carbon and steroids [21,22].

3.5. Adsorption Kinetics

3.5.1. Pseudo First-order (PFO) and Pseudo Second-order (PSO) Kinetics

An essential factor of adsorption rate process for consideration dur-
ing adsorption study design is the adsorption kinetics. It plays a vi-
tal role by examining the potential rate controlling effect and aids in
choosing optimum working conditions for full-scale application opti-
mization. For this study, the pattern of adsorption was considered using
PFO and PSO kinetic models grounded on aqueous phase concentrations
of estrone (E1 ) and 𝛽-estradiol (E2 ). The adsorption kinetics determina-
tion using the pseudo-first-order (PFO) and pseudo-second-order (PSO)
model [16,25,30,33,42] are described in Equations (3) and (4).
( ) 𝑘 𝑡
log 𝑞𝑒 − 𝑞𝑡 = log 𝑞𝑒 − 1
2.303
𝑡 1 1
= + 𝑡 (4)
𝑞𝑡 𝑘2 𝑞𝑒2 𝑞𝑒
Where 𝑘1 = pseudo-first-order adsorption rate constant (min−1 ), t is
the contact time (min), 𝑞𝑒 and 𝑞𝑡 are the quantity of the adsorbate at
equilibrium time (mg/g), and at a given time t (min), respectively. The
pseudo-first-order plot of In(𝑞𝑒 – 𝑞𝑡 ) against 𝑡 give a direct relationship
from which 𝑘1 in (min−1 ) is calculated. A plot of 𝑞𝑡 against 𝑡 gives a
𝑡
linear relationship and a rate constant 𝑘2 (g/mg min) for pseudo-second-
order adsorption kinetics obtained from the slope and intercept of the
graph.
Table 1 illustrates the results articulated for the pseudo-first-order
and pseudo-second-order kinetic model for estrone (E1 ) and 𝛽-estradiol
(E2 ). Correlation coefficient (R2 ) for pseudo-first-order and pseudo-
second-order kinetic models for the sorption of steroids onto MAC were
(R2 = 0.9872) for estrone (E1 ) and (R2 = 0.9916) for 𝛽-estradiol (E2 ).
The plots displayed a good fit of adsorption equilibrium statistics con-
cerning the pseudo-second-order (PSO) kinetic model due to the higher
correlation coefficient (Table 1), and this agrees with the estimated and
the trial 𝑞𝑒 values [18,30]. Consequently, a chemisorption mechanism is
predicted for this adsorption fitting in PSO. Although the pseudo-first-
order exhibited a fairly good fit (physisorption mechanism), the second-
order was found larger concerning the correlation coefficient. This is a
suggestion that chemisorption is the rate-controlling step, as articulated
by Ho [43]. Previously, physisorption and chemisorption have been con-
veyed by investigators in literature for the sorption of pollutants (or-
ganics and inorganics) unto adsorbents. However, thermodynamics in-
vestigations are essential for additional conclusion on the mechanistic
elucidations [25,30,33,44].
3.6. Adsorption Isotherms
In view to understanding the equilibrium relationships or mecha-
nism of the adsorption between adsorbate concentration and the quan-
tity of adsorbate (steroids) that were accrued on the adsorbent active
sites, the adsorbent-adsorbate interaction phenomena were explained
by the adsorption isotherms [22-25,44]. The adsorption results were
fitted into two isotherm models, specifically Langmuir and Freundlich
isotherms.
Figure 10. Langmuir isotherm plot for the steroids adsorption onto MAC
(3)
3.6.1. Langmuir isotherm model
The elementary postulation of the Langmuir model is that the de-
velopment of monolayer occurs on the surface of the adsorbing mate-
rials. It demonstrates that single steroids molecule might be adsorbed
on one adsorption site, thereby causing a decrease in the intermolecu-
lar forces with the distance. Also, the adsorbent surface been homoge-
neous is assumed, possessing energetically and identical same adsorp-
tion sites [24,25,29]. The monolayer sorption onto the surface with a
limited number identical site is given by the Equation (5),
𝑞𝑚 𝑘𝐿 𝐶𝑒
𝑞𝑒 = (5)
1 + 𝑘𝐿 𝐶𝑒
Where 𝑞𝑚 = Langmuir parameters relating to maximum adsorption
capacity (mg/g), 𝑘𝐿 = free energy of adsorption and binding sites affin-
ity (L/mg). 𝐶𝑒 = the equilibrium concentration in the aqueous solution
(mg/L), 𝑞𝑒 = the equilibrium adsorption capacity of adsorbent (mg/g).
