Desalination and Water Treatment 320 (2024) 100824

Contents lists available at ScienceDirect

Desalination and Water Treatment

journal homepage: www.sciencedirect.com/journal/desalination-and-water-treatment/

Optimization study of methylene blue dye adsorption on Chamaerops

humilis fibers biosorption using a central composite design
Soufiane Hmamouchi a,* , Yousra Abbad a , Ahmed El Yacoubi a,b , Aziz Boulouiz b,
Brahim Sallek a , Brahim Chafik El Idrissi a
a
Laboratory of Advanced Materials Engineering, Faculty of Sciences, Ibn Tofail University, BP.133, Kenitra 14000, Morocco
b
Mineral Solid Chemistry Team, Laboratory of Applied Chemistry and Environment, Faculty of Sciences, Mohamed First University, Oujda 60000, Morocco

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

Keywords: This research explores the effectiveness of Chamaerops humilis (CH) fibers as a biosorbent for the adsorption of
Biosorption Methylene Blue (MB) dye from aqueous solutions. The fibers were characterized using X-ray diffraction (XRD),
Chamaerops humilis Fourier-transform infrared spectroscopy (FTIR). To optimize the dye removal process, a Design of Experiments
Methylene blue
methodology, specifically Central Composite Design (CCD), was applied. Factors such as solution pH, adsorbent
RSM
CCD
dosage, contact time, and temperature were varied. The CCD analysis identified the optimal conditions for
Kinetics maximum removal efficiency (99.87 %) of a 10 mg/L MB solution, which were: 1.06 g/L of CH fiber dosage, pH
9.6, and a contact time of 60 min. The adsorption process aligned well with a pseudo-second-order kinetic model,
and the maximum adsorption capacity of CH fibers was determined to be 9.422 mg/g. Thermodynamic pa­
rameters, including Gibbs free energy (ΔG◦ ), enthalpy (ΔH◦ ), and entropy (ΔS◦ ) changes, were calculated,
confirming that the adsorption is spontaneous and endothermic. The study highlights the potential of Cha­
maerops humilis fibers as an efficient and eco-friendly adsorbent for MB dye removal, offering a sustainable and
cost-effective solution for wastewater treatment, particularly in industrial effluent management.

1. Introduction where it can cause respiratory problems and behavioral changes in fish
and other organisms [9]. Additionally, human exposure to methylene
In recent years, the escalating environmental concerns regarding the blue can lead to skin irritation and potential carcinogenic effects with
discharge of synthetic dyes into aquatic systems have driven extensive prolonged exposure. Focusing on MB allows for a targeted investigation
research on eco-friendly and cost-effective approaches for wastewater into its removal and management, which is essential for developing
treatment [1]. Apart from posing significant environmental threats, effective treatment strategies and addressing its environmental and
synthetic dyes also impose serious health risks on human populations. health-related challenges. In response to these challenges, the applica­
Exposure to these dyes has been linked to various health issues, tion of adsorption processes using natural materials has garnered
including cancer, tumors, mutations, and heart disease [2–5]. Methy­ considerable attention as a sustainable solution [10]. Various conven­
lene Blue dye, widely utilized in various industrial processes, is one such tional techniques have been employed for the treatment of
pollutant that poses significant threats to both environmental ecosys­ dye-containing wastewater, including biological methods [11], elec­
tems and human health [6]. trochemical oxidation [12], adsorption processes [13], and photo­
MB dye has been chosen as the target pollutant due to its extensive catalytic oxidation [14]. These established methods have been
use and significant impacts on both the environment and human health. extensively studied and applied to address dye pollution, each offering
It is widely used across various industries, including textiles, pharma­ its own advantages and limitations. However, with the increasing
ceuticals [7], and biological staining [8], making it a common concern for sustainable and eco-friendly solutions, there is a growing
contaminant in wastewater. The dye’s persistence in aquatic environ­ interest in exploring innovative approaches that harness the potential of
ments and its resistance to degradation contribute to prolonged pollu­ natural materials, such as Chamaerops humilis, for effective dye
tion issues. MB poses notable risks, including toxicity to aquatic life, removal from wastewater. Dyes can be broadly categorized into

* Corresponding author.
E-mail address: Soufiane.hmamouchi@uit.ac.ma (S. Hmamouchi).

https://doi.org/10.1016/j.dwt.2024.100824
Received 22 July 2024; Received in revised form 17 September 2024; Accepted 4 October 2024
Available online 6 October 2024
1944-3986/© 2024 The Authors. Published by Elsevier Inc. This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-
nc/4.0/).
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

synthetic and natural types. Synthetic dyes are man-made and encom­ includes a set of central points and factorial points that allow for the
pass various classes, such as azo dyes, anthraquinone dyes, and indigo estimation of both linear and quadratic terms. Through the incorpora­
dyes. These dyes are extensively used in industries including textiles, tion of axial points, the CCD enables the assessment of curvature effects
food, and pharmaceuticals. In contrast, natural dyes are derived from and the optimal identification operating conditions for maximum
natural sources like plants, insects, or minerals, with examples including adsorption efficiency. By conducting a series of CCD experiments, we
indigo, turmeric, and beetroot dyes [15]. intend to generate a response surface model that accurately predicts the
The environmental and public health risks associated with dyes are behavior of Methylene Blue dye adsorption onto Chamaerops humilis
significant. Many synthetic dyes contain toxic chemicals that can pose under different conditions. This statistical analysis will offer valuable
health hazards if ingested, inhaled, or if they come into contact with the insights into the optimal levels of influential variables, leading to a
skin, potentially leading to allergies, cancers, and other health problems. cost-effective and sustainable strategy for dye removal. By employing
Additionally, synthetic dyes are often resistant to degradation, resulting CCD, we can assess the impact of critical factors on the Chamaerops
in long-term pollution of water bodies. Some dyes also accumulate in the humilis adsorption efficiency. The application of CCD in this research
food chain, which can affect wildlife and, subsequently, human health will enable us to generate a response surface model that describes the
[16]. Various methods exist for removing dyes from aqueous solutions. relationship between the experimental factors and the adsorption
Physical methods include filtration, which uses membranes or filters to response. The insights gained from this model will aid in optimizing the
separate dye particles from water, and adsorption, which involves using operating conditions to achieve maximum dye removal efficiency.
materials that bind to dye molecules and remove them. Chemical Through this study, we strive to contribute valuable scientific knowl­
methods involve oxidation, where agents like ozone or hydrogen edge on the adsorption potential of Chamaerops humilis for Methylene
peroxide break down dye molecules, and chemical precipitation, which Blue dye removal, furthering the development of eco-friendly and sus­
adds chemicals to form insoluble compounds with the dye, making it tainable wastewater treatment practices. Additionally, the findings from
easier to remove. Biological methods include bioremediation, which this research will shed light on the interaction mechanisms between the
employs microorganisms or enzymes to degrade dye molecules [17], natural adsorbent and the synthetic dye, paving the way for future in­
and phytoremediation [18], which uses plants to absorb and break down vestigations in the field of environmental remediation. By combining the
dyes from water. Among these methods, adsorption is particularly ad­ advantages of a Design of Experiments approach with the unique char­
vantageous due to its efficiency, as it can remove a wide range of dyes acteristics of Chamaerops humilis, we aim to present a comprehensive
from aqueous solutions. It is also cost-effective, as adsorbents can often and innovative approach to tackle the issue of dye pollution, moving
be reused or regenerated, which helps reduce costs. Furthermore, the towards a cleaner and healthier environment for present and future
adsorption process is relatively simple and can be implemented with generations. To the best of our knowledge, there is no prior report
minimal infrastructure. The utilization of plant-based adsorbents pre­ regarding the utilization of Chamaerops humilis plant fibers for waste­
sents a promising avenue in the pursuit of environmentally benign and water treatment. Consequently, this study represents the inaugural
efficient wastewater treatment strategies. Adsorption, a well-established investigation into the efficient removal of Methylene Blue (MB) dye
and environmentally friendly technique, has shown promise in miti­ from water using Chamaerops humilis fibers as a wastewater treatment
gating dye pollution from aqueous systems [19]. In this context, Cha­ medium. The biosorbent was subject to comprehensive characterization
maerops humilis, commonly known as the Mediterranean fan palm, a and employed for MB dye adsorption in aqueous solutions. We system­
native plant found in various regions, offers several advantages as an atically assessed the influence of operational parameters such as pH,
adsorbent material, including its widespread availability, biosorbent dosage, and sorption time. The experimental data were
cost-effectiveness, and eco-friendliness. The unique structural charac­ subjected to kinetic modeling. Additionally, the regeneration of spent
teristics of its fibrous components and porous surface enhance its biosorbent was examined. Recently, Response Surface Methodology
adsorption potential, making it an attractive candidate for wastewater (RSM) has emerged as a suitable statistical modeling approach to reduce
treatment applications. The Response Surface Methodology (RSM) offers operational time, experimental cycles, and chemical consumption. To
numerous advantages, particularly for the optimization of complex this end, the Central Composite Design (CCD) within the framework of
experimental processes. One of its key benefits is the ability to reduce RSM was employed to explore the interplay among key operational
the number of experiments needed to study the simultaneous influence factors (pH, dosage, and contact time) and determine the optimal con­
of multiple variables, which significantly lowers both the cost and time ditions for MB dye adsorption onto CH fibers. By comprehensively
required for testing [20]. Unlike traditional approaches that analyze studying the adsorption process, we aim to gain a deeper understanding
factors individually, RSM assesses the interactions between different of the interaction between Methylene Blue dye and Chamaerops humilis,
variables, providing a deeper understanding of their overall impact. it is hoped that the findings presented herein will pave the way for
Additionally, RSM utilizes full quadratic models, which allow for highly further exploration of Chamaerops humilis as a natural adsorbent for
accurate predictions of results based on various parameter combina­ diverse dye pollutants, fostering a cleaner and healthier environment for
tions, leading to detailed optimization, as often required in adsorption future generations.
studies. The response surfaces and contour plots generated by RSM make
it easier to visualize the effects of variables and identify optimal con­ 2. Materials and methods
ditions [21]. Finally, by optimizing key factors within a single set of
experiments, RSM maximizes process efficiency while minimizing 2.1. Materials
resource use, whether it be raw materials, time, or energy. Its mathe­
matical model also enables highly precise predictions of system re­ Chamaerops humilis (CH), a native plant, was collected from the
sponses, even beyond the tested conditions, making it particularly useful region of Tetouan, North of Morocco. The plant material was thoroughly
for exploratory studies. The current study aims to investigate the washed to remove any extraneous impurities and dried at room tem­
adsorption behavior of Methylene Blue dye by Chamaerops humilis perature. Subsequently, the dried plant material was ground into fine
using an Experiments Design approach with CCD in response surface particles and stored in airtight containers for further use as the natural
methodology (RSM). This statistical methodology allows for a system­ adsorbent. The ground material was sifted through a 1 mm mesh sieve to
atic and efficient exploration of the adsorption process by varying separate the fine particles. Only the small ground particles were
multiple factors simultaneously. The Central Composite Design is a retained, which will be used later as adsorbents. Hydrochloric acid (HCl,
powerful experimental tool that facilitates the construction of a 37 %) and sodium hydroxide (NaOH, 97 %) were obtained from Sigma
comprehensive model, capturing the non-linear relationships between Aldrich. These chemicals were used for adjusting the pH of the Methy­
the factors and the response variables [22,23]. The experimental design lene Blue (MB) dye solution and the adsorbent, as required. Distilled

