DOI: 10.1002/tqem.

21703

RESEARCH ARTICLE

Adsorptive removal of heavy metals from industrial effluents

using cow dung as the biosorbent: Kinetic and isotherm
modeling

Sushil Kumar Saraswat1 Muslum Demir2 Vijayalakshmi Gosu3

1
Department of Chemical Engineering, MBM
Engineering College, Jai Narain Vyas Abstract
University, Jodhpur, Rajasthan, India
This article investigated an eco-friendly technique for the removal of heavy met-
2
Department of Chemical Engineering,
als using biosorbent derived from cow dung. Heavy metals bearing wastewater
Osmaniye Korkutata University, Osmaniye,
Turkey were collected from a common effluent treatment plant located at Sangariya,
3
Department of Chemical Engineering, Jodhpur (Rajasthan, India) to evaluate the removal efficiency of synthesized cow
Malaviya National Institute of Technology,
Jaipur, Rajasthan, India
dung–activated carbon. The prepared activated carbon materials have a high surface
area in the range of 948–1072 m2 /g and also have significant quantities of micropore
Correspondence
and mesopore volumes. Furthermore, pore diameters were in the range of 2.24–
Sushil Kumar Saraswat, Department of Chem-
ical Engineering, MBM Engineering College, 2.33 nm. Surface morphology was improved after being treated with NaOH. The
Jai Narain Vyas University, Jodhpur 342011,
adsorbent material was found to be an efficient medium for the removal of Cr(VI) and
Rajasthan, India.
Email: sksaraswat.chem@jnv.edu.in; Cd(II). The results revealed that more than 95.6% of Cr(VI) and 66.88% of Cd(II) were
dr.sushilsaraswat@gmail.com
achieved at the optimized condition of pH12.0, initial concentration of heavy metals
Funding information 10 mg/L, 300 min of contact time, and the dose of 0.2 g/L, whereas only 16.3% removal
TEQIP-III of MBM Engineering efficiency was observed for Ni(II). Equilibrium data have been analyzed by Langmuir,
College, Jodhpur
Freundlich, Temkin, and Redlich and Peterson (R–P) isotherm models with the help of
nonlinear regression analysis. Experimental data were best fitted for Freundlich and
R–P isotherms.

KEYWORDS
adsorption, biosorbent, cow dung–activated carbon (CDAC), heavy metal

1 INTRODUCTION electroplating, steel, refining ores, paint manufacture, pesticides,

Pure water, vital for a healthy environment, is a resource that is
adversely affected both quantitatively and qualitatively by man-made
activities. Rapid industrialization and urbanization have brought a real
water crisis. Industries continue to be a major cause of water pollution
due to diverse kinds of waste, especially toxic heavy metal ions released
in water bodies, without adequate treatment (Nguyen et al., 2013).
Water quality changes significantly with the presence of toxic heavy
metals (Ni, Cd, Zn, Hg, Cr, Pb, Cu, and As) when the level exceeds pre-
scribed limits. Thus, it becomes potentially harmful to all kinds of life on
this planet. Heavy metals in water streams originate from the effluent
of smelters, mines, and various industries such as batteries, tanneries,
fertilizers, pigment manufacture, printing, and photographic sectors
(Babalola, 2018). The nature and composition of industrial effluents
depend mainly on raw materials, process, and treatment methods.
The ingestion of heavy metals via the food chain, in concentra-
tions above the permissible limit, has a detrimental effect on human
physiology and other biological systems. Due to their hazardous ten-
dency of accumulation and toxicity, they pose a severe threat to the
function of different organs in the human body and aquatic animals
(Fu, & Wang, 2011; Rangabhashiyam, Jayabalan, Rajkumar, & Balasub-
ramanian, 2019). Various agencies, viz., the U.S. Environmental Pro-
tection Agency (EPA), the Bureau of Indian Standards (BIS), and the
Indian Council of Medical Research (ICMR), set regulatory limits for

Environ Qual Manage. 2020;1–10. wileyonlinelibrary.com/journal/tqem © 2020 Wiley Periodicals LLC 1

2 SARASWAT ET AL .

EXHIBIT 1 BIS standard of heavy metals in different water Exhibit 2 shows the various biosorbents employed for the removal of
bodies heavy metals from wastewater (Luo et al., 2006; Padmavathy, 2008;
Into inland Into Pehlivan, Yanık, Ahmetli, & Pehlivan, 2008; Preetha & Viruthagiri,
surface Into public marine 2007; Vilar, Botelho, & Boaventura, 2007; Wang et al., 2006).
S. No. Heavy metals (mg/L) water sewage coastal Cow dung is considered an eco-friendly and inexpensive adsorbent,
1 Nickel 3.0 3.0 5.0 which contains 12% calcium oxide, 0.9% magnesium oxide, 0.3% cal-
2 Cadmium 2.0 2.0 1.0 cium sulfate, 20% aluminum oxide, 20% iron oxide, and 61% silica
3 Hexavalent chromium 0.1 2.0 1.0 (Kaur, Mor, & Ravindra, 2016; Vasanthakumar & Bhagavanalu, 2003).

