Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138

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Journal of the Taiwan Institute of Chemical Engineers

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Adsorption of Black MNN reactive dye from tannery wastewater using

activated carbon of Rumex Abysinicus
Jemal Fito Nure a, *, Ashagrie Mengistu b, *, Mikiyas Abewaa c, Kenatu Angassa d,
Welldone Moyo a, Zebron Phiri a, Potlako J. Mafa a, Alex T. Kuvarega a, Thabo T.I. Nkambule a
a
Institute for Nanotechnology and Water Sustainability (iNanoWS), College of Science, Engineering and Technology, Florida Science Campus, University of South Africa,
1710, Johannesburg, South Africa
b
The Federal Democratic Republic of Ethiopia, Manufacturing Industry Development Institute, Leather and Leather Products Industry Research and Development Center,
P.O. Box 1180, Addis Ababa, Ethiopia
c
Department of Chemical Engineering, College of Engineering and Technology, Wachemo University, Hossana, Ethiopia
d
Department of Environmental Engineering, Addis Ababa Science, &Technology University, Addis Ababa, Ethiopia

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

Keywords: Background A high concentration of Black MNN reactive dye in untreated tannery wastewater can cause adverse
Adsorbent effects on public health and environmental sustainability. Therefore, this study aimed to investigate the
Biomass adsorptive performance of Rumex Abyssinicus-based activated carbon (RAAC) to remove Black MNN reactive
Industrial effluent
dye from tannery wastewater.
Kinetics
Wastewater treatment
Method The stem of Rumex Abyssinicus was impregnated with 50 % diluted phosphoric acid at the ratio of 1:3
Water pollution (w/w biomass to acid) and then it was carbonized in the muffle furnace at 600◦ C. The Box-Behnken experimental
design of 34 was used to optimize the removal efficiencies under the response surface methodology.
Significant findings Characteristics of the adsorbent were described by SEM for surface morphology with high
cracks, FTIR spectrometry for multi-functional groups (O–H at 3443.08 cm− 1, aromatic C = C 1633.78 cm− 1,
vibrational and stretching motion of -OH 1205.65 cm− 1and vibrational motion of C–O-C 1045.46 cm− 1), BET
with specific surface area of 3619.7 m2/g, and X-RD with amorphous structure. The maximum dye adsorption of
99.9 % was observed at experimental conditions of 150 mg/L, 0.25 mg/100 mL, pH 2, and 90 min. The
experimental data were evaluated in terms of Langmuir, Freundlich, Temkin, and Spis isotherms which showed
the Langmuir model was found to be the best fit with the experimental data at R2 0.99. This shows that the
adsorbent surface is homogeneous and monolayer. Furthermore, the kinetic study confirms that the Pseudo
second-order model best describes the experimental data at R2 0.99. Finally, statistical analysis showed that the
experimental values are almost the same as the predicted data which were indicated by the Adjusted R2 0.99 and
predicted R2 0.97. In conclusion, Rumex Abyssinicus is a good precursor material for adsorbent development to
remediate industrial and municipal wastewater.

1. Introduction
Nowadays, freshwater consumption is growing alarmingly due to
uncontrollable fast industrialization, agricultural boosting, and sudden
world population explosion [1]. Industrialization has a vital role in the
economic development of the nations. It is seen as a motor behind many
of the changes usually termed social transformation and modernization.
However, the environmental crisis due to industrial wastewater
discharge has reached an unprecedented level across the globe which is
exerting considerable negative pressure on the biosphere. Particularly,
surface and groundwater quality depletion and deterioration have been
a global challenge to achieving sustainable development [2]. Gaol 6 of
sustainable development aimed to realize safe, affordable, clean, and
sufficient water for all mankind by 2030 [3]. However, water scarcity
and quality deterioration have become global challenges to meeting
sustainable development goals [2]. Basically, water scarcity refers to the
availability of freshwater below 1000 L per person per year, and it is
estimated that 40 % of the world’s population will end up with water
scarcity by 2030. In line with water scarcity, 4.8–5.7 billion people will
be at risk by 2050 [4]. This needs a call not only for action for the

* Corresponding authors.
E-mail addresses: fitojemal120@gmail.com (J.F. Nure), ashagmen2017@gmail.com (A. Mengistu).

