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OPEN Adsorptive removal of malachite

green dye from aqueous solution
using Rumex abyssinicus derived
activated carbon
Mikiyas Abewaa 1*, Ashagrie Mengistu 2, Temesgen Takele 1, Jemal Fito 3 & Thabo Nkambule 3
The potential for malachite green dye saturated effluent to severely affect the environment and
human health has prompted the search for effective treatment technologies. Thus, this study was
conducted with the goal of developing activated carbon from Rumex abyssinicus for the adsorptive
removal of malachite green dye from an aqueous solution. Unit operations such as drying, size
reduction, impregnation with ­H3PO4, and thermal activation were used during the preparation of the
activated carbon. An experiment was designed considering four main variables at their respective
three levels: initial dye concentration (50, 100, and 150 mg/L), pH (3, 6, and 9), contact period
(20, 40, and 60 min), and adsorbent dosage (0.05, 0.01, and 0.15 g/100 mL). Optimization of the
batch adsorption process was carried out using the Response Surface methodology’s Box Behnken
approach. The characterization of the activated carbon was described by SEM for surface morphology
with cracks and highly porous morphology, FTIR for multi-functional groups O–H at 3506.74 ­cm−1
and 3290.70 ­cm−1, carbonyl group stretching from aldehyde and ketone (1900–1700 ­cm−1), stretching
motion of aromatic ring C=C (1543.12 ­cm−1), stretching motion of –C–H (1500–1200 ­cm−1), vibrational
and stretching motion of –OH (1250.79 ­cm−1), and vibrational motion of C–O–C (1049.32 ­cm−1),
pHpzc of 5.1, BET for the specific surface area of 962.3 ­m2/g, and XRD for the presence of amorphous
structure. The maximum and minimum dye removal efficiencies of 99.9% and 62.4% were observed
at their respective experimental conditions of (100 mg/L, 0.10 mg/100 mL, pH 6, and 40 min) and
(100 mg/L, 0.15 mg/100 mL, pH 3, and 20 min), respectively. Langmuir, Freundlich, Toth, and Koble-
Corrigan models were used to evaluate the experimental data, in which Koble-Corrigan model was
found to be the best fit with the highest value of ­R2 0.998. In addition to this, the kinetic studies were
undertaken using pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Boyd models,
and as a result, the pseudo-second-order model proved to have a better fit among the kinetic models.
The kinetics and isotherm analysis revealed that the nature of the adsorption to be homogenous and
monolayer surfaces driven by chemosorption. Furthermore, the thermodynamics study revealed the
nature of adsorption to be feasible, spontaneous, and endothermic. On the other hand, the reusability
study depicted the fact that the adsorbent can be utilized for five cycles with a negligible drop in the
removal efficiencies from 99.9 to 95.2%. Finally, the low-cost, environmentally benign, and high
adsorption capacity of the adsorbent material derived from Rumex abyssinicus stem could be used to
treat industrial effluents.

Uncontrolled industrialization and urbanization have been proven to be the major contributors to the depletion
of natural resources as well as varying degrees of environmental degradation. In line with this, rapid industri-
alization, urbanization, and improper utilization of natural resources end up with the discharge of substantial
amounts of untreated wastewater, which puts fresh water under ­stress1,2. Moreover, the current environmental
condition has reached the Antrophocene epoch of the geological time scale, where human activities are highly

1
Department of Chemical Engineering, College of Engineering and Technology, Wachemo University, P. O. Box 667,
Hossana, Ethiopia. 2The Federal Democratic Republic of Ethiopia, Manufacturing Industry Development Institute,
P. O. Box 1180, Addis Ababa, Ethiopia. 3Institute for Nanotechnology and Water Sustainability (iNanoWS), College
of Science, Engineering and Technology, University of South Africa, Florida Science Campus, Johannesburg 1710,
South Africa. *email: [email protected]