4 Total chromium 2.0 2.0 2.0
5 Copper 3.0 3.0 3.0
6 Lead 0.1 1.0 1.0
7 Zinc 5.0 15.0 16
the amounts of heavy metals in water provided by public water sys-
tems (Abas, Ismail, Kamal, & Izhar, 2013; Indian Standard, 2012).The
BIS standard of heavy metals in different water bodies is depicted in
Exhibit 1.
Furthermore, heavy metals are stable and persistent in nature;
thus, they cannot be degraded and destroyed easily. Numerous pro-
cesses have been developed to remove dissolved heavy metal ions,
such as ion exchange, chemical precipitation, ultrafiltration, reverse
osmosis, coagulation, and electrolysis (Ahluwalia & Goyal, 2007; Ates
& Uzal, 2018; Kobya, Demirbas, Senturk, & Ince, 2005; Purkayastha,
Mishra, & Biswas, 2014). These methods have significant disadvan-
tages and accompany many problems such as energy-intensive, incom-
plete removal, and generation of toxic sludge (Ghomi, Asasian-Kolur,
Sharifian, & Golnaraghi, 2020; Gunarathne et al., 2019).
Recently, various techniques have been employed for the removal
of heavy metals from industrial wastewater via economical and eco-
friendly methods. Adsorption techniques have become an attrac-
tive way to remove heavy metals from wastewater owing to their
high efficiency, low energy requirements, reuse, and regeneration of
adsorbents (Apiratikul & Pavasant, 2008; Burakov et al., 2018; Lalmi,
Bouhidel, Sahraoui, & Anfif, 2018). Activated carbon has been effec-
tively used for a long time for the treatment of polluted water due to
its well-developed porous structure and high surface area. However,
the above-mentioned techniques are of high cost and limited reusabil-
ity that necessitate the development of an alternative adsorbent from
natural sources (Jusoh, Shiung, & Noor, 2007; Karnib, Kabbani, Holail, &
Olama, 2014; Ngah & Hanafiah, 2008). Numerous research works have
been carried out to explore a low-cost adsorbent through agriculture
waste, an industrial by-product, or natural substances for the removal
of heavy metals from wastewater. Various low-cost natural materials
such as potato peels, sawdust, black gram husk, eggshell, seed shells,
coffee husks, sugar beet, and orange peel have also been extensively
utilized as potential biosorbents for heavy metals removal (Ajmal, Rao,
Ahmad, & Ahmad, 2000; Aman, Kazi, Sabri, & Bano, 2008; Amuda, Ade-
lowo, & Ologunde, 2009; Kaczala, Marques, & Hogland, 2009; Mata,
Blázquez, Ballester, González, & Munoz, 2009; Oliveira, Franca, Alves,
& Rocha, 2008; Park, Jeong, Yang, Kim, & Lee, 2007; Saeed, Iqbal, &
Akhtar, 2005). However, no material satisfies all the desired criteria.
The higher percentage of silica in cow dung increases the consider-
able affinity toward metal ions. The main advantage of cow dung as
activated carbon not only is inexpensive but also resolves environ-
mental issues of foul odor (Eissa, 2019; Qian, Machida, & Tatsumoto,
2008). However, more research is needed to address the issues faced
in the application of cow dung synthesized biosorbent. In the present
study, an attempt has been made to utilize cow dung as an adsorbent
to remove heavy metals from wastewater with the aim to increase
biosorption capacity. Synthesized bioadsorbent was characterized to
understand the physicochemical properties, and isotherm behavior
was investigated to find the feasibility of the biosorption process.
2 EXPERIMENTAL METHOD
2.1 Synthesis of adsorbent
Completely sun-dried cow dung was collected, and safety measures
were taken to avoid any contaminations. Cow dung was crushed with
pestle and mortar to average size (0.4–0.7 mm) and kept in an air-
tight flask. Crushed cow dung was thermally activated in a muffle fur-
nace (Smitha Scientific, India, SMFF-4S) at 450◦ C for 4 h. Thermally
activated material (20 g) treated with NaOH at different impregna-
tion ratios (IR) (0.5, 1.0, and 2.0) for about 3 h at 50◦ C. The resulted
homogeneous mixture was dried overnight at 110◦ C. The chemically
treated adsorbent was activated using a muffle furnace at 650◦ C for
2 h under nitrogen atmosphere. The prepared cow dung–activated
carbon (CDAC) was washed thoroughly with distilled water and dried
completely at 100◦ C for 2 h. The prepared adsorbent was then kept in
desiccators to avoid contact with moisture. Further, the same proce-
dure was adopted to prepared CDAC of a different impregnation ratio
named CDAC (0.5), CDAC (1), and CDAC (2).
2.2 Characterization techniques
The surface area of all the synthesized CDACs was evaluated with
the help of a nitrogen adsorption–desorption isotherm in the rel-
ative pressure range from 0.04 to 0.2 using Micromeritics ASAP
2010, USA analyzer at −273◦ C. A CDAC sample was kept in a sam-
ple tube and thereby degassed for 4 h at 150◦ C under vacuum to
remove contaminants present in the sample. Surface morphologies
of the CDAC samples were done by scanning electron microscopy
(SEM) using a ZEISS EVO-50 instrument microscope operated at
an acceleration voltage of 30 kV. Atomic absorption spectrometer
SARASWAT ET AL . 3

EXHIBIT 2 List of biosorbents employed for heavy metals removal

Operating conditions
Type of pH, dose (D) (g/L), initial Sorption
heavy concentration (Co ) (mg/L), capacity
S. No. metals Type of biosorbent temperature (T) (◦ C) (mg/g) Reference
1 Cr(Vl) Rhizopus arrhizus pH = 1.3; T = 30; Co = 200 25 Preetha & Viruthagiri, 2007
2 Cd(II) Dried activated sludge pH = 1.3; T = 25; Co = 50 22.5 Wang et al., 2006
3 Cd(II) Waste activated sludge pH = 5.3; T = 25; D = 3 0.15 Luo et al., 2006
4 Cd(II), Sugar beet pulp pH = 5.0–5.5; T = 25; Co = 50 46 Pehlivan et al., 2008
Pb(II) 44
5 Cr(Vl) Agar extraction algal waste T = 25; Co = 150 14.5 Vilar et al., 2007
6 Ni(II) Baker yeast T = 27; pH = 6.5; D = 1; Co = 100 8.2 Padmavathy, 2008
7 Ni(II) Peat pH = 5.0–7.0, Co = 100, D = 0.5 14 Bartczak et al., 2018
Pb(II) 20
8 Pb(II) Banana Peel pH = 5.5, Co = 200, D = 0.5 124 Amin et al., 2018
9 Cr(III) Waste fish scales D = 0.8 , pH = 5.0 Co = 150 18.36 Teshale, Karthikeyan, & Sahu,
2020
10 Ni(II) Cow dung D = 0.2, pH = 12.0, T = 300 min, 8.72 Present study
Cd(II) Co = 10 33.44
Cr(VI) 47.8

(Analytik-JenaNova-400) measurements were evaluated on flame and final concentrations of a heavy metal ion in an aqueous solution
mode with a single beam to estimate heavy metal ion concentrations. (mg/mL), respectively, and W is the adsorbent weight (g).