https://doi.org/10.1016/j.jtice.2023.105138
Received 13 July 2023; Received in revised form 12 September 2023; Accepted 13 September 2023
Available online 17 September 2023
1876-1070/© 2023 The Authors. Published by Elsevier B.V. on behalf of Taiwan Institute of Chemical Engineers. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
J.F. Nure et al.
efficient allocation of water resources but also for the potential reuse of
wastewater streams from different industrial setups. Industries extract
materials from natural resources and release both products and wastes
into the environment. Industries are causing serious environmental di­
sasters, which have yet to be brought under control. Tanning industries
are well known to be one of the most water-intensive industries that
discharge a considerable volume of wastewater toward the nearby
ecosystem. The beam house, tan yard, and retaining operations in the
tanning industry consume a considerable amount of freshwater making
it a water-intensive industry [5]. Tannery wastewater consists of a sig­
nificant number of toxic pollutants that have the capability of affecting
human health and damaging the ecosystem [6]. Pollutants commonly
discharged from the tanning industries at unit operations include toxic
dyes, harmful and toxic chemicals like chromium, limes, sulfides, acids,
bases, salts, and other chemicals [7]. Particularly, a considerable num­
ber of reactive dyes are being used during the dyeing and fat liquoring
stages of the tanning processes. Studies reported that only 85–90 % of
the dye applied is exhausted by the material and the rest 10–15 % is
being lost with the effluent imparting color and toxicity to the natural
receiving water bodies [8]. Some dyes like Black MNN reactive have
carcinogenic properties and they are recalcitrant, resistant to aerobic
digestion, and stable to light (heat) and other oxidizing agents. This
phenomenon can make a difficult condition for wastewater treatment.
Therefore, searching for advanced and new wastewater treatment
technologies is essential.
The removal of dyes from industrial effluents using conventional
wastewater treatment methods is inefficient due to the complex nature
of wastewater. On the other hand, many advanced wastewater treat­
ment techniques such as advanced oxidation process, reverse osmosis,
ion exchange, and electro dialysis are attracting the attention of scholars
to overcome the shortcomings of conventional wastewater treatment
techniques. However, these technologies on the other hand require large
capital investment and are non-sustainable. Contrary to those technol­
ogies, adsorption technology has been used in a variety of important
industrial applications to remediate wastewater [9]. Adsorption is
low-cost, easy to apply, and economically and environmentally friendly.
Consequently, several investigative studies on the development of acti­
vated carbon have been conducted for the removal of pollutants using
locally available plant materials and plant byproducts. However, the
most commonly used activated carbon is the coal-based adsorbent which
is expensive and not sustainable. Hence, researchers striving to examine
locally available materials and their treatment efficiencies in water and
wastewater remediation. For instance, the removal of chemical oxygen
demand (COD) from distillery using bagasse fly ash [10], adsorption of
fluoride from aqueous solution and groundwater using avocado seed
[5], chromium removal from tannery wastewater, and methylene blue
removal from textile industrial wastewater using activated carbon
derived from parthenium hysterophorus have been investigated [2].
Under this consideration, many precursor materials have been used
including avocado seed, bagasse, cassava peel, parthenium hysterophorus,
watermelon rinds, willow peat, orange waste, bagasse fly ash, agricul­
tural wastes, the bark of the Vitex negundo morinda, bamboo, ramie
bars, cotton, sludge, macro-algae, sawdust, walnut shells, buffalo weed,
pine tar, orange peel, coconut husks, miscanthus straw, reed straw,
hemp stem, wheat straw, wood pellets, tinctorial bark, crocus sativus
leaves, etc., [11–21]. It was also reported that activated carbon has
gotten top attention for industrial applications due to its well-developed
pore structures and adsorption properties. However, due to minimal
adsorption capacity, poor regeneration, and long contact time, it was
found important to investigate the adsorbent with high removal effi­
ciency, short contact time, and good performance with the minimum
dosage. Hence, low-cost agricultural and weed biomasses containing
high amounts of natural polymers such as cellulose, hemicellulose, and
lignin can be taken as an alternative raw material to produce efficient,
low -cost and green adsorbents [22]. The development of the Rumex
Abyssinicus-based activated carbon (RAAC) was carried out to mitigate
2
Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
such challenges. In line with this, valorization of the stem and leaves of
the Rumex Abyssinicus is limited. Moreover, no research study has been
conducted on the application of activated carbon synthesized from the
stem of Rumex abyssinicus for tannery dye decolorization. However, we
developed an adsorbent from this plant and applied it for industrial
wastewater treatment. This water treatment application was not enough
to draw a concrete conclusion [23,24]. However, the application of this
adsorbent for chromium removal was missing. Hence, the study inten­
ded to evaluate the efficacy of chromium removal from aqueous solution
under the response surface methodology approach. On the other hand,
the search for alternative raw materials for the adsorption of toxic and
persistent dyes such as Black MNN reactive dye is increasing. This
phenomenon happened due to the non-sustainability and cost of com­
mercial activated carbon. An optimization process was used to study the
interaction between the adsorbent and adsorbate under factorial
experimental design. The adsorption study includes adsorbent dose, pH,
contact time, and initial concentration with their two levels employed.
Therefore, this research work aimed to use the stem of Rumex-abyssinicus
as an adsorbent to remove reactive black MNN dye from tannery
wastewater.
Aqueous
2. Materials and methods
2.1. Materials and equipment
The sun-dried stems of the Rumex Abyssinicus plant were collected
from Addis Ababa Science and Technology University which is located
at Akaky Kaliti sub-city of Addis Ababa. Analytical grade chemicals and
reagents were used for laboratory experiments such as sodium hydrox­
ide pellet 99.0 %; hydrochloric acid 37 % w/w, phosphoric acid 88 %;
mercuric sulfate crystals 99 %; sulfuric acid,98.0 %; silver sulfate 99 %;
potassium dichromate 99.5 %. electronic balance (Shimazu-AUX220),
digital pH meter (PHS-3C), coffee grinder (model: XFYC810, 240 V,60
Hz), orbital shaker ( Model: SK-600, 230VAC, 50 Hz, 0.2A by QTEX),
UV/VIS spectrometer (Evolution 300, UV–vis by Maalab), hot air oven
(Model: J-dvo1, supplier: JISICO), muffle furnace (Carbolite AAF 1100),
testing equipment such as Kjeldahl (Buchi KjelSampler K-376), Fourier
transform infrared spectroscopy ( FT-IR), IR Affinity, Shimadzu), X-ray
power diffraction (XRD-X-ray tube cu40kv, 44 mA, Rugaku, Ultima IV)
and scanning electron microscope (model JSM840A SEM microscope
operating at 10 kV) were the equipment employed during the study.
2.2. Wastewater sampling and characterization
Wastewater samples were collected from Elico-Awash tannery and
characterization was done for some physicochemical parameters such as
pH, temperature, total suspended solids, total solids, five days biological
oxygen demand (BOD5), and chemical oxygen demand (COD). The an­
alyses done are described in Table 1. The Awash tannery is located in
Addis Ababa at a geographical coordinate of 8◦ 56′ 33′’ N and 38◦ 45′41’’
E and an altitude between 2100 and 2360 m above sea level. The tannery
has a daily soaking capacity of 8991 pieces of skin and 1305 cowhides.
Data collected from the tannery showed that it has an average monthly
Table 1
Selected tannery wastewater physicochemical parameters and the analysis
methods used.
S/No Parameters Methods used for testing
1 pH Hach HQD field case model 58,258–00
2 Temperature Hach photometer HQD field case, Model 58,258–00
3 EC Hach photometer HQD field case, Model 58,258–00
4 TSS APHA 5220 B, Total solid dried at 103–105 ◦ C
5 TS APHA 5220 B, Total solid dried at 103–105 ◦ C
6 COD APHA 5220 B, Open reflux method
7 BOD5 APHA 5210 B, 5-day BOD test
J.F. Nure et al.
wastewater discharge of 3100 m3. The wastewater from the tannery was
composed of tan yard operation to the chrome recovery unit in addition
to the others from the beam house and post-tanning operations. A
composite wastewater sampling method was used twice for monthly
intervals and the sampled wastewater was delivered to the laboratory
for characterization. The analyses of those parameters were carried out
after the wastewater samples were collected in polyethylene plastic
bottles which were well-washed and disinfected. The wastewater sam­
ples were stored in a refrigerator at 4 ◦ C and analyzed according to
standard methods for the examination of water and wastewater (APHA
1998).
2.3. Adsorbent preparation
The collected stems of Rumex Abyssinicus were taken to the research
laboratory at the Leather and Leather Products Industry Research and
Development Center and washed with tap water several times to remove
any dust particles on the surface and then rinsed with distilled water.
The plant was identified at the herbarium at Addis Ababa University’s
herbarium and the plant specimen was deposited but with no voucher
ID. All methods were performed by the relevant guidelines/regulations/
legislation by including a statement in the methods section. The washed
raw material was dried using a fan and further dried in an oven at 110 ◦ C
for 12 h. The detailed procedures followed during raw material collec­
tion and sample preparation were described diagrammatically as shown
Fig. 1. Diagrammatic description of activated carbon preparation from Rumex Abyssinicus plant (A) raw Rumex-Abyssinicus stem (B) size reduction for washing (C)
size reduced for impregnation (D) impregnation of the raw sample (E) drying after soaking (F) pyrolyzed activated carbon (G) washing of the activated carbon (H) fan
drying after washing of the activated carbon with activated carbon of 106μm particle size
3
Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
in Fig. 1 (A–H). The dried sample was ground to a reduced size to make it
suitable for the subsequent stages of sample preparation. Then, the size-
reduced samples were impregnated or soaked in 88 % phosphoric acid
diluted to 50 % solution at a 1:3 (wt/wt) ratio of Rumex Abyssinicus to
phosphoric acid (H3PO4). This helped to attain a better carbon structure
and large surface area [1,2]. The soaking activity was conducted for
about 24 h at room temperature which was followed by drying for 8 h in
a hot air oven at 105◦ C. Thereafter, pyrolysis of the impregnated sample
was carried out at 600◦ C in a muffle furnace for 2 h. The carbonized
sample was removed from the furnace and kept in the desiccator for
further cooling to room temperature. The cooled samples were ground
to make them suitable for washing. Washing was carried out using 0.01
N NaOH solution and distilled water separately to remove the acid used
during impregnation [1,2]. The washing was repeated until the pH of
the washing water reached pH 7. Finally, the washed activated carbon
was dried using the fan and then further dried using an oven at 105◦ C for
12 h. Finally, the dried and powdered activated carbon was analyzed for
its particle size and stored in a zip-lock plastic bag to avoid moisture and
contamination by any other foreign materials till the subsequent activ­
ities of characterization and batch adsorption experiments [6].
2.4. Adsorbent characterization
Proximate analysis of the RAAC was performed to determine the four
proximate parameters, where the three of them moisture content, ash
J.F. Nure et al.
content, and volatile matter were directly analyzed based on the
experimental result whereas the fixed carbon was calculated from the
result of these three parameters as per the standard methods for Amer­
ican Society for Testing and Materials (ASTM) [1,6]. Similarly, the
surface area determination was done by Brunauer, Emmett, and Teller
(BET) method [25,26], surface morphologies by SEM (model
JCM-6000PLUS BENCHTOP SEM (JOEL), Japan) [24,27], surface
functional group by FTIR spectrophotometer (SHIMADZU IR
Affinity-1S) [2,6,18], crystalline structure by XRD instrument
(XRD-X-ray tube cu 40kv, 44 mA, Rugaku, Ultima IV) [28,29] and point
of zero charges by mass titration and acid titration methods [24,30].
2.5. Design of experiment and batch adsorption process
2.5.1. BOX-Behnken experimental design method
The experimental design was conducted using the design expert of
version 7 in which the Box-Behnken Experimental design Method
(BBDM) was used under Response Surface Methodology (RSM). RSM is a
technique used for developing an empirical model by mathematical and
statistical analysis to optimize the response or output variable that is
influenced by the input variables. Minimum numbers of experimental
runs were used to generate regression model equations and optimized
conditions [31]. Preliminary, laboratory experiments using synthetic
tannery dye and data from the previously published articles were used in
deciding the range of the selected variables [2,8]. As indicated in
Table 2, contact time (min), initial dye concentration (mg/L), pH, and
adsorbent dosage (mg/100 mL) were the considered experimental var­
iables with three levels. Finally, the removal efficiency of the dye was
taken as a response variable.
The lower level of each factor was designed as ‘‘− 1,’’ the middle
value was represented by ‘‘0,’’ and the higher level by ‘‘+1.’’ The
experiment was designed expressed as 34 and is anticipated to generate
81 runs; however, the number of experimental runs was reduced to 30
using design expert. Interactions between the four variables and their
impacts on the response variable were evaluated using the response
surface method. A random combination of each variable from their three
levels was done. The interaction effects of all four factors on the response
variable were studied. Variance analysis of the model (ANOVA) was
used to check the adequacy of the model. Experimental design results
with three-level were fitted using the model represented by the desired
response Eq. (5).
∑
n ∑
n n− 1 ∑
∑ n
Y = bo + bi Xi + bii Xi2 + bij Xi Xj + ε
i=1 i=1 i=1 j=2
where the X1 X2… Xn is the input factors that can influence the response
Y; n is the number of variables, bo is the constant intercept, bii (i = 1, 2…
n) is the quadratic coefficient, bij (i = 1, 2… n; j = 1, 2… n) is the
interaction of the coefficient, and ε represents the random error. The
regression model and response surface methods were used to investigate
the highest projected dye removal.
2.5.2. Batch adsorption experiment and optimization
Synthetic wastewater was used to conduct batch adsorption based on
the designed experiments and dye adsorption from real tannery waste­
water. The adsorption was performed under the optimization process. A
Table 2
Experimental design using the Box-Behnken design method for the selected
factors with their levels.
Variables Units Low (-) Middle (0)
pH 2 5.5
Time min 30 60
Adsorbent dosage g/100 mL 0.15 0.2
Dye concentration mg/L 90 120
Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
stock solution of synthetic wastewater (1000 mg/L) was prepared from
the anionic tannery dye. Then, the required concentrations of the
experimental solutions were made using the dilution principle, in which
distilled water was used to dilute the stock solution. pH Adjustments for
the experimental solutions were done using 0.1 M HCl and 0.1 M NaOH
solutions depending on the basicity or acidity of the required experi­
mental solutions. In general, the dilution principle was used to prepare
150, 120, and 90 mg/L solutions of synthetic anionic dye [6]. The
adsorption experiment was done in a 250 mL conical flask, in which the
required amount of adsorbate and adsorbent was added based on the
designed experiment in 100 mL solution mixtures. Thereafter, the flasks
with the experimental solutions were agitated using an orbital shaker
(Model: SK-600; Lab-companion, by QTEX) at 125 rpm. After comple­
tion of the adsorption contact time, the experimental solutions were
filtered using the Whatman filter paper 42. Finally, filtrate solutions
were taken for further analysis to determine the percentage of dye
removed. The absorbance of dyes remaining in the solutions was
determined using Uv–visible spectrophotometer (Agilent technology,
Cary 100 UV–visible Spectrophotometer) at 665 nm. The amount of dye
that remained in the purified water was determined using a calibration
curve drawn using known concentrations of synthetic wastewater con­
taining the Black MNN reactive dye. Six solutions having dye concen­
trations of 60, 80,100,120, 140, and 160 mg/L were used to develop the
calibration curve. In real wastewater analysis, the tannery effluent was
collected from the retannig and dyeing section of leather processing. The
wastewater sample was filtered to remove interfering from dissolved
and suspended solid materials. The concentration of the dye was
determined using the calibration curve. The adsorbent’s adsorption
capacity and efficiency of removing pollutants were determined using
Eqs. (1) and (2), respectively. In addition, the study findings were
documented in the form of means plus standard deviation [1].
qt = (Co − Ct ) ×
V
(1)
M
(Co − Ct )
%R = × 100 (2)
Co
where R is the dye removal efficiency, qt is the adsorption capacity at the
time ‘‘t’’ (mg/g), Co is the initial dye concentration, Ct is the dye con­
centration at the time ‘‘t’’ in (mg/L), V is the volume of the aqueous
solution (mL) and M is dry mass of the adsorbent (g) [32,33].
(5) 2.6. Adsorption isotherm
Adsorption isotherm models were used to describe how the adsor­
bate molecules of dye interact with the surface adsorption sites and to
study the relationship between the amounts of pollutant adsorbed at
equilibrium and the mass of the sorbent utilized, in which dye concen­
trations ranging from 90 to 150 mg/L. However, the other three pa­
rameters were kept at their optimum values of adsorbent dose of 0.25 g/
100 mL, solution pH 2, and contact time of 90 min. The fitness of data
and determining whether the adsorbent surfaces are heterogeneous or
homogenous were studied using Langmuir and Freundlich isotherms.
Langmuir isotherm assumes that adsorbates accumulate forming a
monolayer on binding sites. The simplified and linearized model is
shown in Eq. (3).
1 1 1 1
= + × (3)
qe qmax KLqmax Ce
where qmax (mg/g) is the maximum monolayer adsorption capacity of
High (+) the adsorbent, Ce (mg/L) is the equilibrium value of the initial concen­
9 tration,qe (mg/L) is the equilibrium adsorption capacity and KL (L/mg) is
90 the Langmuir constant which is related to the free energy of adsorption.
0.25 Furthermore, the dimensionless separation factor constant (RL) shown in
150
Eq. (4) is used to estimate Langmuir’s isothermal feasibility [34,35].
4
J.F. Nure et al. Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138