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responsible for the environmental pollution our planet is facing n ­ owadays3. Hence, initiatives to ensure the sus-
tainability of industrialization, both in terms of preventing environmental d ­ amage4 and fostering more environ-
5
mentally friendly industries are urgently ­needed . Different organic, microbiological, and inorganic contaminants
are becoming the cause of most water pollution, posing major environmental and human health challenges.
These pollutants are either manufactured or naturally occurring substances that enter the environment through
anthropogenic activities, including freshwater sources and w ­ astewater6. On the other hand, increased demand
for textile products necessitates the expansion of textile industries, leading to a dramatic increase in wastewater
discharge, making the sector one of the most serious sources of pollution ­worldwide7. Dyes, degradable organ-
ics, detergents, stabilizing agents, desirers, inorganic salts, and heavy metals are among the contaminants found
in textile industry e­ ffluent8.
Malachite green (4[4-(dimethylamino) phenyl] (phenyl) methylidene-N N-dimethylcyclohexa-2, 5-dien-
1-iminium chloride) is a solid, cationic, and crystalline dye characterized by a molecular formula of ­C23H25CIN2
and a molecular weight of 346.11 g/mol9,10. Additionally, its higher solubility in water, synthetic nature, higher
stability, and affordability increased malachite green demand in various industrial ­sectors11,12. It is widely applied
in manufacturing industries like textile dying, leather, food, pulp and paper production, paint and pigment
production, wool, and s­ ilk11. Moreover, malachite green is used as an antiseptic, parasiticide, and fungicide in
­aquaculture13. However, there are environmental and human health issues associated with malachite green dye.
Malachite green is persistent (resists natural bio-degradation), bio-accumulative, mutagenic, carcinogenic, and
­teratogenic14–16. Furthermore, malachite green ingested through water poises the kidney, heart, and breast, which
­ umans10. Diseases such as skin, gastrointestinal, and respiratory irritation are associated with
are vital organs of h
the ingestion of malachite-contaminated ­water15. Moreover, the biochemical reduction of malachite green in
the mammalian body system forms a chemical substance that, if accrued in the body for more than five months,
increases liver tumors and facilitates lung adenomas in F344 males known as leucomalachite (LMG)9. The reduc-
tion of water surface oxygenation resulting from the obstruction of light penetration caused by the discharge
of malachite green dye effluent puts aquatic life in ­peril17. Indeed, the use of malachite green as a food coloring
additive is banned in countries like the USA, Canada, China, the UK, and the European ­Union18. Hence, for
environmental preservation and human health protection, the decontamination of persistent dyes like malachite
green has become a serious agenda item for the global community.
Due to the ineffectiveness of conventional wastewater treatment techniques for decontamination of persistent
and toxic pollutants like malachite green dye, advanced wastewater treatment methods have become the choice
of experts working in the areas of public health and environmental protection 19. Scholars have extensively
researched the decolorization of malachite green dye using advanced wastewater technologies. For instance,
membrane filtration 20,21, Fenton oxidation 22, ultraviolet assisted advanced oxidation 23,24, and catalyst assisted
advanced oxidation process 25. However, these technologies have their own limitations, such as the lack of
sustainability and short life span of membrane technology due to the clogging of filter pores by dye molecules
and the exaggerated cost to ­acquire26,27, capital intensiveness, tailoring of complex chemistry, excess peroxide
requirement for advanced oxidation processes, requirement of large amounts of chemicals, and the generation
of excessive toxic sludge by chemical ­precipitation28, unbearable investment cost and expensive electricity supply
for electrochemical ­methods29. On the other hand, adsorption, being low-cost, eco-friendly, effective, sustainable,
and non-complex, has become an alternative pollutant detoxification ­mechanism30. Activated carbons, biochar,
and magnetic biochar/activated carbons are a class of adsorbents whose state of art is thoroughly e­ stablished31.
Commercial activated carbon, which is widely installed in various industrial wastewater treatment sectors, is
known for its excellent adsorption capability and ­effectiveness32. Even though commercial activated carbon is
efficient and reliable, the preparation cost and non-sustainability limit its ­application33. Hence, many researchers
have continued to search for adsorbent materials that are especially versatile in terms of both local availability
and low cost.
Nowadays, the development of biomass-based adsorbent materials has been thoroughly investigated to over-
come the limitations associated with commercial activated carbons. To make sure this, the inexpensive, freely
available, and easily utilizable agro-waste-based adsorbent ­materials34 such as banana peel 35, orange peel 36,
watermelon peel 37, and desert date seed shell 38 are under investigation for their effectiveness in removing mala-
chite green dye. However, these studies have the limitations of low adsorption capacity, a substantial amount
of adsorbent consumption for a small amount of pollutant adsorption, a small specific surface area, and a long
contact time for pollutant detoxification. Hence, Rumex abyssinicus, a plant that is mostly distributed in tropical
Africa, specifically Ethiopia, has been selected to tackle disadvantages like low removal efficiency and the longer
contact time requirement of biomass-based activated carbons. So far, the application of the roots and root barks
of Rumex abyssinicus for medicinal purposes has been thoroughly s­ tudied39–41. However, a few s­ tudies42,43 have
been conducted to valorize the stem of Rumex abyssinicus for environmental clean-up. Moreover, the previous
studies did not consider the thermodynamics study, which has a great implication in the design of the adsorption
system. Furthermore, the ratio of precursor material (Rumex abyssinicus) to activating agent (­ H3PO4) was 1:3 and
1:2, which is very high and results in a substantial amount of chemical consumption. On the other hand, linear
forms of isotherm and kinetics models were used, resulting in errors in data analysis. Hence, this research work
was conducted with the aim of filling the gaps mentioned above. So far, the valorization of the stem and leaves
of Rumex abyssinicus for the removal of malachite green dye from aqueous solutions or industrial wastewater
is missing. Therefore, this study was aimed at investigating the adsorptive performance of Rumex abyssinicus-
derived activated carbon for the removal of malachite green dye from aqueous solution with the simultaneous
evaluation of isotherm, kinetics, and thermodynamics studies and examining the regeneration and reusability
potentials of the developed adsorbent.

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Materials and methods

Adsorbent preparation. The precursor material used for activated carbon synthesis, i.e., the stem of
Rumex abyssinicus, was collected from Addis Ababa, Ethiopia. The collected sample was thoroughly washed with
tap water before being rinsed with distilled water. The dust-freed sample was sundried and then placed in the
oven (Model BOV-T50F) at 105 °C for 24 h to remove the remaining moisture. Thereafter, the oven-dried sam-
ple was impregnated with phosphoric acid in a 1:1(m/v) ratio and soaked thoroughly. Then, it was oven-dried
for 8 h after which it was pyrolyzed in the furnace at 500 °C for 2 h. The prepared adsorbent material was then
taken out of the furnace, cooled in a desiccator, and thoroughly washed with distilled water until its pH became
neutral. Finally, the activated carbon was ground to a particle size of 250 µm and placed in airtight plastic until
the subsequent ­experiments44,45. All the methods were carried out in accordance with relevant guidelines and
legislation of institutional, national, and international.

Adsorbent characterization. The Rumex abysiniccus-derived adsorbent was characterized for pH point
of zero charge (pHpzc), scanning electron microscope (SEM), Brunner emitter and teller (BET), Fourier Trans-
form Infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) following methods described b ­ y42.The func-
tional group present in the adsorbent material as well as its crystalline nature were determined using the Fourier
transform infrared Shimazu IRAffinity-1 s and X-ray diffraction XRD (Rigabu Miniflex 600n diffractometer),
respectively. The FTIR scanning was carried out at a wavelength range of 400–4000 ­cm−1. However, XRD scan-
ning was performed along 2 of 10◦–80◦ . Additionally, SEM and BET were used for surface morphology and
specific surface area determination, ­respectively46,47.

Malachite green adsorption experimental design. An experimental design considering four variables
with their respective three levels was established to examine the use of activated carbon obtained from Rumex
abyssinicus for the removal of malachite green from an aqueous solution. The response variable is removal effi-
ciency (%), and the independent variables are pH, contact time, initial dye concentration, and adsorbent dos-
age. The levels of the experimental variables were denoted as lower (−), middle (0), and higher (+). In essence,
81 experimental runs were produced via 3­ 4 factorial designs. However, to reduce the number of experimental
runs to 30, the design expert’s optimization strategy was utilized. Table 1 indicates the experimental design for
the Box-Behnken technique approach to the response surface methodology. The experimental values are set in
accordance with the results of earlier experiments.