2.3 Experimental procedure 2.4 Adsorption isotherms

The experiments were conducted in 500 mL Griffin beaker, graduated
at intervals, with industrial wastewater (common effluent treatment
plant located at Sangariya, Jodhpur, India) having a working volume of
300 mL. Various wastewater samples from different points were col-
lected to choose the metal ion concentration range and measured the
average Cr(VI), Cd(II), and Ni(II) concentration in the effluents. The pH
of the solution was adjusted by using 0.5 N of hydrochloric acid (HCl)
and 0.1 N of sodium hydroxide (NaOH) (Sigma-Aldrich, UK) of analyti-
cal grade. Furthermore, the pH meter (HACH, Sension 1, Model 51935-
00) equipped with a gel-filled pH electrode was utilized to measure the
sample’s pH. Prepared CDAC (60 mg) was added to the beaker and
agitated at room temperature. The reaction mixture was stirred with
a constant speed of 200 revolutions per minute (rpm) throughout the
experiment. The samples (15 mL) were collected at regular time inter-
vals, and the final sample was taken after 20 h. After each run, the
obtained solution was filtered with Whatman filter papers. The metal
uptake capacity and metal percentage removed by CDAC during the
batch reaction experiments were calculated from equations (1) and (2).
( )
q = V Ci − Cf ∕1000 W, (1)
( )
Biosorption efficiency R (%) = Ci − Cf ∕Ci × 100%, (2)
where q is the specific metal uptake by biomass (mg/g), V is the volume
of the solution in the contact batch flask (mL), Ci and Cf are the initial
An equilibrium study was carried out to describe the adsorption
characteristics of the present system. Various adsorption isotherms
such as Freundlich (1906), Langmuir (1918), Tempkin and Pyzhev
(1940), and Redlich and Peterson (R–P) (1959) were employed to
know the nature of adsorption through appropriate correlation of
the equilibrium curve. The empirical correlation equations of these
isotherms are represented from equation (3) to (6). The theories asso-
ciated with isotherms described in studies such as Ahmad, Khan, Giri,
Chowdhary, and Chaturvedi (2020) and Barot and Bangla (2012), and
Srivastava, Mall, and Mishra (2007). Recently, nonlinear regression
gained more attention for minimizing the quadratic error between
experimental data and model outputs. The best isotherm model was
found out with the help of four error functions of nonlinear regression,
namely, Marquardt’s percent standard deviation (MSDP), hybrid frac-
tional error function (HYBRID), sum of square of error (SSE), and abso-
lute error (CH12) using the solver add-in functions of Microsoft Excel
software (Suresh, Vijayalakshmi, Rajmohan, & Subbaramaiah, 2012).
Among these, SSE is commonly used for the high adsorbate concentra-
tion, where the square of errors rises with an increase in the concentra-
tion of adsorbate. To overcome the limitations and to improve the SSE
at low adsorbate concentration, HYBRID was investigated. Further, a
divisor is incorporated as a term for the number of degrees of freedom.
Geometric mean error distributions improved due to the degree of
freedom function analogous to MSDP function, and absolute errors
are utilized for assessment of the goodness of fit to select the optimum
4 SARASWAT ET AL .

EXHIBIT 3 Surface area characterization of activated carbon

SBET Vmicro Vtotal

IR (m2 /g) (cm3 /g) (cm3 /g) Dp (nm)
CDAC (0.5) 948 0.42 0.82 2.42
CDAC (1.0) 986 0.48 0.89 2.38
CDAC (2.0) 1072 0.59 0.97 2.33

isotherms. The error functions of nonlinear regression are shown in

equations (7)–(10).

qm Ce KL
qe = , (3)
(1 + KL Ce )
( )
1∕n
qe = KF Ce , (4)

qe = BT ln(KT ) + BT ln(Ce ), (5)

EXHIBIT 4 SEM micrograph of the NaOH-activated carbon after
KR Ce
qe = ( ), (6) carbonization
𝛽
1 + 𝛼R Ce
√ ( )2
1 ∑ n
qe,i,exp − qe,i,cal pared NaOH-activated biosorbent (CDAC) increased from 948 to
MPSD = 100 , (7)
nm − np qe,i,exp 1072 m2 /g. The enhancement of the total pore and micropore vol-
i=1

