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Adsorption of Methylene Blue from Textile Industrial Wastewater onto

Activated Carbon of Parthenium hysterophorus

Article  in  International Journal of Environmental Research · July 2020

DOI: 10.1007/s41742-020-00273-2

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International Journal of Environmental Science and Technology
https://doi.org/10.1007/s13762-021-03230-4

ORIGINAL PAPER

Adsorption of chemical oxygen demand from textile industrial

wastewater through locally prepared bentonite adsorbent
A. Tebeje1,3 · Z. Worku1 · T. T. I. Nkambule2   · J. Fito1,2 

Received: 30 August 2020 / Revised: 24 November 2020 / Accepted: 15 February 2021

© Islamic Azad University (IAU) 2021

Abstract
The rapid expansion of industrialization has a significant contribution to the economic development of many nations. But,
the untreated discharge from the textile factory is severely impacting freshwater and public health. Therefore, this study
was aimed to prepare activated bentonite for removal of chemical oxygen demand (COD) from textile industrial waste-
water, and the optimization process was studied using design expert software version 11. The activation of the bentonite
was performed using diluted sulfuric acid and followed by a thermal process. Adsorbent characterization was carried out
using the proximate analysis (moisture content), bulk density, BET method of specific surface area, scanning electron
microscope, Fourier transform infrared spectroscopy, and X-ray diffraction. The COD and pH of textile industrial effluent
were 569 ± 23 mg/L and pH 6 ± 0.3, respectively. The specific surface area of modified bentonite was found to be 265 ­m2/g.
Maximum COD removal of 76.5% was recorded at the optimum condition of contact time 120 min., pH 10, and adsorbent
dosage 2 g, whereas the maximum predicted COD removal was 76.0%. COD removal was highly influenced by the adsorbent
dose described by the regression analysis ­(R2 = 0.98). Increasing the adsorption factors and interaction effects resulted in
increasing the COD removal and vice versa, but the interaction effect between the pH and adsorbent dose was inversely
proportional to COD removal. Generally, the adsorption results were encouraging and modified bentonite is a promising
candidate to be implemented for organic matter removal from textile industrial wastewater.

Keywords  Activated adsorbent · Characterization · Industrial effluent · Removal · Treatment efficiency · Water pollution

Introduction industry that is significantly contributing to the economic

Industrialization is a fastly growing sector to satisfy
the increasing demand of the world population and also
intended to ensure environmental and economic sustain-
ability. Among the manufacturing industries, the textile
industry is a well-established and rapidly progressing
Editorial responsibility: Samareh Mirkia.
* J. Fito
fitojemal120@gmail.com
1
Department of Environmental Engineering, Nanotechnology
Canter of Excellence, Addis Ababa Science, and Technology
University, P.O. Box 16417, Addis Ababa, Ethiopia
2
Institute for Nanotechnology and Water Sustainability
(iNanoWS), University of South Africa, Science Campus,
Florida, Florida, South Africa
3
Department of Chemical Engineering, Addis Ababa Science
and Technology University, Addis Ababa, Ethiopia
development of many nations. The demand and yield of
textile products are incredibly increasing from time to time
across the globe (Yang et al. 2019). But, the production pro-
cedures and stages are very complicated with long-chained
processes (Jesudoss et al. 2020). The common raw materi-
als utilized in the factory are cotton, flax, rayon, linen, silk,
mohair, and wool from natural resources, whereas the syn-
thesized fibers are polyester, polyamide, nylon, and acrylic
obtained from petroleum derivatives (Yaseen and Scholz
2018). These materials are expected to undergo the spin-
ning, weaving, and knitting activities. Additionally, textile
industrial production procedures are mainly subjected to
the wet finishing process that could be undertaken through
different unit operations such as sizing, de-sizing, sourc-
ing, bleaching, mercerizing, dyeing, printing, and functional
finishing (Paździor et al. 2018). Dyeing of 1 kg of cotton
required 0.6 kg of salts, 0.04 kg of dyes, 150 L of water with
other chemicals such as sodium hydroxide, hydrogen per-
oxide, detergents, softening, dispersing, and fixing agents