Batch adsorption experiments for malachite green dye removal. The batch adsorption experi-
ment for malachite green dye removal through Rumex abyssinicus-derived adsorbent was conducted in a 100-
mL solution. A malachite green dye solution was prepared by dissolving 50, 100, and 150 mg into 1 L of distilled
water separately. This gave a dye concentration of 50, 100, and 150 mg/L, respectively. The solution pH was
adjusted using NaOH (0.1 M) and HCl (0.1 M) based on the required acidity and basicity of the solution. Then, a
fixed amount of adsorbent dosage was added to an Erlenmeyer flask containing a 100-mL pH-adjusted solution
of malachite green dye. Thereafter, the solution was stirred using an orbital shaker at 125 rpm for the specific
duration of contact time. As contact time completed, the solution was filtered using Whatman filter paper 42,
where supernatants were removed, and the filtrate was used for the determination of the amount of dye remain-
ing in the aqueous solution. Then, various sampling bottles were used to collect the dye-containing supernatants,
which in turn were used to determine the amount of dye remaining in the solution. The amounts of malachite
green dye remaining in the solution were collected using various sampling bottles. Finally, the final dye con-
centration was determined using an ultraviolet (UV)-visible spectrophotometer (Agilent Technology, Cary 100
UV–visible Spectrophotometer) at a maximum wavelength of 620 nm. For calibration curve development, the
stock solution for malachite green dye was prepared by weighing 1 g of malachite green powder and dissolving it
into 1 L of solution to get 1000 mg/L of malachite green dye solution. Thereafter, a serial dilution was performed
using distilled water in order to get the desired malachite green dye concentrations of 30, 50, 70, 90, 110, 130,
and 150 mg/L. Thereafter, the standard solutions are transferred into cuvettes. The standard solution containing
cuvettes is placed in the UV–VIS spectrophotometer at a maximum wavelength of 620 nm. Then, absorbance
readings for each sample were obtained and recorded on a spread sheet. The absorbance data (y axis) was plotted
against the concentration (x axis) and examined for the best linear curve fit. Finally, the unknown concentrations
were determined using an equation generated from a linear plot. The removal efficiency and adsorption capacity
were calculated using Eqs. (1) and (2), respectively.

Variables Unit Low (−) Middle (0) High (+)

pH 3 6 9
Adsorbent dosage g/100 mL 0.05 0.1 0.15
Dye concentration mg/L 50 100 150
Contact time min 20 40 60

Table 1.  Box Behnken approach of experimental design.

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Ci − Cf
R(%) = ( ) ∗ 100. (1)
Ci
 
Co − Ce
Qe = ∗V (2)
m
where, R is removal efficiency, Qe is adsorption capacity, m is mass of the adsorbent, V is volume of the solution,
Ci and Cf are initial and final malachite green concentration ­respectively48.

Adsorption isotherm. Adsorption isotherms provide information regarding the interaction of adsorbate
and adsorbent at equilibrium. Moreover, these equilibrium relationships help us understand the basic adsorp-
tion mechanisms and surface characteristics of adsorbate and adsorbent. There are various adsorption isotherms
used in modelling the adsorption isotherm, of which Langmuir and Freundlich isotherm models are the most
widely used ones in the adsorption system. The Langmuir isotherm model assumes a monolayer and homog-
enous adsorption surface with strong binding of adsorbate and adsorbent, whereas the surface of the adsorption
system is expected to improve itself in the Freundlich isotherm. In the Freundlich isotherm model, there is het-
erogeneous and multilayer surface interaction. Moreover, the adsorption mechanism is said to be chemisorption
if Langmuir isotherm was found to be explanatory and physical sorption when Freundlich isotherm was found
to represent more of the adsorption data. The adsorption isotherm study was undertaken keeping pH, contact
time, and adsorbent dosage at 6, 40 min, and 0.1 g/100 mL, respectively, while varying the initial dye concentra-
tion (50, 70, 90, 110, 130, and 150 mg/L). The Langmuir and Freundlich equations are presented in Eqs. (3) and
(4), respectively.
QmaxKLCe
(3)
1 + KLCe

Qe = KFCe1/n (4)
Additionally, the adsorption dimensionless factor constant (RL) that is used to estimate Langmuir isothermal
feasibility is indicated by Eq. (5).
1
RL = (5)
1 + KL Ce
where ­qmax is the maximum Langmuir adsorption capacity, K ­ L is the Langmuir constant related to adsorption
capacity, and ­KF and n are Freundlich constants related to adsorption capacity and ­intensity49. In addition, Toth
and Koble-Corrigan isotherm models were investigated in order to further examine the best data fit. Equation (6)
shows the relation between parameters for Toth isotherm models, where K and nt are Toth isotherm constants
indicating surface affinity and degree of heterogeneity, r­ espectively50,51.
Qmax KCe
Qe = (6)
[1 + (KCe)nt )]1/nt
Similarly, the Koble-Corrigan model is shown in Eq. (7), where parameters such as A and B are Koble-
Corrigan constants in (mg/g) and (L/mg)n, respectively. Meanwhile, adsorption intensity is represented by ­nk52,53.

ACe nk
Qe = (7)
(1 + BCe nk )

Adsorption kinetics. Adsorption kinetics is studied to determine the potential rate-controlling step in the
adsorption process. Moreover, that also allows for an understanding of kinetic mechanisms and the rate of dye
uptake. In the current study, the four widely used kinetics models were examined to determine the nature of the
adsorption that occurs between Rumex abyssinicus-derived activated carbon and malachite green dye. These
kinetic models are pseudo-first-order (PFO), pseudo-second-order (PSO), Intraparticle diffusion and Boyd
models. Normally, PFO is related to physical adsorption, whereas PSO is associated with chemisorption. Fun-
damentally, chemical sorption results in strong attachment between adsorbate and adsorbent with slow attach-
ment. However, in physical adsorption, the adsorption process is fast with weak interactions between adsorbate
and adsorbent. Hence, physical adsorption is easily reversible, whereas it is difficult to reverse chemical adsorp-
tion. pH 6, an adsorbent dosage of 0.1 g/100 mL, and an initial dye concentration of 100 mg/L with varying
contact times of 20, 30, 40, 50, and 60 min were used for the kinetics study. Basic equations used to determine
parameters related to PFO and PSO are presented in Eqs. (6) and (7), respectively.

