Bioresource Technology Reports 24 (2023) 101602

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Bioresource Technology Reports

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Degradation of ammonaical nitrogen (NH3-N) in leachate by zinc oxide

loaded activated carbon: Process parameters modelling and optimization
through RSM design
Kulbir Singh a, b, Rajesh Kumar Lohchab b, *, Vikas Kumar c, d, Ajay Kumar e
a
Department of Civil Engineering, MM Engineering College, Maharishi Markandeshwar (Deemed to be University), Mullana, Ambala 133207, Haryana, India
b
Department of Environmental Science & Engineering, Guru Jambheshwar University of Science and Technology, Hisar 125001, Haryana, India
c
Department of Biotechnology, Maharishi Markandeshwar (Deemed to Be University), Mullana, Ambala, Haryana 133207, India
d
Department of Microbiology, International Medical School, UIB, Almaty, Kazakhstan
e
University Center for Research & Development (UCRD), Biotechnology Engineering & Food Technology, Chandigarh University, Gharuan, Mohali 140413, Punjab,
India

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

Keywords: In this study, NH3-N will be removed from a leachate sample using a zinc oxide (ZnO) nanocomposite that is
Leachate combined with corncob-activated carbon. A simple impregnation and pyrolysis procedure was used to create the
Corncob nanocomposite, and BET, XRD, and FTIR studies were used to validate its creation. Under optimized conditions
ZnO nanoparticle
pH 7, temperature 30◦ C, adsorbent dose 1.50 g/50 L, and a contact time of 160 min, resulting the highest NH3-N
Adsorption
removal efficiency of 73.5 %. The experimental data were successfully fitted to various isotherms (Hill,
Ammonia Nitrogen removal
Koble–Corrigan, Redlich–Peterson, Khan and Toth) and Pseudo-second-order kinetics were found suitable for
NH3-N reduction. Furthermore, the lower value of RMSE (0.47) obtained through RSM-CCD indicated a minimal
difference between the experimental (73.5 %) and model-based (71.2 %) removal percentages of NH3-N, con­
firming the model’s suitability for adsorption method. The promising results of the adsorption study provide
valuable insights and indicating the potential of nanocomposite material for sustainable leachate treatment.

1. Introduction
Landfill leachate is the liquid resulting from the combination of
waste decomposition in landfills and the infiltration of rainwater into
the waste (Oliveira et al., 2014; Yang et al., 2023). This leachate con­
tains substantial quantities of hazardous chemicals, including heavy
metals and nitrogen-enriched compounds (Detho et al., 2021; El-Saad­
ony et al., 2023; Naji et al., 2020). The formation of ammoniacal ni­
trogen has made landfill leachate (LFL) a recurrent problem for landfill
operators for many years (Detho et al., 2022). Due to the delayed
leaching of nitrogen-generating wastes, these high ammoniacal nitrogen
concentrations persist for longer periods of time (Singh et al., 2023;
Yuan et al., 2022). Unfortunately, landfills lack significant and reliable
transformation mechanisms for NH3-N (Haslina et al., 2021). The
leachate typically contains such high concentrations of organic and
inorganic materials that even a minute quantity of it can contaminate
groundwater supplies (Shadi et al., 2020; Singh, 2021; Beinabaj et al.,
2023). This ineffective landfill management and disposal practices pose
serious threats to ecosystems, surface water quality, and public health
(Zamrisham et al., 2023). Consequently, waste management in various
areas has become increasingly concerned with proper leachate
treatment.
For the treatment of fresh leachate, biological methods are preferred,
though they are unsuitable for dealing with old or stabilized leachate (Li
et al., 2018; Zamrisham et al., 2023b). Here, the direct application of
biological means to leachate with high ammoniacal nitrogen concen­
trations leads to low elimination rates due to the toxicity and inhibition
of the nitrification process. Therefore, to effectively remove bio-
recalcitrant organic waste, physiochemical procedures are required for
the biologically treated effluent. As a result, physicochemical treatment
has gained popularity in landfill leachate treatment. The use of various
adsorbents to remove ammoniacal nitrogen has been studied by a
number of researchers, with an increasing interest in doing so using
reasonably priced and commercially available materials (Aziz et al.,

* Corresponding author.
E-mail address: rajeshlohchab@gmail.com (R.K. Lohchab).

https://doi.org/10.1016/j.biteb.2023.101602
Received 3 June 2023; Received in revised form 22 August 2023; Accepted 23 August 2023
Available online 25 August 2023
2589-014X/© 2023 Elsevier Ltd. All rights reserved.
K. Singh et al. Bioresource Technology Reports 24 (2023) 101602