13
Vol.:(0123456789)

(Azzaz et al. 2019). This wet process consumed a huge vol-
ume of water which resulted in the discharging of extremely
polluted wastewater into the environment. Principally, dye-
ing, and finishing processes are water-intensive tasks that
can generate a large volume of wastewater (Gilpavas et al.
2019).
The fabric production process required a large amount
of freshwater which is ranged from 30 to 308 L/kg of the
product (Pathak et al. 2020). It was also reported that water
consumption in the textile factory can reach up to 933 L/
kg of the textile product (Blus et al. 2020). The substan-
tial raising in wastewater generation in the world is mainly
attributed to the rapid growth of the manufacturing sector.
In line with this, the amount of wastewater generated from
the textile industry is rated at 200 − 350 ­m3 per ton of fin-
ished product (Mahdi et al. 2020). Concerning pollution,
about 5000 tons of dyeing stuff is annually dumped into
the environment with no management intervention (Liyana
et al. 2019). Principally, the textile industrial wastewater
is composed of textile dyes, suspended solids, mineral
oils, high amounts of chemical oxygen demand (COD),
and toxic heavy metals such as lead (Pb), chromium (Cr),
and cadmium (Cd) (Khadijah et al. 2020). However, the
main pollutant is COD which is attributed to the intensive
consumption of dyes and other chemicals in the factory
(Bouazizi et al. 2016; Azzaz et al. 2019). Generally, textile
industrial effluent is described as high-strength wastewater
with a COD concentration of up to 8,000 mg/L (Paździor
et al. 2018). The nature of the effluent is recalcitrant, toxic,
non-biodegradable, mutagenic, carcinogenic, colorful, and
environmentally unacceptable effluent which is normally
far beyond the maximum permissible discharging limit
(Yaseen and Scholz 2018). Today, the major challenge that
confronting the earth’s environment is industrial water pol-
lution that is mainly attributed to the irresponsible dumping
of industrial wastewater (Hussain et al. 2018; Kaur et al.
2018). The release of colored textile industrial wastewater
into the aquatic ecosystem can block sunlight penetration
which resulted in the reduction of photosynthetic activity.
This is highly impacting the interaction of flora and fauna in
the aquatic ecosystem (Collivignarelli et al. 2019).
The direct discharge of textile industrial wastewater is
restricted by environmental regulatory agencies (Kaur et al.
2018). The legislations of the many countries obligate tex-
tile industries to carry out effective wastewater treatment
before they discharge into the nearby water bodies. How-
ever, conventional wastewater treatment methods such as
the physicochemical methods (coagulation, flocculation,
filtration, etc.) are not effective to treat textile industrial
wastewater (Kaur et al. 2018). In contrary to this, the bio-
logical wastewater treatment method (oxidation pond, acti-
vated sludge, trickling filter, etc.) is attractive with no toxic
secondary by-products, but it only remediated the dissolved
13
International Journal of Environmental Science and Technology
pollutants. Furthermore, the biodegradability values of the
textile industrial wastewater were between 0.10 and 0.29
(Huang et al. 2017a; Paździor et al. 2018; Fito and Hulle
2020). Generally, the use of conventional wastewater treat-
ment is very limited due to the large quantities of chemicals
required, low treatment efficiencies, and huge volume of
sludge production (Lidiya et al. 2019; Núñez et al. 2019).
However, advanced physicochemical and biological waste-
water treatment technologies such as ion exchange, reverse
osmosis, membrane filtration, adsorption, and advanced
oxidation process have been applied (Núñez et al. 2019;
Ayanpeju et al. 2020). But, the drawbacks of these technolo-
gies are low thermal and chemical resistivity, membrane
fouling, energy-intensive, expensive, requiring high opera-
tional and capital inputs, needing advanced technologies,
and skilled manpower which limits their application (Fito
et al. 2019; Khadijah et al. 2020). Nevertheless, compared
to other treatment methods, adsorption is a superior and the
most promising technology (Salazar et al. 2019; Yang et al.
2019; Bedada et al. 2020).
Adsorption is environmentally friendly, economically
feasible, and efficient treatment technology (Huang et al.
2017a). Additionally, it is a flexible, efficient, simple to
design, and cost-effective treatment method (Singh et al.
2017). The most commonly used adsorbent categories
are activated carbon, zeolite, and clay matter. However,
the application of commercially activated carbon in many
nations is very limited because of the production cost which
strives and triggered the scientific community to search for
adsorbent with low cost, efficient, high carbon content and
prepared from locally available precursor materials (Fito
et al. 2020). In line with this, many efforts have been made
to develop effective local activated carbon from cassava
peel, cotton, orange peel, the bark of morinda tinctorial,
parthenium hysterophorus, the bark of the vitex negundo,
willow peat, bagasse fly ash, bamboo, wheat straw, coconut
husks, sawdust, avocado seed, and crocus sativus leaves
(Suneetha et al. 2015; Amalraj and Pius 2017; Dehghani
et al. 2018; Niazi et al. 2018; Fito et al. 2019, 2020; Rizzo
et al. 2019; Choong et al. 2020). But these adsorbents still
have severe limitations in terms of treatment performance,
preparation time, cost, regeneration challenge, and adsorp-
tion capacity. Besides that, these technologies are still
under investigation and not yet tested at the industrial level,
practically. Therefore, researchers are currently making a
paradigm shift from activated carbon to zeolite to develop
effective adsorbent.