Qt = Qe(1 − e(−K1t) ) (8)

Qe2 K2 t
Qt = (9)
1 + QeK2 t

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where the qt andqe (mg/g) are adsorption capacity at time t and equilibrium adsorption capacity, respectively;
Kf andKs are pseudo-first-order (g/(mg min)) and pseudo- second-order (g/(mg min)) adsorption rate constants,
respectively 54. Intraparticle diffusion and Boyd models are used to examine the presence of films or bulk dif-
fusion in the adsorption process. If the intraparticle diffusion model is found to fit the data best, it is the bulk
diffusion that governs the rate of adsorption. Equations (10) and (11) depict the relations between parameters
for intraparticle diffusion and Boyd models, respectively.

Qe = Kit 1/2 + Ci (10)

Qt 6
F= = 1 − ( 2 )exp(−Bt) (11)
Qe π
where Ki is the intraparticle diffusion constant, Ci is concentration, F is the fraction of pollutant adsorbed at
time t, and ­Bt is the mathematical function of ­F55,56.
The criteria for best fitting were evaluated using error analysis (reduced chi square) and the coefficient of
determination ­(R2). The coefficient of determination represents the variance about the mean; it is used as a model
performance indicator in adsorption kinetics and isotherm studies. The coefficient of determinant indicates the
degree of fitting of the kinetic and isotherm with experimental data and it is given by Eq. (12).
 2
2 Qecal − Qmexpt
R =  2  2 (12)
Qecal − Qmexpt + Qcal − Qmexpt

where Qexpt represents the amount of adsorbate adsorbed by the adsorbent during the experiment in mg/g,
Qcal is the amount of adsorbate obtained by kinetic and isotherm modelling in mg/g, and Qmexpt stands for
the average of Qexpt in mg/g. Reduced chi square is used to indicate the discrepancy between the experimental
and calculated data, which is used to judge the goodness of fitting for experimentally obtained data. Reduced
chi square is chi square per variance and is given by Eq. (13).
n (Qecal−Qemeas)2
i=1 Qemeas (13)
v
where Qecal is the calculated adsorption capacity, Qemeasured represents the measured adsorption capacity,
and v denotes the degree of freedom. Finally, Origin Pro software was used for data fitting and error a­ nalysis57,58.

Adsorption thermodynamics. The adsorption thermodynamics is of great importance since it provides

information about the spontaneous or non-spontaneous nature of the adsorption process. Moreover, it helps
to determine whether the process is endothermic or exothermic, the energy associated with the adsorption
process, and the feasibility of the adsorption. The thermodynamic study of the adsorption of malachite green
dye from an aqueous solution was conducted by varying the temperature of the system (25, 35, 45, 55, and 65)
while holding other variables constant at their optimum values (pH of 6, contact time of 40 min, adsorbent dos-
age of 0.1 g/100 mL, and dye concentration of 100 mg/L)51. The Van’t Hoff equation was used to determine the
three essential parameters, namely enthalpy change (ΔHo), entropy change (­ So) and Gibbs free energy (ΔGo) by
employing Eqs. (13)–(16).
G = −RT ln KC (14)

qe
KC = (15)
Ce

S H
ln KC = − (16)
R RT

G = H − TS (17)
where, R is the universal gas constant (8.314 J/mol. K), KC represents the thermodynamic constant, and T is
the absolute temperature (K). Ce denotes the amount of MB dye concentration at equilibrium; qe represents the
amount of dye adsorbed on the adsorbent at equilibrium (mg/g). The changes in entropy, enthalpy, and Gibbs free
energy are denoted by the letters G, S, and H, respectively. The slope and intercept from the plot between
ln KC and 1/T were used to calculate the values of H and S 59.

Reusability and regeneration study. Industries are still facing the problem of solid waste disposal,
including spent ­adsorbents60. Regeneration is a one-of-a-kind method that allows exhausted adsorbents to regain
their adsorption ability by desorbing pre-adsorbed i­mpurities61. Regeneration of spent adsorbent is required to
eliminate solid hazardous waste for sustainable d ­ evelopment60. It is frequently thought of as a less expensive and
superior alternative to replacing the adsorbents. The regeneration process is influenced by the experimental tem-
perature, pH, time, and ­processing61. The regeneration of the used Rumex abyssinicus-derived activated carbon
was carried out using chemical methods and then used for several cycles to examine the reusability potential
of the prepared adsorbent. The methods used ­by43,45 were followed for the regeneration of the used adsorbent.

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Ethical approval and consent to participate. All procedures are carried out per the institution’s poli-
cies and rules. The institution’s ethical clearance committee gave its approval to each experimental protocol.
During sample collection, our institute gave a support letter to permit sample collection, and Addis Ababa Sci-
ence Technology University permitted sample collection.

