Materials Today: Proceedings 37 (2021) 3980–3986

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Adsorption of Crystal Violet from aqueous solution onto eco-friendly

native Carpobrotus edulis plant
Abdelkader Dabagh ⇑, Abdellah Bagui, M’hamed Abali, Rachid Aziam, Mohamed Chiban,
Fouad Sinan, Mohamed Zerbet ⇑
Laboratory LACAPE, Faculty of Science, Ibn Zohr University, BP. 8106, Hay Dakhla, Agadir, Morocco

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

Article history: The recent interest in the adsorption of pollutants on biomaterials has been gaining widespread atten-
Received 29 June 2020 tion, especially in the utilization of natural materials of vegetable origin-based composite biomaterials.
Received in revised form 14 September In this study, the equilibrium and the kinetics of Crystal Violet adsorption onto native Carpobrotus edulis
2020
Mediterranean plant, which is biodegradable and less expensive, was investigated. Experiments were car-
Accepted 15 October 2020
Available online 19 November 2020
ried out as a function of adsorbent dose (0.08–1 g), contact time initial (5–180 min), ionic strength of salt
NaCl (0.05–0.5 M), and solution pH (2–12). pH and ionic strength do not have a major influence on the
adsorption of Crystal Violet on the biomaterial studied. The adsorption process followed a kinetic model
Keywords:
Adsorption
of the pseudo-second-order. These results suggest that the native Carpobrotus edulis plant could poten-
Carpobrotus edulis tially be used as an environmentally friendly adsorbent for eliminating cationic dyes from aqueous
Crystal Violet solutions.
Kinetics Ó 2020 Elsevier Ltd. All rights reserved. Selection and peer-review under responsibility of the scientific
Biomaterials committee of The International Conference on Water Depollution and Green Energy 2019.

1. Introduction low cost, and available in tonnage quantities [8,9] is of vital

The main source of dye wastewater is textile, leather, pulp, rub-
ber, plastics, cosmetics, pharmaceutical, and food industries.
Because dye wastewater always comes as large quantities, com-
plex composition, depth of color, and is highly toxic, it causes sev-
ere environmental pollution and hazards to human health if it is
not properly treated before discharging into natural water [1,2,3].
Current techniques for treating dye wastewater includes physical,
chemical, and biological processes, and so on adsorption [4,5],
chemical coagulation, separation of the liquid membrane, electrol-
ysis, biological procedures, oxidation, and other processes have
been studied in different removal methods [6]. These processes
vary in their effectiveness, cost, and environmental impact [7].
However, the adsorption process is much more efficient among
these processes than other processes because of its ready availabil-
ity, lower cost, and wider application range. The hunt for adsor-
bents that meet water treatment industry requirements and
standards and are also environmentally friendly, highly effective,
⇑ Corresponding authors.
E-mail addresses: abdelkader.dabagh@gmail.com (A. Dabagh), zerbetmoha-
med@gmail.com (M. Zerbet).
importance.
Crystal Violet, also known as genetic violet, is a triaryl-methane
dye, widely used as a violet dye for cotton and silk dyeing in textile
industries. It also finds application in paint and printing inks
[10,11,12]. It is used as a biological stain within the medical profes-
sion and is the active ingredient in Gram’s stain. It is used as a bac-
teriostatic agent in animal and veterinary medicine. The dye can
also be used in humans as a disinfectant for the exterior skin. It
is used as an additive to poultry feed to inhibit mold, intestinal par-
asites, and fungal propagation [13,14]. Crystal Violet is a protein–
dye and is thus used as a bloody fingerprint additive. Crystal Violet
is carcinogenic and has been identified as a recalcitrant molecule
because it is poorly metabolized by microbes is non-
biodegradable, and may persist in a variety of environments. The
dye can cause moderate eye irritation, which brings light to painful
sensitization. This can also cause permanent corneal and conjunc-
tive damage because the drug includes a cationic dye. It is extre-
mely poisonous to mammalian cells and can cause skin irritation
and digestive tract irritation if absorbed in harmful amounts
through the skin. It can also cause respiratory and renal failure in
extreme situations [15,16,17,18].
Natural materials of vegetable origin offer several advantages;
they are biodegradable, non-toxic, low-cost, and contain in their