n [ ] umes of CDAC indicate the growth of porosity. The development of

1 ∑ qe,i,exp − qe,i,cal
HYBRID = , (8) pores may be due to the evolution of gaseous carbonization prod-
n−p qe,i,exp i
i=1
ucts (such as CH4 , CO2 , H2 , and H2 O) through carbonaceous masses
∑
n
( )2 and metallic salts produced during carbonization reactions. Poros-
SSE = qe,exp − qe,cal i
, (9)
i=1 ity may be improved during the washing step of NaOH-impregnated
n [ ] biosorbento wing to the removal of metal salts from the internal vol-
∑ qe,exp − qe,cal
CH = . (10) ume. This trend is consistent with the results of previous studies
qe,exp i
i=1
(Hu & Hurt, 2001).
The morphology of the prepared NaOH-impregnated biosorbent
2.5 Preliminary study after a carbonization reaction at 650◦ C (IR = 2.0) is depicted in
Exhibit 4. Further, cavities were observed from the micrographs
A few preliminary experiments were carried out for the biosorption of the NaOH-impregnated biosorbent on the external surface. It
of heavy metals using different sorbents, such as CDAC (0.5), CDAC may be ascribed to the evaporation of NaOH during carboniza-
(1), and CDAC (2). Among these, significant sorption was observed for tion, thereby leaving the space earlier occupied by the NaOH. How-
CDAC (2) as compared with other synthesized sorbents. The charac- ever, numerous small pits distributed over the surface indicate the
terization (BET surface area) results show good agreement with the occurrence of carbon gasification on the external surface during
experimental data and, therefore, CDAC (2) was selected for further carbonization.
experiments and analysis.

3.2 Effect of contact time

3 RESULTS AND DISCUSSION
3.1 Characterization of CDAC
The impregnation ratio is the most important parameter that depicts
the influence of porous structure development in the synthesized
activated carbon during the chemical activation process. The physi-
cal properties of activated carbons, such as BET surface area (SBET ),
micropore volume (Vmicro ), total pore volume (VT ), and average pore
diameter (Dp ) of produced biosorbent from cow dung, are depicted
in Exhibit 3. It can be observed from Exhibit 3 that by increasing
the NaOH/dung ratio from 0.5 to 2.0, the BET surface area of pre-
In adsorption systems, contact time plays a significant role, apart from
other reaction parameters. Determining the optimum contact time to
achieve the highest removal efficiency is considered as an essential
benchmark in batch sorption experiments. In order to investigate
the effect of contact time, other parameters such as adsorbent dose,
initial pH, and temperature were kept constant. Exhibit 5 revealed
that by an increase in contact time, the removal efficiency of heavy
metal increased until a stable plateau region appeared at 300 min,
indicating an equilibrium condition (Jeyaseelan & Gupta, 2016). For
Cr(VI), removal efficiency increased from 18.2% to 93.4% when the
contact time was increased from 15 to 300 min, which may be due to
SARASWAT ET AL .
E X H I B I T 5 Effect of contact time on % removal of heavy metals
[Color figure can be viewed at wileyonlinelibrary.com]
the presence of vacant sites at the initial stage (Barot & Bangla, 2012;
Nwosu-Obieogu & Okolo, 2020).However, there is no appreciable
change in efficiency with further increase in contact time due to
the deposition of ions available on adsorption sites and intraparticle
diffusion processes that dominate over adsorption (Amin, Alazba, &
Shafiq, 2018). A similar trend was observed for both Cd(II) and Ni(II)
metals where the removal efficiency increased from 8.2% to 65.4%
and 4.7% to 16.3%, respectively. Further, subsequent experiments of
biosorption were evaluated at 1200 min.
3.3 Effect of pH
The adsorption capacity of CDAC is strongly dependent on the pH of
the solution. It ascribes to the chemistry of the species in a different
solution. To analyze the effect of pH on the removal efficiency of
metal ions, the pH of the solution was changed from 7.0 to 12.0 and
continuously measured by pH meter. The pH was adjusted in each
run of the experiment by adding 1 N NaOH and 1 N HCl. The pH
range for the biosorption study was selected due to the precipitation
formation of hydroxide ions, which produced chromium below pH 7.0
as it exists in Cr(III) form in acidic solution. The observations were
carried out after certain time intervals, and the percentage of removal
of heavy metals was calculated, whereas biosorbent concentration
remains constant. The effect of pH on the biosorption of metal ions
is shown in Exhibit 6. The results revealed that an increase in pH led
to an enhancement of the metal removal efficiency. For Cr(VI), the
removal efficiency increased in the range of ∼81% to 94%, with pH
increased from 7.0 to 12.0, whereas the removal efficiency for Cd(II)
and Ni(II) increased from ∼56% to 65% and ∼9% to 16%, respectively.
Heavy metal ions such as Cr(VI), Cd(II), and Ni(II) associated with the
biosorbent compete with the hydronium ions (H3 O+ ) for the active
sites. At low pH, the H3 O+ concentration exceeds far beyond the
metal ions and, therefore, it may bound to the sorbent; while at higher
pH, the concentration of H3 O+ decreases due to the absorption of
5
positive-charged metal ions on the active sites of biosorbent (Parab
et al., 2006). Apart from this, at low pH, the adsorption decreased
due to the electrostatic repulsion of the positive-charged (H+ ) ions
(Barot & Bangla, 2012; Parlayici &Pehlivan, 2019). When the pH of
the solution increases, the removal percentage increases owing to
electrostatic attraction of the positively charged surface over OH- ions
(Bayuo, Pelig-Ba, & Abukari, 2019; Nwosu-Obieogu & Okolo, 2020).
3.4 Effect of initial metal ion concentration
The effect of the initial metal concentration of Cr(VI), Ni(II), and Cd(II)
was carried out by batch biosorption experiments at 30◦ C ± 2◦ C
using various initial metal ion concentrations (10, 20, 40, 60, 80, and
100 mg/L) at pH = 12.0. The results depicted in Exhibit 7 indicate that
with an increase in initial metal ion concentration, removal efficiency
decreases (Saiffudin & Raziah, 2007). The results indicated that the
sorption increases with an increase in initial metal ion concentration up
to a certain limit and above which there is no more sorption (Jeyasee-
lan & Gupta, 2016). It may be attributed to the unavailability of adsorp-
tion sites on the adsorption surface. The maximum removal of ∼93%
Cr(VI), ∼65% Cd(II), and ∼16 % Ni(II) was achieved at an initial metal
concentration of 10 mg/L. But when the metal concentration increases,
the available vacant sites decrease, which leads to a lower sorption rate
(Barot & Bangla, 2012). The present study has a good agreement with
the results of Malik, Jain, and Yadav (2017) for heavy metals removal
by low-cost adsorbents.
3.5 Sorption equilibrium study
The Langmuir, Freundlich, Tempkin and Pyzhev, and Redlich and Peter-
son (R–P) isotherm constants of heavy metals (Cr(VI), Cd(II), and Ni(II))
were determined from the plots of qe versus Ce , as illustrated in
Exhibit 8(a–c). Further, all the isotherm constants of heavy metals
along with the correlation coefficient (R2 ) are given in Exhibit 9. Error
functions calculated for isotherm analysis are shown in Exhibit 10.
The comparison of all the isotherms showed that Freundlich and R–
P models were best fitted for the experimental data. The indicator
of the adsorption capacity (KF ) in the Freundlich isotherm for heavy
metals is in the range of 2.85–54.04 mg/g (Febrianto et al., 2009). It
can be seen from Exhibit 9 that Cr(VI) has a high adsorption capac-
ity in comparison with other metals. The smaller value of 1/n indi-
cates a better interaction of heavy metals with the biosorbent. In the
present study, the value of 1/n is estimated in the range of 0.43 to
0.51 for Cr(VI) denoting a strong interaction with the biosorbent. The
Langmuir isotherm was applied for the monolayer saturation at equi-
librium, while R–P isotherm for the homogeneous and heterogeneous
systems. R–P isotherm constant (β) lying in between 0 and 1 indicates
a favorable adsorption condition (Preetha & Viruthagiri, 2007; Srivas-
tava et al., 2007).
Note that Ce (mg/L) and qe (mg/L) represent equilibrium concen-
tration and adsorption capacity, respectively. qm (mg/g) and KL are
6 SARASWAT ET AL .
E X H I B I T 6 Effect of pH on the removal efficiency of
Cr(VI), Cd(II), and Ni(II) metal ions [Color figure can be
viewed at wileyonlinelibrary.com]
E X H I B I T 7 Effect of initial metal concentration on
Cr(VI), Cd(II), and Ni(II) ion removal by CDAC [Color
figure can be viewed at wileyonlinelibrary.com]
Langmuir equilibrium constants indicating the theoretical maximum
adsorption capacity. BT and KT are heat of sorption and Temkin
isotherm constant, respectively. KF and 1/n are the Freundlich con-
stants indicating adsorption capacity and intensity, respectively. KR and
αR are R–P isotherm constants, and β is the exponent that lies between
0 and 1.
4 PRACTICAL APPLICATION OF COW DUNG
AS AN ADSORBENT
The bioadsorbent has recently gained attention owing to its low cost,
less toxicity, its use in environmental applications for the removal
of toxic compounds from various industries, including textiles, pulp,
paper, petroleum and so on. Exhibit 2 shows different biosorbents
employed for the removal of heavy metals in water. The synthesized
biosorbent has high efficiency, low energy requirements, reuse, and
regeneration and is best suitable for the removal of organic and inor-
ganic pollutants in small-scale industries. In addition, the bioadsor-
bent can be utilized in an effluent treatment plant after secondary
treatment to remove the trace amount of heavy metals. The regener-
ated biosorbent is employed as a solid fuel in construction industries
due to high porosity, crushing strength, and binding properties. Fur-
ther, these biosorbents are beneficial in the removal of fluoride from
drinking water and are an eco-friendly electrode material for energy
production.
SARASWAT ET AL . 7