Zeolite and clay adsorbent like pozzolana have good
adsorption efficiency compared to the activated carbon
(Titchou et al. 2020). Removal of COD from textile waste-
water using the non-carbon adsorbent was gained significant
attention (Huang et al. 2017a; Azzaz et al. 2019; Ayanpeju
et al. 2020). The preparation of new low-cost adsorbents from
International Journal of Environmental Science and Technology
bentonites precursor materials demonstrates promising results
that increase the interest of the researchers recently (Pandey
2017). Adsorption capacity, specific BET surface area, low
adsorption equilibrium, and breakthrough time are factors to
be considered during appropriate adsorbent selection (Sam-
sami et al. 2020). In this regard, bentonite material is a very
good precursor material that can be used as an adsorbent for
water and wastewater treatment technologies (Bouazizi et al.
2016). The attempts to produce cheaper adsorbents from ben-
tonite have been investigated, and encouraging dye removal
results were also obtained (Huang et al. 2017a; Ayanpeju
et al. 2020). Even though bentonite adsorbent has got special
attention in wastewater treatment, most of such adsorbents are
not suitable for organic removal unless the surface modifica-
tion is made (Meng et al. 2020). The maximum adsorption
capacity of organic modification of bentonite for removal of
rhodamine B and acid red 1 dyes from aqueous solution was
found to be 173.5 mg/g and 157.4 mg/g at the initial con-
centration of 300 mg/L at pH 9 and 8, respectively (Huang
et al. 2017b). Similarly, polyhedral oligomeric silsesquioxane-
modified bentonite was applied for methylene blue removal
from wastewater, and a maximum 157.7 mg/g adsorption
capacity was recorded (Meng et al. 2020). Another surface
modification of octadecyl trimethyl ammonium bromide was
investigated for tartrazine removal from an aqueous solution
and resulted in an efficiency of 201.0 mg/g (Sahnoun et al.
2018). Modified bentonite by Keggin cation was also applied
for pesticides (heptachlor epoxide, dieldrin, and endrin) reme-
diation, and removal up to 98% was achieved (Farghali et al.
2020). With respect to textile wastewater, maximum COD
removal of 92.5% was achieved using composite adsorbent
of bentonite, Fuller’s earth, China clay, and zeolite under
conventional approach (Patel and Vashi 2010). Finally, HCl
and ­H2SO4 functionalization in natural bentonite was carried
out which resulted in adsorption capacity of 274.7 mg/g and
266.3 mg/g for methylene blue removal, respectively (Fer-
nandes et al. 2020). These studies still indicated that there is
no intensive investigation of COD removal from real textile
wastewater through activated bentonite under different sce-
narios. Therefore, this study aimed to develop local adsorbent
from bentonite precursors and evaluate its performance for
COD removal from textile industrial wastewater using differ-
ent experimental factors such as contact time, pH, and adsor-
bent dose. Finally, the interaction of the adsorption process
was studied using a response surface methodology based on
the quadratic regression model.
Materials and methods
Adsorbent preparation
Bentonite clay sample was collected from the Ledi area in
the Afar Regional state which is located in the northeastern
part of Ethiopia. This sample was composed of ten equally
weighted samples that were collected from the sample sites
in 10-m intervals. The sample was then purified by wash-
ing with distilled water three times to remove the adhered
impurities. The solid suspension was stirred vigorously and
centrifuged to filter out the liquid. This sample was then
dried in an oven at 105 °C. The dried sample was ground
using the Schutte Buffalo Hammermill (WA6HSE Model)
and sieved using a sieving machine (IC-205/EV) at the sieve
pore of 75 µm. The bentonite activation process was per-
formed on the range of the sulfuric acid concentration (0.1
to 10 M), but in this study, the reasonable sulfuric acid
concentration of 2 M was taken with the corresponding
surface area produced. Hence, the activation of adsorbent
was carried out using a diluted ­H2SO4 solution of 2 M and
agitated by a magnetic stirrer at 180 rpm at temperatures
80ºC for 2 h of reaction time. This clay matter was soaked
into sulfuric acid in the ratio of 1:10 (10 g into 100 mL).
The activated bentonite was then washed several times with
double-ionized water until the supernatant solution is nearly
pH neutral. Then, the thermal activation was carried out by
the calcination process at a temperature of 100 °C muffle
furnace for 2 h. The different stages of the adsorbent prepa-
ration and activation are indicated in Fig. 1. Finally, the
activated bentonite was cooled and placed in the desiccator
until it was used for treatment (Huang et al. 2017a; Tayebee
and Mazruy 2018).
Adsorbent characterization
The moisture content of the adsorbent was determined
directly according to standard methods of the American
Society for Testing and Materials (ASTM), as it was also
used in many adsorption studies (Milne et al. 1990; Nure
et al. 2017; Fito et al. 2019). The bulk density of the adsor-
bent was calculated by weighing the mass of the adsor-
bent and placed into 10 c­ m3 of the cylinder. Then, the bulk
density (kg/m3) was obtained by dividing the mass of the
adsorbent by its volume. The pH of point of zero charges
­(pHpzc) was determined by adding 0.15 g of bentonite adsor-
bent into several Erlenmeyer flasks (50 mL of 0.1 M NaCl)
which was ranged in the pH of 2 to 12. The pH adjustment
was made using 0.1 M ­H2SO4 or 0.1 M NaOH solution.
Finally, the pH of the solutions was measured after 48 h,
and the p­ Hpzc was calculated from the intersection point of
pH final and pH initial curve.
13
 International Journal of Environmental Science and Technology