2004; Bai et al., 2021; Detho et al., 2022). For instance, Wang et al. 2. Methodology
(2017) developed three types of biochar, including commercial acti­
vated carbon, as well as biochar derived from pyrolysis of rice husks and Analytical-grade materials from Sigma-Aldrich, including zinc oxide
nutshells, these biochar demonstrated significant adsorption capabilities nanoparticles (<100 nm), phosphoric acid (85 %), ethanol (99.9 %), and
for (NH+ 4 -N) in biogas slurry. Viglašová et al. (2020) reported that concentrated nitric acid (≥90.0 %), along with hydrochloric acid, were
chemically modified biochar made from bamboo biomass effectively utilized in the synthesis of the adsorbent. An agro-waste corncob was
removed nitrogen compounds from water in a dose-dependent manner. collected from local market, Hisar and subjected to a cleaning process to
Moreover, previous studies have identified the synthesis of activated remove impurities and contaminants. Ash, volatile, and moisture con­
carbon utilizing corncob agrowaste (Ahsaine et al., 2018). It has been tents of raw corncob were determined using the proper ASTM tech­
determined that adding potassium hydroxide and ferric chloride to niques. The raw corncob underwent an elemental analysis using the
activated maize stover biochar progressively increases the presence of Elementar Vario Micro Cube to determine its levels of Carbon,
oxygen-containing functional groups, improving the biochar’s ability to Hydrogen, Nitrogen, and Sulfur. In an anaerobic bioreactor, leachate
adsorb NH4 + -N ammonium nitrogen (Wang et al., 2023). Furthermore, sample was prepared from solid waste at laboratory scale. The leachate
Vu et al. (2018) exhibited that activated carbon consequent from collected, identified, and used for post-treatment following stabilization
corncob exhibited a greater capacity for adsorbing ammonium from (Table 1).
groundwater using batch and column experiments.
In recent years, researchers have been investigated the application of 2.1. Synthesis and characterization of adsorbents
activated carbon composites incorporated with metal oxide to enhance
their adsorption properties. This innovative technique provides various After being pulverized and sieved, the corncob was placed in a tube
advantages, including increased active sorption locations, improved furnace with a nitrogen flow. After that, the phosphoric acid was applied
thermal stability, and greater production of biochar. Studies carried out to the carbonized corncob in a 1:3 ratio. The activated carbon generated
by Liu et al. (2020), Pourali et al. (2023) and Rodriguez-Narvaez et al. from the corncob underwent pyrolysis at 700 ◦ C for 90 min in the N2
(2019) have reported the effectiveness of this approach. For instance, flow tube furnace, as described in Singh et al. (2022). To dissolve 0.5 g of
Abdullah et al. (2023) utilized a composite of TiO2 with activated carbon ZnO nanoparticles, a 1:1 solution of ethanol and water was used; 1.5 mL
sourced from corncobs to effectively break down ceftriaxone sodium of diluted HNO3 was then added to make sure the nanoparticles were
antibiotic found in pharmaceutical wastewater. Despite these promising distributed evenly. 1 g of corncob activated carbon was added to this
outcomes, it appears that corncob-based activated carbon loaded with solution and vigorously stirred over the course of 2 h with a stirrer. The
ZnO has not yet been explored for the removal of NH3-N from leachate. final product, ZnO@CCAC, was obtained after a 60-min bath sonication.
Further investigation into this particular domain could be beneficial for The composites were then heated to 200◦ C during calcination to
prospective applications in leachate treatment. securely bind the nanoparticles inside the porous pores of the activated
In this particular investigation, a highly efficient and cost-effective carbon.
corncob agro-waste was utilized for creating an adsorbent material. The synthesized adsorbent ZnO@CCAC underwent several charac­
This was accomplished through a two-step procedure that involving terizations, including Brunauer–Emmett–Teller (BET) analysis, X-ray
phosphoric acid for chemical activation and subjecting the material to diffraction (XRD), and Fourier Transform Infrared Spectroscopy (FTIR).
higher temperatures for physical activation. Subsequent to this, zinc BET surface area analysis of ZnO@CCAC had been performed by using
oxide nanoparticles were incorporated into the activated material, the BET liquid nitrogen adsorption-desorption method (Quantachrome
resulting in the synthesis of ZnO@CCAC adsorbent. The ZnO@CCAC Instruments, ASI-CI-11). A sample tube containing 0.0335 g of dried
was extensively characterized to assess its properties, and its potential sample was kept at 77.3 K for 478.4 min to get rid of the volatile ma­
for eliminating NH3-N from leachate samples was evaluated. The terials and humidity. Pore density and surface area of adsorbents were
exclusive combination of corncob activated carbon and zinc oxide find out using the N2 adsorption-desorption isotherms. Powder X-ray
nanoparticles was an innovative approach aimed at enhancing the diffraction data generated with Cu K radiation (λ = 1.5418 Å) in the 2θ
adsorption capacity for NH3-N removal from leachate. Remarkably, this range of 10◦ to 80◦ were analysed using the RigakuMiniflex-II diffrac­
particular combination had not been explored before, making it a novel tometric, with 2◦ /min scanning rate. The FTIR of adsorbents was ana­
and unexplored approach for the leachate treatment. lysed in the ranges of 400–4000 cm− 1 to 1 cm− 1 using a Perkin Elmer
Consequently, this novel material may hold great promise for more instrument to verify the effectiveness of ZnO in activated carbon syn­
effective leachate treatment techniques. For the experimental setup, the thesis. A little amount of powder sample was combined with KBr salt in
Response Surface Methodology (RSM) was utilized. RSM is a widely the proper proportions, and the prepared homogenous mixture was
recognized and efficient approach renowned for optimizing diverse pressed onto the disc. Through the use of an FTIR spectrophotometer,
processes in a cost-effective manner (Amouei et al., 2016; Pourali et al., the produced pellets of several materials were evaluated.
2022). The Central Composite Design (CCD) method, a quadratic model,
was employed within RSM to determine the influential parameters by
conducting necessary designs (Singh et al., 2021). Through this
approach, we optimized and predicted the best response value while Table 1
evaluating the effects of independent variables on NH3-N removal per­ Characterization of leachate sample after stabilization through the bioreactor.
formance. In addition to the above, our study encompassed various at­ Parameters Values Parameters Values
tributes of NH3-N removal from leachate using adsorption approaches.
pH 6.2 ± 0.21 Na+ 312 ± 2.3
This included kinetics, thermodynamic studies, and equilibrium iso­
EC (dS m− 1 or mS cm− 1) 16 ± 0.91 PO3−4 65 ± 0.9
therms, all of which were thoroughly investigated to identify key aspects Turbidity 63 ± 2 Ca2+ 652 ± 1.7
of the process. Through this investigation, the study aims to contribute COD 9250 ± 158 Mg2+ 190 ± 2.8
to more effective and sustainable leachate treatment methods, BOD 2420 ± 40 SO2−4 150 ± 1.1
addressing the longstanding challenge of high ammoniacal nitrogen BOD5/COD 0.26 Cl− 940 ± 18
2+
Alkalinity 3200 ± 34 Fe 25 ± 1.1
concentrations in landfill leachate and its associated environmental Total dissolved solids 9321 ± 172 Zn 3.47 ± 0.2
impacts. Fixed solid 94 ± 3 Co 0.58 ± 0.07
Volatile solid 304 ± 5 Ni 0.34 ± 0.04
NH3-N 735 ± 9 Pb 0.99 ± 0.08
Pb 0.99 ± 0.08 Cd 0.79 ± 0.09