The linearized version of Langmuir equation (Eq. 6) can be written as,
𝐶𝑒 1 1
= + 𝐶 (6)
𝑞𝑒 𝑞𝑚 𝑘𝐿 𝑞𝑚 𝑒
The values of 𝑞𝑚 and 𝑘𝐿 of Langmuir adsorption isotherm were esti-
𝐶
mated from the slopes and intercept of the direct plot of 𝑞 𝑒 versus 𝐶𝑒 as
𝑒
shown in Figure 10 and data presented in Table 2.
3.6.2. Freundlich isotherm model
The Freundlich equation is based on heterogeneous surface sorption,
and this can be derived by assuming that a logarithmic reduction in the
enthalpy of adsorption with a rise in the fraction of the occupied sites.
This Freundlich model is purely an empirical equation grounded on the
heterogeneous surface with non-uniform distribution of adsorption heat
sorption [25,29,33,44]. It is given by the Equation (7):
1∕𝑛
𝑞𝑒 = 𝐾𝑓 𝐶𝑒 (7)
The linearized form of Freundlich isotherm (Eq. 8) can also be writ-
ten as,
1
ln 𝑞𝑒 = ln𝐾𝑓 + ln 𝐶𝑒 (8)
n
Where 𝐾𝑓 = the Freundlich constants (mg/g (L/mg)1/n ) that indi-
cate adsorption capacity, n = adsorption intensity. 𝑞𝑒 = the equilibrium

6
K.D. Elias, I.P. Ejidike, F.M. Mtunzi et al.
Table 2
Langmuir and Freundlich isotherm models for the adsorption study of steroids onto MAC
Langmuir model
𝑞𝑚 (mg.g−1 ) 𝑘𝐿 (L.mg−1 ) R2
22.0 0.42 0.9785
Figure 11. Freundlich isotherm plot for the steroids adsorption onto MAC
adsorption capacity of adsorbent (mg/g), and these are coefficients in-
tegrating the factors affecting the adsorption capacity (Figure 11).
The Langmuir isotherm was observed to be linear over the full range
of concentration studied (Figure 10) with an excellent linear correlation
coefficient (R2 = 0.9785) for the adsorption of steroids onto MAC. It at-
tributes that Langmuir equation characterizes the best fit of investiga-
tional data demonstrating the monolayer adsorption of steroids onto the
surface of macadamia activated carbon through electrostatic force [44].
The value of 𝐾𝑓 and n was estimated from the linear plot of ln 𝑞𝑒 versus
ln 𝐶𝑒 , with 1𝑛 and ln𝐾𝑓 . They are corresponding to the slope and inter-
cept of the line, respectively (Figure 11), and the outcomes presented in
Table 2. The value of “n” is dependent on the level of non-linearity be-
tween adsorption and solution concentration such that: the adsorption
is linear when the value of n is equal to unity; when the value is lower
than unity, this suggests that adsorption process is chemical, and when
the value of n is above unity, then adsorption is a favourable physical
process [24,39]. In this study, the value of n (0.1 < n < 1) indicated
a favourable adsorption process of steroids at experimental conditions.
And the correlation coefficient value (R2 = 0.7188) is lesser than the
value of Langmuir isotherm. Hence, the results of Langmuir and Fre-
undlich implies that the adsorption of estrone (E1 ) and 𝛽-estradiol (E2 )
onto the macadamia activated carbon (MAC) show a complex mecha-
nism involving both monolayer and heterogeneous surface condition.