Fig. 1  Different stages of the bentonite activation processes indicated by letters from ‘A’– ‘D’

The adsorbent specific surface area was calculated by the Optimization of COD adsorption
BET method. The adsorbent sample of 0.4 g was placed in
three preparation sample tubes which were degassed under Adsorption experiments were carried out at room tempera-
vacuum condition at 100 °C for 2 h. The surface area was ture (22 ± 2 °C) under batch mode delivery. COD removal
determined based on the isotherms of adsorption and des- was taken as response variables, while the three selected
orption of nitrogen gas at atmospheric pressure of 700 mm experimental factors with the three levels (contact time,
using a surface area analyzer (SA-9600 Horiba). The pH, and adsorbent dosage) were used (Table 1). The lev-
adsorbent surface morphology was studied using scanning els of the factors were fixed based on previous experimen-
electron microscopy (SEM). The analysis was carried out tal studies (Hegazy et al. 2014). The maximum predicted
using the machine (SEM INSPECT F 50) at the 10 kV and COD removal was studied using the quadratic regression
beam size of 7.0 with magnifications of 3000X and 9000X model and response surface methodology. Essentially,
(Hegazy et al. 2014; Nure et al. 2017). The functional group this adsorption was performed with the help of a factorial
on the surface of the adsorbent was studied using the FTIR
spectrophotometer which was scanned in the range of 4000
to 400 ­cm−1 (PerkinElmer 65 FTIR) (Hegazy et al. 2014; Table 1  The three selected adsorption factors with their respected
Nure et al. 2017). Finally, the mineral species of activated levels under full factorial design
bentonite was evaluated using X-ray diffraction techniques Variables Low (−) Middle (0) High ( +)
which is a powerful non-destructive technique that char-
acterizes the presence of crystalline materials with a dif- pH 2 6 10
fraction angle of 2θ from 2 to 80º using OLYMPUS BTXH Time (min) 30 60 120
X-ray diffraction instrument. Adsorbent dose 0.5 1.25 2
(g/110 mL)