2
K. Singh et al.
2.2. Batch adsorption experiment
The ability of prepared adsorbent ZnO@CCAC to remove the NH3-N
having initial concentration of 735 mg/L in leachate sample was
examined in batch mode conditions. The various parameters of the study
varies from pH 2 to 10, time duration 20–200 min., dose 5–50 g/L, and
temperatures in the range of 25 to 40 ◦ C. The pH level of solutions was
kept constant by adding (0.1 M) hydrochloric acid (HCl) and sodium
hydroxide (NaOH) and a pH metre was used to track them. To minimise
interference with NH3-N measurement, the adsorbent mixtures were
filtered, and the remaining concentration of NH3-N was calculated using
a titrimetric (4500-NH3) method. The NH3-N reduction (R) for each
condition is determined by calculating the difference between the initial
concentration Co (mg/L) and the final concentration C (mg/L) of NH3-N
in the leachate sample. It is expressed as a percentage of the reduction in
initial concentration, calculated as ((R = (Co − C) / Co) × 100). Simi­
larly, the adsorption capacity at equilibrium qe (mg/g) is calculated
using the equation (((Co − C) × V / M) × 100), where V (L) is the
sample’s volume and M (g) is the adsorbent’s mass.
Nonlinear equations were included into monolayer and multilayer
adsorption techniques using various isotherm models (Supplemen­
tary1). For the investigation of NH3-N adsorption rate, using linear plots
the adsorption kinetic models were applied. This study used a central
composite design of the response surface approach to investigate the
relationship between adsorption of NH3-N on the surface of ZnO@CCAC
and its input parameters. Güven et al. (2008) suggest that CCD proves to
be a highly efficient design, particularly suited for sequential experi­
mentation. This method enables researchers to gather a significant
amount of information and effectively test the lack of fit, especially
when an ample number of experimental values are available. Using
Design-Expert® software 12 program, CCD-RSM was used to build
design for removing NH3-N of leachate sample. The study’s findings
showed that four major elements, including pH (4–9), dosage
(1.25–2.25 g/50 mL), duration (100–200 min), and temperature
(25–40 ◦ C), had an impact on the outcome. These variable ranges were
carefully chosen based on experimental data to ensure meaningful
observations.
There were five levels for each independent variable (− 1, 0, +1, − α,
+α). The total number of experiments conducted for the four factors was
30, which was determined using the formula 2k + 2 k + 6, where k
represents the number of factors (k = 4). Twenty-four experiments were
conducted with six replications each to assess the pure error. Based on
the level for these components, the pure quadratic polynomial Eq. (1)
was used to evaluate the interactions between independent factors and
responses (Bezerra et al., 2008).
∑
k ∑
k ∑
k ∑
k
Ypred = β0 + β i xi + βij xi xj + β i i x2 + ei
i=1 i=1 j=i+1 i=1
Where Ypred represents the predicted response variable, xi and xj are the
input variables, βo is a constant coefficient, βi, βii, βij are the interaction
coefficients for the linear, quadratic, and second-order terms respec­
tively; and ei denotes the error term. The quality of the polynomial
model’s fit was determined by the correlation coefficient (R2). The main
indicators demonstrating the significance and adequacy of the model
include the model F-value (Fisher variation ratio), adequate precision
and the probability value (Prob>F) (Bashir et al., 2010). In order to
examine multiple responses concurrently, the analysis of variance
(ANOVA) and model graphs were employed to investigate the outcomes
of NH3-N removal using the ZnO@CCAC adsorbent. Also, RMSE (Root
Mean Squared Error) was employed to assess the accuracy of a predic­
tive model. This metric calculates the average squared difference be­
tween the predicted values and the actual values. The formula is as
follows:
Bioresource Technology Reports 24 (2023) 101602
√̅̅ / )
RMSE = (Σ(predicted value − actual value)2 n (2)
2.3. Reusability of synthesized adsorbent
The nanoparticles loaded activated carbon (adsorbent) was recycled
and utilized again in the adsorption procedure. The organic material
that had been coated with spend adsorbent (1 g) was rinsed with HCl at
various concentrations (0.05, 0.1, and 0.15 M), then shaken for 180 min
at 150 revolution per minute (rpm). The adsorbents that had been
washed in acidic water were neutralized by rinsing them with distilled
water and then being dried in a hot air oven. Worn adsorbents could be
reused for up to three more NH3-N reduction cycles.
3. Results and discussions
3.1. Characterization of adsorbents
The analysis showed that raw corncob contains high carbon (45.90
%) and volatile content (75.23 %) as compared to low ash content (0.8
%). Because of this, it is better suited for creating porous activated
carbon. The ZnO@CCAC adsorbent porous nature were analysed using
N2 adsorption-desorption technique (Fig. 1a). The activation of adsor­
bent was done using phosphoric acid, specify better pore development in
microporous and mesoporous area. At isotherm IV, the differential
pressure between capillary condensation and evaporation caused the
formation of the H4 hysteresis loop. (Ramirez-Gutierrez et al., 2020a).
The analysis reports that ZnO@CCAC possesses a specific surface area of
148.3 m2/g, an average pore size of 3.35 nm, and a total pore volume of
0.157 cm3/g.
Additionally, X-ray diffraction was utilized to analyse the crystal
behavior of two distinct adsorbents created, i.e. 1CC (activated corn
cob) and 2CC (ZnO nanoparticle loaded corn cob). The two wide peak
situated at 24.4◦ and 43.2◦ consistent to the diffraction plane of (002)
and (100) were displayed in the 1CC spectrum. (Fig. 1b). These broad
peaks shown the carbonaceous crystalline structure and good alignment
layers (Kumar and Jena, 2016). The discovery of diffraction peaks at 2
values of 31.9◦ , 34.2◦ , 37.6◦ , 50.32◦ , 58.94◦ , and 68.04◦ , which corre­
spond to the (100), (002), (101), (102), (110) and (112) planes,
respectively, in the X-ray spectra revealed the existence of ZnO in 2CC
(ZnO loaded on corncob activated carbon). These finding are more
promise with the study of Saleh et al. (2015).
FTIR spectra provide details about the functional groups and any
potential trace minerals in the biomass. The bands associated with
lignocellulosic compounds found in the FTIR spectrum include those
(1) associated to various functional groups i.e. C–H bonds, esters, aromatic
rings, ethers, aldehydes, hydroxyl and amine (Ţucureanu et al., 2016).
However, any spectral section absorption bands must be required of
activated carbon as a description (Ramirez et al., 2020). In Fig. 1 we see
the FTIR spectra of corncob materials in three different states: 1CC (raw
corncob), 2CC (corncob that has been physically and chemically acti­
vated), and 3CC (corncob that has been activated and loaded with ZnO
nanoparticles). The data showed that 3CC was the least polluted
adsorbent tested. Picks at 2099 cm− 1 in 3CC were attributed to C– –C
vibrations, which are characteristic of the alkynes family (Singh et al.,
2022). C– – C groupings were seen at 1566 cm− 1 and 1570 cm− 1 in 2CC
and 3CC, respectively. Additionally, the stretching vibrational modes of
ZnO in 3CC were characterized by a band at 492 cm− 1 (Zbair et al.,
2018). The broad band at 3315 cm− 1 in 1CC indicated the presence of
water molecules (Singh et al., 2021). For acyclic C-O-C groups, the 1CC
material’s 529 nm absorption bands stand in as a representation. The
acyclic C-O-C groups are represented by the absorption bands at 529 in
1CC material (Ahsaine et al., 2018). In a nitrogen flow environment,
sample thermal stability has been evaluated from ambient temperature
to 800 ◦ C. The investigation revealed that ZnO@CCAC exhibited a lower
3
K. Singh et al. Bioresource Technology Reports 24 (2023) 101602