https://doi.org/10.1016/j.matpr.2020.10.349
2214-7853/Ó 2020 Elsevier Ltd. All rights reserved. Selection and peer-review under responsibility of the scientific committee of The International Conference on Water
Depollution and Green Energy 2019.
A. Dabagh, A. Bagui, M’hamed Abali et al.
structure several functional groups that can create bonds and fix pol-
luting entities. The selection of Carpobrotus edulis plant is based on
their relative abundance in different areas of Morocco and their
adsorbent capacity to various organic and inorganic pollutants.
[19,20].
The aim of this study was therefore to explore the potential of the
native Carpobrotus edulis plant as a low-cost adsorbent to remove
Crystal Violet from aqueous solutions using the batch equilibration
technique. The effects on Crystal Violet adsorption rates of the adsor-
bent dose, contact time, ionic strength, and solution pH were inves-
tigated. The adsorption kinetics was also evaluated and reported.
2. Materials and methods
2.1. Preparation of biomaterial
The adsorbent used in this study was collected from native Car-
pobrotus edulis plants that are a Mediterranean plant. In an oven at
35 °C for 72 h, the microparticles of Carpobrotus edulis plants were
dried and ground with an electric grinder to obtain fine powders.
The obtained microparticles (<250 lm) were used as bioadsorbent
material without further pretreatment in batch experiments.
2.2. Preparation of dye solutions
Crystal Violet’s synthetic dye solution was the sorbate used in
this study, and without further purification, the cationic dye was
used. Crystal Violet dye properties are shown in Table 1. Sigma-
Aldrich bought the synthetic dye that was used in this study. A
stock solution of 1000 mg/L in cationic dye was prepared by accu-
rately dissolving the weighed amount of Crystal Violet dye in dou-
ble distilled water. All the compounds used to prepare reagent
solutions were analytical reagent grade and double distilled water
was used in all experiments.
2.3. Study of adsorption in batch systems
Crystal Violet adsorption was achieved at room temperature
using the batch technique. Well-established amounts of native Car-
pobrotus edulis plants were placed in Erlenmeyer 100 mL flasks
containing 40 mL of known concentration and pH dye solution.
Table 1
Properties of Crystal Violet dye.
Molecular structure H3C
N
H3C
H3C
Molecular formula C25H30ClN3
Molar mass 407.979 g/mol
C.I. number 42,555
CAS number 548–62-9
Type Cationic
kmax 580 nm
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Materials Today: Proceedings 37 (2021) 3980–3986
Solutions were vigorously stirred for a period of time to achieve
equilibrium. For every cycle, the stirring rate was kept constant
to ensure even mixing. The resulting solutions were centrifuged
at 5000 rpm for 10 min after different contact times (tc), and the
supernatant was filtered through a membrane filter of 0.45 lm,
and the filtrate was analyzed.
Studies of adsorption equilibrium at the initial dye solution
were conducted. The pH was not fixed but was measured before
and after each test. The equilibrium data were obtained by adding
0.08 to 1 g of a native plant to a 100 mL Erlenmeyer series each
filled with 40 mL of Crystal Violet solution to 20 and 100 mg/L
and setting the contact time at 6 h (h).
The effect of the contact time on the adsorbed amount of
Crystal Violet was analyzed as follows: a series of 100 mL of
Erlenmeyer flask each containing a fixed adsorbent mass and
40 mL of a Crystal Violet solution varying concentrations were
shaken with different contact time at room temperature
(23 ± 2 °C) and the natural pH.
The adsorption experiments for the pH effect of the initial solu-
tion were performed as follows: A fixed mass of adsorbent was sus-
pended in 40 mL of 100 mg/L solution of Crystal Violet. The pH of
the solution was adjusted to 2–12 by adding a dilute solution of
hydrochloric acid or sodium hydroxide (0.1 M NaOH or 0.1 M
HCl), the stirring time was set to 2 h and the temperature was
23 ± 2 °C.
Finally, the effect of ionic strength on dye uptake was studied
by adding a NaCl concentration ranging from 0.05 to 0.5 M.
2.4. Analysis of Crystal Violet dye
The analysis of the Crystal Violet dye concentration at equilib-
rium was performed using a UV–Visible spectrophotometer (Tech
Comp UV 2300 spectrophotometer) at a wavelength of 580 nm.
The concentrations retained Cr (mg/L) by the biomaterial at