E X H I B I T 8 Equilibrium isothermal adsorption of (a) Ni(II), (b) Cd(II), and (c) Cr(VI) onto CDAC at different initial concentrations [Color figure
can be viewed at wileyonlinelibrary.com]

EXHIBIT 9 Equilibrium parameters for the adsorption of heavy EXHIBIT 10 Error functions for isotherm analysis
metals
Metals Models MPSD HYBRID SSE CHI
Isotherms Constants Ni(II) Cd(II) Cr(VI) Ni(II) Langmuir 10.68 7.42 7.45 0.68
Langmuir qm (mg/g) 28.63 170.50 240.21 Freundlich 2.59 2.16 39.86 0.35
KL (L/mg) 0.03 0.04 0.06 Tempkin 38.76 35.40 20,958.35 131.11
2
R 0.99 0.99 0.99 R–P 2.67 1.97 40.96 0.38
Freundlich 1/n 0.51 0.57 0.43 Cd(II) Langmuir 10.19 8.38 506.63 4.51
KF [(mg/g)/ 2.85 17.23 54.03 Freundlich 9.11 6.13 383.73 3.87
(mg/L)1/n ]
Tempkin 38.76 35.40 20,958.35 131.11
R2 0.99 1.00 1.00
R–P 2.67 1.97 40.96 0.38
Tempkin B1 (L/g) 8.00 13.85 50.46
Cr(VI) Langmuir 31.37 17.30 2251.06 36.39
KT (J/mol) 0.30 6.59 3.16
Freundlich 9.11 6.13 383.73 3.87
R2 0.99 0.97 0.94
Tempkin 0.94 33.92 26.17 5317.54
R–P αR (L/mg) 35.00 10.40 40,791.02
R–P 9.84 7.16 383.71 3.88
KR (L/g) 96.78 186.40 2,204,101.44
B 0.48 0.43 0.57
2
5 CONCLUSIONS
R 0.99 1.00 1.00