Fig. 1. (a) Adsorption-desorption curve for N2 and pore size distribution of ZnO nanoparticle loaded activated corncob.
(b) XRD pattern of the synthesized material,1 CC (activated corncob), 2CC (ZnO nanoparticle loaded activated corncob).
(c) FTIR spectra of different form of Corn cob materials, 1CC (raw corn cob), 2 CC (activated corn cob), 3CC (ZnO nanoparticle loaded activated corn cob).

total weight loss, indicating enhanced stability of this innovative ma­
terial as temperatures increased (Singh et al., 2022).
3.2. NH3-N removal assay
At various pH, dosage, time duration, and temperature conditions,
the percentage of NH3-N removed from leachate was examined and
discussed with their mechanism. One parameter’s value was altered
during the optimization process while the values of the other variables
remained the same.
3.2.1. pH
In the adsorption process study pH of solution is one of the key pa­
rameters, which affects both the adsorbate speciation and the functional
group on the adsorbent (Chauhan et al., 2020; Wu et al., 2012). To
explore this influence, tests were conducted across a pH ranges between
2 and 10, while keeping all other factors constant. It was discovered that
during the experiment, the removal percentage of NH3-N rose up to pH
7, with the best elimination rate being 73.5 % (Fig. 2a). The pHpzc
(point of zero charge) of ZnO@CCAC was 6.8 has been reported in Singh
et al. (2022). However, the low adsorption of NH3-N obtained in acidic
condition attributed probably by the repulsive interactions between the
pollutants and positively charged surface of ZnO@CCAC, induced by the
presence of hydrogen ions. On the other hand, the NH3-N removal
decreased as the pH exceeded 7, which is consistent with the findings of
(Hu et al., 2016). Ammonium ions were neutralized by hydroxyl ions at
high pH levels, turning them into ammonia, which prevented this form
of ammonia from adhering to the adsorbent. As a result, at high pH
values, ZnO@CCAC showed decreased effectiveness (Ferraz and Yuan,
2020; Mosanefi et al., 2021). As a result, pH 7 was chosen as the ideal pH
range for more investigation.
3.2.2. Dose
The amount of adsorbent used in a given operation determines how
effective the adsorption process will be overall. The determination of
adsorbent dosage effect on removal of NH3-N concentration was eval­
uated by varying the ZnO@CCAC dose (0.25 g/50 mL to 2.5 g/50 mL)
while keeping constant the other parameters. The NH3-N concentration
exhibited a reduction from 22.9 % to 81.5 % with varying dosages
(Fig. 2b). This trends described by the fact that with increasing the dose
of adsorbent, it creates more binding sites or surface area, resulting to an
enhanced NH3-N removal capacity (Hashemian et al., 2014). However,
after reaching a dose of 1.50 g/50 mL, no further significant effect was
observed. This finding is consistent with a study by Thamilselvi and