1 of Awash-Elico Tannery wastewater were analyzed for their physico­

RL = (4)
1 + KL × Ce chemical properties and the results were tabulated in the form of mean
plus standard deviation as shown in Table 3. The pH for effluent
where Co (mg/L) is the initial concentration, RL is the affinity between discharge from the tan yard operation was found to be 3.90±0.67 which
the adsorbate and the adsorbent, and its value for favorable adsorption is a direct discharge from the tanning operation being carried out at pH
should be between 0 and 1, and for unfavorable adsorption, the RL value (4) and the discharge from other sections (beam house and post tanning)
should be more than 1, whereas RL values of 1 and 0 suggest linear and was found to be 9.1 ± 0.48. The variation in pH is an indication that
irreversible adsorption processes, respectively [36]. different process operations need different pH values. A higher pH of 9.1
In addition, the Freundlich isotherm model has an assumption that in ± 0.48 for the second line was generated from the mixtures of soaking,
the adsorption process, the total surface of the activated carbon is liming, batting, pickling, re-chroming, neutralization, and dyeing (fat
multilayered and has a linearized isotherm model equation as in Eq. (5). liquoring) which had a pH of 10, 12, 8, 2.8, 4, 5.5, and 3.6, respectively.
1 The pH value tested at the mixing point of the two lines after chrome
logqe = logKf + × logCe (5) recovery was found to be pH (7.68±0.70) which is within the range of
n
Ethiopian industrial permissible discharge limits for pH of 6–9 [6,42].
Where Kf is the Freundlich constant showing adsorption capacity The result shows that discharge of the wastewater does not affect the
(mg/g), 1/n is the empirical parameter related to the intensity of biochemical reactions in the water bodies due to its pH.
adsorption indicating favorable conditions if its value is laid between 0.1 An average temperature of 22.4 ± 1.8 ◦ C was recorded which is
and 1 [8,37,38]. below the standard for Ethiopian tannery industrial effluent discharge
Temkin adsorption isotherm model states that there is a linear limit of 40 ◦ C [2]. High-temperature industrial effluent discharge is not
reduction of the heat of heat instead of logarithmic during the course allowed due to its accelerating effect on the biochemical reaction rate in
adsorption. The linear form of the Temkin equation is shown by Eq. (6). the biosphere and hydrosphere. In this specific case, the recorded tem­
RT RT perature is much lower than the temperature limit set for Ethiopian
Qe = ln KT + ln Ce (6)
b B wastewater effluent from tanneries, 40 ◦ C [6]. This implies that dis­
charging the wastewater into the ecosystem or water bodies does not
Where KT is the equilibrium binding constant (L/mg), b is the Temkin
have any effect on the biochemical and physicochemical reactions in the
heat of adsorption constant, R is the universal ga constant (8.314 J/
water bodies due to their temperature. COD and BOD5 are the two sig­
Kmol), and T(K) is the system temperature. Sips adsorption isotherm is
nificant parameters used to identify the extent of organic matter present
the combination of the Freundlich and Langmuir model used for pre­
in wastewater. Untreated Elico-Awash has values of 1820.0 ± 28.67
dicting the adsorption on heterogeneous surfaces and its linear form is
mg/L and 1350.0 ± 35.36 mg/L which are beyond the allowable
shown by Eq. (7).
discharge limits of 250 mg/L and 60 mg/L, respectively [2]. Besides this,
( )
Qe 1 the ratio of BOD5 to COD, which refers to the biodegradability index,
ln = lnCe + ln(ks)ns (7)
Qmax − Qe ns was found to be 0.74, indicating either biological or chemical treatment
to be applied to decrease the organic matter level in the tannery effluent
where 1/ns and ks are the sips constant related to intensity and [43]. The presence of such organic matter in the wastewater can cause
adsorption capacity, respectively severe pollution of the receiving water bodies and dry land. This in­
dicates that measures have to be taken on the efficiency of the chrome
2.7. Adsorption kinetics recovery plant and the reuse of the organic matter as resource energy,
biogas.
Adsorption kinetic models were used to determine the uptake rate of The results of physical wastewater analysis showed that the effluent
adsorbate, and the kinetic data were fitted to the pseudo-first-order, has TS of 12,522.5± 265.20 mg/L and TSS of 1840.0 ± 28.67 mg/L.
pseudo-second-order, and intraparticle diffusion models to study the Such a high TS in the effluent is the result of filterable and non-filterable
kinetics of tannery anionic dye adsorption. The linear equations of the particulate matter in the wastewater samples. Discharging effluents with
three-adsorption equilibrium kinetic models were shown in Eqs. (8), (9), such high TDS and TSS into water bodies can cause high turbidity and
and (10), respectively. To evaluate the kinetics, the time of contact reduce the transparency of the water bodies, which disturbs the natural
varied between 40 and 90 min with a constant incremental change of 10 aquatic ecosystem. Furthermore, such a high concentration of TS causes
min. depletion of dissolved oxygen in the water bodies, which disturbs the
interaction of living organisms and biochemical reactions endangering
Kf × t
log(qe − qt ) = logqe − (8) aquatic life. Black MNN dye in the tannery wastewater was analyzed to
2.303

t 1 t
= + (9) Table 3
qt Ks × q2e qe
Physicochemical properties of Elico-Awash tannery untreated wastewater.

qt = Kp × t0.5 + C (10) Parameters Value for line-1 Value for line- Value for the
2 mixture

where qtandqe (mg/g) are the adsorption capacity at time t and equi­ pH 3.9± 0.67 9.1± 0.48 7.7± 0.70
librium adsorption capacity, respectively; KfandKs are the pseudo-first- Temperature ( C) 28.0 ± 1.20 20.5± 2.00 22.4± 1.80
○

Conductivity 15.7± 3.85

order (g/(mg min)) and pseudo- second-order (g/(mg min)) adsorp­
– –
(mScm− 1)
tion rate constants, respectively; KP (mg/(g min0.5)) is the rate constant COD (mg/L) 2823.0 ± 212.13 891.9± 2.40 1820.0 ± 28.67
for intraparticle diffusion and C (mg/g) is intraparticle diffusion model TSS (mg/L) 2122.5± 24.75 1680.0 ± 1840.0 ± 141.42
intercept [39–41]. 113.14
TS (mg/L) 57,317.5± 11, 8895.0 ± 12,522.5±
982.00 650.54 265.20
3. Results and discussion Cr2O3 (g/L) 6.2± 0.87 0 3.4± 0.85
BOD5 (mg/L) – – 1350.0 ± 75.36
3.1. Tannery wastewater characteristics Original dye 0 92.76± 4.26 92.76± 4.26
concentration
(mg/L)
The two-discharge lines (the discharging points from unit operation)

5
J.F. Nure et al. Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138

have an average concentration of 92.8 ± 4.26 mg/L. Such high con­ content refers to the undesired inorganic oxides. In general, all the
centrations of reactive dye in the effluent can severely affect the envi­ proximate analysis parameters are within the standard range of acti­
ronment and public health. Some dyes are carcinogenic, recalcitrant, vated carbon quality standards based on SNI [48].
resistant to aerobic digestion, and stable to light, heat, and other
oxidizing agents which makes the situations difficult to remediate [8, 3.2.2. Determination of specific surface area
44]. The BET theory was used to determine the total surface area of the
material per unit mass of the activated carbon, which is based on the
physical adsorption phenomenon of gasses on the overall surfaces of the
3.2. Characteristics of activated carbon
adsorbent material. The adsorbent was degassed using an N2 atmo­
sphere at a temperature of 200 ◦ C to study the BET isotherm. BET test
3.2.1. Proximate analysis
result revealed the specific surface area for carbon precursor to being
Proximate analysis of moisture, volatile matter, fixed carbon, and ash
3619.40 m2/g when sample washing was done using distilled water.
content was done by the prescribed methods according to ASTM D 121.
However, a reduction in specific surface area to 550 m2/g was observed
The results were tabulated in the form of mean and standard deviation as
for the sample washed using 0.01 M NaOH solution. This shows that
shown in Table 4. The adsorbent has percentage moisture, volatile
distilled water best suit for pH adjustment. The recorded specific surface
matter, ash, and fixed carbon content of 2.97±0.75, 15.71±3.33, 9.83
area is far more than the largest value obtained from bagasse of sugar
±0.68, and 71.50±1.58 %, respectively. The moisture content of an
cane, 3554.82 m2/g) [49]. Such a significantly large area indicates that
activated carbon indicates its hygroscopic nature. Therefore, the more
the material is rich in active sites for the adsorption of pollutants.
hygroscopic the adsorbent is the less will be its adsorption capacity
Thereby, making the adsorption process more economical and
because when the adsorbent is left open to the atmosphere the moisture-
cost-effective by increasing its adsorptive capacity. However, washing
laden atmospheric air will penetrate the pore space of the adsorbent and
the sample using a dilute NaOH solution affects the surface character­
get absorbed. Normally, High moisture content adds mass to the acti­
istics of the precursor material. Many researchers have also reported
vated carbon without contributing to adsorption hence reducing the
adsorbents with surface areas of 90.00, 253.25, 1359.50, 1000.00, and
share of the carbonous material. This condition forces us to utilize more
5.73 m2/g from sewage sludge, eucalyptus biochar, mesopore-rich
adsorbent dosage to attain the desired degree of adsorption, which
badam-shell biochar, and onopordom heteracanthom pyrolysis,
indirectly affects the adsorption capacity. Therefore, the less amount of
respectively. However, the current specific surface area is extremely
moisture in this specific adsorbent indicates the hygroscopic nature of
large compared to those previously reported research findings [50]. This
the adsorbent is less which makes It has more free active sites for the
indicates that the adsorbent material can significantly improve the
pollutants to be adsorbed and leads to an increase in adsorption ca­
adsorption capacity and is more economical to scale up to an industrial
pacity. obtained moisture content was in agreement with the standard
scale.
quality of activated carbon based on SNI 06–3730–1995, which set the
maximum allowable water content as 15 % but fewer results were re­
3.2.3. The SEM analysis
ported [1,2]. The proximate analysis of this adsorbent is in good
The SEM analysis was used to examine the surface morphology of the
agreement with the previous study. In another study, it was reported
adsorbent and the result was depicted in Fig. 2A and B before and after
that proximate analysis bagasse fly ash was composed of ash (16.8 %)
adsorption respectively. The SEM analysis of the activated carbon pro­
moisture content (5 %), volatile substances (16.8 %), and fixed carbon
vided information about the form of the material comprising shape, size,
(42.2 %) [28].
structure, and pore spaces generated during the activation and pyrolysis
Volatile matter is used as a parameter to determine the amount of
processes. During SEM analysis of examining the surface morphology,
organic volatile materials (H2, CO,CO2,CH4,N2 and Hydrocarbons) that
the surface of activated carbon was magnified at a resolution of 600
escaped during the pyrolysis process of carbonization at the pre­
times (X600), with pore size 50 μm at 15 kV, and pores of different sizes
determined temperature [45]. A volatile matter of 15.71 ± 3.33 % was
and volumes. Generally, heterogeneous and non-uniform shapes were
obtained, which is below the maximum volatile matter allowed by the
observed on the activated carbon which is caused by chemical activation
Indonesian National Standard (SNI) (25 %). The result is very low
done using phosphoric acid and pyrolysis at a high temperature of
compared with the one recorded from kenaf core fiber [46]. However, it
600◦ C. The different pore sizes and distributions were observed from the
is higher compared to those results obtained from parthenium hyster­
magnified image of the RAAC sample, showing some irregularity in the
ophorus stem and oil palm empty fruit bunch [2,18,47]. The larger
shape of the pores, which is important for creating a binding site for
percentage of volatile matter is an indication that the precursor material
adsorbates varying in size and distribution. After adsorption, it seems
has a larger specific surface area due to the creation of many pores and
the voids and irregularities are decreased showing the successful
pore spaces compared with the above-reported values. On the contrary,
attachment of the pollutant onto Rumex Abyssinicus-derived activated
the solid yield of activated carbon production will be affected due to
carbon. In addition, the broad spectrum of the adsorbent porosity such
much loss of materials during the carbonization stage. However, having
as large pores, roughage, and cracks could result in the conducive op­
a larger percentage yield does not mean that the activated carbon has a
portunity to interact with multi pollutants in real wastewater simulta­
high adsorption capacity. Fixed carbon and ash content are used as
neously [6].
important parameters to determine adsorbent quality, where precursors
are suitable for mass production and should contain a high percentage of
3.2.4. The FTIR analysis results
fixed carbon and a very small amount of ash. The fixed carbon that
The FTIR spectra of the precursor material and raw Rumex abyssi­
determines the yield of the activated carbon resulted from the
nicus sample are shown in Fig. 3, respectively. The FTIR spectrum was
non-volatile carbon in the original treated raw material whereas the ash
used to identify the functional groups of the raw Rumex Abyssinicus
sample and RAAC. It was observed that a large number of peaks were
Table 4 displayed at the raw stage; however, some of the peaks disappeared or
Proximate analysis results of activated carbon.
diminished after activation, which is due to the escaping of volatile
Parameters of proximate analysis Analysis result ( %) in terms of mean± SD components of the original sample as shown in Fig. 4. The FTIR spec­
Moisture content 2.97± 0.75 trum under transmittance mode is expected to have peaks due to the
Volatile matter 15.81± 3.33 characteristic structure and specific motion of important functional
Ash content 9.83 ± 0.68 groups on the surface of the activated carbon such as –CH2, -CH3,-C = O,
Fixed carbon 71.50± 1.14
C = C, C –
– C, and -C-H was found [51,52]. The peaks at the wavelengths
–