13
International Journal of Environmental Science and Technology
experimental design of ­33 under three factors with the three
levels which are intended to generate 27 runs. COD removal
was expressed as an independent variable that was evaluated
using the adsorption performance in percentages (%). The
lower level of each factor was designated as “ − 1,” the mid-
dle value was represented by “0,’’ and the higher level was
by “ + 1.” However, the maximum number of adsorption
experiments was set to 20 runs using experimental design
software under the optimization approach. The total num-
ber of the experiments was 60 runs which were obtained
by replicating each experiment. But, the average value was
reported. The textile industrial effluent sample was col-
lected from the Ketema Kebede textile factory of Addis
Ababa, Ethiopia. The COD concentration of the effluent was
569 ± 23 mg/L which was later used throughout the study
period, whereas the effluent pH was found to be 6 ± 0.3.
While the adsorption experiment was performed at the labo-
ratory, the adsorbent residue and the supernatant solution
were separated using the centrifugal process at 3200 r/min-
ute for 20 min using the centrifugal machine (Pro Analytical
C2004 Centrifuge of UK). Finally, the main and interaction
effects of the adsorption were evaluated using the quadratic
regression model.
The COD concentration of textile industrial wastewater
was determined using the HANNA digester and COD ana-
lyzer according to the standard methods for the examination
of water and wastewater. The COD removal percentage was
calculated using Eq. 1
( )
CODi − CODf
%R = X100 ( 1)
CODi
where %R is the COD removal percentage, CODi (mg/L) is
the initial COD concentration, and ­CODf (mg/L) is the final
COD concentration (APHA 1998).
The regression analysis was carried out using the quad-
ratic model equation and response surface methodology.
The main and interaction effects on the COD removal were
described. Compared to the linear and cubic regression
models, the quadratic regression model was well described
as the experimental data. The detailed explanation is given
by Eq. 2.
YCOD = 0 + 1 A + 2 B + 3 C + 11 A2 + 22 B2 + 33 C2 + 12 AB + 13 AC + 23 BC(2)
where ­YCOD is the predicted COD removal, and A, B, and C
are the contact time, pH, and adsorbent dosage, respectively.
But β0 is intercepted, β1, β2, β3 are linear coefficients, β11,
β22, β33 are the squared coefficients, and β12, β13, β23 are the
interaction coefficients. Finally, the ANOVA was applied for
the quadratic regression model, adsorption treatment.
Results and discussion
Characteristic of the activated adsorbent
The moisture content of activated bentonite was found to
be 13% which was reasonably low as compared to simi-
lar studies. In another study, the local activated bentonite
moisture content of 17% was reported (Nure et al. 2017).
The specific surface area of the bentonite was found to be
265 ­m2/g. This is a relatively very high amount of surface
area for the locally prepared adsorbent. Concerning the sur-
face area, the activated bentonite adsorbent was very good
which can adhere to sufficient adsorbate from the solution.
In another study of bentonite adsorption, the maximum spe-
cific surface area of 138.4 m ­ 2/g was reported (Taha et al.
2016). This indicates the current specific surface is a little
bit higher than this finding, showing more available active
sites that were ready for the adsorption process. The pH
point of zero charges ­(pHpzc) of adsorbents is the pH at
which the net charge of the total particle surface is equal to
zero. The plot to assess the point of zero-point charges for
bentonite is demonstrated in Fig. 2. The p­ Hpzc of the raw
and activated bentonite was determined to be 6.9 and 2.3,
respectively. The pH greater than the zero-point charges is
expected to adsorb cationic pollutants, whereas the pH less
than the zero-point charges can adsorb anionic pollutants.
But, both the cationic and anionic pollutants in the textile
industrial wastewater can contribute to the concentration
of the COD.
The surface structure of bentonite was studied before
and after the activation using scanning electron microscopy
indicated in Fig. 3. In both cases, the surface magnification
was 50 µm and the difference between the two surfaces was
observed. During the activation process, smaller pore sites
were occurred because the impurities (water molecule) are
the elimination of the impurities that could be replaced by
the cations of H­ + ions. These physio-chemical reactions
regulate the structure of the clay as the pores open up and
the clay surface appears to be extra porous and homogene-
ous. Generally, the activated bentonite turned out to be dark
which indicates the passage of electrons beam through the
(2)
pores created following the activations. Due to the rough-
ness of the surface on the raw bentonite, the electron beam
reflected the detector; as a result, a bright image was pro-
duced. This was also evidenced by the increment of the
adsorbent surface area.
Characterizing mineral species of the raw and activated
bentonite was studied using an X-ray diffraction (OLYM-
PUS BTXH) instrument equipped with Cu Ka radiation
13
 International Journal of Environmental Science and Technology

B
A 12
pH final
pH Final Y=X
12 Y=X
10
10

pH final
pH Final

6
6

4 4

2 2

2 4 6 8 10 12 2 4 6 8 10 12
pH Initial pH Initial

Fig. 2  The determination of the pH of the point of zero charges for a raw bentonite, b activated bentonite

Fig. 3  The surface morphology of the adsorbent a raw bentonite and b activated bentonite

(40 kV,40 mA). The diffraction structure of the raw and
activated bentonite changes in the diffractogram of the acti-
vated bentonite is indicated in Fig. 4. The significant dif-
fraction peaks X-ray diffraction and corresponding angles
were 620 montmorillonite (Mo), 20.8° opal, 23.7°hematite
(H), 26.5° quartz (Q), 27.6° feldspar (F), and 50.2°calcite
(Ca) found for both raw and activated bentonite. On the
surface of activated bentonite, additionally two new and
significant peaks at 32° and 45° were observed which are
corresponding to the quartz. It was pointed out a decline
in the intensities of montmorillonite and other impurities
except for quartz and feldspar. This implies the components
are resistant to this activation, but the activation effect was
more pronounced in montmorillonite phases (Huang et al.
2017a). It can be concluded that bentonite is crystalline
with a significant amount of inorganic constituents (Nure
et al. 2017).
FTIR analysis of activated bentonite was done which
was later used for COD removal. The major spectra of the
analysis are indicated in Fig. 5. The bentonite spectrum
bands at 3450 and 1630 ­cm−1 are assigned to the stretching
and bending vibrations of the water molecule of hydration