4
K. Singh et al.
Fig. 2. Effect of different parameters (pH, Dose, Contact time and temperature) on the removal percentage.
Radha (2017) and; Dethoada et al. (2022) in wastewater treatment. In
contrast, the NH3-N removal capacity of the adsorbent decreased from
47.78 mg/g to 11.77 mg/g as the biosorbent dosage increased, indi­
cating that a higher doses of biosorbent were required. Aggregation at
high adsorbent doses, which results in a decreased biosorbent surface
area overall, may be to blame for this phenomena (Alorabi et al., 2020;
Singh et al., 2022). Based on these findings, the optimal dose was
determined to be 1.50 g/50 mL, which resulted in a 73.5 % decrease in
NH3-N and an uptake capacity of 18.01 mg/g.
3.2.3. Time
The term “contact time” denotes the duration during which the
adsorbent comes into contact with the waste sample in batch adsorption
experiments. It holds significant importance as a parameter that directly
impacts the adsorption process. The study investigated the impact of
varying time durations within the range of 20 to 200 min at a pH value of
7, using a dosage of 1.50 g/50 mL, an effective temperature of 30 ◦ C, and
an initial NH3-N concentration of 735 mg/L (as shown in Fig. 2c). During
the first 20 min, the ZnO@CCAC adsorbent gradually removed NH3-N,
achieving 39.6 % with an adsorption capacity of 9.70 mg/g. Subse­
quently, as the contact time extended to 160 min, the NH3-N removal
increased significantly by 73.5 % and an adsorption capacity reaching of
18.01 mg/g. The increased availability of active sorption sites on the
adsorbent, which results in a higher sorption rate, is responsible for this
improved removal. However, beyond this contact time, no further sig­
nificant increase in NH3-N removal was observed. This behavior is
probably caused by the adsorbent reaching equilibrium and the active
sites becoming saturated as contact time increased. This caused a drop in
sorption capacity (Faisal et al., 2020).
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Bioresource Technology Reports 24 (2023) 101602
3.2.4. Temperature
The impact of temperature on the adsorption process was analysed
across various studies to determine its exothermic or endothermic na­
ture. The effect of temperature on NH3-N removal was examined in the
study at temperatures ranging from 25 ◦ C to 40 ◦ C (Fig. 1d). The per­
centage of NH3-N removal exhibited an upward trend, from 65.2 % to
79.9 % with increasing temperature that signifying an endothermic
mechanism. These finding were validated by the assessment of Gibbs
free energy and enthalpy in Section 3.5. Due to the increased tempera­
ture, this behavior may be attributed to improved adsorbate diffusion
over the exterior boundary layer and intraparticle diffusion within the
adsorbate’s pores (Peng et al., 2012). Hadi et al. (2020) conducted
research on the use of Imperata cylindrica for oil adsorption and observed
that higher temperatures (20 to 60 ◦ C) led to increased adsorption ca­
pacity, with similar findings discussed by Alomar et al. (2022). In
contrast, temperatures beyond 30 ◦ C had an adverse effect on adsorp­
tion. The maximum NH3-N removal occurred at 30 ◦ C, reaching 73.5 %
with an adsorption capacity of 18.01 mg/g. Further temperature in­
creases had no discernible impact on NH3-N absorption, indicating that
30 ◦ C was the ideal temperature for the ensuing procedure. Adewoye
et al. (2021)) also reported a decrease in adsorption capacity of func­
tionalized multi-walled carbon nanotubes with a temperature change
from 30 to 50 ◦ C.
3.3. Adsorption isotherms
The link between qe and Ce is shown in Fig. 3 in the adsorption
isotherms of NH3-N reduction by ZnO@CCAc at various adsorbent
dosages. Hill model suggested that the adsorption of NH3-N onto
ZnO@CCAC involved a binding interaction with nh value of 1.15796,
K. Singh et al.
Fig. 3. Plots showing the isotherm study for NH3-N removal.
supporting this fact. The Freundlich isotherm was favored by the Khan
model for NH3-N adsorption because the exponent value (Ak 0.1257)
was <1, and the ultimate concentration value (Ce) was relatively high
(Table 2). Particularly, the Redlich-Peterson isotherm followed the
Langmuir isotherm at low concentrations, but when the concentration
was large (bR almost 0), it resembled the Freundlich model. The
Freundlich model was supported since the computed value of bR was
0.13, which was close to zero. Additionally, the Toth isotherm, which
depicts adsorption with a quasi-Gaussian energy asymmetry
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Bioresource Technology Reports 24 (2023) 101602
distribution, was evident in the adsorption of NH3-N by ZnO@CCAC at
both low and high concentrations. The Toth isotherm constant (t) for
NH3-N adsorption was calculated as 1.879E21. Furthermore, systems
with heterogeneous adsorption commonly employ the Koble-Corrigan
isotherm, which combines features of the Langmuir and Freundlich
isotherms. The computed value of parameter D was 1.1254, which was
>1, indicating that the Koble-Corrigan isotherm could be suitable for
describing the experimental results. The Freundlich isotherm was
determined to be suitable for characterizing the adsorption process of
K. Singh et al. Bioresource Technology Reports 24 (2023) 101602

Table 2 min− 1),

Values for NH3-N against various parameters of nonlinear adsorption isotherms. Kid- Rate constant (mg/ g min− 1/2) related to intra-particle diffusion.
Isotherms Factors Values Various parameters C- Boundary layer thickness.
In the context of the pseudo-first order, the values of the slope (K1)
Hill Qh 3862.24 Qh- Hill isotherm uptake value
(mg/L) and the intercept (log qe) are determined from the linear plot of log (qe-
Kd 1.08E8 Kd–Constant for Hill model qt) versus time (Fig. 4a). This linear analysis form revealed an adsorption
nh 1.15796 nh- Hill coefficient for binding capacity (qe) of 12.33 mg/g for the reduction of NH3-N, deviates from
interaction the experimental result of 15.58 mg/g (Table 3), which indicates that
R2 0.9917
Koble-Corrigan A 0.0000432 A- Koble–Corrigan model
the process doesn’t conform precisely to the pseudo-first-order kinetics.
constant (Lnmg1− n/mg) Conversely, within the framework of the pseudo-second-order model,
B 0.0000 B- Constant for Kobel (L/mg) the values of qe and K2 are derived from the slope and intercept of the
D 1.1254 D- Intensity value for adsorption plot t/qt versus time (Fig. 4b). Notably, the calculated qe value (17.98
R2 0.9925
mg/g) is in closer agreement to the experimental value. Furthermore,
Redlich–Peterson KR 0.0008683 KR- Constant for Redlich–Peterson
(L/mg) significantly higher correlation coefficient R2 (0.99) along with the
aR 19.5212 aR- Redlich model constant (1/ lower average relative error (ARE %) convincingly indicate that the
mg) pseudo-second-order model provides a superior representation of the
bR 0.1393 bR- Redlich–Peterson exponent NH3-N reduction process. These results align with prior research find­
R2 0.9995
Khan Qk 0.0000314 Qk- Theoretical value for isotherm
ings (Couto et al. Couto et al., 2017; Mahmoud et al., 2020). The
saturation capacity (mg/mg) diffusion rate constant (Kid) and intercept (C) that tells the boundary
Bk 1.325 Bk- Constant for Khan model layer effect, were calculated through qt vs. t1/2 plotting (Fig. 4c). The
Ak 0.1257 Ak- Khan model exponent rate-controlling phase is all that remains if the plot does not converge to
R2 0.9925
the origin. According to the correlation coefficient (R2) of 0.96, the
Toth Kt 0.0000895 Kt- Toth model constant (mg/mg)
at 4.8532 at- Constant for Toth isotherm (L/ intraparticle kinetic study is not significant for NH3-N reduction. Indi­
mg) cating that intraparticle diffusion is not the rate-controlling step is the
t 1.879E21 t- Toth constant fact that the graph does not pass through the origin.
R2 0.9803
Freundlich Kf 0.000432 Kf-Adsorption capacity
n 1.1363 Freundlich constant ((mg/mg) 3.5. Thermodynamic studies
(mg/L)-1/n)
2
R 0.9925 n - Freundlich constant for
intensity (dimensionless) Temperature during the study has a more notable impact on the
adsorbent capacity. In order to the thermodynamic analyses of NH3-N
adsorption was carried out at temperature of 298 K, 303 K, 308 K, and
NH3-N reduction by ZnO@CCAC based on the nonlinear model pa­ 313 K. Gibb’s free energy change (ΔG0), entropy change (ΔS0), and
rameters, with a high R2 value of 0.9925 and a 1/n value of 1.1363, as enthalpy change (ΔH0) factors were determined by applying the
shown in Table 2. The fitting of models suggested that multilayer following thermodynamic equations:
adsorption could occur during the reduction of NH3-N by ZnO@CCAC
ΔS ΔH
adsorbent. lnKd = − (6)
R RT