The present study demonstrates an easy and efficient conversion of

biological waste material to a value-added product. Synthesized CDAC
8 SARASWAT ET AL .
samples possess a high surface area with a significant amount of micro-
pores and mesopores. The results revealed that the activated carbon
derived from cow dung efficiently removes 95.6% Cr(VI) and 66.88%
Cd(II) from industrial effluent. However, produced activated carbon is
not effective for the removal of nickel Ni(II) metal species. The effects
of pH, contact time, and initial metal ion concentration are the most
influencing parameters for the removal of heavy metals from industrial
wastewater. The obtained experimental data are best fitted for Fre-
undlich and R–P isotherm models.
ACKNOWLEDGMENT
The financial support provided by TEQIP-III of MBM Engineering
College, Jodhpur, for carrying out this study is gratefully acknowl-
edged.
CONFLICTS OF INTEREST
The authors declare no conflict of interest whatsoever.
ORCID
Sushil Kumar Saraswat https://orcid.org/0000-0002-4720-644X
REFERENCES
Abas, S. N. A., Ismail, M. H. S., Kamal, M. L., & Izhar, S. (2013). Adsorption
process of heavy metals by low-cost adsorbent: A review. World Applied
Sciences Journal, 28(11), 1518–1530.
Ahluwalia, S. S., & Goyal, D. (2007). Microbial and plant derived biomass
for removal of heavy metals from wastewater. Bioresource Technology,
98(12), 2243–2257.
Ahmad, A., Khan, N., Giri, B. S., Chowdhary, P., & Chaturvedi, P. (2020).
Removal of methylene blue dye using rice husk, cow dung and sludge
biochar: Characterization, application, and kinetic studies. Bioresource
Technology, 306, 123202. https://doi.org/10.1016/j.biortech.2020.
123202.
Ajmal, M., Rao, R. A. K., Ahmad, R., & Ahmad, J. (2000). Adsorption studies
on Citrus reticulata (fruit peel of orange): Removal and recovery of Ni (II)
from electroplating wastewater. Journal of Hazardous Material, 79(1–2),
117–131.
Aman, T., Kazi, A. A., Sabri, M. U., & Bano, Q. (2008). Potato peels as
solid waste for the removal of heavy metal copper (II) from waste
water/industrial effluent. Colloids and Surfaces B: Biointerfaces, 63(1),
116–121.
Amin, M. T., Alazba, A. A., & Shafiq, M. (2018). Removal of copper and lead
using banana biochar in batch adsorption systems: Isotherms and kinetic
studies. Arabian Journal Science and Engineering, 43(11), 5711–5722.
Amuda, O., Adelowo, F., & Ologunde, M. (2009). Kinetics and equilibrium
studies of adsorption of chromium (VI) ion from industrial wastewater
using chrysophyllum albidum (Sapotaceae) seed shells. Colloids and Sur-
faces B: Biointerfaces, 68(2), 184–192.
Apiratikul, R., & Pavasant, P. (2008). Batch and column studies of biosorp-
tion of heavy metals by caulerpa lentillifera. Bioresource Technology, 99(8),
2766–2777.
Ates, N., & Uzal, N. (2018). Removal of heavy metals from aluminum anodic
oxidation wastewaters by membrane filtration. Environmental Science and
Pollution Research, 25, 22259–22272.
Babalola, B. (2018). Investigating adsorption characteristics of delonix regia
for heavy metals removal in wastewater and its potential for remediating
contaminated soils. Lancaster University, PhD Thesis.
Barot, N. S., & Bagla, H. K. (2012). Eco-friendly waste water treatment by
cow dung powder (adsorption studies of Cr(III), Cr(VI) and Cd(II) using
tracer technique). Desalination and Water Treatment, 38(1–3), 104–113.
Bartczak, P., Norman, M., Klapiszewski, L., Karwańska, N., Kawalec, M.,
Baczyńska, M., . . . Jesionowsk, T. (2018). Removal of nickel(II) and lead(II)
ions from aqueous solution using peat as a low-cost adsorbent: A kinetic
and equilibrium study. Arabian Journal of Chemistry, 11, 1209–1222.
Bayuo, J., Pelig-Ba, K. B., & Abukari, M. A. (2019). Adsorptive removal
of chromium (VI) from aqueous solution unto groundnut shell. Applied
Water Science, 9(107), 1–13.
Burakov, A. E., Galunin, E. V., Burakova, I. V., Kucherova, A. E., Agarwal, S.,
Tkachev, A. G., & Gupta, V. K. (2018). Adsorption of heavy metals on con-
ventional and nanostructured materials for wastewater treatment pur-
poses: A review. Ecotoxicology and Environmental Safety, 148, 702–712.
Eissa, M. A. (2019). Effect of cow manure biochar on heavy metals uptake
and translocation by zucchini (Cucurbita pepo L). Arabian Journal of Geo-
sciences, 12(2), 48. https://doi.org/10.1007/s12517-018-4191-1.
Febrianto, J., Kosasih, A. N., Sunarso, J., Ju, Y. H., Indraswati, N., & Ismadji,
S. (2009). Equilibrium and kinetic studies in adsorption of heavy met-
als using biosorbent: A summary of recent studies. Journal of Hazardous
Materials, 162(2–3), 616–645.
Freudlich, H. (1906). Over the adsorption in solution. Journal of Physical
Chemistry, 57, 385–471.
Fu, F., & Wang, Q. (2011). Removal of heavy metal ions from wastewaters: A
review. Journal of Environmental Management, 92(3), 407–418.
Ghomi, A. G., Asasian-Kolur, N., Sharifian, S., & Golnaraghi, A. (2020). Biosor-
pion for sustainable recovery of precious metals from wastewater. Jour-
nal of Environmental Chemical Engineering, 8(4), 103996. https://doi.org/
10.1016/j.jece.2020.103996.