equilibrium and the adsorption quantities Qads (mg/g) are given
by the following relationships:
C r ðmg=LÞ ¼ ðC i  C e Þ ð1Þ
V
qe ðmg=g Þ ¼ ðC i  C e Þ ð2Þ
m
CH3
N
CH3
N
CH3
Cl-
A. Dabagh, A. Bagui, M’hamed Abali et al.
where m: mass of the biomaterial (g), V : total volume (L), Ci : initial
concentration (mg/L), Ce : equilibrium concentration (mg/L), qe:
amount adsorbed per 1 g of biomaterial at equilibrium (mg/g).
The percentage of removable dye was calculated as follows:
ðC i  C e Þ
%Remov al ¼  100
Ci
3. Results and discussion
3.1. Effect of operating parameters
3.1.1. Determination of the ratio
The ratio R (R = adsorbent mass/volume solution) corresponds
to the lowest mass of the biomaterial that leads to a maximum
removal rate of Crystal Violet. This ratio was determined from
the change in the percentage of Crystal Violet adsorbed as a func-
tion of the R ratio (Fig. 1). This variation was investigated for an ini-
tial low concentration Ci = 20 mg/L and another high concentration
Ci = 100 mg/L.
For the two initial concentrations, it can be seen that 88% of the
quantity retained is obtained from a maximum value correspond-
ing to a ratio (m/V) equal to 5 g/L. This result indicate that 0.2 g of
native Carpobrotus edulis plant per 40 mL of the solution can
achieve optimum adsorption for Crystal Violet.
3.1.2. Effect of contact time of Crystal Violet
Table 2 illustrates the effect of contact time by a native Carpo-
brotus edulis plant on the adsorbed amount of Crystal Violet from
solutions with different initial dye concentrations of 20, 100 mg/L
at 25 °C. Crystal Violet dye’s adsorption capacity increased rapidly
with the first 30 min contact time and reached equilibrium within
60 min. In every batch adsorption experiment, 1 h was selected for
the adsorbent of Carpobrotus edulis native to ensure a complete
adsorption equilibrium.
(Fig. 2) also shows that adsorption efficiency increased with an
increase in initial Crystal Violet dye concentration, and then the
initial Crystal Violet dye concentration had no major impact on
the equilibrium time. It was found that for native Carpobrotus edu-
lis plant, the equilibrium adsorption amount of Crystal Violet dye
Fig. 1. Effect of the biosorbent ratio on biosorption of Crystal Violet onto native Carpobrotus edulis plant, T = 23 ± 2 °C ; tc = 6 h. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
Materials Today: Proceedings 37 (2021) 3980–3986
increased by 3 at 17.70 mg/g as the initial concentration increased
from 20 to 100 mg/L. The increased adsorption capacity is possibly
due to higher interaction between the adsorbent and the
adsorbent.
ð3Þ
3.1.3. Effect of pH
In this study of the influence of pH on CV adsorption on Carpo-
brotus edulis native, a pH range between 2 and 12 was chosen
(Fig. 3).
The results shown (Fig. 3) suggest that the initial pH of the solu-
tion does not influence the adsorbed amount of Crystal Violet sig-
nificantly. From these study results, the absorption of Crystal Violet
remains constant at all pH points studied for Carpobrotus edulis
native.
The measurement of the equilibrium pH of the solutions tested
(Table 2) indicates that the pH of the equilibrium solution does not
vary in the same order as the initial pH. Thus, biomaterial should
have a pH regulating effect and thus the difference in the amount
retained is not important while the initial pH varies considerably.
3.1.4. Effect of ionic strength
Various substances that may interfere with the test molecule
are charged in the wild, polluted waters. The ionic strength is a sig-
nificant factor that regulates the adsorption in this situation.
Increasing ionic strength can improve or decrease organic com-
pound adsorption. The adsorption can also be insensitive to ionic
strength variations. For example, NaNO3, CaCl2, NaCl, and their
concentration. In this study, we add to the system Crystal Violet
solution/biomaterial a NaCl solution with different concentrations
to examine the impact of ionic strength. The results showed that
the Crystal Violet adsorption remained unchanged with the
increased concentration of NaCl (Fig. 4). This shows that ionic
strength has no impact on the biomaterial’s adsorption capacity.
The adsorption capacity is not modifying due to the absence of
competition for surface adsorption from Cl- anions with Crystal
Violet.
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Table 2
Values of the initial pH and the pH at equilibrium.