13
International Journal of Environmental Science and Technology

Fig. 4  X-ray diffraction picture Activated Bentonite

to identify the crystalline nature Q Raw Bentonite
of bentonite adsorbent Q
F

Mo Op
H Q
Mo
Ca Mo

Intensity
Q

Mo Op
Mo H MO
Ca Mo

0 10 20 30 40 50 60 70 80
2-Thetha

Fig. 5  An infrared spectrum of

raw a and activated b bentonite

13
 International Journal of Environmental Science and Technology

­(OH− groups), which are embedded on the bentonite sur- 76.5% was recorded at a contact time of 120 min, pH of
face, whereas the hydroxyl groups coordinated to octahedral 10, and adsorbent dosage of 2 g, whereas the minimum
­Al3+ cations are point out at stretching and vibration band of removal was found to be 38.8% at the optimum point of the
3620 ­cm−1. Moreover, the wavelength found at 3620 ­cm−1 contact time of 30 min, pH 2, and adsorbent dosage 0.5 g.
assigned to O­ H− vibration which indicated a moderate fall Lowering the values of the three factors at a time resulted
in the absorption band as a result of octahedral cations in a reduction of the adsorption performance significantly.
removal, thus resulting in the loss of water and hydroxyl But increasing the three factors at a time increases the
groups assigned to them. The spectra found at 1030 ­cm−1 COD removal by 37.7% since the change in both the main
indicate the inorganic structure which establishes three- and interaction effects enhanced the adsorption efficiency.
dimensional networks of amorphous silica that might be This maximum removal efficiency was very encouraging
exposed to more adsorption sites. The band vibrations asso- since it reduced the initial COD concentration from 569
ciated with Si–O-Al at 520, 698, and 784 ­cm−1 demonstrate to 140 mg/L. As a consequence of this adsorption experi-
the incomplete exhaustion of Al, Mg, and Fe from the clay ment, about 456 g of chemical oxygen demand was removal
structure as per the modification of chemical composition. from 1L of textile industrial wastewater. The Ethiopian
Furthermore, the quartz spectrum band was also found at Ministry of the Environment, Forest, and Climate Change
the 698 ­cm−1. Normally, a silicate structure is known for has established maximum permissible discharging limits
stretching and vibration of Si–O bands at 1030 ­cm−1. The for industrial effluent for certain parameters. Accordingly,
spectrum bending at 460 ­cm−1 was noticed for Si–O–Al 250 mg/L of COD concentration is the maximal permis-
and (octahedral) for the silicon-based functional group of sible discharging limit for textile industrial wastewater. As
Si–O–Si. per this standard, the textile industrial wastewater is safe
to be discharged into water bodies or another ecosystem.
Adsorption performance of COD removal Therefore, this treatment is promising to be scaled up at the
industrial level, but it is more advisable to check first the
The experiment and predicted values of the COD removal treatment experiment at the pilot scale.
percentages from textile wastewater are shown in Table 2.
In the adsorption experiment, maximum COD removal of
Development of regression model equation
Table 2  Adsorption performance for COD removal percentages of
experimental and the predicted values The quadratic regression model COD removal is described
by Eqs. (2). In this study, several regression analyses such
Run Contact pH Dosage (g) COD Predicted
time (min) Removal COD removal as the linear, interactive, quadratic, and cubic models were
% % checked. The fitness of the models was tested using the
sequential model sum of squares and model summary sta-
1 30 2 0.5 38.8 39.6
tistics methods. Then, the sequential model sum of squares
2 120 2 0.5 42.1 41.9
has used the p value for model fitness among the regres-
3 30 6 2 62.2 63.3
sion equations, whereas the model summary statistics
4 30 6 1.25 60.1 61.0
method is used the regression coefficient of determination
5 30 2 1.25 56.4 54.5
­(R2). Accordingly, in both aspects, the quadratic regression
6 120 2 1.25 58.4 60.2
model was best described the experimental data at the p
7 60 6 0.5 57.7 57.9
value of 0.0001 and ­R2 0.98. This quadratic model was used
8 120 6 1.25 73.8 72.6
to determine the predicted value of the COD removal. But,
9 120 6 0.5 61.9 59.3
the interaction values of A ­ 2 (contact time), B
­ 2 (pH), and
10 60 10 1.25 67.3 67.8 2
­C (adsorbent dose) which represented the quadratic terms
11 30 10 0.5 53.9 52.9
are insignificant and excluded from this quadratic equation.
12 60 6 0.5 58.2 57.9
13 120 10 1.25 74.8 75.4 YCOD =71.4 + 5.80A + 4.6 B + 7.80 C
14 120 10 2 76.5 76.0 + 3.0AB + 1.6 AC − 5.0BC (3)
15 60 6 0.5 56.4 57.9
16 60 2 2 68.5 69.0 where ­YCOD is the COD removal, A is the contact time, B is
17 60 10 1.25 69.0 67.8 the pH, and C is the adsorbent dosage, whereas the AB, AC,
18 120 10 0.5 65.6 67.2 and BC refer to interaction effects of the contact time with
19 120 6 1.25 72.1 72.6 pH, the contact time with adsorbent dose, and the pH with
20 60 2 2 70.1 69.0 adsorbent dose, respectively.