The maximum adsorption capacity (mg/g) observed for the adsorption
of estrone (E1 ) and 𝛽-estradiol (E2 ) onto the macadamia activated carbon
(MAC) is low compared to those reported by Altıntıg et al. [21,23,29]
and Tuzen et al. [32]. However, the capacity is comparable to those
reported by Lesaoana et al. [33].
3.7. Thermodynamic study
The temperature effect on the sorption of estrone (E1 ) and 𝛽-estradiol
(E2 ) onto the macadamia activated carbon (MAC) was investigated via
three necessary thermodynamic constraints such as Gibb’s free energy
(∆G°), enthalpy change (∆H°) and entropy change (∆S°). The parame-
ters: ∆G°, ∆H°, and ∆S° [24-27, 30] for the adsorption process of steroids
were obtained using Equation (9).
Δ𝐺𝑜 = −𝑅𝑇 ln 𝐾 (9)
7
Chemical Thermodynamics and Thermal Analysis 3–4 (2021) 100013
Freundlich model
n 𝐾𝑓 (mg.L1/n /g) R2
0.74 28.79 0.7188
Figure 12. Plot of ln K versus 1/T for steroids adsorption on the macadamia
activated carbon (MAC)
Where K = thermodynamic equilibrium constant. The values of K
𝑞
was calculated by plotting ln 𝐶𝑒 against 𝑞𝑒 , and then extrapolate to zero,
𝑒
where 𝑞𝑒 and 𝐶e are the adsorbed steroids concentration at equilib-
rium and equilibrium concentration in solution. The effect of enthalpy
changes of sorption as a temperature function on thermodynamic con-
stant was determined using Equation (10)
Δ𝐻 𝑜
𝑑 (ln 𝐾) = 𝑑𝑇 (10)
𝑅𝑇 2
The process becomes endothermic (ΔH° > 0), when the equilibrium
constant increases with a rise in temperature, however, as the temper-
ature is increased when the equilibrium constant decreases, the process
becomes exothermic (ΔH° < 0). The ∆H° and ∆S° values were then es-
timated from the slope and intercept of the linear plot (Eq. 11), of ln 𝐾
vs 𝑇1 as described in Figure 12.
Δ𝑆 𝑜 Δ𝐻 𝑜
𝑙𝑛𝐾 = − (11)
𝑅 𝑅𝑇
The Gibbs free energy is given by Equation (12), where, ∆G° is the
free energy change (J/mol); R = gas constant (8.314 J/(molK)), and
T = absolute temperatures (K).
Δ𝐺𝑜 = ΔH − 𝑇 Δ𝑆 𝑜 (12)
Table 3 presents the thermodynamic parameters for the sorption of
steroids calculated for the temperatures (15, 20, 25, 30, and 35°C). The
Gibbs free energy (∆G°) is an essential criterion of spontaneity. ∆G° val-
ues of –1.223 to –1.308 kJ/mol were negative, suggesting that the sorp-
tion process of steroids on the macadamia activated carbon (MAC) was
spontaneous. Importantly, the reduction in the values of ∆G° as the tem-
perature increases is an indication that the adsorption became thermo-
dynamically less favourable at higher temperatures [19,21,24,25,30].
The obtained value for ∆G° was found to be less than –20 kJ/mol
signifying electrostatic communication between the steroids and the
MAC, which maintained the physisorption mechanism. In general, for
the mechanism of adsorption to be steady with electrostatic interaction
occurring amongst adsorbates and adsorbent active sites (physical ad-
sorption), a value of ∆G° must lie between 0 and –20 kJ/mol. Also,
for adsorption mechanism involving charge transfer or sharing from the
K.D. Elias, I.P. Ejidike, F.M. Mtunzi et al.
Table 3
Thermodynamic properties for ∆G°, ∆H° and ∆S° of steroids adsorbed on the MAC
Temp (K) ∆S° (J/ mol K)
288 37.34
293
298
303
308
adsorbent active sites to the adsorbates leading to the formation of a co-
ordinate bond (chemisorption), a more negative ∆G° value in the range
–80 to –400 kJ/mol is required [20-27].