Initial pH 2 4 6 8 10 12
pH at equilibrium 2.08 4.71 5.82 6.18 6.95 9.75

Fig. 2. Effect of contact time on the amount of Crystal Violet onto native Carpobrotus edulis plant and T = 23 ± 2 °C. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

Fig. 3. Effect of initial pH on adsorption of Crystal Violet onto native Carpobrotus edulis plant: Ci = 100 mg/L, T = 23 ± 2 °C and tc = 2 h.

3.2. Adsorption kinetics [23] were used in this study to analyze the kinetic experimental
adsorption data.
The design of adsorption treatment systems requires knowl-
edge of kinetic processes due to the many varied chemical systems, 3.2.1. Pseudo-first order kinetics model
the nature of the various adsorbents, and the various designs of The pseudo-first-order model kinetics equation and its lin-
contacting systems. For this reason, three kinetic models of earized form may be represented as:
liquid-phase adsorption, the pseudo-first-order model [21],
ln ðqe  qt Þ ¼ ln qe  k1 tðlinearformÞ ð4Þ
pseudo-second-order model [22], and intraparticle diffusion model
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A. Dabagh, A. Bagui, M’hamed Abali et al. Materials Today: Proceedings 37 (2021) 3980–3986

Fig. 4. Effect of the ionic strength on the adsorption capacity of Crystal Violet onto native Carpobrotus edulis plant, Ci = 100 mg/L and T = 25 °C.

Fig. 5. Pseudo-first order adsorption kinetics of Crystal Violet onto native Carpobrotus edulis plant at different dye concentrations. (For interpretation of the references to color
in this figure legend, the reader is referred to the web version of this article.)

Table 3
where, k1 (min1) is the rate constant for the pseudo-first order Parameters of the pseudo-first, pseudo-second order and intraparticle diffusion
kinetic models for Crystal Violet dye adsorption onto native Carpobrotus edulis plant
kinetics model, qe (mg/g), qt (mg/g) are the amounts of Crystal Vio-
at different initial dye concentrations.
let retained on weight unit of adsorbent at equilibrium and at any
time t (min), respectively. Kinetic models Parameters Ci (mg/L)
The plot of ln(qe  qt) versus the native Carpobrotus edulis plant 20 100
contact time t gives a straight line of slope k1 and intercepts ln qe qe, exp (mg/g) 3.562 17.703
(Fig. 5). Table 3 presented the values of the theoretical adsorption First-order kinetic model k1 (1/min) 0.032 0.058
capacity (qe,cal), the rate constant for the pseudo-first-order kinet- qe, Cal (mg/g) 0.558 3.400
ics model (k1), and the correlation coefficient (R2). R2 0.954 0.972
Second-order kinetic model k2 (g/mg.min) 0.184 0.045
From (Fig. 5) and (Table 3) it can be observed that in the case of
qe, Cal (mg/g) 3.594 17.921
the use of pseudo-first order kinetics model, the values of the cor- R2 0.999 0.999
relation coefficients are lower and the value of the adsorption Intraparticle diffusion Kp (mg. g-1min1/2) 0.048 0.219
capacity of equilibrium (qe, cal, mg/g) calculated from this equation c (mg/g) 3.015 15.356
R2 0.804 0.733
is much lower than the experimental value (qe, exp, mg/g).