13
International Journal of Environmental Science and Technology

In ANOVA, the p value is used to judge whether the
main and interaction effects are statistically significant or
not, whereas the regression coefficient of determination
­(R2) is the degree of the response variable that is explained
by the given regression model (Nure et al. 2017). In this
regard, these interaction effects were excluded from the
quadratic regression equation since the p values for these
factors in the regression analysis were greater than 0.05 at
which the 95% confidence interval was fixed in the analysis.
The detailed statistical analysis of adsorption ANOVA is
indicated in Table 3. Statistical analysis of COD removal
resulted in the coefficient of determination ­R2 of 0.98, and
the adjusted R ­ 2 was 0. 97 which was in close agreement
with the predicted ­R2 that was 0.84. This is revealed by the
good fitness of the predicted and experimental results.
Generally, any interaction effects with p values greater
than 0.05 were excluded from the regression equation, indi-
cating that the insignificance of the terms in the model.
The regression coefficient of determination (­ R2) in this
study was 0.98 which implies 98% of COD removal is well
explained by this quadratic equation. Besides, the coeffi-
cient of determination (­ R2) is much closer to 1, implying
the model was the perfect fit with the experimental data.
Regarding the coefficient of the regression term, the sign
of the coefficient refers to the direction of impact, whereas
the magnitude of the coefficient is represented the degree of
the influence of the main and interaction effects. Precisely,
the positive coefficient of terms indicated the synergistic
effect on the response variable, while the antagonistic effect
was defined by the negative value of the factors (Okoro
et  al. 2019). Hence, the degree of influences on COD
removal was in the order of C > A > BC > B > AB > AC,
but the interaction effect between the B and C suppressed
the response variable. In this regard, increasing the values
of the adsorption factors increases the removal efficiency
of COD and vice versa, but the removal was inversely pro-
portional to the interaction effect of B and C. The pH has a
significant effect as a result of electrostatic attraction force
and reaches equilibrium at pH 10. Generally, COD removal
was highly influenced by the value of the adsorbent dose
but insignificantly affected by the interaction effect of the
contact time and adsorbent dose. This indicates that the
regression model provides an excellent explanation for the
relationship between the independent and response vari-
ables. Generally, this model has sufficient reasons to con-
clude the goodness of fit.
The interaction effects on COD removal
The interaction effect of pH and contact time
The three-dimensional response surface plots were used to
estimate combinations of the independent variables on COD
removal. The interaction effect of contact time and pH on
adsorption was investigated, and the pattern of the inter-
action is demonstrated in Fig. 6. This concept was elabo-
rated with the response surface plots and its corresponding
contour plot for COD removal. Increasing the contact time
will increase the removal efficiency of COD to a significant
level. The maximum COD removal efficiency of 75% was
observed at the interaction effect between the interaction of
contact time of 70 min and a pH of 6 which was depicted
by the darkest red region of the plots. It was observed that
the interaction effect is positively enhanced the removal
efficiency of the COD removal. Under the triplicate experi-
mental condition, the maximum COD removal was 76.5%,
whereas the predicted removal value was 75%. This showed
that the predicted COD removal efficiency and the experi-
mental COD removal efficiency have a good agreement.
Hence, the maximum removal point determined by the
response surface methodology was successfully described
the experimental facts, and the regression quadratic model
was appreciated.