2
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

water was used in all experiments to prepare the dye solutions and for percentages were calculated from the following Eq. (2) [25]:
dilutions and to wash the plant.
A0 − A
%Adsorption = .100 (2)
A0
2.2. Characterization techniques
Where, A0 and A are the initial and the equilibrium Absorbance of
MB solution. The batch biosorption experiments provided essential data
Structural and functional analyses of the prepared Chamaerops
on the adsorption capacity and kinetics of Chamaerops humilis for
humilis fibers were conducted using X-ray diffraction (XRD) and
Methylene Blue dye. The results obtained from the batch biosorption
Fourier-transform infrared spectroscopy (FTIR) techniques. X-ray
experiments provided insights into the optimal conditions for maximum
diffraction analysis was performed using a Shimadzu 6100 diffractom­
dye removal efficiency. By employing CCD, the study was able to
eter with Cu-Kα radiation at a wavelength of 1.5406 Å. The diffraction
identify the most favorable combinations of pH, Chamaerops humilis
scans were carried out in the 2θ range of 10◦ to 80◦ with a step size of
mass, and contact time, these experiments contribute to a comprehen­
0.02◦ and a measurement time of 5 s per step. The XRD patterns ob­
sive understanding of the adsorption behavior and the potential appli­
tained provided insights into the crystalline structure of the Chamaerops
cability of Chamaerops humilis as a promising and eco-friendly
humilis fibers without utilizing the KBr pellet method. For FTIR analysis,
biosorbent for dye removal in wastewater treatment. It is important to
infrared spectra were acquired using an FTIR instrument in the wave­
note that each experiment was performed in duplicate.
numbers range of 4000–400 cm− 1. The FTIR spectra allowed the iden­
tification of functional groups present on the surface of the Chamaerops
2.4. Determination of point of zero charge (pHpzc)
humilis fibers. This analysis facilitated the characterization of chemical
bonds and molecular vibrations in the natural adsorbent. The XRD and
In the realm of surface chemistry and material interactions, the
FTIR characterization techniques provided valuable information on the
concept of the point of zero charge (pHpzc) emerges as a fundamental
structural and chemical properties of the Chamaerops humilis fibers,
parameter with profound implications. The pHpzc, often referred to as
essential for understanding their potential as an effective biosorbent for
the isoelectric point, signifies the equilibrium state at which a solid
Methylene Blue dye removal. The data obtained from these analyses
surface carries no net electrical charge [26]. This pivotal pH value is a
played a crucial role in evaluating the suitability of the natural adsor­
direct consequence of the balance between protonation and deproto­
bent for the adsorption process and elucidating the mechanisms
nation reactions occurring on the surface functional groups [27].
involved in dye removal.
Experimentally determining the pHpzc involves titrating the surface
under consideration with solutions of varying pH levels and observing
2.3. Batch biosorption experiments the shift in surface charge. Notably, the pHpzc holds substantial signifi­
cance in diverse applications, such as colloid stabilization, adsorption
Batch biosorption experiments were conducted to evaluate the phenomena, and catalytic processes. Its accurate identification lays the
adsorption performance of Chamaerops humilis for the removal of groundwork for tailoring interfacial properties, ultimately influencing
Methylene Blue (MB) dye from aqueous solutions. The experimental the behavior of materials in intricate environments. By comprehending
design utilized CCD to optimize key factors, including the pH of the the principles underpinning the pHpzc, researchers can ingeniously
solution, the mass of Chamaerops humilis, and the contact time. A test manipulate and engineer material interfaces for enhanced performance,
was carried out to determine the adsorption effect of the Chamaerops without traversing the boundaries of scholarly integrity. To determine
humilis plant. Initially, 50 mg of Chamaerops humilis sample was the pHpzc, a series of experiments was conducted in adherence to
dispersed in 50 mL of a 10 mg/L MB dye solution in a 100 mL beaker. established protocols. The pH values of nine NaCl solutions (0.1 M) were
The mixture was vigorously shaken to ensure homogeneity, and then meticulously adjusted within the range of 2.5 to 11. Subsequently, a
subjected to continuous agitation at a constant speed of 700 rpm and precisely measured quantity of the sorbent, amounting to 15 mg, was
room temperature. During the adsorption process, the absorbance of the introduced into each solution. The mixtures were subjected to individual
treated MB solution was measured at 664 nm using a spectrophotom­ agitation and allowed to reach equilibrium over a span of 24 h.
eter. To determine the equilibrium concentration of MB, 5 mL samples of Following this equilibration period, the ultimate pH of each solution was
the treated solution were collected at various time intervals throughout ascertained at a designated time point [28]. By plotting the initial pH
the experiment. The CCD matrix allowed for the systematic variation of against the ΔpH of the solutions, the pHpzc was reliably deduced through
the experimental factors. The pH of the MB solution was adjusted to the a systematic analysis of the experimental data.
desired levels and different masses of Chamaerops humilis were used for
each experimental run. Additionally, the contact time was varied to 2.5. Modeling and experimental designs
explore its impact on the adsorption efficiency and the initial concen­
tration of MB dye and temperature were set at 10 mg/L and room Response Surface Methodology (RSM) stands as a versatile multi­
temperature respectively. During the adsorption process, the absorbance variate statistical instrument employed to delve into the repercussions of
of the treated MB solution was monitored at 664 nm using a spectro­ manipulating individual operational parameters, as well as their inter­
photometer. A volume of 5 mL of the treated MB solution was sampled at dependent interactions, within the realm of the biosorption process
specific time intervals to determine the concentration of the remaining [29]. To ascertain the operational range of a particular process, it is
MB dye. The concentration of MB dye was calculated based on the crucial to adhere to a well-structured design of experiments that opti­
measured absorbance using a calibration curve established with stan­ mizes the relevant parameters. This research undertook the selection of
dard MB solutions. The decrease in the absorbance of MB over time three operational parameters, informed by a thorough literature review,
indicated the adsorption of the dye onto the Chamaerops humilis fibers. and applied the one factor at a time approach to screen these parame­
The adsorption capacity at the equilibrium (qe) of Chamaerops humilis ters. The selected parameters for screening encompassed Initial pH,
was determined using the following Eq. (1) [24]: adsorption time (min) and adsorbent dosage (g/L). Subsequently, an
C0 − Ce analysis was conducted to assess their influence on the adsorption ca­
qe = .V (1) pacity and removal efficiency of MB. In this study, the optimization of
m
factors influencing the percentage of MB adsorption onto CH fibers was
Where, C0 and Ce are the initial and the equilibrium concentration of MB conducted using Design-Expert software (version 13, Stat-Ease, Inc). The
in the solution (mg/L), respectively. V is the volume of the solution (L), software served as a powerful tool for the comprehensive analysis of the
and m is the mass of Chamaerops humilis used (g). The MB removal regression model, facilitating the identification of critical variables of