Result and discussion

Adsorbent characteristics. The crystalline nature of the activated carbon synthesized from Rumex abys-
sinicus was examined using XRD, and the result of the finding is depicted in Fig. 1. From the XRD analysis, it can
be observed that the general structure of the adsorbent is amorphous. Basically, amorphous surfaces are suitable
for the adsorption of multipollutant varying in size and structure compared to crystalline structures. 62.
The BET-specific surface area of an activated carbon synthesized from Rumex abyssinicus was determined by
employing the principle of nitrogen gas adsorption-desorption63. During BET-specific surface area analysis of the
adsorbent under consideration, a degassing temperature and time of 200 °C and 1 h were guaranteed, respectively.
Fundamentally, the higher the specific surface of the adsorbent, the greater the affinity for pollutant adsorption
will be due to the availability of sufficient active sites at the specified surface of the a­ dsorbent64. Normally, the rate
of adsorption is highly dependent on the nature of the adsorbent material and its surface area. Owing to their
more adsorbing sites, materials with a higher surface area increase the extent of the adsorption. On the other
hand, porous materials provide a larger surface area, leading to both higher removal efficiency and adsorption
capacity. Fundamentally, finely dividing (powdering) the adsorbent increases the surface area of the adsorbent,
which eventually enhances the adsorption performance. The specific surface area of the activated carbon (Rumex
abyssinicus) was found to be 962.3 ­m2/g. This extremely high specific surface area enables the adsorbent in minute
quantities to adsorb substantial pollutants. Compared to biomass-based activated carbons, the specific surface
area recorded in this study is higher. For instance, water hyacinth-derived activated c­ arbon65, Rumex-abyssinicus
based activated carbon 524 ­m2/g 43, Parthenium hysterophorus based activated carbon 265 m ­ 2/g 66.
The morphological analysis of the prepared adsorbent was undertaken using SEM, and the findings are
depicted in Fig. 2. It can be observed from the image that the adsorbent is determined to have a porous structure,
which enables it to adsorb pollutants varying in size and s­ tructure67. Morphological cracks such as holes and
irregular shapes are observed due to the chemical and thermal activation undertaken to enhance the adsorption
capacity of the activated c­ arbon68. Similar findings were reported by 42,43 for Rumex abyssinicus-derived activated
carbon applied for dye decolorization.
The functional group analysis of Rumex abyssinicus-based activated carbon before and after adsorption was
successfully carried out using FTIR, as shown in Fig. 3a, b, respectively. The adsorbent was found to be composed
of several functional groups capable of adsorbing various pollutants varying in structure and s­ ize69. For FTIR
analysis of Rumex abyssinicus activated carbon before adsorption, the broad peaks observed at 3506.74 and
3290.70 ­cm−1 are attributed to –OH containing functional groups like hydroxyl and water. On the other hand,
the shoulder peak observed at 2656.09 ­cm−1 demonstrates the vibration of carboxyl functional groups. The clear,
sharp peaks observed between 1900 and 1700 ­cm−1 are attributed to the existence of C=O or C=C stretching
vibrations of acid derivatives, which are characteristics of the carbonyl group stretching from aldehydes and
ketones. A smaller peak located at 1543.12 ­cm−1 is associated with the stretching motion of aromatic rings. The
relatively less intense peak observed in the region of 1500–1200 ­cm−1 corresponds to the stretching motions of
-C-H groups. The wider peaks observed at 1172.27 and 1049.32 ­cm−1 are attributed to C-O bonds. Finally, the
peak located at 484.15 ­cm−1 indicates the presence of ­H3PO447. Compared to the FTIR spectra before adsorp-
tion, the pollutant-loaded activated carbon displayed significant changes in peaks. Diminishing and shifting
peaks were observed after adsorption. The significant shifts (2656.09 ­cm−1 to 2667.07 ­cm−1), (2332.04 ­cm−1 to

140
XRD Spectrum for Rumex abyssinicus activated carbon

120

100
Intensity (a.u)

80

60

40

20

10 20 30 40 50 60 70 80 90
Brag's angle (2 theta)

Figure 1.  Crystalline structure analysis for Rumex abyssinicus based activated carbon.

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Figure 2.  SEM morphology of activated carbon synthesized from Rumex abysiniccus.

50 (a)Before adsorption
3506.74

45

40
Tranismittance (%)

1425.16

35
1172.77

30
2116.00
3290.7

1049.32
2656.09

25
484.15
1813.16
2332.04

1728.29
1543.12
1280.79

20

15

10

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)

50
(b)After adsorption
45

40
Transmittance(%)

35

30
2112.14
2667.67

25
1774.59

1022.32
2339.75

20
1539.26

15

10
4000 3500 3000 2500 2000 1500 1000 500

Wavenumber(cm-1)

Figure 3.  FTIR analysis of Rumex abyssinicus-derived activated carbon before (a) and after adsorption (b).

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2339.75 ­cm−1), (2116.00 ­cm−1 to 2112.94 ­cm−1), (1813.16 ­cm−1 to 1774.59 ­cm−1), (1543.12 ­cm−1 to 1539.36 ­cm−1),
and (1049 ­cm−1 to 1022.32 ­cm−1) were observed from before adsorption to after adsorption, reflecting the effect
of carboxyl, C=O, C=C, –C–H, and C–O, on the Rumex abyssinicus-based activated carbon surface during
adsorption. Furthermore, the vanishing of several peaks such as 3506.74, 3290.70, and 1728.29, 1425.46, 1280.79,
1172.77, and 484.15 ­cm−1 were observed after adsorption, indicating no more presence of H ­ 3PO4 and –OH in
the sample.
The pH point of zero charge (pH at which the surface charge of an adsorbent becomes neutral) was deter-
mined to be 5.1, as shown in Fig. 4. A nearly similar finding, i.e., 5.04, was reported b ­ y42. Basically, at pHpzc
the adsorbent has an equal amount of positively and negatively charged surfaces. More importantly, at the pH
of the adsorbents below pHpzc, adsorption of anions favors due to the dominance of positive surface ­charges70.
On the other hand, cations (positively charged substances like malachite green dye) are sufficiently adsorbed at
a pH above pHpzc. Finally, the maximum removal of 99.9% attained at a pH of 6 supports the pHpzc concept.

Batch adsorption performance. The adsorption of malachite green dye from an aqueous solution was
performed in batch mode using activated carbon synthesized from the stem of the Rumex abyssinicus plant. The
adsorption performance of the adsorbent material under varying experimental conditions is depicted in Table 2.
The maximum and minimum removal efficiencies recorded in this study were found to be 99.9% and
62.4%, respectively. The maximum removal efficiency achieved in this study was recorded at optimum work-
ing conditions of pH 6, contact time of 40 min, initial dye concentration of 100 mg/L, and adsorbent dosage of
0.1 g/100 mL. On the other hand, the minimum removal efficiency (62.4%) was recorded at experimental condi-
tions of pH, contact time, dye concentration, and adsorbent dosage of 3, 20 min, 100 mg/L, and 0.15 g/100 mL,
respectively. Normally, various conditions should be considered while comparing the performances of differ-
ent adsorbents on dye detoxification. These include the nature of the wastewater (real or aqueous), activation
mechanism (thermal, chemical, or both), adsorbent dosage utilized, specific surface area, concentration of the
pollutant, and so on. The adsorptive performance and surface area of Rumex abyssinicus-derived activated carbon
applied for the removal of malachite green dye are compared with modified adsorbent materials such as SBA-15,
MCM-41, and MCM-48. Consecutively, the surface area and maximum removal efficiency recorded in this study
were found to be comparable. For ­instance71, reported a maximum removal efficiency of 99% for porous MCM-
­ 2/g. Additionally, the 126 mg/g adsorption capacity of malachite green dye for
41 with a surface area of 1500 m
MCM-41 has a surface area of 507 ­m2/g72, removal efficiency of 64% and surface area of 878 ­m2/g for MCM-4173,
97.1% removal efficiency for modified MCM-4174, surface area of 1420 m ­ 2/g was reported b
­ y75, 755.62 ­m2/g sur-
76
face area and 140 61 mg/g adsorption capacity using SBA-15 . Furthermore, Table 3 presents a comprehensive
comparison of previously done experiments on malachite green dye adsorption onto biomass-based adsorbents.