3.4. Adsorption kinetic studies ΔG0 = ΔH 0 − T ΔS0 (7)

Investigating the kinetics of adsorption under various operational Ca

conditions provides valuable insights into comprehending the mecha­
nisms of removal inherent to the adsorption process, which govern the
rate of removal at the interface between the solid and liquid phases
(Maazouzi et al., 2023). To investigate the removal of NH3-N using
ZnO@CCAC adsorbent, three kinetic models were employed: Pseudo-
first-order (Yuh-Shan, 2004), pseudo-second-order (Ho and McKay,
1999), and intraparticle diffusion (Hameed et al., 2009). These models
aim to elucidate the phases that control the rate of removal. The equa­
tions used for these models are as follows:
Pseudo-first-order
log(qe − qt ) = logqe −
K1
t (3)
2.303
Pseudo-second-order
t 1 t 3.6. RSM-CCD Design
= +
qt K2 q2e qe
Intraparticle diffusion
qt = Kid t1/2 + C
Where:
qe: Equilibrium final NH3-N concentration (mg/g).
qt: The final NH3-N concentration measured in minutes.
K1: Pseudo-first order (min− 1) kinetic constant.
K2, the pseudo-second order model’s kinetic constant (g mg−
Kd = (8)
Ce
Note: Kd: Equilibrium constant; Ca: NH3-N adsorbed concentration (mg/
L); Ce: NH3-N concentration at equilibrium (mg/L); T: Temperature; R:
Constant 8.314 (J mol− 1 K− 1).
To determine the degrees of ΔH◦ and ΔS◦ , linear graphs of lnKd
against 1/T were used. The negative value of ΔG0 here indicated
spontaneous NH3-N adsorption by ZnO@CCAC, and the trend of
decreasing values with rising temperature confirmed that temperature
increase promoted adsorption (Table 4). The results of ΔH0 = 37.43
kJmol− 1 and ΔS0 = 131.24 Jmol− 1 K− 1 specified the endothermic
behavior and change in structures due to increases in randomness of the
adsorption process.
(4)
3.6.1. Response surface statistical analysis
Table Supplementary 2 presents the details of the 30 runs experiment
(5) conducted using the RSM-CCD approach. Table 5 includes the six rep­
lications of the independent variables for the central point, such as pH,
dosage, time, and effective temperature, along with their upper and
lower values. As shown in Table 6, the correlation between the factors
and responses was determined to be reasonable and appropriate for
forecasting NH3-N adsorption. It is expressed by the quadratic Eq. (9)
1
below.

7
K. Singh et al. Bioresource Technology Reports 24 (2023) 101602

Fig. 4. Representation of NH3-N removal by ZnO@CCAc in kinetic studies plots: (a) Pseudo first order; (b) Pseudo second order; (c) Intra-particle diffusion.

Table 3 Table 4
Kinetic models parameter study for reduction of NH3-N using ZnO@CCAC. Thermodynamic parameter for removal of NH3-N using ZnO@CCAC at different
Isotherm Factors Values Name of factors
temperature.
− 1 Temp. (K) ΔG0 (KJ mol− 1) ΔH◦ (KJ mol− 1) ΔS0 (J molK)
Pseudo-first K1 (min ) 0.020 K1-Kinetic constant for Pseudo-
order qe (mg/g) 12.33 first order (min− 1) 298 − 1.6807
R2 0.71 qe-Final NH3-N concentration at 303 − 2.3369 37.43 131.24
ARE% 20.86 equilibrium (mg/g) 308 − 2.9931
Pseudo-second K2 (g/mg 0.00185 K2: kinetic constant for Pseudo- 313 − 3.6493
order min− 1) second order model (g mg− 1
qe (mg/g) 17.98 min− 1)
R2 0.99
ARE% 15.4 Table 5
Intraparticle Kid (mg/ g 0.78 Kid- Rate constant related to Intra- Quadratic model statistics for NH3-N reduction with level of Independent
diffusion min− 1/2) particle diffusion (mg/ g min− 1/2) variables.
C 5.34 C- Boundary layer thickness
R2 0.96 Parameters Lower limit Centre Upper limit − Alpha Alpha
Experimental qe(mg/g) 15.58 (− 1) (0) (+1) (− α) (α)
value pH 4 6.5 9 1.5 11.5
Note: qt: Final NH3-N concentration in t time duration (min). Dose 1 1.63 2.25 0.37 2.87
Time 100 150 200 50 250
Temperature 25 32.50 40 17.5 47.5

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K. Singh et al. Bioresource Technology Reports 24 (2023) 101602

Table 6
Biostatical analysis (ANOVA) on NH3-N removal percentage.
Source Sum of squares Degree of freedom Mean square F-value p-Value