3
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

the process and the calculation of the statistical model equations. Table 1
Through its advanced capabilities, Design-Expert enabled us to sys­ Encoded parameters and their values that impacted MB adsorption.
tematically investigate and interpret the intricate relationships between Factors Factors Units Factors level -α +α
the input parameters, providing valuable insights into the MB adsorp­ code studied
-1 0 +1
tion process. Utilizing this software played a pivotal role in streamlining
our experimental design and enhancing the precision of our results, A pH ​ 2 7 12 − 1,40896 15,409
B Biosorbent mg/ 10 55 100 − 20,6807 130,681
ultimately contributing to a more efficient and insightful investigation. dosage 50 mL
This study’s primary objective revolves around the anticipation of of MB
extreme responses, necessitating the consideration of corner points in C Contact Min 10 65 120 − 27,4986 157,499
the experimental design. Central Composite Design (CCD) was adopted, time
which incorporates a factorial design and is well-suited for sequential
experimentation. The approach involves a rational allocation of design
immersed in 50 mL of 0.1 M HCl for a duration of 2 h and subsequently
points to handle input variables within predefined ranges. Additionally,
rinsed thoroughly with distilled water, as per the methodology outlined
the adequacy of the model fit was assessed using the curvature estima­
by [35]. The revitalized biosorbent was then prepared for a new
tion method [30]. In the context of this study, a three-parameter CCD
adsorption test, and this entire regeneration process was iterated five
with a complete factorial run was implemented. This encompassed a
times. The desorption yield was calculated employing the following
total of 18 experiments, with 14 trials focusing on non-center points and
expression as mentioned in Eq. (4), as specified by [36]:
four trials on center points. The lower and upper bounds for each
parameter were established to guide the software in generating designs CDesorbed
%Desorption = .100 (4)
within the designated experimental limits. The parameters were coded CAdsorbed
and corresponded to the following limits: A) pH (2− 12), B) time Here, Cadsorbed represents the concentration of MB dye that has been
(10–120 minu) and C) dosage (0.01–0.1 g). Once the independent var­ adsorbed, while Cdesorbed signifies the concentration of MB dye that has
iables and their respective ranges were determined, each independent been desorbed.(Fig. 1)
variable was transformed into a coded form across three levels (− 1, 0,
and +1) [29]. To conduct the Response Surface Methodology analysis,
3. Results and discussion
The Design-Expert Software (Version 13, Stat-Ease, Inc) was employed.
Statistical quadratic models, incorporating interaction and polynomial
3.1. Characterization of Chamaerops humilis fibers
terms, were developed to describe the behavior of the response vari­
ables. The experimental outcomes underwent statistical analysis utiliz­
3.1.1. X-ray diffraction analysis of Chamaerops humilis fibers
ing a second-order quadratic polynomial model [31], to provide insight
The XRD analysis of Chamaerops humilis (CH) fibers was conducted
into the observed effects of the operational parameters. This model can
within the angular range of 2θ = 5–80◦ , as illustrated in Fig. 2. The X-ray
be expressed as shown Eq. (3):
diffraction spectrum unveiled four distinct crystalline peaks observed at
k
∑ k
∑ ∑ 15.4◦ , 16.6◦ , 22.42◦ and 35.44◦ . These peaks can be attributed to the
Y= α0 + αi Xi + αii X2i + αij Xi Xj + e (3) respective crystallographic planes (110), (110), (002), and (004) within
i=1 i=1 i<j
the cellulose I structure [37]. These distinct peaks in the XRD pattern
Herein, Y signifies the efficiency of MB dye removal, denoted as the indicates the existence of the crystalline phase in the CH fibers. The
response variable. Xi corresponds to the chosen independent variables. positions and intensities of these peaks provide valuable insights into the
The parameters a0 (intercept), ai (linear effect), aii (quadratic effect), crystalline properties and composition of the CH fibers sample,
and aij (interaction effect) stand as coefficients within the model, while k contributing to a comprehensive understanding of its material structure.
represents the overall count of variables employed in the optimization of
the adsorption process and e stands for random error. The polynomial 3.1.2. FTIR analysis of the Chamaerops humilis fibers
model of the highest degree was chosen based on sequential p-values of Fourier-Transform Infrared (FTIR) spectroscopy was employed to
≤ 0.05, an absence of significance in the lack of fit test (p-value > 0.05), gain insights into the chemical composition and functional groups
as well as the attainment of adjusted R-squared and predicted R-squared
values that were maximized and remained below 0.2. In addition,
further scrutiny was applied to assess the significance of additional
terms, with preference given to non-aliased models. The chosen model
subsequently underwent scrutiny through Analysis of Variance
(ANOVA). Subsequently, the most suitable model was identified by
examining the potential necessity for transformations that would align
with statistical assumptions. In conclusion, the interaction effects be­
tween the considered process parameters and their impact on the re­
sponses were elucidated through a regression equation derived from the
statistical model, in conjunction with Response Surface Methodology
(RSM) contour plots [32,33]. Different variables, the symbols, and levels
are shown in Table 1.

2.6. Regeneration of the used Chamaerops humilis biosorbent

Regeneration following the utilization of an adsorbent in the

adsorption process is a pivotal and prominent aspect. Following the
attainment of adsorption equilibrium, the used adsorbent materials were
subjected to regeneration using a 0.1 M Hydrochloric acid solution
(HCl) desorption agent, as detailed by [34]. The regeneration process
followed this procedure: the adsorbent, laden with MB dye, was Fig. 1. The fibers of the Chamaerops humilis plant.

4
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

of the cellulose, hemicellulose, and lignin structures [42]. The FTIR

analysis provides valuable insights into the chemical composition and
molecular structure of the sample, offering a comprehensive under­
standing of its key functional groups and their potential contributions to
its properties and behavior.

3.2. Optimization using CCD and RSM studies

3.2.1. CCD model analysis

To grasp the intricate relationship between various experimental
factors and their influence on the adsorption efficiency of the CH fiber
biosorbent for MB dye removal, a series of systematic experiments was
conducted using the Central Composite Design (CCD) approach. The
CCD matrix was designed to investigate the effects of three key factors:
pH, biosorbent dosage (mg/50 mL), and contact time (min). Table 2
presents both the experimental and predicted values of adsorption effi­
ciency obtained from these CCD experiments. The experimental design
included a range of coded variables (− 1, 1) for each factor, which were
Fig. 2. XRD patterns of Chamaerops humilis fibers sample. then converted into actual variables for conducting the experiments.
Numerical values assigned in the corresponding plane to each influ­
present in Chamaerops humilis (CH) fibers. The FTIR spectrum shown in encing parameter (A, B and C) and responses for the adsorption of three
Fig. 3, obtained within the wavenumber range of 4000 - 400 cm− 1, different factors. The pH (A) factor plays a crucial role in determining
revealed distinctive bands associated with various molecular vibrations, the surface charge of CH fibers, affecting the electrostatic interactions,
shedding light on the structural characteristics of CH fibers. The FTIR influencing the removal efficiency of MB dye, with a more pronounced
spectrum of the sample revealed distinct bands, each indicative of spe­ positive impact observed. This phenomenon can be attributed to the
cific functional groups and molecular vibrations within the analyzed elevation of positively charged binding sites, which results from an in­
material. In the infrared spectrum, a prominent and broad band is crease in pH. This, in turn, facilitates the adsorption process based on
observed within the range of 3500 - 3300 cm− 1, which corresponds to electrostatic attraction, particularly with the cationic MB dye [43].
the stretching vibrations of O-H bonds. These vibrations are inherent in Essentially, as the pH rises, the increased negative charge on the binding
the molecular structures of cellulose, hemicellulose, and lignin [38]. sites enhances the electrostatic interaction with the cationic dye mole­
Moving to the region between 2950 - 2850 cm− 1, the observed bands cules, promoting their adsorption onto the adsorbent surface. The ex­
can be attributed to the stretching vibrations of C-H bonds, originating periments covered a range of pH values, from low acidity to near-neutral
from the CH2 and CH3 groups present in carbon chains [39]. Notably, a conditions. Biosorbent Dosage (B) is the amount of CH fibers used for
distinct band at 1737 cm− 1 can be linked to the stretching vibration of adsorption is essential for achieving effective removal of MB dye. The
C––O bonds, specifically associated with the acetyl groups found in the experiments examined different levels of biosorbent dosage, from a
hemicellulose structure [40]. At 1609 cm− 1, an observable peak is lower to a higher quantity. Contact Time (C) is the duration of contact
–C bonds within the aromatic rings
attributed to the vibrations of the C– between the biosorbent and MB solution is a critical parameter for
present in both lignin and hemicellulose [41]. Furthermore, the emer­ adsorption kinetics. The experiments varied contact times to assess their
gence of a peak at 1374 cm− 1 is connected to the deformation of O-H impact on adsorption efficiency. The Experimental column in Table 2
bonds, a characteristic feature within the cellulose structure. In the displays the actual values of adsorption efficiency obtained through
range of 1300 - 1000 cm− 1, a cluster of bands corresponds to the experimentation. These values represent the real-world outcomes of the
stretching vibrations of C-O and/or C-O-C bonds. These vibrations are CCD experiments. In contrast, the Predicted column presents the values
indicative of various functional groups, including carboxylic acids, es­ of adsorption efficiency that were predicted by the developed quadratic
ters, ethers, alcohols, and phenols, all of which are integral components model. This model, based on the CCD data, allowed us to estimate
adsorption efficiency under different combinations of factors. Upon
comparing the experimental and predicted values, it is evident that the
developed quadratic model closely approximates the actual adsorption
efficiency outcomes. The predicted values align well with the experi­
mental results, reinforcing the reliability and accuracy of the model in
describing the complex adsorption process of CH fibers for MB dye.
These findings highlight the effectiveness of the CCD approach in sys­
tematically exploring the influence of pH, biosorbent dosage, and con­
tact time on adsorption efficiency. Moreover, the close agreement
between experimental and predicted values underscores the model’s
robustness and its potential utility in optimizing the adsorption process
for practical applications in wastewater treatment.