Effects of operating parameters. The effect of contact time on the removal of malachite green dye was
examined on Rumex abyssinicus activated carbon for different contact times with a fixed adsorbent dose, pH,
and initial concentration, as shown in Fig. 5. According to the results obtained, for a concentration of 100 mg/L,
substantial malachite green dye removal occurred at 40 min, showing a 99.8% removal rate. The amount of
malachite green dye adsorbed onto the adsorbent material increases with an increase in contact time; this is
mainly due to the availability of a large number of vacant sites and pores on Rumex abyssinicus activated carbon
adsorbent material for the adsorption of malachite green dye, and when time increases, the probability of dye
molecules getting adsorbed increases. However, after 40 min of contact time, the removal efficiency decreased,
showing the attainment of equilibrium. At 50 min, the removal efficiency reduced to 85.4%. This is probably due
to the non-availability of the active site for malachite green dye ions to get adsorbed onto Rumex abyssinicus-
derived adsorbent material and a decrease in the driving ­force77.
The initial malachite green dye concentration is an important factor in the adsorption capacity in terms of
providing a higher driving force to overcome mass transfer resistances of the dye molecules between the aque-
ous solution and solid ­phases78. The effect of malachite green dye adsorption on various malachite green dye
concentrations (50–150 mg/L) by activated carbon prepared from Rumex abyssinicus was thoroughly examined,
as indicated in Fig. 6. It is observed that at 50 mg/L, the efficiency of adsorbed malachite green dye onto adsor-
bent material was 95.9%. However, increasing the malachite green dye concentration increased the removal, as
it reached a maximum at a dye concentration of 100 mg/L. Accordingly, 100 mg/L was selected as the optimal
initial malachite green dye adsorption for the coming experiments.

1
pH initial-pH final

0
0 2 4 6 8 10 12 14
-1

-2
pH initial

Figure 4.  pHpzc of Rumex abyssinicus derived activated carbon.

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Run no. pH Dye con (mg/L) Adsorbent dosage (g/100 mL) Contact time (min) Actual removal efficiency (%)
1. 9 50 0.050 60 85.67
2. 9 150 0.150 60 91.94
3. 6 150 0.150 60 89.35
4. 3 50 0.050 60 95.08
5. 6 150 0.1000 60 85.55
6. 6 50 0.050 20 84.26
7. 3 100 0.050 20 79.95
8. 6 150 0.150 20 76.14
9. 3 100 0.050 20 76.69
10. 6 150 0.100 20 66.66
11. 3 100 0.150 40 68.87
12. 9 50 0.150 40 95.41
13. 6 50 0.050 40 97.46
14. 3 100 0.050 40 88.88
15. 6 150 0.150 40 83.23
16. 9 50 0.150 60 94.28
17. 3 100 0.050 60 92.63
18. 9 150 0.150 60 90.95
19. 9 50 0.100 60 95.48
20. 9 150 0.050 60 71.28
21. 6 100 0.100 40 99.90
22. 3 50 0.050 40 98.14
23. 9 50 0.100 40 95.87
24. 6 50 0.150 40 86.78
25. 9 100 0.050 40 63.33
26. 3 100 0.150 20 62.40
27. 3 100 0.100 20 66.98
28. 6 100 0.100 20 89.95
29. 3 150 0.100 20 77.72
30. 9 150 0.100 20 71.62

Table 2.  Batch adsorption performances of Rumex abyssinicus for malachite green dye removal.

Removal efficiency/adsorption
Biomass capacity Isotherm model Kinetics model Thermodynamics References
Musa paradisiacal L. leaf > 99% Redlich-Peterson Avrami fractional model Spontaneous and exothermic 10

Syzyium samarangense 95.5% Langmuir Pseudo second-order Spontaneous and exothermic 11

Salacca zalacca 69.44 mg/g Langmuir Pseudo second order – 88

12
Grape stalks 87.7% Langmuir Pseudo second order Spontaneous and exothermic
15
Walnut shells 154.56 mg/g Langmuir Pseudo second order Spontaneous and exothermic
Bambusa tulda 99.73% Langmuir 16

Salix alba L 98.5% Freundlich Pseudo second order Spontaneous and exothermic 89

Cocos nucifera shells 32.787 mg/g Freundlich Intraparticle diffusion 17

Stipa tenacissima L.) leaf powder 110.98 mg/g Langmuir Pseudo second order Spontaneous and exothermic 90

91
Okra stalks waste 99.63 mg/g Langmuir Pseudo second order
Nutraceutical industrial fenugreek seed 79
105.00 mg/g Langmuir Pseudo second order Spontaneous
spent
Catha edulis 5.62 mg/g Freundlich Pseudo second order 13

Lantana camara L. stem 100 mg/g Langmuir Pseudo second order Spontaneous and endothermic 92

Rumex abyssinicus 99.90% Koble Corrigan Pseudo second order Spontaneous and endothermic Present study

Table 3.  Comparative study of biomass based activated carbons for malachite green dye adsorption.

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120

100

Removal efficiency(%)
80

60

40

20

0
0 10 20 30 40 50 60 70
Contact time (min)

Figure 5.  Effect of contact time on malachite green dye adsorption.

120

100
Removal efficiency

80

60

40

20

0
0 20 40 60 80 100 120 140 160
Initial dye concentration(mg/L)

Figure 6.  Effect of initial dye concentration on malachite green dye adsorption.