As indicated in Table 3, the extent of ∆G° ranged from –1.223 to
–1.308 kJ/mol, showing clearly that electrostatic interactions occurred
between MAC active sites and the steroids, thereby support physisorp-
tion mechanisms. The plot of ln 𝐾 vs 𝑇1 (Eq. 11) was linear, as presented
in Figure 12. The value of enthalpy change (∆H°) was estimated to
be –11.72 kJ/mol, and the entropy change (∆S°) computed as 37.34
J/mol k (Table 3) for the temperatures range of 15 – 35°C. The negative
∆H° suggests that the adsorption process progressed favourably at lesser
temperatures and the sorption mechanism was exothermic. A positive
∆S° indicate an upsurge in the degree of freedom (or disorderliness)
of the adsorbed estrone (E1 ) and 𝛽-estradiol (E2 ) onto the macadamia
activated carbon (MAC) was not restricted. Conclusively, the thermody-
namic properties for ∆G°, ∆H° and ∆S° of steroids adsorbed on the MAC
indicate that the adsorption is spontaneous and exothermic, indicating
that physisorption mechanism predominates [21,24-27,30].
4. Conclusion
The adsorption of two endocrine-disrupting chemicals: estrone (E1 )
and 𝛽-estradiol (E2 ) onto the macadamia activated carbon (MAC) as
representatives of steroids from aqueous phase was studied and their
kinetics, thermodynamics and equilibrium isotherms investigated. The
functional groups present at the surface of activated carbon support-
ing adsorption activities were identified using FTIR. SEM revealed MAC
to possess mesoporous texture, highly carbonaceous nature, and active
surface area. The results of the batch studies showed that the maxi-
mum percent 85% of estrone and 82% of 𝛽-estradiol removal was ac-
complished at low concentrations (0.1–1.0 mg/L), time (120 min), pH
7, and dosage (0.1 g), temp. (25°C), and a solution volume of 25 mL.
The kinetics studies confirmed that the pseudo-second-order kinetics
model could explain the steroids-MAC adsorption system. The overall
analysis of the equilibrium model investigation specifies the fitness of
Langmuir isotherm model to Steroids-MAC adsorption system, thus, sug-
gesting monolayer adsorption of steroids onto the MAC surface. Steroids
adsorption capability of MAC was observed to be diminishing with an in-
crease in temperature; therefore, signifying that the adsorption process
was exothermic in nature. The negative Gibb’s free energy value rec-
ommends that adsorption of phenol onto MAC was a spontaneous pro-
cess. The isotherm and thermodynamic information attained all attest to
the fact that the adsorption mechanism of estrone (E1 ) and 𝛽-estradiol
(E2 ) could be mainly electrostatic interactions, supporting physisorption
mechanisms.
Declaration of Interest statement
The authors declare that they have no conflict of interest.
Acknowledgment
Authors acknowledge the Research Directorate, Vaal University of
Technology, Vanderbijlpark Campus, South Africa, for the financial sup-
port received during this study.
8
Chemical Thermodynamics and Thermal Analysis 3–4 (2021) 100013
∆H° (kJ mol−l ) ∆G° (kJ mol−1 )
-11.72 -1.223
-1.266
-1.273
-1.287
-1.308
References
[1] K. Fent, A. Anna, A.A. Weston, D. Caminada, Ecotoxicology of human pharmaceuti-
cals, Aquat. Toxicol. 76 (2006) 122–159.
[2] S.H. Jeong, D.J. Kang, M.W. Lim, C.S. Kang, H.J. Sung, Risk assessment of growth
hormones and antimicrobial residues in meat, Toxicol. Res. 26 (2010) 301–313.
[3] K.B. Simmons, L.B. Haddad, K. Nanda, K.M. Curtis, Drug interactions between
non-rifamycin antibiotics and hormonal contraception: A systematic review, Am.