Gunarathne, D. S., Udugama, I. A., Jayawardena, S., Gernaey, K. V., Mansouri,
S. S., & Narayana, M. (2019). Resource recovery from bio-based produc-
tion processes in developing Asia. Sustainable Production and Consump-
tion, 17, 196–214.
Hu, Y., & Hurt, R. H. (2001). Thermodynamics of carbonaceous mesophase:
II. General theory for nonideal solutions. Carbon, 39(6), 887–896.
Indian Standard. (2012). Bureau of Indian standards drinking water specifi-
cations. BIS.10500. New Delhi, India.
Jeyaseelan, C., & Gupta, A. (2016). Green tea leaves as a natural adsorbent
for the removal of Cr (VI) from aqueous solutions. Air, Soil and Water
Research, 9(1), 13–19.
Jusoh, A., Shiung, L. S., & Noor, M. (2007). A simulation study of the removal
efficiency of granular activated carbon on cadmium and lead. Desalina-
tion, 206(1–3), 9–16.
Kaczala, F., Marques, M., & Hogland, W. (2009). Lead and vanadium
removal from a real industrial wastewater by gravitational set-
tling/sedimentation and sorption onto Pinus sylvestris sawdust.
Bioresource Technology, 100(1), 235–243.
Karnib, M., Kabbani, A., Holail, H., & Olama, Z. (2014). Heavy metals removal
using activated carbon, silica and silica activated carbon composite.
Energy Procedia, 50, 113–120.
Kaur, K., Mor, S., & Ravindra, K. (2016). Removal of chemical oxygen demand
from landfill leachate using cow-dung ash as a low-cost adsorbent. Jour-
nal of Colloid and Interface Science, 469, 338–343.
Kobya, M., Demirbas, E., Senturk, E., & Ince, M. (2005). Adsorption of heavy
metal ions from aqueous solutions by activated carbon prepared from
apricot stone. Bioresource Technology, 96(13), 1518–1521.
Lalmi, A., Bouhidel, K. E., Sahraoui, B., & Anfif, C. H. (2018). Removal of lead
from polluted waters using ion exchange resin with Ca (NO3 )2 for elution.
Hydrometallurgy, 178, 287–293.
Langmuir, I. (1918). The adsorption of gases on plane surfaces of glass, mica
and platinum. Journal of the American Chemical Society, 40(9), 1361–1403.
Luo, S. L., Lin, Y., Chai, L. Y., Min, X. B., Wang, Y. Y., Yan, F., & Pu, W. (2006).
Biosorption behaviors of Cu2+ , Zn2+ , Cd2+ and mixture by waste acti-
vated sludge. Transactions of Nonferrous Metals Society of China, 16(6),
1431–1435.
Malik, D. S., Jain, C. K., & Yadav, A. K. (2017). Removal of heavy metals from
emerging cellulosic low-cost adsorbents: A review. Applied Water Science,
7, 2113–2136.
SARASWAT ET AL .
Mata, Y. N., Blázquez, M., Ballester, A., González, F., & Munoz, J. (2009).
Sugar-beet pulp pectin gels as biosorbent for heavy metals: Preparation
and determination of biosorption and desorption characteristics. Chemi-
cal Engineering Journal, 150(2–3), 289–301.
Ngah, W. W., & Hanafiah, M. (2008). Removal of heavy metal ions from
wastewater by chemically modified plant wastes as adsorbents: A
review. Bioresource Technology, 99(10), 3935–3948.
Nguyen, T., Ngo, H., Guo, W., Zhang, J., Liang, S., Yue, Q., . . . Nguyen, T. V.
(2013). Applicability of agricultural waste and by-products for adsorp-
tive removal of heavy metals from wastewater. Bioresource Technology,
148, 574–585.
Nwosu-Obieogu, K., & Okolo, B. I. (2020). Biosorption of chromium (VI) from
textile waste water using luffa cylindrica activated carbon. Environmental
Quality Management, 1–9. https://doi.org/10.1002/tqem.21687.
Oliveira, L. S., Franca, A. S., Alves, T. M., & Rocha, S. D. (2008). Evaluation
of untreated coffee husks as potential biosorbents for treatment of dye
contaminated waters. Journal of Hazardous Materials, 155(3), 507–512.
Padmavathy, V. (2008). Biosorption of nickel (II) ions by baker’s yeast:
Kinetic, thermodynamic and desorption studies. Bioresource Technology,
99(8), 3100–3109.
Parab, H., Joshi, S., Shenoy, S. N., Lali, A., Sarma, U., & Sudersanan, M.
(2006). Determination of kinetic and equilibrium parameters of the
batch adsorption of Co (II), Cr (III) and Ni (II) onto coir pith. Process Bio-
chemistry, 41(3), 609–615.
Park, H. J., Jeong, S. W., Yang, J. K., Kim, B. G., & Lee, S. M. (2007). Removal
of heavy metals using waste eggshell. Journal of Environmental Sciences,
19(12), 1436–1441.
Parlayici, S., & Pehlivan, E. (2019). Comparative study of Cr (VI) removal by
bio-waste adsorbents: Equilibrium, kinetics and thermodynamics. Jour-
nal of Analytical Science and Technology, 10(15), 10–15.
Pehlivan, E., Yanık, B., Ahmetli, G., & Pehlivan, M. (2008). Equilibrium
isotherm studies for the uptake of cadmium and lead ions onto sugar
beet pulp. Bioresource Technology, 99(9), 3520–3527.
Preetha, B., & Viruthagiri, T. (2007). Batch and continuous biosorption of
chromium (VI) by Rhizopus arrhizus. Separation and Purification Technol-
ogy, 57(1), 126–133.
Purkayastha, D., Mishra, U., & Biswas, S. (2014). Comprehensive review on
Cd (II) removal from aqueous solution. Journal of Water Process Engineer-
ing, 2, 105–128.
Qian, Q., Machida, M., & Tatsumoto, H. (2008). Textural and surface chemical
characteristics of activated carbons prepared from cattle manure com-
post. Waste Management, 28(6), 1064–1071.
Rangabhashiyam, S., Jayabalan, R., Rajkumar, M. A., & Balasubramanian, P.
(2019). Elimination of toxic heavy metals from aqueous systems using