6
J.F. Nure et al.
Fig. 2. SEM surface image of Rumex Abyssinicus activated carbon (A) before adsorption (B) after adsorption.
Fig. 3. The FTIR spectrum for the raw Rumex-Abyssinicus sample and the activated carbon.
of 3329.29, 2893.35, 1724.44, 1624.13, 1313.58, 1234.50, 1024.25,
and 785.06 cm− 1 were observed from raw Rumex Abyssinicus sample.
However, after activation of the sample, the number of peaks observed
was reduced to the wavelength values of 3443, 1634, 1316, 1206, 1045,
and 546 cm− 1. The relatively broad peak at 3443.08 cm− 1 corresponds
to the intermolecular bound hydroxyl group i.e., due to
hydrogen-bonded -O-H motion of stretching vibrations (polyphenolic
group), absorbed atmospheric moisture, and -NH group. A shift to
3404.51cm− 1 due to the change in stretching motion as shown in the
spectrum of Fig. 4 was also observed which might be due to the for­
mation of intra and intermolecular hydrogen bonds [35]. The peak at
2893.3cm− 1 is attributed to the O–H and C–H stretching vibrations of
carboxylic acid, alcohol, or alkene groups Fig. 4. The clear sharp peaks
located at 1724.44 cm− 1 and 1624.19 cm− 1 (Fig. 4) indicate the exis­
tence of C = O or C = C stretching vibration of acid derivatives, which
are characteristics of carbonyl group stretching from aldehyde and ke­
tones [33]. Smaller peaks observed between 15,000–1600 cm− 1 are
associated with the stretching motion of aromatic rings. The relatively
7
Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
less intense peak observed in the region of 1500 –1210 cm− 1 corre­
sponds to the stretching motions of -C-H groups. However, the intense
sharp peak at 1647.37 cm− 1 is due to the stretching vibration of the
carbonyl (-C = O) functional group [35]. The stretching vibration of
-C-C- functional groups was observed at 1205.65 cm− 1. The diminished
peak displayed between 1200 and 1500.52 cm− 1 was due to the
bending vibration of the -CH2 functional group. The long sharp peak at
1024.24cm− 1 was an indicator of the presence of single C–O bonds. In
general, the phenol (OH), amine (NH), carboxyl (C = O) and carboxylic
(COOH) groups are the main contributors to the peaks observed on the
FTIR spectrum [33].
3.2.5. The XRD results
The existence of crystalline structures and the amorphous nature of
the matrix of the RAAC were studied using X-ray diffraction and the XRD
power diffraction spectra for the adsorbent was presented as shown in
Fig. 4. The analysis was undergone at a scan speed of 6 rev/min over an
angle range of 10 to 80 . According to the XRD power diffraction result,
○
J.F. Nure et al. Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138

Fig. 4. The XRD pattern for activated carbon.

the RAAC showed two peaks at 2θ = 23o and2θ = 43.74o.In general, the
X-ray diffraction pattern showed that the activated carbon has a natural
amorphous structure. However, there is a special place on (2θ) with a
peak where the crystalline nature of the activated carbon was observed.
Normally, amorphous structures create favorable conditions for the
adsorption of different pollutants varying in size and shape, whereas, in
crystalline structures, the adsorption capacity becomes difficult due to
the crystalline structure’s uniform shape [24]. This material showed
amorphous properties and insignificant peaks were not observed [28].
Therefore, the surface of the adsorbent has an equal number of posi­
tively and negatively charged surface functions [24]. The pHpzc for
RAAC was found to be 7.2, showing that the activated carbon adsorbs
more of anionic pollutants like Black MNN dye in tannery effluent below
this pHpzc and cationic dyes are more likely to adsorb on the positively
charged surface of the adsorbent above pH 7.2. The adsorbent of the pH
point of zero charges became neutral. It was reported that the pHpzc of
the adsorbent was found to be 5.03. The surface of the adsorbent is
negatively below and positively above the point, respectively [6].

3.2.6. pH point of zero charge

The point at which the adsorbent’s surface becomes neutral was
determined using a pH point of zero charges (pHpzc) as depicted in Fig. 5.

Fig. 5. Determination of the pH point of zero charge.

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J.F. Nure et al. Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138

3.3. Batch adsorption performances
3.3.1. Box-Behnken design method results
The most important parameters affecting the dye removal efficiency
are adsorbent dosage (g/100 mL), dye concentration (mg/L), and con­
tact time (min). The adsorption experiments were carried out for
different combinations of the physical parameters using statistically
designed experiments to study the combined effect of these factors. The
batch adsorption experiment on anionic dye removal from synthetic
tannery wastewater was studied using the Box-Behnken design method
under Response Surface Methodology (RSM). Known concentrations of
synthetic anionic tannery dye solutions were used to draw the calibra­
tion curve. Concentrations of the remaining dyes in the solution after the
batch adsorption process were determined using the drown calibration
curve with a correlation coefficient of 0.98 as indicated in Table 5.
In general, the lower removal efficiency of 47.6 % was observed at
pH 5.5, a dye concentration of 150 mg/L, an adsorbent dose of 150 mg/
100 mL, and a contact time of 90 min, whereas the maximum dye
removal efficiency of 99.9 % was observed at 150 mg/L, pH 2, adsorbent
dose of 250 mg/100 mL, and contact time of 90 min. Several studies
have been conducted on the biomass adsorbent-based removal of tan­
nery and textile reactive dyes. Table 6 depicts the comparison of the
performances of adsorbent in different adsorption studies on reactive
dyes.
3.3.2. Statistical analysis and fit summary
The experimental data were statistically analyzed using RSM and the
analysis of Variance (ANOVA) of the percentage removal is presented in
Table 7. The output of different models was compared and focus was
given to the non-aliased model maximizing the Adjusted R2 (0.9923)
and the predicted R2 (0.9746) values and additional terms being sig­
nificant. Furthermore, the two values are in agreement with a difference
of less than 0.2. Therefore, the quadratic model was suggested.
The quadratic regression model was found to be the model relevant
for the response prediction, in which an F-value of 141.64 indicates that
the model is significant. P-values below 0.05 indicate that model terms
are significant for terms A, AB, AC, BC, A2, B 2 and C2 are significant
model terms. However, p-values greater than 0.100 indicates that the
model terms are not significant in which the model terms B, C, AD, and
D2 are insignificant. This implies linear interaction between pH and dye
concentration, pH and adsorbent dosage, adsorbent dosage, and dye
concentration, adsorbent dosage and contact time, dye concentration
and contact time, and the quadratic interaction effect of pH, adsorbent
dosage and dye concentration affect significantly the removal efficiency
of dye. The quadratic polynomial model was used to develop the
mathematical relationship between the response and the independent
process variables. The output of the fit summary of three different
models is presented in Table 8. The selection of the best-fit model
focused on non-aliased model maximizing, the Adjusted R2 and the
predicted R2 values being large and additional terms being significant.
Therefore, the quadratic model was suggested. The signal-to-noise ratio
of 47.05, which is greater than 4 indicates that the model has an
adequate signal and can be used to navigate the design space.
3.3.3. Empirical model by response surface estimation
The input data for variables from the experimental design based on
the selected range and experimental response variables are shown in
Table 5. The Box-Behnken Design was used to develop an empirical
model for the maximum removal of reactive dye from wastewater by
building a relationship between the four independent variables and dye
removal efficiency from an aqueous solution using a second-order
polynomial equation. Based on the model analysis, a quadratic model
was fitted to the data model to predict the response variable. An
empirical relationship between the response and the independent vari­
ables is shown by the following quadratic model Eq. (11).