Model 4564.18 14 326.01 731.70 <0.0001 Significant

A-pH 1510.51 1 1510.51 3390.16 <0.0001
B-Dose 163.28 1 163.28 366.47 <0.0001
C-Time 13.80 1 13.80 30.98 <0.0001
D-Temp. 7.26 1 7.26 16.29 0.0011
AB 1.21 1 1.21 2.72 0.1201
AC 2.25 1 2.25 5.05 0.0401
AD 3.61 1 3.61 8.10 0.0123
BC 1.32 1 1.32 2.97 0.1055
BD 1.56 1 1.56 3.51 0.0807
CD 0.5625 1 0.5625 1.26 0.2788
A2 1430.14 1 1430.14 3209.79 <0.0001
B2 1742.65 1 1742.65 3911.19 <0.0001
C2 199.34 1 199.34 447.39 <0.0001
D2 328.05 1 328.05 736.27 <0.0001
Residual 6.68 15 0.4456
Lack of fit 5.73 10 0.5735 3.02 0.1168 Not significant
Pure error 0.9483 5 0.1897
Cor total 4570.86 29

NH3 − N (%)removal Ypred = + 70.68 + 7.93 A + 2.61 B + 0.7583 constant. The findings showed that the NH3-N removal efficiency
C–0.5500 D + 0.2750 AB + 0.3750 AC ranged between 26.1 % and 71.2 %. The pH ranged from 4 to 6.5,
leading to an increase in NH3-N reduction. However, beyond a pH of 6.5,
–0.4750 AD + 0.2875 BC + 0.3125 BD
the NH3-N reduction started to decrease, indicating an inhibitory effect
–0.1875 CD–7.22 A2 –7.97 B2 –2.70 C2 –3.46 D2 at higher pH levels. Similarly, an increase in the dose from 1 g to 1.63 g
(9) resulted in a higher efficiency of NH3-N reduction, but no significant
change was observed beyond 1.63 g. Fig. 6 demonstrates the interactive
Where, the coded form of pH, dose, time duration, and effective tem­
effects of contact time, temperature, and pH on the NH3-N removal
perature is represented by variables A, B, C, and D, respectively. The
percentage. The highest NH3-N removal (71.2 %) was achieved at a pH
statistical analysis demonstrates strong significance with p < 0.0001 and
of 6.5, a dose of 1.63 g, a contact time of 150 min, and a temperature of
F-value of 731.70, obtained through ANOVA for NH3-N adsorption,
32.5 ◦ C, which was determined using the RSM-CCD algorithm model.
indicating a well-fitted model. This is supported by the high F-value and
The model’s accuracy was validated by comparing the predicted values
P-value <0.05, which are essential for the model’s suitability (Singh
from the RSM models with the experimentally determined values. The
et al., 2019). Moreover, the developed quadratic model is confirmed to
lower value of RMSE i.e., 0.47 indicated a minimal difference between
be within a 95 % confidence level. The model assesses the effects of
the experimentally determined (73.5 %) and model-based (71.2 %)
linear (A, B, C, D), quadratic (A2, B2, C2, D2) and interaction values (AB,
removal percentages of NH3-N. It confirming the model’s suitability for
AC, AD, BC, BD, CD) using F and p values. The ANOVA results reveals
optimizing the ZnO@CCAC adsorbent for NH3-N reduction and high­
that A, B, C, D, AC, AD, A2, B2, C2 and D2 have significant impact on NH3-
lighting its potential for effective application.
N removal with P-values <0.05 and high F-values. Specifically, the P-
values for these terms are <0.0001, <0.0001, <0.0001, 0.011, 0.0401,
3.7. NH3-N removal efficiency of ZnO@CCAc
0.0123, <0.0001, <0.0001, <0.0001 and < 0.0001, respectively; while
the corresponding F-values are 3390, 366, 30, 16, 5, 8, 3209, 3911, 447
For a wastewater treatment method to be both affordable and sus­
and 736, respectively. All factors, namely pH, dose, time duration, and
tainable, adsorbent regeneration efficiency is crucial. An excellent
effective temperature, significantly influence the removal of NH3-N.
adsorbent ought to have higher adsorption efficiency and be important
This is evident from the high correlation coefficient (R2 = 0.9985) ob­
in terms of regeneration and reusability. By increasing the molar content
tained in the study, indicating that over 99.85 % of the total dissimilarity
of HCl from 0.05 to 0.15 M, the removal of NH3-N by the adsorbent was
can be explained by this empirical model. A correlation coefficient value
enhanced (Fig. 7). At the optimal concentration of HCl 0.15 M, the
above 0.80 is considered acceptable for a well-fitted model, and in this
removal efficiencies were determined to be 67.5, 56.1, and 51.6 % in
case, it exceeds that threshold.
cycles 1, 2, and 3, respectively. Fig. 7 showed that as the number of
Adequate precision (signal to noise ratio) was found above 4 i.e.
cycles rose, the percentage of NH3-N removal dropped. Similar finding
94.81, that specifies the model’s authenticity and suitability. The study’s
has been recorded with corncob loaded on the silver nanoparticles
findings were found to be consistent with a Coefficient of Variation of
(Thamilselvi and Radha, 2017). The economical and notable qualities of
2.26 %. For NH3-N adsorption, the corrected R2 was 0.9972, while the
synthesized ZnO@CCAC were disclosed by the elimination of >50 % of
expected R2 was 0.9925. The difference between these values is <0.2, it
NH3-N in three regeneration cycles of the adsorbent.
suggests the quadratic model’s predetermined experiment matches were
accurate (Fig. 5a).
3.8. Potential application of synthesized adsorbent
3.6.2. Plots and optimization of response surface
The quadratic model’s three-dimensional surface and contour plots ZnO@CCAC exhibits significant benefits as a very effective adsorbent
were generated using Design-Expert® software 12 to illustrate the for removing NH3-N from leachate by comparison with prior research.
interactive relationships between independent variables and the The incorporation of zinc oxide nanoparticles onto corncob activated
response (see Fig. 5b–d & Fig. 6). Each plot represents the variation of carbon creates additional active sorption sites, resulting in a signifi­
two variables within experimental ranges while keeping the other two cantly higher NH3-N adsorption capacity. Moreover, the presence of zinc
constant. The study concentrated on the effects of operational variables, oxide nanoparticles enhances the adsorption kinetics, leading to a faster
specifically pH and dosage, while keeping time and temperature and more effective NH3-N removal from leachate. Additionally, the
introduction of metal oxide nanoparticles also improves the thermal