Adsorption efficiency = +88,69 + 17,60A + 10,19B + 6,62 C - 7,72AB +

5,34AC + 0,7575BC - 14,65A2 - 6,08B2 + 1,41 C2 (5)

The equation in terms of coded factors can be used to make pre­

dictions about the response for given levels of each factor using the Eq.
(5). By default, the high levels of the factors are coded as + 1 and the low
levels are coded as − 1. By comparing the coefficients of the factors, this
coded equation can be employed to determine the relative impact of the
Fig. 3. FTIR spectra of Chamaerops humilis fibers sample. factors. The adsorption efficiency equation derived from our CCD

5
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

Table 2
Comparative Analysis of Observed and Modeled Adsorption Efficiency from CCD Experiments.
Experimental Factors Response

Coded variables Actuel variables Adsorption efficiency (%)

Std Run A B C pH Biosorbent dosage (mg/50 mL) contact time Yobs Ypred
(min)
1 16 − 1 − 1 − 1 2 10 10 33,15 31,81
2 5 1 − 1 − 1 12 10 10 71,56 71,79
3 7 − 1 1 − 1 2 100 10 70,72 69,14
4 14 1 1 − 1 12 100 10 78,31 78,24
5 13 − 1 − 1 1 2 10 120 36,05 35,90
6 1 1 − 1 1 12 10 120 95,86 97,22
7 12 − 1 1 1 2 100 120 70,65 70,21
8 2 1 1 1 12 100 120 99,52 100,65
9 15 − 1 0 0 2 55 65 52,93 56,44
10 9 1 0 0 12 55 65 94,29 91,64
11 6 0 − 1 0 7 10 65 72,52 72,42
12 11 0 1 0 7 100 65 91,84 92,80
13 4 0 0 − 1 7 55 10 80,71 83,47
14 17 0 0 1 7 55 120 98,62 96,72
15 3 0 0 0 7 55 65 90,34 88,69
16 8 0 0 0 7 55 65 87,89 88,69
17 10 0 0 0 7 55 65 89,52 88,69
18 18 0 0 0 7 55 65 88,71 88,69

experiments provides valuable insights into the relationship between the adsorption efficiency is expected to increase by 6.62 units, assuming
key experimental factors (A, B, and C) and their influence on the other factors are unchanged. The interaction terms (AB, AC, BC) involve
adsorption efficiency of CH fibers for MB dye as shown the equation xx. pairs of factors. For example, the coefficient (− 7.72) for AB represents
the constant term which equal represents the baseline adsorption effi­ the combined effect of pH (A) and biosorbent dosage (B) on adsorption
ciency when all factors (A, B, and C) are at their central values (zero efficiency. A negative coefficient suggests that the interaction between A
levels) within the experimental range. It signifies the inherent adsorp­ and B has a diminishing effect on adsorption efficiency. Similar in­
tion capacity of CH fibers under standard conditions. The coefficient terpretations apply to the AC and BC interaction terms. The quadratic
(+17.60) for Factor A indicates the effect of pH on adsorption efficiency. terms (A2, B2, C2) capture the curvature in the relationship between each
Specifically, for each unit increase in pH, the adsorption efficiency is factor and adsorption efficiency. For instance, the coefficient (− 14.65)
expected to increase by 17.60 units, assuming all other factors are held for A2 suggests that the relationship between pH (A) and adsorption
constant. The coefficient (+10.19) for Factor B illustrates the impact of efficiency is not purely linear; there is a curvature effect. A negative
biosorbent dosage on adsorption efficiency. For each unit increase in coefficient indicates that the relationship is concave, implying that
biosorbent dosage (mg/50 mL), the adsorption efficiency is predicted to extreme values of pH may not lead to further significant increases in
increase by 10.19 units, assuming other factors remain constant. The adsorption efficiency. Similar interpretations apply to B2 and C2.
coefficient (+6.62) for Factor C signifies the influence of contact time on In Fig. 4, the graphical representation illustrates the relationship
adsorption efficiency. With each additional minute of contact time, the between observed and predicted values pertaining to the MB dye

Fig. 4. Experimental versus predicted values (a) and normal plot of residuals (b) for MB dye adsorption efficiency using CH fibers.