Table 5
Batch dye adsorption experiment results for synthetic tannery aqueous solution.
Run No. pH Dye con. (mg/L) Adsorbent dosage (g/100 mL) Contact time (min) Absorbance @665nm Actual removal efficiency ( %) Adsorption capacity
(mg/g)

2 120 0.25 90 0.004002 98.85 47.448

9 90 0.2 60 0.065381 74.95 7.525
2 150 0.25 30 0.006003 98.62 59.172
2 90 0.15 90 0.003002 98.85 59.310
5.5 90 0.2 30 0.094012 63.98 28.791
5.5 90 0.25 30 0.108132 58.57 21.085
2 150 0.2 30 0.004002 99.08 74.31
2 120 0.25 60 0.005986 98.28 47.174
5.5 150 0.2 60 0.172999 60.23 45.173
2 90 0.15 60 0.003993 98.47 59.082
5.5 120 0.2 90 0.094969 72.71 43.626
9 120 0.2 90 0.074994 78.45 47.07
9 90 0.25 60 0.056011 78.54 28.274
5.5 120 0.25 90 0.057342 78.03 40.091
9 150 0.15 30 0.211019 51.49 51.490
2 120 0.15 30 0.005985 98.28 78.624
2 150 0.25 90 0.000044 99.99 59.994
2 90 0.15 60 0.015008 94.25 56.550
5.5 90 0.2 60 0.092003 64.75 29.138
2 150 0.25 60 0.009005 97.93 58.758
2 150 0.2 90 0.000087 99.98 44.985
5.5 120 0.25 30 0.111952 67.83 32.558
2 120 0.2 60 0.006995 97.99 58.794
9 150 0.15 60 0.222894 48.76 48.760
2 90 0.15 30 0.006003 97.7 58.620
5.5 150 0.15 90 0.217239 50.06 50.060
9 120 0.25 30 0.188929 75.71 21.941
9 150 0.25 90 0.105270 75.8 45.480
5.5 150 0.15 90 0.227985 47.59 47.590
9 90 0.15 90 0.076995 70.5 42.300

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J.F. Nure et al. Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138

Table 6
Comparison of the adsorptive performance of biobased adsorbents on tannery and textile reactive dyes.
No Adsorbent Mechanism Pollutant Removal efficiency Reference
( %) and Adsorption capacity(mg/g)

1 Rumex-Abyssinicus H3PO4/Thermal Black MNN reactive dye 99 %, Present study

60.00
mg/g
2 Palm shell powder Sulphuric acid Reactive red-141 13.95 [18,53]
mg/g
3 Marine sea weed Thermal decomposition Reactive red-120 85 %, [54]
107.13 mg/g
4 Bagasse pith H3PO4/ Pyrolysis Reactive orange – [55]
5 Coconut shell Coagulant and pyrolysis Reactive Black-5 96 % [56]
6 Thespesia7populnea pod H2SO4/ Pyrolysis Orange-G reactive dye 96 %, 9.13 [57]
mg/g
7 Palm shell Acid/pyrolysis Remazol reactive dye 90 %, 7.00 mg/g [57]
8 Periwinkle shell CO2 activation/pyrolysis Remazol Brilliant blue 83 %, 312.00 [58]
mg/g
9 Saw dust Carbonization/ Al2(SO4)3 Brilliant blue reactive dye 98 % [59]
10 Jatropha Curcas H2SO4/Pyrolysis Remazol brilliant blue 95 % [57]
11 Tea leaf Potassium acetate Methylene blue 83 % [57]
12 Tea leaf Potassium acetate Acid Blue-29 80 % [57]
13 Lignocellulosic waste Hydrothermal Reactive Blue-19 97 %, [57]
71.60
mg/g
14 Lignocellulosic waste Hydrothermal Reactive red-218 94 %, [57]
63.30
mg/g

Table 7
Analysis of variance for adsorption of dye.
Source Sum of Squares Df Mean Square F-value p-value

Model 9753.21 14 696.66 141.64 0.0001 Significant

A-pH 1170.77 1 1170.77 238.04 0.0001
B-Adsorbent dose 12.68 1 12.68 2.58 0.1292
C-dye concentration 2.16 1 2.16 0.4387 0.5178
D–Contact time 99.82 1 99.82 20.29 0.0004
AB 182.91 1 182.91 37.19 < 0.0001
AC 65.91 1 65.91 13.40 0.0023
AD 3.41 1 3.41 0.6927 0.4183
BC 105.64 1 105.64 21.48 0.0003
BD 43.29 1 43.29 8.80 0.0096
CD 28.15 1 28.15 5.72 0.0303
A2 1631.67 1 1631.67 331.75 < 0.0001
B2 33.91 1 33.91 6.89 0.0191
C2 57.37 1 57.37 11.66 0.0038
D2 11.15 1 11.15 2.27 0.1529
Residual 37.37 15 2.49
Lack of fit 6.28 11 2.83 1.67 0.263
Pure error 6.28 4 1.57
Cor Total 9826.99 29

Table 8
Fit summary and lack of fit for the three models.
Source Sequential p-value Lack of fit p-value Adjusted R2 Predicted R2 Adeq. Precision

Linear <0.0001 0.0005 0.5898 0.4864

2FI 0.0555 0.0007 0.0.701 05,254
Quadratic < 0.0001 0.3294 0.9923 0.9746 47.048 Suggested
Cubic 0.8126 – 0.9737 Aliased
Source Sum of squares Df Mean square F-value P-value
Linear 2953.49 21 140.64 64.53 0.0005
2FI 1886.5 15 125.77 57.70 0.0007
Quadratic 31.09 11 2.83 1.67 0.263 Suggested
Cubic 0.000 0 Aliased
Pure Error 6.28 4 1.57

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J.F. Nure et al. Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138

Removal efficiency(%) = 69.22 − 10.88 × A + 0.8411 × B − 0.5584 × C
+ 2.97 × D + 2.25 × AB − 3.44 × AC + 0.5864
× AD + 2.05 × BC + 0.9832 × BD − 1.83 × CD
+ 19.15 × A2 − 0.7091 × B2 − 4.29 × C2 + 1.43
× D2
(11)
where A is the solution pH, B is the adsorbent dose, C is the dye con­
centration, and AB, AC, BC, A2, and B2 are their linear interaction effect
and quadratic effect, respectively. A, D, AB, AC, BC, BD, CD, A2, B2, and
C2 have a significant effect on the response variable as the P-value for all
is less than 0.05 (P <0.05). However, P-values for B, C, AD, and D2 are
greater than 0.1000 indicating that the model terms are not significant.
The model equation describes how the dye removal efficiency was

Fig. 6. (a) plot of actual versus predicted values and (b) residual versus predicted points for adsorption of tannery reactive dye using RAAC.