Table 3  ANOVA for response Source Sum of Squares df Mean Square F-value p-value Status
surface quadratic model for
COD removal Model 1898.36 9 210.93 76.92  < 0.0001 Significant
A-Contact time 334.97 1 334.97 122.15  < 0.0001 Significant
B-pH 216.09 1 216.09 78.80  < 0.0001 Significant
C-Adsorbent Dosage 550.27 1 550.27 200.66  < 0.0001 Significant
AB 64.33 1 64.33 23.46 0.0007 Significant
AC 14.19 1 14.19 5.17 0.0462 Significant
BC 133.33 1 133.33 48.62  < 0.0001 Significant
Residual 27.42 10 2.74
Lack of Fit 21.08 5 4.22 3.33 0.1066
Pure Error 6.34 5 1.27
Cor Total 1925.78 19

13

Fig. 6  The interacting effect of pH and contact time on COD removal described by response surface and contour plots
The interaction effect of adsorbent and contact time
In this subsection, the interaction effect of the adsorbent
dose and contact time on COD removal performance
was investigated and the trend of the interaction result is
depicted in Fig. 7. This interaction was positively enhanced
the adsorption performance to a certain extent at the steady
state and then after expected to be declined. This was vis-
ibly observable from both the surface and contour plots.
The maximum COD removal efficiency of 75% was found at
the optimum condition of the contact time of 85 min and an
adsorbent dose of 1.6 g. It can be seen from the sketch that
13
International Journal of Environmental Science and Technology
both the pH and adsorbent have a positive effect on COD
removal from textile wastewater. After this steady-state
condition, increasing both the contact time and adsorbent
dose, no significant change in the removal of the response
variable was observed.
The interaction effect of adsorbent and pH
COD removal was studied as the function of the interaction
effect of the pH and adsorbent dosage and the contour and
response surface plots were obtained using the response
surface methodology approach (Fig. 8). But, separately
International Journal of Environmental Science and Technology
Fig. 7  The interacting effect of adsorbent dose and contact time on COD removal by the response surface and contour plots
both the pH and adsorbent dose were influenced the
COD removal positively. This implies that COD removal
increased with the increase in adsorbent dosage and pH.
Normally, an increase in percentage COD removal due to
the increase in dosage increases the availability of more
surface area and accommodates more adoption area. But,
it was observed that the higher percentages of the COD
removal have occurred at a lower interaction effect of the
pH and dosage. The pH has a significant effect as a result
of electrostatic attraction force which reaches equilibrium
condition at the steady-state condition. The maximum COD
removal of 70% was recorded at the predicted value of pH
5.5 and adsorbent dosage of 1.3 g. The removal of the COD
started to decline at the end of this steady-state condition as
the result of too many OH- ions on the solution that resists
the flow of organic pollutants.
Conclusion
This study examined the adsorption efficiency of COD
removal from textile industrial wastewater using activated
bentonite under three independent variables. Bentonite
material was activated using sulfuric acid and thermal
13

Fig. 8  The interacting effect of adsorbent dose and pH on COD removal by the response surface and contour plots
processes at a high temperature. The activated bentonite
was characterized, and the maximum specific surface area
of 265 ­m2/g was recorded. Furthermore, the results of the
X-ray diffraction and FTIR spectra showed that benton-
ite was a crystalline structure mainly composed of mont-
morillonite. This is indicated that the bentonite material
is a good precursor for adsorbent development. Textile
industrial wastewater was characterized by a COD con-
centration of 569 ± 23 mg/ and a pH of 6 ± 0.3. Through
analysis of the response surfaces methodology and quad-
ratic regression, each main and interaction effects have
a significant impact on adsorption efficiency, the COD
removal. Maximum COD removal of 76.5% was found at
13
International Journal of Environmental Science and Technology
the optimum condition contact time 120 min, pH 10, and
adsorbent dosage 2 g, whereas the predicted COD removal
value of 76% was observed. The predicted values of COD
removal value were perfectly fitted with the experimental
values, implying the model was satisfactorily describing
the experimental reality. It is confirmed that response sur-
face methodology can be applied to optimize the adsorp-
tion of COD from textile wastewater using activated ben-
tonite adsorbent. In general, it can be concluded that the
activated bentonite is a promising adsorbent and potential
to be implemented at the industrial level for water and
wastewater remediation.
International Journal of Environmental Science and Technology
Acknowledgements  We would like to thank Ethiopian Road Authority
(ERA) for the research fund and Addis Ababa Science and Technology
University (AASTU) for the research facilities.
Funding  This research work was supported by Ethiopian Road
Authority.
Availability of data and materials  All data are fully available without
restriction.
Code availability  Not applicable.
Compilance with ethical standards  6740. https://​doi.​org/​10.​1016/j.​arabjc.​2020.​06.​027
Conflict of interest  The authors declared that they have no conflict
of interests.
Consent for publication  Not applicable.
Ethics approval  Not applicable.
Consent to participate  Not applicable.
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