6
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

adsorption efficiency. The figure unmistakably demonstrates a right­ model. Their low P-values indicate their strong influence on degradation
ward skew in the data distribution, affirming a strong correlation be­ efficiency. Conversely, the interaction BC and the quadratic term C2
tween experimental outcomes and statistical predictions. Consequently, exhibit P-values greater than 0.1, suggesting that they are not statisti­
our developed model offers a robust assessment and analysis of MB cally significant for this model. Examining the Lack of Fit F-value of 7.18
adsorption onto CH fiber surfaces. To ascertain the model’s validity reveals an associated probability of 6.77 %, signifying that there is a
against actual experimental data, we conducted a goodness-of-fit anal­ 6.77 % chance that a Lack of Fit F-value of this magnitude could be
ysis for the adsorption responses. As depicted in Fig. 4, a normal prob­ attributed to random noise [49]. A Lack of Fit is typically undesirable, as
ability plot was observed, demonstrating that the data points generated it indicates that the model may not adequately fit the data [50]. In this
by the model align closely along a linear trajectory with minimal out­ case, the relatively low probability (<10 %) associated with Lack of Fit
liers. This consistent pattern is also evident when examining the pre­ warrants attention and suggests that further investigation or model
dicted and observed MB adsorption efficiencies, as depicted in Fig. 4. refinement may be necessary to improve the model’s fit. To summarize,
This highlights a substantial correlation between the experimental re­ the ANOVA outcomes underscore the overarching significance of the
sponses and the model’s predictions [44]. Fig. 4 provides an overview of quadratic model, revealing the substantial impact of various critical
the model’s performance in representing both experimental and pre­ factors and interactions on degradation efficiency. Nevertheless, the
dicted values. The validation of experimental results against those pro­ existence of Lack of Fit signals the requirement for circumspect evalu­
jected by the model is essential for assessing the model’s credibility. To ation and potential refinements to enhance the model’s alignment with
ensure the robustness of this validation process, we verified that the the observed data. This suggests an avenue for further exploration and
residual data values adhere to a normal distribution, enabling the uti­ optimization to achieve a more precise fit between the model and
lization of normal distribution techniques to assess the precision of the empirical observations.
predictive model [45,46]. Additionally, the degree of alignment be­ The results from our Central Composite Design (CCD) experiment for
tween predicted and experimental values can be assessed by examining the adsorption of MB dye onto CH fibers are highly promising. The co­
their proximity to the linear regression line. Data points closely efficient of determination (R2) is exceptionally high at 0.9936, indi­
following the line indicate a favorable model fit, while substantial de­ cating that the model explains 99.36 % of the variability in the response.
viations may imply potential limitations in accurately characterizing the The adjusted R2 value (R2adj ) of 0.9864 further confirms the robustness of
data. the model. The predictive R2 (R2pre ) value of 0.9533 demonstrates the
model’s ability to accurately forecast outcomes. The low coefficient of
3.2.2. Analysis of variance (ANOVA)
variation (C.V.%) at 2.98 % suggests good precision and reproducibility
The analysis of variance (ANOVA) table for the quadratic model
of the experimental data. Moreover, the Adequate Precision value of
provides valuable insights into the significance of the model terms and
39.7469 exceeds the desired threshold of 4, indicating that the model is
their impact on the adsorption efficiency of the system [47], as illus­
suitable for predicting MB dye adsorption onto CH fibers with a high
trated in Table 3. The Model F-value of 137.97 is indicative of the overall
degree of reliability [51].
significance of the model. This substantial F-value suggests that the
model is highly significant in explaining the variation in adsorption ef­
3.2.3. Response-surface assessment
ficiency. Importantly, the probability associated with such a large
The utilization of a CCD model allowed for the generation of
F-value is exceedingly low at 0.01 %, emphasizing the model’s robust­
insightful 2D contour and 3D response surface plots as shown Fig. 5,
ness and reliability in capturing the underlying trends in the data. The
shedding light on the interplay between three critical variables: solution
P-values associated with individual model terms offer further insights.
pH, CH fiber dosage and contact time. In Fig. 5(a), we present the 2D
Terms with P-values less than 0.05 are considered statistically signifi­
contour and 3D response surface plots illustrating how alterations in the
cant [48]. In this context, factors A (pH), B (Biosorbent dosage), C
solution’s pH and CH fiber dosage impact the percentage of MB dye
(contact time), as well as interactions AB and AC, along with the
adsorption. These 2D and 3D plots offer a visually intuitive represen­
quadratic terms A2 and B2, are all deemed significant contributors to the
tation of the complex relationships within our system. They clearly
demonstrate that the MB adsorption percentage increases in tandem
Table 3 with simultaneous increments in both CH fiber dosage and solution pH.
Analysis of Variance (ANOVA) results for the quadratic model in CCD experi­ Specifically, the plots reveal a notable trend wherein the highest MB
ments on MB dye adsorption by CH fibers. adsorption, reaching a remarkable 95.21 %, occurs at a pH of 7 when the
Source Sum of df Mean F- p-value Significant CH fiber dosage is set at 1.4 g/L. The application CCD model has also
Squares Square value allowed us to gain valuable insights into the interplay between two
Model 6704,25 9 744,92 137,97 < 0.0001 * pivotal variables: solution pH and contact time, as depicted in Fig. 5(b).
A-Ph 3099,01 1 3099,01 573,98 < 0.0001 * In this section, the 2D contour and 3D response surface plots offer a
B- 1038,36 1 1038,36 192,32 < 0.0001 * graphical representation of the intricate relationships within our
Biosorbent
experimental system. These plots unequivocally reveal that the per­
dosage
C-Contact 438,91 1 438,91 81,29 < 0.0001 * centage of MB adsorption experiences a simultaneous increase with
time rising values of both contact time and solution pH. Remarkably, our
AB 476,79 1 476,79 88,31 < 0.0001 * findings illustrate that the highest level of MB adsorption, reaching an
AC 227,70 1 227,70 42,17 0,0002 * impressive 100 %, occurs at a pH of 9.5 when the contact time is set at
#
BC 4,59 1 4,59 0,8502 0,3835
A2 581,31 1 581,31 107,67 < 0.0001 *
95 min Fig. 5(c) illustrates the graphics of the 2D contour and 3D
B2 100,07 1 100,07 18,53 0,0026 * response surface plots derived from the CCD model, specifically exam­
C2 5,37 1 5,37 0,9951 0,3477 #
ining the influence of CH fibers dosage and contact time on the
Residual 43,19 8 5,40 ​ ​ ​ adsorption of MB dye. These visual representations provide valuable
#
Lack of Fit 39,86 5 7,97 7,18 0,0677
insights into the complex interplay between CH fibers dosage and con­
Pure Error 3,33 3 1,11 ​ ​ ​
Cor Total 6747,44 17 ​ ​ ​ ​ tact time in our adsorption system. Both the 2D contour and 3D response
surface plots distinctly demonstrate a concurrent increase in the per­
R2 = 0.9936, R2adj = 0.9864, R2pre = 0.9533, C.V.% = 2.98, Adeq Precision centage of MB adsorption with simultaneous increments in contact time
= 39.7469. and CH fibers dosage. Notably, our investigation reveals that the peak
*
= Significant level of MB adsorption, achieving a remarkable 100 %, was achieved at
#
= Not significant

7
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

Fig. 5. 2D contour and 3D response surface plots for MB adsorption efficiency using CH fibers biosorbent as a function of: (a) CH fibers dose combined with pH, (b)
contact time combined with pH and (c) contact time combined with CH fibers dose.

8
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

a CH fibers dosage of 1.76 g/L and a contact time of 115 min.

This finding underscores the importance of optimizing pH solution,
CH fibers dosage and contact time to achieve the highest level of MB dye
adsorption on our CH fiber adsorbent. The 2D contour and 3D response
surface plots serve as valuable tools for comprehending the intricate
dynamics between these variables and identifying the precise conditions
that lead to optimal adsorption efficiency.

3.2.4. Optimal conditions and model validation

The primary objective of this statistical study is to maximize
adsorption efficiency by optimizing three crucial physico-chemical pa­
rameters. To this end, the CCD model facilitated the determination of the
highest achieved adsorption percentage for MB dye which was 99.87 %.
This optimal performance was attained under specific conditions,
including an initial MB concentration of 10 mg/L, a pH level of 9.6, a CH
fiber dosage of 1.06 g/L, and a contact time of 60 min. These conditions
were identified through the model’s predictions and were subsequently
employed in experimental trials to assess their practicality. To validate
the model’s accuracy and reliability in predicting optimal conditions, an Fig. 6. Point of Zero Charge (PZC) determination for CH fibers biosorbent.
additional set of experiments was conducted under the recommended
parameters. It was observed that the highest adsorption efficiency was
increases beyond the pHpzc, the surface of CH fibers undergoes a tran­
achieved when the experimental values closely matched the predicted sition, becoming progressively more negatively charged due to the
values. A desirability factor of 1 was attained, indicating the successful
deprotonation of functional groups. This shift in surface charge char­
alignment of experimental and predicted values. The results of this acteristics is critical in improving the adsorption efficiency. At higher pH
validation experiment were striking, with predicted and actual adsorp­
values, a strong electrostatic attraction develops between the cationic
tion efficiencies reaching 100 % and 99.87 %, respectively. This MB dye molecules and the negatively charged surface of the CH fibers.
impressive concordance between predicted and actual outcomes further This attraction facilitates the adsorption process, leading to increased
underscores the robustness of the CCD model in optimizing the adsorption efficiency [53]. The electrostatic forces of attraction between
adsorption process, thereby enhancing its practical applicability and the positively charged MB molecules and the negatively charged CH
efficiency. These findings not only underscore the model’s ability to fibers dominate, driving the adsorption of MB onto the CH fibers.
identify optimal conditions accurately but also validate its utility in
guiding practical applications within the realm of MB dye adsorption
onto CH fibers. 3.4. Kinetics of MB Adsorption by Chamaerops humilis Fibers

3.3. Point of Zero Charge (PZC) determination Adsorption kinetics, which study the rate at which a substance is
adsorbed onto a surface, are of crucial importance in understanding the
The Point of Zero Charge (PZC) is a critical parameter in under­ adsorption mechanism. In this study, we examined the adsorption ki­
standing the surface chemistry and electrostatic properties of a material, netics of the dye MB on CH fibers. The mathematical expressions
especially in the context of its adsorption behavior. It represents the pH describing the kinetics of the adsorption process are formulated as fol­
at which the surface charge of a material becomes neutral, indicating a lows (Eqs. (6) and (7)) [54,55]:
state where the electrostatic forces between the material’s surface and
ln(qe − qt ) = lnqt − k1 t (6)
ions in solution are minimized. At this point, the material exhibits
minimal interaction with ions and can be considered electrically neutral.
t 1 t
In our study, the determination of the PZC for CH fibers was carried out = + (7)
qt k2 q2e qe
to gain insights into their surface charge characteristics. It helps in un­
derstanding the electrostatic interactions between the biosorbent sur­ In these equations, the variables qt and qe denote the adsorption
face and the target adsorbate molecules. In our study, the pHpzc of CH capacity measured in mg/g at time t and at equilibrium, respectively.
fibers was determined to be 7.51, as illustrated in Fig. 6. This parameter, The parameter t represents the contact time, measured in min. Addi­
pHpzc, is critical as it denotes the pH at which the surface charge of the tionally, k1 and k2 represent the constants associated with the PFO and
material becomes neutral, indicating a transition from positive to PSO kinetic rate equilibrium, respectively. k1 is measured in min− 1,
negative surface charge characteristics. This information is valuable in while k2 is measured in g.mg− 1.min− 1.
explaining the favorable adsorption behavior observed under the The results shown in Fig. 8 reveal a pseudo-second-order reaction
optimal pH conditions, as discussed in previous sections. It also con­ behavior, characterized by a high coefficient of determination R2
tributes to the overall understanding of CH fibers as an effective bio­ = 0.997. The pseudo-second-order model involves more complex
sorbent for the removal of dyes and other contaminants from aqueous adsorption and is often associated with a stronger chemical interaction
solutions. Below the pHpzc the surface of CH fibers tends to be positively between the adsorbent CH fibers and the adsorbate MB. The high R2
charged. This positive charge arises from the protonation of functional = 0.997 indicates that this model is in excellent agreement with our
groups on the surface. In the context of our study, this is a significant experimental data, suggesting that the adsorption kinetics of MB on CH
observation because the MB dye used is a cationic dye, carrying a pos­ fibers mainly follows a pseudo-second-order mechanism. In contrast, we
itive charge. Consequently, at lower pH values, there is a predominance also examined the pseudo-first-order model, which is generally associ­
of positive charges both on the MB dye molecules and on the positively ated with less specific physisorption processes. In this case, the pseudo-
charged sites of CH fibers. This situation results in electrostatic repulsion first-order model showed an R2 = 0.724, indicating that this model does
between the positively charged MB dye and the positively charged not fit our experimental data as well. These results support the idea that
adsorption sites on the CH fibers. This repulsive force impedes the MB adsorption by CH fibers is mainly governed by a pseudo second-
adsorption of MB molecules onto the CH fibers, leading to relatively low order mechanism. Furthermore, it is important to note that the experi­
adsorption efficiency at lower pH values [52]. As the pH of the mixture mental value of Qmax (maximum adsorption capacity) that we obtained

9
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

Fig. 7. Van’t Hoff curve representing this adsorption of the dye MB by CH fibers.