11
J.F. Nure et al.
affected by individual variables by their (linear and quadratic) terms or
double interaction. Negative coefficients indicate that factors negatively
affect the response variable. In this specific study, the double interaction
effect of pH and dye concentration, dye concentration, and time is
negatively affecting the yield of the efficiency. Similarly, the quadratic
effects of adsorbent dose and dye concentration were antagonistically
affecting the performances.
3.3.4. Adequacy checks for the developed model
The goodness of fit of the model was checked using multiple corre­
lation coefficients (R2). The quality of model fit for the adsorption
Fig. 7. The response surface (a) and contour map (b) show the interaction of adsorbent dose and pH.
12
Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
process was evaluated using Fisher’s test (F-value), the probability value
(p-value), the lack of fit, the coefficient of determination (R2), and
adjusted R2 (R2adj), and predicted R2 (R2pred). F-value and P-value of
the quadratic model were found to be 141.64 and 0.0001, respectively.
This implies that the quadratic model is significant and the model can
sufficiently predict the removal efficiency of reactive dye from waste­
water. The correlation coefficient (R2) was 0.996 indicating that the
regression is statistically significant [31]. The quality of the fit was also
examined by comparing the actual values against the predicted re­
sponses by the model of the reactive dye removal shown in Fig. 6. Fig. 6
(a) depicts that the predicted values are quite close to the actual
J.F. Nure et al.
experimental result both spreading closer to the straight line, which
indicates that the model fits the experimental data. Thus, it confirms that
the regression model exhibits excellent stability for dye adsorption on
activated carbon. Therefore, it can be concluded that the developed
response surface model proved to be satisfactory for the prediction of the
dye adsorption system. In addition to this, the adequacy of the model
was also checked using residual analysis as in Fig. 6(b). The zero residual
line in the plot was used to detect whether the points were scattered
around the horizontal band or clustered in a curved pattern. In this
specific study, the data points form a detectable pattern at almost the
same distance from the zero residual line. Furthermore, the residual data
points fluctuate more or less in a random fashion within the horizontal
Fig. 8. The response surface and contour map showing the interaction of dye concentration and pH.
13
Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
band, indicating that the model is desirable, and there are no visible
model defects.
3.4. Interaction effect of variables on dye removal efficiency
3.4.1. Adsorbent dosage and pH
Response surface methodology was employed to study the combined
effect of initial solution pH and adsorbent dose on Black MNN reactive
tannery effluent dye removal efficiency. The response surface and the
contour map are indicated in Fig. 7A and B. The benefit of the Box-
Behnken design approach is to study the interaction effect of experi­
mental variables on response variables and develop a response surface
J.F. Nure et al.
showing various conditions of interaction effects. In this specific case,
the effect of solution pH and dosage on the percentage removal of
anionic tannery dye was studied. To study the interaction effect, dye
concentration and contact time were kept constant at 150 mg/L and 90
min, respectively. The 3D view of the response surface and contour map
depicts the removal efficiency of the anionic tannery dye (Black MNN)
which varied between 47.6 % at pH 5.5 and 99.9 % at pH 2 indicating
that the anionic tannery dyes are better adsorbed at pH 2. This is because
the more drop-in solution pH the more the number of protons in the
aqueous solution. This gives more positive charge to the adsorbent
which helps to adsorb more anionic dye molecules [20]. The removal
efficiency was seen to drop further to 47.4 % beyond the experimental
minimum (47.6 %) at pH values between 6.8 and 7.2. Specifically, there
are no opposite charges to interact with because of the neutrality of the
Fig. 9. The response surface and contour map showing the interaction of dye concentration and dosage.
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Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
aqueous solution at this pH range. On the other hand, it is observed that
the percentage of dye removal increased with the amount of adsorbent.
That means increasing the adsorbent dose leads to an increase in
adsorbent surface area and the availability of more sorption sites [60].
However, the excessive addition of adsorbent beyond the required
amount makes the adsorption process uneconomical. In general, keeping
values of dye concentration and contact time constant, the optimum
value of removal efficiency was not affected by the interaction between
pH and adsorbent dosage implying that the percentage removal effi­
ciency was positively affected by their interaction.
3.4.2. Concentration and pH
The interaction effect due to different levels of initial dye concen­
tration and solution pH on the response variable is shown in Fig. 8. In the
J.F. Nure et al.
figure, it was observed that both the independent variables strongly
affect the dye adsorption process. The experimental condition to study
this interaction was conducted keeping dosage and the time of contact,
at the constant values of 0.24 g/100 mL and 88 min, respectively. The
3D plot and contour map depict better responses which were obtained at
higher dye concentrations and lower pH values. The maximum removal
efficiency of 99.9 % was achieved at the initial pH of 2 and dye con­
centration of 150 mg/L. From this situation, it can be inferred that
increasing dye concentration at a lower solution pH increases the
driving force, which enhances the adsorption process [61]. A relatively
strong interaction existed between initial concentration and pH, which
Fig. 10. The response surface and contour map showing the interaction of dye concentration and contact time.
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Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
was reflected by the corresponding P-value (P<0.001) [62]. Besides this,
an increase in protons due to the lowering of pH provides a suitable
medium for the interaction of adsorbent active sites with the anionic
tannery dye molecules. This is because the chemistry of the dye mole­
cules was affected by the solution pH and the activity of functional
groups on the adsorbent surface. Moreover, the competition of due
molecules with hydrogen ions for the binding active sites was also
observed [63]. However, a further increase of dye concentration while
the adsorbent active sites remain constant will saturate the adsorbent
which causes the driving force to remain the same until the adsorption
process reaches equilibrium. In general, the interaction between pH and
J.F. Nure et al.
dye concentration negatively affects the removal efficiency.
3.4.3. Dye concentration and adsorbent dosage
The response surface and contour map depicting the effects due to
the interaction of the dye concentration and adsorbent dose on dye
removal efficiency are shown in Fig. 9. Experimental data and the pre­
dicted removal efficiency values were used to generate a response sur­
face showing the coexistence of the above two experimental variables at
which the pH and contact time were kept constant at 2 and 88 min,
respectively. The 3D response surface plot and contour map show that
better response was observed at the dye concentration of 125 mg/L and
adsorbent dose of 0.24 g/100 mL. Further increasing the adsorbent dose
keeps the dye concentration at 125 mg/L which will end up in the
reduction of removal efficiency and adsorption capacity. This might be
due to the interference of adsorbents with each other for the dye mol­
ecules not to have direct contact with the active sites and due to
excessive active sites above the required amount [64]. That is, even if a
dose of too much adsorbent tends to have better removal efficiency, the
adsorption capacity drops due to excessive utilization of the adsorbent
beyond the optimum limit [65]. On the other hand, an increase in dye
concentration in an aqueous solution at a constant dosage of 0.24 mg/L
ends up with free dye molecules due to the saturation of the adsorbent.
Hence, a drop in the response variable was observed. Therefore, the
interaction of adsorbent dosage and dye concentration positively affects
the removal of anionic tannery dye.
3.4.4. Contact time and dye concentration
The 3D plot and contour map in Fig. 10 show the combined effect of
dye concentration and contact time. The experiment was done keeping
pH 2 and adsorbent dosage (0.24 mg/100 mL) constant. It is observed
from the contour map that an optimum removal efficiency of 100 % is
obtained at a contact time of 75 min and dye concentration of 135 mg/L.
The interaction effect of these parameters can be described as moving
along the 100 % contour line, which means that to get the same removal
efficiency of 100 % across the dye concentration above the optimum
135 mg/. But it requires more time of contact. This is because the
amount of dye in the effluent increases the competition of dye molecules
for the active site increases so that the probability of contact between the
dye molecules and the adsorbent active site decreases. Moreover, this is
because the more concentrated the dye the better the driving force and
the frequency of contact with the adsorbent [61,64]. This can be
described considering the dye concentration of 148 mg/L which needs a
contact time of 80 min to have the dye molecules removed. Similarly,
with the drop in the concentration of dye molecules below 135 mg/L,
the time of contact required again increases due to a reduction in the
probability of dye molecules interacting with the adsorbent active sites.
In another situation, a drop in removal efficiency is observed due to a
decrease in dye concentration at the constant contact time, which is due
to a reduction in the frequency of contact with the fixed amount of
adsorbent. Therefore, to have better interaction of dye molecules with
the active sites at constant contact time higher concentration dye mol­
ecules are required. In general, the interaction of dye concentration and
time of contact affects the response variable negatively.
3.5. Adsorption isotherms
The plot of 1/Qe versus 1/Ce resulted in the Langmuir correlation
coefficient of 0.97 shown in Fig. 12a. The Langmuir adsorption capacity
(qmax) and binding energy constant (KL) were calculated to be 38.46 mg/
g and 0.32 L/mg, respectively. The Langmuir separation factor (RL) was
calculated using Eq. (10) and found to be (0.07). This represents a
favorable adsorption process showing the effectiveness of the interac­
tion of the adsorbent with the anionic tannery dye. On the other hand,
the model for Freundlich isotherm for the adsorption process on a het­
erogeneous adsorbent surface layer was presented in Fig. 12b. The
isotherm plot of logqeversus logCe gave a correlation coefficient of 0.96.
16
Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
Using 1n = 0.1616 and logKf = 1.3989from the isotherm model, the
Freundlich constant, n was calculated to be 6.19 at Kf = 25.05con­
firming the capacity of the adsorptive removal of synthetic tannery dye
on RAAC. Additionally, the plot of ln Ce versus Qe resulted in the
Temkin correlation coefficient of 0.96 as shown in Fig. 12c. Temkin
equilibrium binding constant (KT) and Temkin heat of adsorption con­
stant were determined to be 163.04 L/mg and 491.712 J/mol, respec­
tively. On the other hand, empirical intensity related to sips isotherm
and equilibrium binding constant for the sips isotherm model was found
to be 0.3629 and 5.53 respectively as shown in Fig. 12d. Values of the
determined correlation coefficient indicate that the adsorption experi­
mental data at the optimum parameters have better fitness for the
Langmuir model (with a maximum R2 of 0.97 as well as insignificance
Residual sum of squares(RSS)), which implies that the Langmuir model
predicts the adsorption trend better. Therefore, it can be inferred that
the adsorbent is homogeneous the active sites of the adsorbent have
linear distribution and the surface of the adsorbed is saturated with a
single attachment of the dye molecules [24,66] (Fig. 11).
3.6. Adsorption kinetic study
Optimum conditions from the batch experiments were used to study
the information about the kinetics of dye adsorption. Experimental
adsorption capacity (qe,exp), calculated adsorption capacity (qe,calc), and
values of parameters like Kf, Ks, and Kp for all three kinetic models were
calculated from the developed model curves as shown in Table 9. The
coefficient of determination (R2) for pseudo-second-order reaction
adsorption kinetics was found to be 0.99, However, a lower value of the
coefficient of determination R2 0.86 was obtained for pseudo-first-order
reaction adsorption kinetics. Therefore, due to its higher coefficient of
determination and the insignificant difference between its equilibrium
and calculated adsorption capacities (q(e,exp) and q(e,calc)) was observed.
It can be concluded that the pseudo-second-order model will describe
anionic dye adsorption kinetics better. Furthermore, chemisorption was
taken to be the rate-limiting adsorption mechanism that results from the
chemical bond between adsorbate molecules and specific surface loca­
tions (active sites) on RAAC. To study the infusibility of the adsorbate to
the interior surface of the adsorbent, a curve of the Intraparticle diffu­
sion model was developed and the Intraparticle diffusion rate constant
(Kp) and the C (mg/g) values were determined to be 0.192 mg/(g.
min^0.5) and 57.55 mg/g, respectively. This showed that the rate of
adsorption is dependent on both reactants(the adsorbent and adsorbate )
and Intraparticle diffusion does not exclusively control the adsorption
process [67–70].
4. Conclusions
Wastewater from Elico-Awash tannery in Ethiopia was analyzed for
the concentration of Black MNN reactive dye pollutant and its concen­
tration was found to be 92.76±4.26 mg/L. Activated carbon was
developed from Rumex Abysinicus using the chemical activation method
followed by thermal activation then applied for the removal of the dye
from the aqueous solution and real tannery wastewater under batch
adsorption mode. The proximate and BET analysis results showed an
extremely large specific surface area of 3620 m2/g. The proximate
analysis results of low volatile matter and moisture content make the
developed activated carbon favorable for the intended adsorption pro­
cess. Furthermore, the FTIR analysis result confirmed the presence of
several functional groups for high interaction whereas the morpholog­
ical void spaces in the adsorbent described by SEM analysis could be the
reason for such a high specific surface area. The maximum dye removal
efficiency of 99.9 % was obtained at the optimum working conditions of
initial dye concentration150 mg/L, pH 2, adsorbent dosage 0.25 mg/
100 mL, and contact time 90 min. However, under the same optimum
working conditions, the removal efficiency from real tannery
 J.F. Nure et al.
17

Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138

Fig. 11. Langmuir (a), Freundlich isotherm (b), Temkin (c), and Sips (c) for tannery dye adsorption at the optimum conditions of parameters.
J.F. Nure et al. Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138