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A. Dabagh, A. Bagui, M’hamed Abali et al. Materials Today: Proceedings 37 (2021) 3980–3986

Fig. 6. Pseudo-second order adsorption kinetics of Crystal Violet onto native Carpobrotus edulis plant at different dye Concentrations. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)

The pseudo-first-order model is not suitable under these condi-
tions to describe the kinetics of Crystal Violet adsorption from
aqueous solutions to the native Carpobrotus edulis plant.
3.2.2. Pseudo-second-order kinetics model
In the case of a kinetic model of pseudo-second order, the rate
equation and its linearized form can be formulated as:
 
t 1 1
¼ 2
þ tðlinearformÞ
qt k2 qe qe
where, k2 (g/mg.min) is the rate constant for the pseudo-second
order kinetics model, qe (mg/g), qt (mg/g) are the amounts of Crystal
Violet retained on weight unit of adsorbent at equilibrium and at
any contact time t (min), respectively.
The pseudo-second order plots for the Crystal Violet adsorbent
system are presented in Fig. 6 at different initial concentrations
and the kinetic parameters are given (Table 3). For the pseudo-
second-order adsorption model, the value of the correlation coeffi-
cients (R2) for both initial concentrations is relatively superior
(>0.99), and the adsorption capacity calculated by the model is also
close to those determined by experiments. It was therefore con-
cluded that the pseudo-second-order adsorption model is more
suitable for describing the adsorption kinetics of Crystal Violet
dye on the native Carpobrotus edulis plant.
ð5Þ
3.2.3. Intra-particle diffusion kinetics model
The kinetics equation of intra-particle diffusion model is:
qt ¼ kp t 1=2 þ cðlinearformÞ ð6Þ
where, kp (mg.g1min1/2) is the intra-particle diffusion rate con-
stant, c (mg/g) is the concentration of Crystal Violet from solution

Fig. 7. Intra-particle diffusion kinetics of Crystal Violet onto native Carpobrotus edulis plant at different dye concentrations. (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of this article.)

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A. Dabagh, A. Bagui, M’hamed Abali et al.
at equilibrium and qt (mg/g) is the amount of Crystal Violet retained
on weight unit of adsorbent at contact time t (min).
If the intra-particle diffusion is the elementary rate-limiting
process, the amount of dye retained on the adsorbent weight unit
varies with the square root of time. The graphic representation of
dependency qt versus t1/2, obtained in the case of Crystal Violet
adsorption on the native Carpobrotus edulis plant (Fig. 7) does not
go through the origin, the region obtained is evaluated using equa-
tion (6), and the values of kp and c, determined from the slopes and
intercepts are noted (Table 3).
4. Conclusion
This study suggested that dried microparticles from the native
Carpobrotus edulis plant can be used as adsorbents for the treat-
ment of cationic dyes contaminated wastewater. Experimental
conditions such as contact time, adsorbent dose, solution pH, and
ionic strength of dye have shown the adsorption process to be
affected. Batch adsorption studies under different experimental
conditions have shown that pH and ionic strength has no major
effect on the adsorption of Crystal Violet to the biomaterial being
studied. The adsorption kinetics followed a pseudo-second order
pattern. The biomaterials used in this study are suitable materials
such as cationic dye-removal adsorbents because they are natu-
rally abundant and relatively cheap materials.
CRediT authorship contribution statement
Abdelkader Dabagh: Conceptualization, Methodology, Formal
analysis, Investigation, Resources, Writing - original draft. Abdel-
lah Bagui: Resources, Software, Writing - review & editing.
M’hamed Abali: Resources, Writing - review & editing. Rachid
Aziam: Writing - review & editing. Mohamed Chiban: Writing -
review & editing. Fouad Sinan: . Mohamed Zerbet: Supervision,
Resources, Software, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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