Table 5
Comparative Analysis of First-Order and Second-Order Kinetic Models for MB
Dye Adsorption.
Kinetic Parameters
model

PFO Qexp(mg/ Qe, cal (mg/ K1 (min− 1) R2

g) g) 0.0022 0.724
9.422 1.875
PSO Qe, cal (mg/ K2 (× 10− 2) (g.mg− 1. R2
g) min− 1) 0.997
9.194 7.1403

obtain key parameters such as free energy (ΔG◦ ), enthalpy (ΔH◦ ), and
entropy (ΔS◦ ), calculations based on temperature-dependent balances
are essential [56]. These fundamental quantities can be determined
utilizing the equations provided in Eqs. (8) to (11):

ΔG◦ = - RT ln(Kd) (8)

Fig. 8. The pseudo-first-order kinetic model (a) and the pseudo-second order
(b) for MB adsorption by CH fibers. ΔG = ΔH – TΔS
◦ ◦ ◦
(9)
◦ ◦
ΔS ΔH
is very close to that calculated as depicted in Table 5. This agreement ln(Kd ) = − (10)
R RT
suggests that our kinetic model is robust and reliable for describing the
adsorption of MB by CH fibers. qe
Kd = (11)
In conclusion, the results of this study indicate that the adsorption of Ce
MB by Chamaerops humilis fibers mainly follows a pseudo-second-order Here, Kd is defined as the adsorption distribution coefficient or the
reaction, involving a strong chemical interaction between the CH fibers thermodynamic equilibrium constant, R represents the gas constant with
and the MB. In addition, the consistency between the experimental and a value of 8.314 J⋅mol− 1⋅K− 1, and T denotes the absolute temperature in
calculated Qmax values reinforces the validity of our kinetic model. Kelvin (K).
These findings contribute to our understanding of the kinetic mechanism The Van’t Hoff scheme pertaining to the adsorption of MB by CH
underlying this important adsorption reaction. fibers is illustrated in Fig. 7. To derive the values of ΔH◦ and ΔS◦ , we
examined the slope and intercept of the Van’t Hoff plot. The lnKd versus
3.5. Studies of thermodynamic 1/T plot, shown in Fig. 7, displays a linear relationship with a satisfac­
tory coefficient. The resulting values for these parameters are tabulated
The assessment of thermodynamic parameters (ΔG◦ , ΔS◦ and ΔH◦ ) is in Table 4.
crucial for comprehending the influence of temperature on the adsorp­ The resulting values of ΔG◦ , ΔH◦ and ΔS◦ were found to be − 2.467,
tion process. In the context of adsorption, it is imperative to conduct a 63.259 KJ/mol and 221.476 J/mol.K, respectively. The obtained ther­
thermodynamic analysis to gain insights into the underlying process. To modynamic parameters provide valuable insights into the adsorption of
Methylene Blue (MB) by Chamaerops humilis fibers. The negative ΔG◦
values suggest that the adsorption of MB onto Chamaerops humilis fibers
Table 4
is thermodynamically favorable. This negative value indicates that the
Thermodynamic parameters for the adsorption process of CH fibers.
process is spontaneous, with greater spontaneity at higher temperatures.
sample T lnKd ΔG◦ (kJ/ ΔH◦ (kJ/ ΔS◦ (J/mol. The positive ΔH◦ value indicates that the adsorption process is endo­
(◦ K) mol) mol) K)
thermic. This suggests that the adsorption of MB onto Chamaerops
CH 293 0,99603 − 2,467736 63,2591 221,476 humilis fibers is favored at higher temperatures, as it requires an input of
fibers 308 2,01522 5,160398
heat energy to occur. The ΔH◦ value observed was found to be positive
−
318 2,78174 − 7,3545089
328 3,37077 − 9,1920628 and ranging from 40 to 800 kJ/mol, indicating that the adsorption of the

10
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

MB dye had undergone a chemisorption process. The positive ΔS◦ value

signifies an increase in randomness or disorder at the solid-liquid
interface during the adsorption process. This implies that the system
becomes more disordered as MB molecules are adsorbed onto the fibers
[57]. In summary, the negative ΔG◦ confirms that the adsorption process
is spontaneous and favored thermodynamically, with increasing favor­
ability at elevated temperatures. The positive ΔH◦ indicates that the
adsorption process is endothermic and benefits from higher tempera­
tures. Lastly, the positive ΔS◦ suggests an increase in randomness at the
solid-liquid interface during adsorption. These findings provide valuable
insights into the temperature-dependent behavior of MB adsorption onto
Chamaerops humilis fibers.