Table 9 Acknowledgments
Parameters for kinetics study tannery effluent dye adsorption.
Pseudo-first –order Pseudo-second-order Intraparticle diffusion The authors would like to acknowledge the Manufacturing Industry
Parameters Values Parameters Values Parameters Values Development Institute, Leather and Leather Products Industry Research
qe,exp (mg/g) 59.95 qe,exp (mg/g) 59.95 and Development Center, which is located in the Akaki Kality sub-city of
qe,calc (mg/g) 4.37 qe,calc (mg/g) 60.17 Kp(mg/(g. 0.192 Addis Ababa, Ethiopia, for giving us support for the research work
min0.5)) including the facilities. Additionally, we would like to appreciate the
Kf(g/(mg. 0.043 Ks(g/(mg. 0.017 C (mg/g) 57.55 contributions from the Institute for Nanotechnology and Water Sus­
min)) min))
R2 0.86 R2 0.99 R2 0.97
tainability (iNanoWS), University of South Africa, Johannesburg, South
Africa, and Addis Ababa Science and Technology University, Addis
Ababa, Ethiopia.
wastewater was found to be 94.6 %, which is lower due to other inter­
fering ions and pollutants. Freundlich and the Langmuir isotherm References
models were used to fit the experimental adsorption isotherm data,
where Langmuir isotherm was found to fit better with the experimental [1] Fito J, Said H, Feleke S, Worku A. Fluoride removal from aqueous solution onto
activated carbon of Catha edulis through the adsorption treatment technology.
data with R2 = 0.973 showing the presence of the homogeneous Environ Syst Res 2019;8. https://doi.org/10.1186/s40068-019-0153-1.
adsorbent surface. Kinetic study showed that the data is best suited to [2] Bedada D, Angassa K, Tiruneh A, Kloos H, Fito J. Chromium removal from tannery
pseudo-second-order kinetics with a correlation coefficient of 0.99. In wastewater through activated carbon produced from parthenium hysterophorus
weed. Energy Ecol Environ 2020;5:184–95. https://doi.org/10.1007/s40974-020-
general, it was observed that adsorbent prepared from Rumex-Abyssini­ 00160-8.
cus was found to be effective in removing dyes from tannery wastewater. [3] Wang M, Janssen ABG, Bazin J, Strokal M, Ma L, Kroeze C. Accounting for
Therefore, it can be applied as a low-cost, locally available, and prom­ interactions between sustainable development goals is essential for water pollution
control in China. Nat Commun 2022;13:1–13. https://doi.org/10.1038/s41467-
ising treatment option for dye removal from tannery industrial waste­
022-28351-3.
water which can be recommendable to be scaled up to an industrial scale [4] Fito J, Abewaa M, Nkambule T. Magnetite-impregnated biochar of parthenium
to mitigate the pollution challenges. However, additional works such as hysterophorus for adsorption of Cr(VI) from tannery industrial wastewater. Appl
thermodynamic study, regeneration, and reusability as well as the Water Sci 2023;13. https://doi.org/10.1007/s13201-023-01880-y.
[5] Tefera N, Mulualem Y, Fito J. Adsorption of fluoride from aqueous solution and
activated carbon surface modification studies need to be done in the groundwater onto activated carbon of avocado seeds. Water Conserv Sci Eng 2020;
future to commercialize the prepared adsorbent. 5:187–97. https://doi.org/10.1007/s41101-020-00093-7.
[6] Moges A, Nkambule TTI, Fito J. The application of GO-Fe3O4 nanocomposite for
chromium adsorption from tannery industry wastewater. J Environ Manage 2022;
Declarations 305:114369. https://doi.org/10.1016/j.jenvman.2021.114369.
[7] Ramamurthy G, Ramalingam B, Katheem MF, Sastry TP, Inbasekaran S,
Thanveer V, Jayaramachandran S, Das SK, Mandal AB. Total elimination of
Data availability
polluting chrome shavings, chrome, and dye exhaust liquors of tannery by a
method using keratin hydrolysate. ACS Sustain Chem Eng 2015;3:1348–58.
The data used to support the findings of this study are included in the https://doi.org/10.1021/acssuschemeng.5b00071.
article and can be obtained from the corresponding author. [8] Geethakarthi A, Phanikumar BR. Adsorption of reactive dyes from aqueous
solutions by tannery sludge developed activated carbon: kinetic and equilibrium
studies. Int J Environ Sci Technol 2011;8:561–70. https://doi.org/10.1007/
BF03326242.
Funding [9] Zvinowanda CM, Okonkwo JO, Shabalala PN, Agyei NM. A novel adsorbent for
heavy metal remediation in aqueous environments. Int J Environ Sci Technol 2009;
6:425–34. https://doi.org/10.1007/BF03326081.
The authors didn’t receive any funds for this research except for the
[10] Fito J, Tefera N, Van Hulle SWH. Adsorption of distillery spent wash on activated
laboratory facilities bagasse fly ash: kinetics and thermodynamics. J Environ Chem Eng 2017;5:
5381–8. https://doi.org/10.1016/j.jece.2017.10.009.
[11] Roh H, Yu MR, Yakkala K, Koduru JR, Yang JK, Chang YY. Removal studies of Cd
Compliance with ethical standards (II) and explosive compounds using buffalo weed biochar-alginate beads. J Ind Eng
Chem 2015;26:226–33. https://doi.org/10.1016/j.jiec.2014.11.034.
[12] Lingamdinne LP, Roh H, Choi YL, Koduru JR, Yang JK, Chang YY. Influencing
Not applicable factors on sorption of TNT and RDX using rice husk biochar. J Ind Eng Chem 2015;
32:178–86. https://doi.org/10.1016/j.jiec.2015.08.012.
[13] Neolaka YAB, Lawa Y, Naat JN, Riwu AAP, Iqbal M, Darmokoesoemo H,
CRediT authorship contribution statement Kusuma HS. The adsorption of Cr(VI) from water samples using graphene oxide-
magnetic (GO-Fe3O4) synthesized from natural cellulose-based graphite (kusambi
Jemal Fito Nure: Conceptualization, Methodology, Software, Vali­ wood or Schleichera oleosa): study of kinetics, isotherms and thermodynamics.
J Mater Res Technol 2020;9:6544–56. https://doi.org/10.1016/j.
dation, Formal analysis, Data curation, Writing – original draft, Writing jmrt.2020.04.040.
– review & editing, Supervision. Ashagrie Mengistu: Conceptualiza­ [14] Lingamdinne LP, Choi JS, Angaru GKR, Karri RR, Yang JK, Chang YY, Koduru JR.
tion, Methodology, Software, Validation, Investigation, Writing – orig­ Magnetic-watermelon rinds biochar for uranium-contaminated water treatment
using an electromagnetic semi-batch column with removal mechanistic
inal draft, Writing – review & editing, Visualization. Mikiyas Abewaa:
investigations. Chemosphere 2022;286:131776. https://doi.org/10.1016/j.
Writing – original draft, Writing – review & editing. Kenatu Angassa: chemosphere.2021.131776.
Writing – original draft, Writing – review & editing. Welldone Moyo: [15] Mishra S, Yadav SS, Rawat S, Singh J, Koduru JR. Corn husk derived magnetized
activated carbon for the removal of phenol and para-nitrophenol from aqueous
Writing – original draft, Writing – review & editing. Zebron Phiri:
solution: interaction mechanism, insights on adsorbent characteristics, and
Writing – review & editing. Potlako J. Mafa: Writing – review & edit­ isothermal, kinetic and thermodynamic properties. J Environ Manage 2019;246:
ing. Alex T. Kuvarega: Writing – review & editing. Thabo T.I. Nkam­ 362–73. https://doi.org/10.1016/j.jenvman.2019.06.013.
bule: Validation, Formal analysis, Data curation, Writing – original [16] Narasimharao K, Angaru GKR, Momin ZH, Al-Thabaiti S, Mokhtar M, Alsheshri A,
Alfaifi SY, Koduru JR, Chang YY. Orange waste Biochar-Magnesium Silicate
draft, Visualization. (OBMS) composite for enhanced removal of U(VI) ions from aqueous solutions.
J Water Process Eng 2023;51. https://doi.org/10.1016/j.jwpe.2022.103359.
[17] Lee JE, Park YK. Applications of modified biochar-based materials for the removal
Declaration of Competing Interest of environment pollutants: a mini review. Sustain 2020:12. https://doi.org/
10.3390/su12156112.
[18] Fito J, Abrham S, Angassa K. Adsorption of methylene blue from textile industrial
The authors declare that they have no known competing financial wastewater onto activated carbon of parthenium hysterophorus. Int J Environ Res
interests or personal relationships that could have appeared to influence 2020;14:501–11. https://doi.org/10.1007/s41742-020-00273-2.
the work reported in this paper.