J. Obstet. Gynecol. 218 (2018) 88 e14-97.e14.
[4] G.R. Tetreault, C.J. Bennett, K. Shires, B. Knight, M.R. Servos, M.E. McMaster, Inter-
sex and reproductive impairment of wild fish exposed to multiple municipal wastew-
ater discharges, Aquat. Toxicol. 104 (2011) 278–290.
[5] C. Green, J. Brian, R. Kanda, M. Scholze, R. Williams, S. Jobling, Environmental
concentrations of anti-androgenic pharmaceuticals do not impact sexual disruption
in fish alone or in combination with steroid oestrogens, Aquat. Toxicol. 160 (2015)
117–127.
[6] O.A. Lykholata, I.P. Grigoryuk, T.Y. Lykholata, Metabolic effects of alimentary es-
trogen in different age animals, Ann. Agrar. Sci. 14 (2016) 335–339.
[7] L. Zubeldia-Brenner, C.E. Roselli, S.E. Recabarren, M.C. Gonzalez Deniselle,
H.E. Lara, Developmental and functional effects of steroid hormones on the neuroen-
docrine axis and spinal cord, J. Neuroendocrinol. 28 (2016), doi:10.1111/jne.12401.
[8] M.S. Diaz-Cruz, M.J. Lopez De Alda, R. Lopez, D. Barcelo, Determination of es-
trogens and progestogens by mass spectrometric techniques (GC/MS, LC/MS and
LC/MS/MS), J. Mass Spectrom. 38 (2003) 917–923.
[9] M. Weerasinghe, F. Konradsen, M. Eddleston, M. Pearson, T. Agampodi, F. Storm,
S. Agampodi, Overdose of oral contraceptive pills as a means of intentional self-poi-
soning amongst young women in Sri Lanka: considerations for family planning, J.
Fam. Plann. Reprod. Health Care. 43 (2017) 147–150.
[10] E. Touraud, B. Roig, J.P. Sumpter, C. Coetsier, Drug residues and endocrine disrup-
tors in drinking water: Risk for humans? Int. J. Hyg. Environ. Health. 214 (2011)
437–441.
[11] J. Aufartová, C. Mahugo-Santana, Z. Sosa-Ferrera, J.J. Santana-Rodríguez,
L. Nováková, P. Solich, Determination of steroid hormones in biological and en-
vironmental samples using green microextraction techniques: an overview, Anal.
Chim. Acta. 704 (2011) 33–46.
[12] K.A. Kidd, M.J. Paterson, M.D. Rennie, C.L. Podemski, D.L. Findlay, P.J. Blanchfield,
K. Liber, Direct and indirect responses of a freshwater food web to a potent synthetic
oestrogen, Phil. Trans. R. Soc. B. 369 (2014) 20130578.
[13] E. Van Donk, S. Peacor, K. Grosser, L.N. De Senerpont Domis, M. Lürling, Pharma-
ceuticals may disrupt natural chemical information flows and species interactions in
aquatic systems: Ideas and perspectives on a hidden global change, in: F.A. Gunther,
P. de Voogt (Eds.), Reviews of Environmental Contamination and Toxicology. Rev.
Environ. Contam. Toxicol. (Continuation of Residue Reviews), 238, Springer, Cham,
2016, pp. 91–105.
[14] P. Hallgren, A. Nicolle, L.-A. Hansson, C. Brönmark, L. Nikoleris, M. Hyder, A. Pers-
son, Synthetic estrogen directly affects fish biomass and may indirectly disrupt
aquatic food webs, Environ. Toxicol. Chem. 33 (2014) 930–936.
[15] J. Reungoat, B.I. Escher, M. Macova, J. Keller, Biofiltration of wastewater treatment
plant effluent: Effective removal of pharmaceuticals and personal care products and
reduction of toxicity, Water Res 45 (2011) 2751–2762.
[16] M. Baziar, R. Nabizadeh, A.H. Mahvi, M. Alimohammadi, K. Naddafi, A. Mesdagh-
inia, H. Aslani, Effect of dissolved oxygen/nZVI/persulfate process on the elimina-
tion of 4-chlorophenol from aqueous solution: Modeling and optimization study,
Korean J. Chem. Eng. 35 (2018) 1128–1136.