3.6. Reusability of the Chamaerops humilis biosorbent

To evaluate the reusability of the biosorbent, we conducted succes­

sive adsorption and desorption cycles under optimal conditions.
Following six cycles of biosorbent utilization, the dye removal rate
remained consistently high at 99.87 %. However, after four additional
Fig. 9. Recycling experiments of removal efficiency of MB over the
usage cycles, this efficiency slightly decreased to 92.09 %. It is observed
CH biosorbent.
that the efficiency of MB adsorption onto CH fibers remains consistently
high during the initial four regeneration cycles. However, a slight
decrease of 6.45 % in adsorption efficiency is noticeable between the Methodology, Formal analysis, Data curation. Yousra Abbad: Software,
fourth and the final regeneration cycles. This decline in adsorption ef­ Methodology, Formal analysis. Brahim Sallek: Supervision, Resources.
ficiency is likely attributed to wear and tear resulting from the repetitive Brahim Chafik El Idrissi: Writing – review & editing, Supervision,
treatment with an HCl eluent solution during the regeneration process. Resources. Ahmed EL YACOUBI: Writing – review & editing, Writing –
These results indicate that Chamaerops humilis exhibits strong potential original draft. Aziz Boulouiz: Software, Investigation, Data curation.
as an effective and sustainable biosorbent for the removal of MB from
aqueous solutions. The removal efficiency of MB onto the CH biosorbent Declaration of Competing Interest
for each cycle is illustrated in Fig. 9.
The authors declare that they have no known competing financial
4. Conclusion interests or personal relationships that could have appeared to influence
the work reported in this paper.
In conclusion, our study demonstrated the effective utilization of
Chamaerops humilis fibers as a promising biosorbent for the adsorption Data Availability
of MB dye. Through a combination of XRD and FTIR analyses, we suc­
cessfully characterized the CH fibers, laying the foundation for their Data will be made available on request.
application in wastewater treatment. The impressive adsorption effi­
ciency of 99.87 % within 60 min of contact time highlights the potential References
of CH fibers in environmental remediation. Employing the CCD
approach, we systematically optimized various factors influencing the [1] Lu L, Li J, Ng DHL, Yang P, Song P, Zuo M. Synthesis of novel hierarchically porous
Fe3O4@MgAl–LDH magnetic microspheres and its superb adsorption properties of
adsorption process. The ANOVA results validated the feasibility of our
dye from water. J Ind Eng Chem 2017;46:315–23. https://doi.org/10.1016/J.
statistical model in simulating the experimental space. The highest JIEC.2016.10.045.
adsorption percentage was achieved under optimal conditions: pH 9.6, [2] Regti A, Laamari MR, Stiriba S-E, El Haddad M. Potential use of activated carbon
derived from Persea species under alkaline conditions for removing cationic dye
biosorbent mass of 1.06 g/L, and a 60 min adsorption time. Our kinetic
from wastewaters. J Assoc Arab Univ Basic Appl Sci 2017;24(1):10–8. https://doi.
study revealed that the adsorption process followed a pseudo-second- org/10.1016/j.jaubas.2017.01.003.
order reaction, indicating a strong agreement between the experi­ [3] Chavaco LC, Arcos CA, Prato-Garcia D. Decolorization of reactive dyes in solar
mental data and the kinetic model. Furthermore, the determination of pond reactors: perspectives and challenges for the textile industry. J Environ
Manag 2017;198:203–12. https://doi.org/10.1016/J.JENVMAN.2017.04.077.
PZC of the CH fibers at 7.51 provided valuable insights into its surface [4] Jayasantha Kumari H, Krishnamoorthy P, Arumugam TK, Radhakrishnan S,
properties. Thermodynamic analysis indicated that the adsorption of MB Vasudevan D. An efficient removal of crystal violet dye from waste water by
onto CH fibers was an endothermic and spontaneous process, which is adsorption onto TLAC/Chitosan composite: a novel low cost adsorbent. Int J Biol
Macromol 2017;96:324–33. https://doi.org/10.1016/J.IJBIOMAC.2016.11.077.
favorable for practical applications. The regeneration study demon­ [5] Barka N, Ouzaouit K, Abdennouri M, Makhfouk MEl. Dried prickly pear cactus
strated that CH fibers maintained their adsorption performance even (Opuntia ficus indica) cladodes as a low-cost and eco-friendly biosorbent for dyes
after four cycles of reuse, emphasizing their sustainability and cost- removal from aqueous solutions. J Taiwan Inst Chem Eng 2013;44(1):52–60.
https://doi.org/10.1016/J.JTICE.2012.09.007.
effectiveness. In summary, Chamaerops humilis fibers emerge as a [6] Jawad AH, Razuan R, Appaturi JN, Wilson LD. Adsorption and mechanism study
compelling alternative biosorbent for the removal of textile effluents. for methylene blue dye removal with carbonized watermelon (Citrullus lanatus)
This research contributes to the growing body of knowledge on sus­ rind prepared via one-step liquid phase H2SO4 activation. Surf Interfaces 2019;16:
76–84. https://doi.org/10.1016/J.SURFIN.2019.04.012.
tainable and efficient wastewater treatment methods, highlighting the
[7] Bouzid T, Grich A, Naboulsi A, Regti A, El Himri M, El Haddad M. Optimizing
potential of CH fibers in addressing environmental challenges associated eriochrome black T adsorption through In-Situ polymerization of Poly(aniline-co-
with dye pollution in the textile industry. Further research in this di­ formaldehyde) on biochar: multivariate approach using full factorial design, Box-
Behnken, artificial intelligence, and DFT. Sep Purif Technol 2024;351:128107.
rection may lead to the development of eco-friendly and economically
https://doi.org/10.1016/J.SEPPUR.2024.128107.
viable solutions for water purification. [8] Bouzid T, et al. Adsorption of Methyl Red on porous activated carbon from
agriculture waste: characterization and response surface methodology
CRediT authorship contribution statement optimization. Inorg Chem Commun 2023;158:111544. https://doi.org/10.1016/J.
INOCHE.2023.111544.
[9] Naboulsi A, Bouzid T, Grich A, Regti A, El Himri M, El Haddad M. Understanding
Soufiane Hmamouchi: Writing – original draft, Software, the column and batch adsorption mechanism of pesticide 2,4,5-T utilizing alginate-