The effect of pH on dye removal efficiency was studied by varying pH from 3 to 9, as depicted in Fig. 7. It
was found that decreasing pH decreased the dye removal efficiency as the dye molecules competed with ­H+
for available active sites at lower pH v­ alues79. Normally, cationic dyes like malachite green dye are significantly
adsorbed at higher pH values because of the absence of r­ esistance80. Herein, the maximum removal efficiency
of 99.9% was recorded at a pH of 6.
Similarly, the effect of adsorbent dosage on dye removal efficiency was evaluated by varying the adsorbent dos-
age from 0.05 to 0.15 g/100 mL, as shown in Fig. 8. Initially, increasing the adsorbent dosage increased removal
efficiency until 0.10 g/100 mL. However, a further increase in adsorbent dosage did not increase the removal
efficiency because of the attainment of equilibrium.

Adsorption isotherm. Adsorption isotherms were assessed using the Langmuir, Freundlich, Toth, and
Koble-Carrigan models, as shown in Fig. 9. The coefficient of determination (­ R2) and reduced chi-square were
taken into consideration when selecting the best curve fit. As a result, it is evaluated that the Langmuir isotherm

120
Removal efficiency(%)

100
80
60
40
20
0
0 2 4 6 8 10
pH

Figure 7.  pH effect on malachite green dye adsorption.

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120

100

Removal efficiency(%)
80

60

40

20

0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
Adsorbent dosage (g/100 mL)

Figure 8.  Adsorbent dosage effect on removal of malachite green dye.

120

100

80

Qe
60
Toth
Qe

Koble Corrigan
40 Freundlich
Langmuir

20

0 10 20 30 40 50
Ce

Figure 9.  Adsorption isotherm model curve fitting.

has a maximum R ­ 2 of 0.97 and a negligible reduced chi-square of 0.97008 compared to the Freundlich isotherm
model. Furthermore, the maximum Langmuir adsorption capacity ­(Qmax) and the Langmuir constant related
to the free energy of adsorption ­(KL) were found to be 98.43 mg/g and 4.41 L/mg, respectively, demonstrating
the effectiveness of the adsorption process. On the other hand, the Freundlich constant (­ KF) and an empirical
parameter related to intensity (1/n) were determined to be 69.47 mg/g and 0.11, respectively, as given in Table 4.
Additionally, the dimensionless separation factor constant (RL), which is used to estimate Langmuir’s isother-
mal feasibility, was found to be 0.0048. The applicability of three-parameter isotherm models for evaluating the
nature of malachite green dye adsorption onto Rumex abyssinicus-based activated carbon was examined employ-
ing the Toth and Koble-Carrigan models. Basically, these three-parameter adsorption isotherm models are an
amalgamation of Freundlich and Langmuir isotherm models, which further signify the homogeneity or hetero-
­ 2 (0.996) and
geneity of the adsorption sites. Accordingly, there is an insignificant discrepancy between Toth’s R
2
Koble-Corrigan’s ­R (0.998). Moreover, the curve fitting analysis suggested that both Toth and Koble-Corrigan
isotherms excellently fit the plot. On the other hand, the nk and nt values for the Koble-Corrigan, and Toth
models are almost unity, indicating the homogeneity of the adsorption surfaces. It has been reported that the
deviation of nk and nt values from unity describes the heterogeneity of the adsorption system, while n and t
values being close to unity indicates monolayer a­ dsorption81,82. Moreover, the maximum monolayer adsorp-
tion capacity predicted by Koble-Corrigan is very close to the one predicted by the Langmuir isotherm model,
proving homogenous distribution sites. Comparatively, the best to poorest fitting regarding ­R2 can be ranked as
Koble-Corrigan > Toth > Langmuir > Freundlich, while error analysis suggested a degree of fitness to be ranked
as Koble-Corrigan > Toth > Freundlich > Langmuir. Generally, from the adsorption isotherm analysis result, it
can be inferred that the adsorption process is favorable (0 < ­RL < 1), normal (1/n < 1), homogenous and mon-
olayer 81,83.

Adsorption kinetics. The adsorption kinetics model, which is used to determine the potential rate-deter-
mining step as well as has great significance in evaluating the time dependency of the dye adsorption, was
determined by using PFO, PSO, intraparticle diffusion, and Boyd kinetics models. Accordingly, the PSO-kinetic

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Isotherm model Parameters

R2 = 0.97
KL = 4.41
Langmuir RL = 0.0048
Qmax = 98.43
Reduced Chi-square = 0.97008
R2 = 0.93
KF = 69.47
Freundlich 1/n = 0.11
n = 9.09
Reduced Chi-square = 0.037
R2 = 0.998
A = 204.88
Koble Corrigan B = 1.83
nk = 0.9827
Reduced Chi-square = 0.0006
R2 = 0.996
Qmax = 97.44
Toth nt = 0.991
K = 13.45
Reduced Chi Square = 0.015

Table 4.  Parameters for Langmuir and Freundlich isotherm models.

model with an ­R2 of 0.99 and a reduced chi-square of 0.00023 was found to fit the data best. Moreover, there is a
negligible discrepancy between Qe calculated (121.24 mg/g) and Qe experimental (120.94) for the PSO-kinetic
model, as depicted in Table 5. The intercept of the intraparticle diffusion model (C) was not zero, suggesting
that intraparticle diffusion does not exclusively limit the rates of adsorption. Hence, both film diffusion and
bulk diffusion govern the adsorption process. Generally, the rate of malachite green dye adsorption onto Rumex
abyssinicus-derived activated carbon is governed by chemical reaction, where both adsorbate and adsorbent
control the rate of the adsorption ­process34.

Adsorption thermodynamics. The adsorption thermodynamics provide information about the energy
associated with the adsorption being undertaken. Additionally, it helps to determine the nature of the adsorption
(spontaneous or non-spontaneous). Basically, the adsorption process is said to be spontaneous if the Gibbs free
energy of the system becomes negative and non-spontaneous if its Gibbs free energy is positive. In this regard,
the Rumex abyssinicus-derived activated carbon applied in the removal of malachite green dye from aqueous
solution was found to be thermodynamically spontaneous (�G < 0) and endothermic (�H = 31.289kJ/mol),
as shown in Fig. 10. In general, from a thermodynamic perspective, the adsorption of malachite green dye onto
Rumex abyssinicus-derived activated carbon is ­feasible84.