[17] M.J. Phele, I.P. Ejidike, F.M. Mtunzi, Adsorption efficiency of activated macadamia
nutshell for the removal Organochlorine pesticides: Endrin and 4,4-DDT from aque-
ous solution, J. Pharm. Sci. Res. 11 (2019) 258–262.
[18] J.M. Yang, R.J. Ying, C.X. Han, Q.T. Hu, H.M. Xu, J.H. Li, Q. Wang, W. Zhang, Ad-
sorptive removal of organic dyes from aqueous solution by a Zr-based metal–organic
framework: effects of Ce(III) doping, Dalton Trans 47 (2018) 3913–3920.
[19] H. Balouchi, M. Baziar, A. Dehghan, H. Alidadi, M. Shams, Combination of electroco-
agulation and MOF adsorption systems for EBT removal from water, Int. J. Environ.
Anal. Chem. (2020), doi:10.1080/03067319.2020.1737035.
[20] J.H. Qiu, Y. Feng, X.F. Zhang, M.M. Jia, J.F. Yao, Acid-promoted synthesis of UiO-66
for highly selective adsorption of anionic Dyes: Adsorption performance and mech-
anisms, J. Colloid Interface Sci. 499 (2017) 151–158.
[21] E. Altıntıg, H. Altundag, M. Tuzen, A. Sarı, Effective removal of methylene blue
from aqueous solutions using magnetic loaded activated carbon as novel adsorbent,
Chem. Eng. Res. Des. 122 (2017) 151–163.
[22] M. Yousefi, M. Gholami, V. Oskoei, A.A. Mohammadi, M. Baziare, A. Esrafili, Com-
parison of LSSVM and RSM in simulating the removal of ciprofloxacin from aqueous
solutions using magnetization of functionalized multi-walled carbon nanotubes: Pro-
K.D. Elias, I.P. Ejidike, F.M. Mtunzi et al.
cess optimization using GA and RSM techniques, J. Environ. Chem. Eng. 9 (2021)
105677.
[23] E. Altıntıg, M. Yenigun, A. Sarı, H. Altundag, M. Tuzen, T.A. Saleh, Facile synthesis
of zinc oxide nanoparticles loaded activated carbon as an eco-friendly adsorbent for
ultra-removal of malachite green from water, Environ. Technol. Innov. 21 (2021)
101305.
[24] A.M. Aljeboree, A.N. Alshirifi, A.F. Alkaim, Kinetics and equilibrium study for the ad-
sorption of textile dyes on coconut shell activated carbon, Arab. J. Chem. 10 (2017)
S3381–S3393.
[25] Z.A. AlOthman, M.A. Habila, R. Ali, A.A. Ghafar, M.S. Eldin Hassouna, Valorization
of two waste streams into activated carbon and studying its adsorption kinetics equi-
librium isotherms and thermodynamics for methylene blue removal, Arab. J. Chem.
2 (2013) 2–12.
[26] N.G. Rincon-Silva, J.C. Moreno-Pirajan, L. Giraldo, Equilibrium, kinetics and ther-
modynamics study of phenols adsorption onto activated carbon obtained from lig-
nocellulosic material (Eucalyptus Globulus labill seed), Adsorption 22 (2016) 33–48.
[27] V. Pakade, T. Ntuli, A. Ofomaja, Bisorption of hexavalent chromium from aqueous
solutions by Macadamia nutshells powder, Appl. Water Sci. 7 (2017) 3015–3030.
[28] B.O. Ogunsile, M.O. Bamgboye, Sorption characteristics of methylene blue onto Nypa
fruiticans lignin, Ife Journal of Science 19 (2017) 201–215.
[29] E. Altintig, M. Onaran, A. Sarı, H. Altundag, M. Tuzen, Preparation, characterization
and evaluation of bio-based magnetic activated carbon for effective adsorption of
malachite green from aqueous solution, Mater. Chem. Phys. 220 (2018) 313–321.