potential biosorbents: A review. Green Buildings and Sustainable Engineer-
ing, 1, 291–311.
Redlich, O., & Peterson, D. L. (1959). A useful adsorption isotherm. Journal of
Physical Chemistry, 63(6), 1024.
Saeed, A., Iqbal, M., & Akhtar, M. W. (2005). Removal and recovery of
lead (II) from single and multimetal (Cd, Cu, Ni, Zn) solutions by crop
milling waste (black gram husk). Journal of Hazardous Materials, 117(1),
65–73.
Saiffudin, N., & Raziah, A. Z. (2007). Removal of heavy metal from industrial
effluent using sacchromyces cervisiae (bakers yeast) immobilised in chi-
tosan. Journal of Applied Sciences Research, 3(12), 2091–2099.
Srivastava, V. C., Mall, I. D., & Mishra, I. M. (2007). Adsorption thermodynam-
ics and isosteric heat of adsorption of toxic metal ions onto bagasse fly
ash (BFA) and rice husk ash (RHA). Chemical Engineering Journal, 132(1–
3), 267–278.
Suresh, S., Vijayalakshmi, G., Rajmohan, B., & Subbaramaiah, V. (2012).
Adsorption of benzene vapor onto activated biomass from cashew nut
shell: Batch and column study. Recent Patents on Chemical Engineering,
5(2), 116–133.
Tempkin, M., & Pyzhev, V. (1940). Heavy metals removal and isotherms
study. Acta Physiochim URSS, 12, 217–222.
9
Teshale, F., Karthikeyan, R., & Sahu, O. (2020). Synthesized bioadsorbent
from fish scale for chromium (III) removal. Micron, 130, 102817.
Vasanthakumar, K., & Bhagavanalu, D. (2003). Adsorption of basic dye from
its aqueous solution on to bioorganic waste. Journal of Industrial Pollution
Control, 19, 20–28.
Vilar, V. J., Botelho, C. M., & Boaventura, R. A. (2007). Chromium and zinc
uptake by algae gelidiumand agar extraction algal waste: Kinetics and
equilibrium. Journal of Hazardous Materials, 149(3), 643–649.
Wang, X. J., Xia, S. Q., Ling, C., Zhao, J. F., Chovelon, J. M., & Nicole, J. R.
(2006). Biosorption of cadmium (II) and lead (II) ions from aqueous solu-
tions onto dried activated sludge. Journal of Environmental Sciences, 18(5),
840–844.
AUTHOR BIOGRAPHIES
Sushil Kumar Saraswat is an associate professor at MBM Engi-
neering College, Jai Narain Vyas University Jodhpur, Rajasthan,
India. He has completed his PhD in Chemical Engineering from
the Indian Institute of Technology (IIT) Delhi, Master’s (MTech.)
in Chemical Engineering with specialization in Industrial Pollu-
tion Abatement from IIT Roorkee, and BE in Chemical Engineer-
ing from the National Institute of Technology (NIT) Durgapur, India.
He has expertise in the field of heterogeneous catalysis, bioenergy,
supercapacitor, photoelectrochemical water splitting and thermo-
catalytic decomposition method to Cox free hydrogen production
focusing on the efficient transformation process. Recently, he was
awarded with India’s most prestigious ‘Raman Postdoctoral Fel-
lowship (2016–17)’ in which he worked at Virginia Commonwealth
University, USA, on recent advancement in semiconductor mate-
rial for photoelectrochemical water splitting using visible light for
hydrogen production. He is also an awardee of Indo-Hungarian
Education Exchange Programme (EEP) Fellowship for the year
2013–14 from the University Grants Commission, New Delhi. He
has four international patents, which include US, European, Cana-
dian and world patents, with more than 13 original research pub-
lication research papers in international peer-reviewed journals
with more than 319 citations and book chapter. He has also pre-
sented research papers in more than 20 international and national
conferences. Apart from this, he is also a member of various Chem-
ical Engineering professional bodies, including AIChE (USA), the
Indian Institute of Chemical Engineers (IIChE), the Indian Society of
Technical Education (MISTE), the Institution of Engineers (AMIE),
and the Catalysis Society of India.
Muslum Demir is an assistant professor at Osmaniye Korkutata
University, Osmaniye, Turkey. He received his PhD in Professor
Ram Gupta’s lab at Virginia Commonwealth University (Virginia,
USA) in 2017. He received his MS in Chemistry from Rutgers Uni-
versity (USA) in 2013 and his BS in Chemistry from Cukurova
University (Turkey) in 2008. His research focused on the devel-
opment of biomass-derived carbon materials for energy storage
and conversion applications. He has published more than 10 peer-
reviewed papers and attended prestigious conferences such as
ACS, AIChE, and ECS meetings.
10
Vijayalakshmi Gosu is an assistant professor at the Department
of Chemical Engineering, MBM Engineering College, Jai Narain
Vyas University, Jodhpur, from January 2018 to January 2020. She
moved to MNIT Jaipur in January 2020. She earned her doctoral
program at IIT Roorkee in 2014 and did MTech from NIT Karnataka
in 2009. Her current research interest includes the green process
for water and wastewater treatment, development of a heteroge-
neous catalyst for waste to energy process.
SARASWAT ET AL .
How to cite this article: Saraswat SK, Demi M, Gosu V.
Adsorptive removal of heavy metals from industrial effluents
using cow dung as the biosorbent: Kinetic and isotherm
modeling. Environ Qual Manage. 2020;1–10.
https://doi.org/10.1002/tqem.21703