9
K. Singh et al.
Fig. 5. NH3-N removal: (a) Actual value vs. predicted value; (b) Contour graph of pH vs. dose; (c) pH vs. time; (d) pH vs. temperature.
stability of the composite, ensuring its efficacy even under varying
temperature conditions. Utilizing corncob, an agricultural waste, as a
cost-effective precursor for activated carbon further optimizes the ma­
terial’s adsorption performance. With the addition of zinc oxide nano­
particles, this composite becomes a viable and economical adsorbent for
NH3-N removal from leachate. The incorporation of metal oxide nano­
particles, coupled with the abundance and cost-effectiveness of corncob
as the precursor, distinguishes this innovative composite from previ­
ously explored adsorbents. It opens up new possibilities for sustainable
leachate treatment methods. Moreover, the prepared adsorbent exhibits
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Bioresource Technology Reports 24 (2023) 101602
exceptional potential for treating diverse types of industrial or domestic
wastewater due to its extensive surface area, porous structure, and
oxygen-containing functional groups (as shown in FTIR results). These
functional groups serve as binding sites for contaminants, enhancing its
efficiency as a water treatment material.
One of the key advantages of this adsorbent is its ability to be re­
generated and reused for multiple treatment cycles (up to 3 cycles),
making it a highly cost-effective solution in the long run. Nevertheless,
further research and testing are essential to optimize its performance
and validate its effectiveness under different leachate conditions.
K. Singh et al.
Fig. 6. Representation of percent NH3-N removal in three dimensional response plots: (a) Dose vs. pH (b) Time vs. pH and (c) Temperature vs. pH.
Additionally, it is crucial to investigate the possibility of any leaching of
zinc nanoparticles in the treated water during the process. By addressing
these aspects, we can ensure that this composite remains a promising
option for sustainable and efficient leachate treatment.
4. Conclusion
In this study successfully utilized corncob as an agricultural waste
precursor to create activated carbon through physical and chemical
activation processes. The resulting adsorbent, ZnO@CCAC, was syn­
thesized by incorporating ZnO nanoparticles. The confirmation of car­
bon and ZnO phase formation was validated through XRD, BET, and
FTIR analyses, confirming the synthesis of this novel adsorbent. Through
comprehensive experimentation, the optimized conditions for NH3-N
removal were determined as follows: a pH of 7, a dose of 1.50 g/50 L, a
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Bioresource Technology Reports 24 (2023) 101602
response time of 160 min, and a temperature of 30 ◦ C, resulting in the
highest adsorption capacity for NH3-N removal to be 18.01 mg/g. The
adsorption behavior was successfully described by nonlinear isotherm
models with high R2 values, indicating multilayer adsorption behavior.
Additionally, the pseudo-second-order kinetics showed a good agree­
ment between the estimated adsorption capacity and the experimental
data, demonstrating the applicability of the modified pseudo-second-
order model for the adsorption method. Thermodynamic analysis
revealed the spontaneous and endothermic nature of the adsorption
process, enhancing the potential of ZnO@CCAC for NH3-N removal. The
surface response approach using the CCD model proved to be highly
effective, with a well-matched correlation data of adjusted R2 (0.9972)
and predicted R2 (0.9925). The peak data from the designed experiment
closely aligned with the experimental data, affirming the accuracy of the
model. Furthermore, the regenerated adsorbent demonstrated
K. Singh et al.
Fig. 7. The effectiveness of regenerated ZnO@CCAc for NH3-N removal.
substantial efficiency for up to three cycles, emphasizing the potential
for cost-effective and sustainable leachate treatment using ZnO@CCAC.
Based on the comprehensive analysis and findings, ZnO@CCAC is
established as a remarkable, economical, and efficient adsorbent for
successful leachate treatment. This offering promising solutions for
addressing the long-standing challenge of ammoniacal nitrogen removal
from leachate. The study contributes valuable insights to the field of
leachate treatment and provides a foundation for further research and
development of environmentally friendly and cost-effective adsorption-
based wastewater treatment technologies.
CRediT authorship contribution statement
We herewith state that the manuscript titled “Assessment of the ef­
ficacy of corncob activated carbon loaded with zinc oxide nanoparticles
for eliminating ammonaical nitrogen (NH3-N) from leachate” contains
original and unpublished work which has not been considered for
publication elsewhere. We confirm that the manuscript has been read
and approved by all the authors and that there are no other persons who
satisfied the criteria for authorship but are not listed. We further confirm
that the order of authors listed in the manuscript has been approved by
all of us. Our contribution to this manuscript as follows– * Kulbir Singh:
Conceptualization, Methodology, Validation, Writing - Original Draft,
Investigation, Software Rajesh Kumar Lohchab*: Supervision, Concep­
tualization, Methodology, Validation, Writing - Original Draft, Investi­
gation, Formal analysis Vikas Kumar: Validation, Methodology,
Conceptualization, Ajay Kumar: Validation, Methodology, Conceptual­
ization. We understand that the corresponding author is the sole contact
for the Editorial process. The corresponding author is responsible for
communicating with the other authors about progress, submissions of
revisions and final approval of proofs.
Funding statement
This research work was funded by Technical Education Quality
Improvement Programme-III with the assistance of World Bank (letter
12
Bioresource Technology Reports 24 (2023) 101602
number TEQIP-III/2018/1841-1142).
Ethical approval
There are no research conducted on the human participants or ani­
mals during this study.
Declaration of competing interest
There are no conflicts of interest between the organizations or the
authors.
Data availability
Data will be made available on request.
Acknowledgments
The authors acknowledge the Department of Environmental Science
and Engineering for their support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.biteb.2023.101602.
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