[30] S. Machedi, I.P. Ejidike, F.M. Mtunzi, V.E. Pakade, M.J. Klink, Chlorinated phenols:
Sorption performance by activated and grafted carbon from macadamia nutshell,
characterization, kinetic and thermodynamic studies, Orient. J. Chem. 35 (2019)
1469–1479.
[31] A.E. Ofomaja, Y.-S. Ho, Equilibrium sorption of anionic dye from aqueous solution
by palm kernel fibre as sorbent, Dyes Pigm 74 (2007) 60–66.
[32] M. Tuzen, A. Sarı, T.A. Saleh, Response surface optimization, kinetic and thermody-
namic studies for effective removal of rhodamine B by magnetic AC/CeO2 nanocom-
posite, J. Environ. Manage. 206 (2018) 170–177.
[33] M. Lesaoana, R.P.V. Mlaba, F.M. Mtunzi, M.J. Klink, P. Ejidike, V.E. Pakade, In-
fluence of inorganic acid modification on Cr(VI) adsorption performance and the
physicochemical properties of activated carbon, S. Afr. J. Chem. Eng. 28 (2019)
8–18.
Chemical Thermodynamics and Thermal Analysis 3–4 (2021) 100013
[34] F.G. Jaravani, M. Butler, P. Byleveld, D.N. Durrheim, P.D. Massey, J. Collins,
J.A. Judd, M. Oelgemöller, Drinking water quality in regional Hunter New Eng-
land, New South Wales, Australia, 2001-2015, Australas, J. Water Resour 24 (2020)
73–83.
[35] S. Yu, X. Wang, Y. Ai, X. Tan, T. Hayat, W. Hu, X. Wang, Experimental and theoreti-
cal studies on competitive adsorption of aromatic compounds on reduced graphene
oxides, J. Mater. Chem. A 4 (2016) 5654–5662.
[36] Z.N. Azwa, B.F. Yousif, Characteristics of kenaf fibre/epoxy composites subjected to
thermal degradation, Polym. Degrad. Stab. 98 (2013) 2752–2759.
[37] A. Kumar, H.M. Jena, High surface area microporous activated carbons prepared
from fox nut (Euryale ferox) shell by zinc chloride activation, Appl. Surf. Sci. 356
(2015) 753–761.
[38] A.H. Rony, L. Kong, W. Lu, M. Dejam, H. Adidharma, K.A.M. Gasem, Y. Zheng,
U. Norton, M. Fan, Kinetics, thermodynamics, and physical characterization of corn
stover (Zea mays) for solar biomass pyrolysis potential analysis, Bioresour. Technol.
284 (2019) 466–473.
[39] K.S. Kumar, S.V. Mohan, P.N. Sama, Sorptive removal of endocrine disruptive com-
pound (Estriol, E3) from aqueous phase by batch and column studies: Kinetic and
mechanistic evaluation, J. Hazard. Mater. 164 (2009) 820–828.
[40] G. Vikal, C. Meenakshi, A comparative research study on Cr (VI) removal from ef-
fluent using leaves of Brassica campestris and Dalbergia sissoo as adsorbents, Res. J.
Chem. Environ. 23 (2019) 10–15.
[41] I.P. Ejidike, C.W. Dikio, D. Wankasi, E.D. Dikio, F.M. Mtunzi, Sorption of Pb2+ from
aqueous solution using polyethylene and polyvinylchloride wastes as adsorbents: A
comparative study, Int. J. Environ. Sci. 75 (2018) 932–949.
[42] Y.S Ho, G. McKay, Pseudo-second order model for sorption processes, Process
Biochem 34 (1999) 451–465.
[43] Y.S Ho, Second-order kinetic model for the sorption of cadmium onto tree fern: A
comparison of linear and non-linear methods, Water Res 40 (2006) 119–125.
[44] P. Maneechakr, S. Karnjanakom, Adsorption behaviour of Fe(II) and Cr(VI) on ac-
tivated carbon: Surface chemistry, isotherm, kinetic and thermodynamic studies, J.
Chem. Thermodyn. 106 (2017) 104–112.