11
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

biomass hydrogel capsule: a computational and economic investigation. Int J Biol [32] Sunny A, Gazliya N, Aparna K. Optimization of regasified liquefied natural gas
Macromol 2024;275:133762. https://doi.org/10.1016/J.IJBIOMAC.2024.133762. based reforming process for syngas production in an ammonia plant. Energy
[10] El Haddad M, et al. Calcined mussel shells as a new and eco-friendly biosorbent to Sources Part A Recovery Util Environ Eff 2020;42(13):1565–79. https://doi.org/
remove textile dyes from aqueous solutions. J Taiwan Inst Chem Eng 2014;45(2): 10.1080/15567036.2019.1604868.
533–40. https://doi.org/10.1016/J.JTICE.2013.05.002. [33] Kaynar ÜH, Çınar S, Çam Kaynar S, Ayvacıklı M, Aydemir T. Modelling and
[11] Shakerian F, Zhao J, Li SP. Recent development in the application of immobilized optimization of uranium (VI) ions adsorption onto nano-ZnO/Chitosan Bio-
oxidative enzymes for bioremediation of hazardous micropollutants – a review. composite beads with response surface methodology (RSM). J Polym Environ
Chemosphere 2020;239:124716. https://doi.org/10.1016/J. 2018;26(6):2300–10. https://doi.org/10.1007/s10924-017-1125-z.
CHEMOSPHERE.2019.124716. [34] Yaashikaa PR, Kumar PS, Saravanan A, Vo D-VN. Advances in biosorbents for
[12] Wang J, Yao J, Wang L, Xue Q, Hu Z, Pan B. Multivariate optimization of the pulse removal of environmental pollutants: a review on pretreatment, removal
electrochemical oxidation for treating recalcitrant dye wastewater. Sep Purif mechanism and future outlook. J Hazard Mater 2021;420:126596. https://doi.org/
Technol 2020;230:115851. https://doi.org/10.1016/J.SEPPUR.2019.115851. 10.1016/j.jhazmat.2021.126596.
[13] Yue J-Y, et al. Metal ion-assisted carboxyl-containing covalent organic frameworks [35] Liu Y, Zhao Y, Cheng W, Zhang T. Targeted reclaiming cationic dyes from dyeing
for the efficient removal of Congo red. Dalton Trans 2019;48(48):17763–9. wastewater with a dithiocarbamate-functionalized material through selective
https://doi.org/10.1039/C9DT04175C. adsorption and efficient desorption. J Colloid Interface Sci 2020;579:766–77.
[14] Murugan P, Ramar P, Mandal AB, Samanta D. Investigating the photocatalytic https://doi.org/10.1016/J.JCIS.2020.06.083.
performances of nanocomposites containing narrow-band-gap copolymers and [36] Moharem M, Elkhatib E, Mesalem M. Remediation of chromium and mercury
ZnO. ChemistrySelect 2019;4(48):14214–21. https://doi.org/10.1002/ polluted calcareous soils using nanoparticles: sorption –desorption kinetics,
slct.201903809. speciation and fractionation. Environ Res 2019;170:366–73. https://doi.org/
[15] Pooladi H, Foroutan R, Esmaeili H. Synthesis of wheat bran sawdust/Fe3O4 10.1016/J.ENVRES.2018.12.054.
composite for the removal of methylene blue and methyl violet. Environ Monit [37] Bahloul A, et al. Characteristics of cellulose microfibers and nanocrystals isolated
Assess 2021;193(5):276. https://doi.org/10.1007/s10661-021-09051-9. from doum tree (Chamaerops humilis var. argentea). Cellulose 2021;28(7):
[16] Foroutan R, et al. Development of a magnetic orange seed/Fe3O4 composite for the 4089–103. https://doi.org/10.1007/s10570-021-03793-y.
removal of methylene blue and crystal violet from aqueous media. Biomass– [38] Adeosun SO. A. E. I, and H. A. Akanegbu, “Thermo-mechanical properties of
Convers Biorefin 2023. https://doi.org/10.1007/s13399-023-04692-x. unsaturated polyester reinforced with coconut and snail shells. Int J Compos Mater
[17] Alizadeh M, Peighambardoust SJ, Foroutan R. Efficacious adsorption of divalent 2015;5(3):52–64. https://doi.org/10.5923/j.cmaterials.20150503.02.
nickel ions over sodium alginate-g-poly(acrylamide)/hydrolyzed Luffa cylindrica- [39] Parlayıcı E, Pehlivan. Fast decolorization of cationic dyes by nano-scale zero valent
CoFe2O4 bionanocomposite hydrogel. Int J Biol Macromol 2024;254:127750. iron immobilized in sycamore tree seed pod fibers: kinetics and modelling study.
https://doi.org/10.1016/J.IJBIOMAC.2023.127750. Int J Phytoremediat 2019;21(11):1130–44. https://doi.org/10.1080/
[18] Peighambardoust SJ, Boffito DC, Foroutan R, Ramavandi B. Sono-photocatalytic 15226514.2019.1606786.
activity of sea sediment@400/ZnO catalyst to remove cationic dyes from [40] Ajouguim S, Abdelouahdi K, Waqif M, Stefanidou M, Saâdi L. Modifications of Alfa
wastewater. J Mol Liq 2022;367:120478. https://doi.org/10.1016/J. fibers by alkali and hydrothermal treatment. Cellulose 2019;26(3):1503–16.
MOLLIQ.2022.120478. https://doi.org/10.1007/s10570-018-2181-9.
[19] Jawad AH, Abdulhameed AS. Mesoporous Iraqi red kaolin clay as an efficient [41] Jawad AH, Saud Abdulhameed A, Wilson LD, Syed-Hassan SSA, ALOthman ZA,
adsorbent for methylene blue dye: adsorption kinetic, isotherm and mechanism Rizwan Khan M. High surface area and mesoporous activated carbon from KOH-
study. Surf Interfaces 2020;18:100422. https://doi.org/10.1016/J. activated dragon fruit peels for methylene blue dye adsorption: optimization and
SURFIN.2019.100422. mechanism study. Chin J Chem Eng 2021;32:281–90. https://doi.org/10.1016/J.
[20] Razali NS, et al. High-surface-area-activated carbon derived from mango peels and CJCHE.2020.09.070.
seeds wastes via microwave-induced ZnCl2 activation for adsorption of methylene [42] Silva MC, et al. H3PO4–activated carbon fibers of high surface area from banana
blue dye molecules: statistical optimization and mechanism. Molecules 2022;27 tree pseudo-stem fibers: adsorption studies of methylene blue dye in batch and
(20). https://doi.org/10.3390/molecules27206947. fixed bed systems. J Mol Liq 2021;324:114771. https://doi.org/10.1016/J.
[21] Zain ZM, Abdulhameed AS, Jawad AH, ALOthman ZA, Yaseen ZM. A pH-sensitive MOLLIQ.2020.114771.
surface of chitosan/sepiolite clay/algae biocomposite for the removal of malachite [43] Kausteklis J, Aleksa V, Iramain MA, Brandán SA. DFT and vibrational spectroscopy
green and remazol brilliant blue R dyes: optimization and adsorption mechanism study of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid.
study. J Polym Environ 2023;31(2):501–18. https://doi.org/10.1007/s10924-022- J Mol Struct 2019;1175:663–76. https://doi.org/10.1016/J.
02614-y. MOLSTRUC.2018.08.014.
[22] Cheng Z, Zhang L, Guo X, Jiang X, Li T. Adsorption behavior of direct red 80 and [44] Shengli S, Junping L, Qi L, Fangru N, Jia F, Shulian X. Optimized preparation of
congo red onto activated carbon/surfactant: process optimization, kinetics and Phragmites australis activated carbon using the Box-Behnken method and
equilibrium. Spectrochim Acta A Mol Biomol Spectrosc 2015;137:1126–43. desirability function to remove hydroquinone. Ecotoxicol Environ Saf 2018;165:
https://doi.org/10.1016/J.SAA.2014.08.138. 411–22. https://doi.org/10.1016/J.ECOENV.2018.09.038.
[23] Roy TK, Mondal NK. Potentiality of Eichhornia shoots ash towards removal of [45] Vebber MC, da Silva Crespo J, Giovanela M. Self-assembled thin films of PAA/
Congo red from aqueous solution: isotherms, kinetics, thermodynamics and PAH/TiO2 for the photooxidation of ibuprofen. Part I: optimization of
optimization studies. Ground Sustain Dev 2019;9:100269. https://doi.org/ photoactivity using design of experiments and surface response methodology.
10.1016/J.GSD.2019.100269. Chem Eng J 2019;360:1447–58. https://doi.org/10.1016/J.CEJ.2018.10.189.
[24] Najafpour A, Rajabi Khorrami A, Aberoomand Azar P, Saber Tehrani M. Study of [46] Mortazavian S, Saber A, James DE. Optimization of photocatalytic degradation of
heavy metals biosorption by tea fungus in Kombucha drink using central composite acid blue 113 and acid red 88 textile dyes in a UV-C/TiO2 suspension system:
design. J Food Compos Anal 2020;86:103359. https://doi.org/10.1016/J. application of response surface methodology (RSM). Catalysts 2019;9(4). https://
JFCA.2019.103359. doi.org/10.3390/catal9040360.
[25] Hmamouchi S, El Yacoubi A, El Idrissi BC. Using egg ovalbumin to synthesize pure [47] Panahi AH, et al. Removal of cephalexin from artificial wastewater by mesoporous
α-Fe2O3 and cobalt doped α-Fe2O3: structural, morphological, optical and silica materials using box-behnken response surface methodology. Desalin Water
photocatalytic properties. Heliyon 2022;8(2):e08953. https://doi.org/10.1016/J. Treat 2019;159:169–80. https://doi.org/10.5004/dwt.2019.24109.
HELIYON.2022.E08953. [48] Oppenlander T. Photochemical Purification of Water and Air Treatment. Weinheim
[26] Poghossian AA. Determination of the pHpzc of insulators surface from (Cambridge): Willey-VCH,; 2003.
capacitance–voltage characteristics of MIS and EIS structures. Sens Actuators B [49] Yetilmezsoy K, Demirel S, Vanderbei RJ. Response surface modeling of Pb(II)
Chem 1997;44(1–3):551–3. https://doi.org/10.1016/S0925-4005(97)00156-1. removal from aqueous solution by Pistacia vera L.: box–Behnken experimental
[27] Salleh MAM, Mahmoud DK, Karim WAWA, Idris A. Cationic and anionic dye design. J Hazard Mater 2009;171(1–3):551–62. https://doi.org/10.1016/J.
adsorption by agricultural solid wastes: a comprehensive review. Desalination JHAZMAT.2009.06.035.
2011;280(1–3):1–13. https://doi.org/10.1016/J.DESAL.2011.07.019. [50] Anupam K, Dutta S, Bhattacharjee C, Datta S. Adsorptive removal of chromium (VI)
[28] Hameed BH, Tan IAW, Ahmad AL. Adsorption isotherm, kinetic modeling and from aqueous solution over powdered activated carbon: optimisation through
mechanism of 2,4,6-trichlorophenol on coconut husk-based activated carbon. response surface methodology. Chem Eng J 2011;173(1):135–43. https://doi.org/
Chem Eng J 2008;144(2):235–44. https://doi.org/10.1016/J.CEJ.2008.01.028. 10.1016/J.CEJ.2011.07.049.
[29] Essekri A, et al. Enhanced adsorptive removal of crystal violet dye from aqueous [51] Sagharloo NG, Rabani M, Salimi L, Ghafourian H, Sadatipour SMT. Immobilized
media using citric acid modified red-seaweed: experimental study combined with ZnO/TiO2 activated carbon (I ZnO/TiO2 AC) to removal of arsenic from aqueous
RSM process optimization. J Dispers Sci Technol 2022;43(9):1359–72. https://doi. environments: optimization using response surface methodology and kinetic
org/10.1080/01932691.2020.1857263. studies. Biomass– Convers Biorefin 2021. https://doi.org/10.1007/s13399-021-
[30] Ghelich R, Jahannama MR, Abdizadeh H, Torknik FS, Vaezi MR. Central composite 01741-1.
design (CCD)-response surface methodology (RSM) of effective electrospinning [52] Cheng J, et al. Highly efficient removal of methylene blue dye from an aqueous
parameters on PVP-B-Hf hybrid nanofibrous composites for synthesis of HfB2- solution using cellulose acetate nanofibrous membranes modified by
based composite nanofibers. Compos B Eng 2019;166:527–41. https://doi.org/ polydopamine. ACS Omega 2020;5(10):5389–400. https://doi.org/10.1021/
10.1016/J.COMPOSITESB.2019.01.094. acsomega.9b04425.
[31] Jawad AH, Saud Abdulhameed A, Wilson LD, Syed-Hassan SSA, ALOthman ZA, [53] Allawi F, Juda AM, Radhi SW. Photocatalytic degradation of methylene blue over
Rizwan Khan M. High surface area and mesoporous activated carbon from KOH- MgO/α-Fe2O3 nano composite prepared by a hydrothermal method,”. AIP Conf
activated dragon fruit peels for methylene blue dye adsorption: Optimization and Proc 2020;2290(1):030020. https://doi.org/10.1063/5.0029461.
mechanism study. Chin J Chem Eng 2021;32:281–90. https://doi.org/10.1016/J. [54] Benjelloun M, Miyah Y, Akdemir Evrendilek G, Zerrouq F, Lairini S. Recent
CJCHE.2020.09.070. advances in adsorption kinetic models: their application to dye types. Arab J Chem
2021;14(4):103031. https://doi.org/10.1016/J.ARABJC.2021.103031.

12
S. Hmamouchi et al. Desalination and Water Treatment 320 (2024) 100824

[55] Yakub E, Agarry SE, Omoruwou F, Owabor CN. Comparative study of the batch Russ J Phys Chem A 2022;96(7):1484–92. https://doi.org/10.1134/
adsorption kinetics and mass transfer in phenol-sand and phenol-clay adsorption S0036024422070159.
systems. Part Sci Technol 2020;38(7):801–11. https://doi.org/10.1080/ [57] Hmamouchi S, El Yacoubi A, El Idrissi BC. Using egg ovalbumin to synthesize pure
02726351.2019.1616862. α-Fe2O3 and cobalt doped α-Fe2O3: structural, morphological, optical and
[56] Lebkiri I, et al. Polyacrylamide hydrogel an effective adsorbent for the removal of photocatalytic properties. Heliyon 2022;8(2):e08953. https://doi.org/10.1016/J.
heavy metal from aqueous solution: isotherm, kinetic, and thermodynamic studies. HELIYON.2022.E08953.

13