18
J.F. Nure et al.
[19] Xiao Y, Lyu H, Yang C, Zhao B, Wang L, Tang J. Graphitic carbon nitride/biochar
composite synthesized by a facile ball-milling method for the adsorption and
photocatalytic degradation of enrofloxacin. J Environ Sci 2021;103:93–107.
https://doi.org/10.1016/j.jes.2020.10.006.
[20] Tebeje A, Worku Z, Nkambule TTI, Fito J. Adsorption of chemical oxygen demand
from textile industrial wastewater through locally prepared bentonite adsorbent.
Int J Environ Sci Technol 2021:1–14. https://doi.org/10.1007/s13762-021-03230-
4.
[21] Sirajudheen P, Nikitha MR, Karthikeyan P, Meenakshi S. Perceptive removal of
toxic azo dyes from water using magnetic Fe3O4 reinforced graphene
oxide–carboxymethyl cellulose recyclable composite: adsorption investigation of
parametric studies and their mechanisms. Surfaces and Interfaces 2020;21:100648.
https://doi.org/10.1016/j.surfin.2020.100648.
[22] Hamad HN, Idrus S. Recent developments in the application of bio-waste-derived
adsorbents for the removal of methylene blue from wastewater: a review. Polymers
2022;14. https://doi.org/10.3390/polym14040783 (Basel).
[23] Mengistu A, Abewaa M, Adino E, Gizachew E, Abdu J. The application of Rumex
abyssinicus based activated carbon for brilliant blue reactive dye adsorption from
aqueous solution. BMC Chem 2023:1–24. https://doi.org/10.1186/s13065-023-
01004-2.
[24] Fito J, Abewaa M, Mengistu A, Angassa K, Ambaye AD, Moyo W, Nkambule T.
Adsorption of methylene blue from textile industrial wastewater using activated
carbon developed from Rumex abyssinicus plant. Sci Rep 2023;13:5427. https://
doi.org/10.1038/s41598-023-32341-w.
[25] Rakić V, Rac V, Krmar M, Otman O, Auroux A. The adsorption of pharmaceutically
active compounds from aqueous solutions onto activated carbons. J Hazard Mater
2015;282:141–9. https://doi.org/10.1016/j.jhazmat.2014.04.062.
[26] Boonpoke A, Chiarakorn S, Laosiripojana N, Towprayoon S, Chidthaisong A.
Synthesis of activated carbon and MCM-41 from bagasse and rice husk and their
carbon dioxide adsorption capacity. J Sustain Environ 2013;2:77–81.
[27] Stabentheiner E, Zankel A, Pölt P. Environmental scanning electron microscopy
(ESEM)-a versatile tool in studying plants. Protoplasma 2010;246:89–99. https://
doi.org/10.1007/s00709-010-0155-3.
[28] Nure JF, Shibeshi NT, Asfaw SL, Audenaer W, Van Hulle SWH. COD and colour
removal from molasses spent wash using activated carbon produced from bagasse
fly ash of matahara sugar factory. Oromiya region, Ethiopia, Water SA 2017;43:
470–9. https://doi.org/10.4314/wsa.v43i3.12.
[29] Hamza NAE. Adsorption of metals (Fe(II), Cr(III) and Co(II)) from aqueous solution
by using activated carbon prepared from mesquite tree. Sci J Anal Chem 2013;1:
12. https://doi.org/10.11648/j.sjac.20130102.12.
[30] Yin Q, Liu M, Ren H. Biochar produced from the co-pyrolysis of sewage sludge and
walnut shell for ammonium and phosphate adsorption from water. J Environ
Manage 2019;249:109410. https://doi.org/10.1016/j.jenvman.2019.109410.
[31] Jawad AH, Rashid RA, Mahmuod RMA, Ishak MAM, Kasim NN, Ismail K.
Adsorption of methylene blue onto coconut (Cocos nucifera) leaf: optimization,
isotherm and kinetic studies. Desalin Water Treat 2016;57:8839–53. https://doi.
org/10.1080/19443994.2015.1026282.
[32] Bayuo J. Decontamination of cadmium(II) from synthetic wastewater onto shea
fruit shell biomass. Appl Water Sci 2021;11:84. https://doi.org/10.1007/s13201-
021-01416-2.
[33] Bayuo J, Pelig-Ba KB, Abukari MA. Adsorptive removal of chromium(VI) from
aqueous solution unto groundnut shell. Appl Water Sci 2019;9:1–11. https://doi.
org/10.1007/s13201-019-0987-8.
[34] Bayuo J. An extensive review on chromium (vi) removal using natural and
agricultural wastes materials as alternative biosorbents. J Environ Heal Sci Eng
2021;19:1193–207. https://doi.org/10.1007/s40201-021-00641-w.
[35] Ali I, Peng C, Ye T, Naz I. Sorption of cationic malachite green dye on phytogenic
magnetic nanoparticles functionalized by 3-marcaptopropanic acid. RSC Adv 2018;
8:8878–97. https://doi.org/10.1039/c8ra00245b.
[36] Bayuo J, Abukari MA, Pelig-Ba KB. Optimization using central composite design
(CCD) of response surface methodology (RSM) for biosorption of hexavalent
chromium from aqueous media. Appl Water Sci 2020;10. https://doi.org/10.1007/
s13201-020-01213-3.
[37] El-Khaiary MI, Malash GF. Common data analysis errors in batch adsorption
studies. Hydrometallurgy 2011;105:314–20. https://doi.org/10.1016/j.
hydromet.2010.11.005.
[38] Adebayo G, Adegoke H, Jamiu W, Balogun B, Jimoh A. Adsorption of Mn(II) and
Co(II) ions from aqueous solution using Maize cob activated carbon: kinetics and
thermodynamics studies. J Appl Sci Environ Manag 2016;19:737. https://doi.org/
10.4314/jasem.v19i4.22.
[39] Shang J, Pi J, Zong M, Wang Y, Li W. Chromium removal using magnetic biochar
derived from herb-residue. J Taiwan Inst Chem Eng 2016;0:1–6. https://doi.org/
10.1016/j.jtice.2016.09.012.
[40] Qu J, Wang Y, Tian X, Jiang Z, Deng F, Tao Y, Jiang Q, Wang L, Zhang Y. KOH-
activated porous biochar with high specific surface area for adsorptive removal of
chromium (VI) and naphthalene from water: affecting factors, mechanisms and
reusability exploration. J Hazard Mater 2021;401:123292. https://doi.org/
10.1016/j.jhazmat.2020.123292.
[41] Zhou L, Liu Y, Liu S, Yin Y, Zeng G, Tan X, Hu X, Hu X, Jiang L, Ding Y.
Investigation of the adsorption-reduction mechanisms of hexavalent chromium by
ramie biochars of different pyrolytic temperatures. Bioresour Technol 2016;218:
351–9.
[42] Ayoub GM, Hamzeh A, Semerjian L. Post treatment of tannery wastewater using
lime /bittern coagulation and activated carbon adsorption. DES 2011;273:359–65.
https://doi.org/10.1016/j.desal.2011.01.045.
19
Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
[43] Bader AC, Hussein HJ, Jabar MT. BOD: COD ratio as indicator for wastewater and
industrial water pollution. Int J Spec Educ 2022;37:2022.
[44] Gomes CS, Piccin JS, Gutterres M. Optimizing adsorption parameters in tannery-
dye-containing effluent treatment with leather shaving waste. Process Saf Environ
Prot 2016;99:98–106. https://doi.org/10.1016/j.psep.2015.10.013.
[45] Ge L, Zhao C, Zhou T, Chen S, Li Q, Wang X, Shen D, Wang Y, Xu C. An analysis of
the carbonization process of coal-based activated carbon at different heating rates.
Energy 2023;267:126557.
[46] Shamsuddin MS, Yusoff NRN, Sulaiman MA. Synthesis and characterization of
activated carbon produced from kenaf core fiber using H3PO4 activation. Proc
Chem 2016;19:558–65. https://doi.org/10.1016/j.proche.2016.03.053.
[47] Hidayu AR, Mohamad NF, Matali S, Sharifah ASAK. Characterization of activated
carbon prepared from oil palm empty fruit bunch using BET and FT-IR techniques.
Proc Eng 2013;68:379–84. https://doi.org/10.1016/j.proeng.2013.12.195.
[48] Maulina S, Iriansyah M. Characteristics of activated carbon resulted from pyrolysis
of the oil palm fronds powder. IOP Conf Ser Mater Sci Eng 2018:12072.
[49] S. Bachrun, N. Ayurizka, Extremely high surface area of activated carbon
originated from sugarcane bagasse Extremely high surface area of activated carbon
originated from sugarcane bagasse, (2020). 10.1088/1757-899X/909/1/012018.
[50] Jia X, Zhang Y, He Z, Chang F, Zhang H, Wågberg T, Hu G. Journal of
environmental chemical engineering mesopore-rich badam-shell biochar for
efficient adsorption of Cr ( VI ) from aqueous solution. J Environ Chem Eng 2021;9:
105634. https://doi.org/10.1016/j.jece.2021.105634.
[51] Wang C, Feng L, Li W, Zheng J, Tian W, Li X. Shape-stabilized phase change
materials based on polyethylene glycol/porous carbon composite: the influence of
the pore structure of the carbon materials. Sol Energy Mater Sol Cells 2012;105:
21–6. https://doi.org/10.1016/j.solmat.2012.05.031.
[52] Romanos J, Beckner M, Stalla D, Tekeei A, Suppes G, Jalisatgi S, Lee M,
Hawthorne F, Robertson JD, Firlej L, Kuchta B, Wexler C, Yu P, Pfeifer P. Infrared
study of boron-carbon chemical bonds in boron-doped activated carbon. Carbon N
Y 2013;54:208–14. https://doi.org/10.1016/j.carbon.2012.11.031.
[53] Rusly SM, Ibrahim S. Adsorption of textile reactive dye by palm shell activated
carbon: response surface methodology. World Acad Sci Eng Technol 2010;43:
892–5.
[54] Mahendran S, Gokulan R, Aravindan A, Rao HJ, Kalyani G, Praveen S, Pushpa TB,
Senthil Kumar M. Production of Ulva prolifera derived biochar and evaluation of
adsorptive removal of Reactive Red 120: batch, isotherm, kinetic, thermodynamic
and regeneration studies. Biomass Convers Biorefinery 2021. https://doi.org/
10.1007/s13399-021-01483-0.
[55] Amin NK. Removal of reactive dye from aqueous solutions by adsorption onto
activated carbons prepared from sugarcane bagasse pith. Desalination 2008;223:
152–61. https://doi.org/10.1016/j.desal.2007.01.203.
[56] Lee JW, Choi SP, Thiruvenkatachari R, Shim WG, Moon H. Evaluation of the
performance of adsorption and coagulation processes for the maximum removal of
reactive dyes. Dye Pigment 2006;69:196–203. https://doi.org/10.1016/j.
dyepig.2005.03.008.
[57] Arulkumar M, Sathishkumar P, Palvannan T. Optimization of Orange G dye
adsorption by activated carbon of Thespesia populnea pods using response surface
methodology. J Hazard Mater 2011;186:827–34. https://doi.org/10.1016/j.
jhazmat.2010.11.067.
[58] Bello OS, Ahmad MA. Response surface modeling and optimization of remazol
brilliant blue reactive dye removal using periwinkle shell-based activated carbon.
Sep Sci Technol 2011;46:2367–79. https://doi.org/10.1080/
01496395.2011.595756.
[59] Eletta OAA, Mustapha SI, Ajayi OA, Ahmed AT. Optimization of dye removal from
textile wastewater using activated carbon from sawdust. Niger J Technol Dev 2018;
15:26. https://doi.org/10.4314/njtd.v15i1.5.
[60] P. Taylor, S. Chowdhury, P.Das Saha, Desalination and Water Treatment Scale-up
of a dye adsorption process using chemically modified rice husk : optimization
using response surface methodology Scale-up of a dye adsorption process using
chemically modifi ed rice husk : optimization using resp, (2012) 37–41. 10.1080/
19443994.2012.661289.
[61] Mondal S, Aikat K, Halder G. Biosorptive uptake of ibuprofen by chemically
modified Parthenium hysterophorus derived biochar: equilibrium, kinetics,
thermodynamics and modeling. Ecol Eng 2016;92:158–72. https://doi.org/
10.1016/j.ecoleng.2016.03.022.
[62] Kalavathy M H, Regupathi I, Pillai MG, Miranda LR. Modelling, analysis and
optimization of adsorption parameters for H3PO4 activated rubber wood sawdust
using response surface methodology (RSM). Colloids Surfaces B Biointerf 2009;70:
35–45. https://doi.org/10.1016/j.colsurfb.2008.12.007.
[63] Chowdhury S, Saha PD. Scale-up of a dye adsorption process using chemically
modified rice husk: optimization using response surface methodology. Desalin
Water Treat 2012;37:331–6. https://doi.org/10.1080/19443994.2012.661289.
[64] Jain M, Garg VK, Kadirvelu K. Investigation of Cr(VI) adsorption onto chemically
treated Helianthus annuus: optimization using response surface methodology.
Bioresour Technol 2011;102:600–5. https://doi.org/10.1016/j.
biortech.2010.08.001.
[65] Roy A, Chakraborty S, Kundu SP, Adhikari B, Majumder SB. Adsorption of anionic-
azo dye from aqueous solution by lignocellulose- biomass jute fiber: equilibrium,
kinetics, and thermodynamics study. Ind Eng Chem Res 2012;51:12095–106.
https://doi.org/10.1021/ie301708e.
[66] Fito J, Abewaa M, Nkambule T. Magnetite ‑ impregnated biochar of parthenium
hysterophorus for adsorption of Cr ( VI ) from tannery industrial wastewater. Appl
Water Sci 2023;13:1–23. https://doi.org/10.1007/s13201-023-01880-y.
[67] Ayele AL, Tizazu BZ, Wassie AB. Chemical modification of teff straw biomass for
adsorptive removal of Cr (VI) from aqueous solution: characterization,
J.F. Nure et al.
optimization, kinetics, and thermodynamic aspects. Adsorpt Sci Technol 2022:
2022. https://doi.org/10.1155/2022/5820207.
[68] Kim S, Lee J, Son Y, Yoon M. Study of the dye adsorption kinetics of metal–organic
frameworks in aqueous media. Bull Korean Chem Soc 2020;41:843–50. https://
doi.org/10.1002/bkcs.12076.
[69] Shahbazi D, Mousavi SA, Nayeri D. Low-cost activated carbon: characterization,
decolorization, modeling, optimization and kinetics. Int J Environ Sci Technol
2020;17:3935–46. https://doi.org/10.1007/s13762-020-02698-w.
20
Journal of the Taiwan Institute of Chemical Engineers 151 (2023) 105138
[70] Bekhoukh A, Moulefera I, Zeggai FZ, Benyoucef A, Bachari K. Anionic methyl
orange removal from aqueous solutions by activated carbon reinforced conducting
polyaniline as adsorbent: synthesis, characterization, adsorption behavior,
regeneration and kinetics study. J Polym Environ 2022;30:886–95. https://doi.
org/10.1007/s10924-021-02248-6.