Reusability and regeneration studies. The chemically regenerated adsorbent was examined for reus-
ability potential for five consecutive cycles, and the adsorption performance is shown in Fig. 11. As can be
observed from the figure, the removal efficiency of malachite green dye onto reused Rumex abyssinicus-derived
activated carbon ranged from 99.9 to 95.2%, demonstrating strong reusability potential. Normally, after repeated
cycles of reusability, the performances of the activated carbon for pollutant detoxification declines gradually due
to incomplete desorption and the decline of active sites found on the surface of the adsorbent.

Adsorption mechanisms. In this specific study, the adsorption of malachite green is a surface phenome-
non, which is a spontaneous process that facilitates adhesion of malachite green molecules from wastewater onto
a surface of Rumex abyssinicus derived activated carbon adsorbent creating a film of the adsorbate on the surface
of the adsorbent. The adsorption mechanism covers various steps including molecular interactions, diffusion
of dye molecules through the boundary layer followed by intraparticle diffusion into the interior of the sorb-
ent, either by monolayer or multilayer and finally adsorption on the surface of a­ dsorbent85.The first step of the
adsorption process is the migration or diffusion of impurities present in water into porous cavities within carbon
particles. Once inside the pore, the impurity molecules are held by internal pore surfaces by weak electrostatic
forces known as Vander Walls ­force86,87. Adsorption continues with the removal of solutes from solution until

Pseudo first order Pseudo second order Intraparticle diffusion Boyd model
R2 = 0.91 R2 = 0.99 R2 = 0.94 R2 = 0.95
K1 ­(min−1) = 1.47 K2 (g/mg min) = 0.58 kd(mg/g ­min0.5) = 0.21 F = 0.92
Qe cal (mg/g) = 104.51 Qe cal (mg/g) = 121.24 C(mg/g) = 2.14 Bt=2.028
Reduced Chi-square = 0.26 Reduced Chi-square = 0.004 Reduced Chi square = 0.0061 Reduced Chi square = 0.36

Table 5.  Kinetics parameters for malachite green dye adsorption.

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5.0
Y= - 31763.51351X + 15.702
R2 = 0.96
∆H = 31.289
4.5
∆S = 130.546

ln KC
4.0

3.5

3.0

0.0029 0.0030 0.0031 0.0032 0.0033 0.0034

1/T

Figure 10.  Adsorption thermodynamics for the adsorption of malachite green onto Rumex abyssinicus
activated carbon.

101
100
Removal efficiency(%)

99
98
97
96
95
94
93
inial 1st 2nd 3rd 4th 5th
cycle cycle cycle cycle cycle
Reusability cycles

Figure 11.  Reusability potential of Rumex abyssinicus derived activated carbon.

the amount of solute remaining in solution is in equilibrium with that at the surface. The mechanism adsorption
on the surface of activated carbon is commonly due to its micropore present or the weak vander waals forces
which can attract the impurities and is the result of specific interactions between functional groups via formation
of donor–acceptor c­ omplexes86,87. On the other hand, the shifting of FTIR bands (2656.09 to 2667.07), (2332.04
to 2339.75), (2116.00 to 2112.94), (1813.16 to 1774.59), (1543.12 to 1539.36), (1049 to 1022.32) before and after
adsorption reflects that carboxyl, C=O, C=C, –C–H, C–O played an important role in the adsorption process.
Finally, the hydrophobicity of the impurity molecule and the affinity of the contaminant molecule towards car-
bon or both facilitate the adsorption of contaminants from waste ­water75.

Conclusion
The Rumex-abyssinicus-derived activated carbon, which was synthesized through chemical and thermal acti-
vation, was characterized for pHpzc, SEM, FTIR, BET, and XRD. The result of the analysis has shown a pHpzc
of 5.1 and an extremely high BET-specific surface of 962.3 m­ 2/g. On the other hand, the presence of multiple
functional groups like –OH (3290.70 ­cm−1), carboxyl (2656.09 ­cm−1), C=O or C=C (1900–1700 ­cm−1), stretching
motion of aromatic rings (1543.12 ­cm−1), stretching motion of –C–H (1500–1200 ­cm−1) and C–O (1172.27 and
1049.32 ­cm−1) were identified by FTIR. Additionally, XRD and SEM analysis revealed the amorphous nature of
the adsorbent with a heterogeneous surface. The removal efficiency recorded throughout the study ranged from
99.9 to 62.4%. The maximum removal efficiency was recorded at optimum conditions of pH 6, a contact time of
40 min, an adsorbent dosage of 0.1 g/100 mL, and a dye concentration of 100 mg/L. The effects of experimental
variables such as pH, contact time, adsorbent dosage, and initial dye concentration were thoroughly examined.
The adsorption isotherm, kinetics, and thermodynamics studies were undertaken with the aim of determining
the nature of the adsorption, mechanism, and heat transfer associated with the adsorption process. Accordingly,

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the Koble-Corrigan isotherm and PSO kinetics models were found to be descriptive, with maximum R ­ 2 values
of 0.998 and 0.99, respectively. This showed that the adsorption process was chemosorption with a homogenous
surface, in which the surface of the adsorbent was saturated with a single attachment of pollutants. The thermo-
dynamics study revealed the nature of adsorption to be spontaneous and endothermic. The regeneration of the
used adsorbent was successfully undertaken using a chemical method that was later applied for the adsorption
of malachite green dye for five cycles. The reusability study demonstrates the excellent adsorption capability of
the Rumex abyssinicus-derived activated carbon, with removal efficiencies ranging from 99.9 to 95.2%. Finally,
this research showed that Rumex abyssinicus-derived activated carbon can be taken as a potential candidate to
be used for the decolorization of textile effluents. However, it is recommended to functionalize the surface of
the adsorbent for enhanced adsorption capability and to study the column analysis.

Data availability
All data are included in the manuscript.

Received: 18 August 2023; Accepted: 4 September 2023

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Acknowledgements
We would like to thank Addis Ababa Science and Technology University and Manufacturing Industry Develop-
ment Institute, Leather and Leather Products Industry Research and Development Centre

Author contributions
M.A. Designed and conducted experiments, M.A., A.M., J.F., T.T. and T.N. wrote and edited the manuscript.

Competing interests
The authors declare no competing interests.

Additional information
Correspondence and requests for materials should be addressed to M.A.
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