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Removal of pollutants from aqueous media using cow dung-based adsorbents

Kingsley O. Iwuozor, Ebuka Chizitere Emenike, Chukwunonso O. Aniagor, Felicitas

U. Iwuchukwu, Enoch Mayowa Ibitogbe, Okikiola Boluwape Temitayo, Patrick E.
Omuku, Adewale George Adeniyi

PII: S2666-0865(22)00042-X
DOI: https://doi.org/10.1016/j.crgsc.2022.100300
Reference: CRGSC 100300

To appear in: Current Research in Green and Sustainable Chemistry

Received Date: 27 December 2021

Revised Date: 28 February 2022
Accepted Date: 7 March 2022

Please cite this article as: K.O. Iwuozor, E.C. Emenike, C.O. Aniagor, F.U. Iwuchukwu, E.M. Ibitogbe,
O.B. Temitayo, P.E. Omuku, A.G. Adeniyi, Removal of pollutants from aqueous media using cow
dung-based adsorbents, Current Research in Green and Sustainable Chemistry (2022), doi: https://
doi.org/10.1016/j.crgsc.2022.100300.

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Removal of pollutants from aqueous media using Cow dung-based adsorbents

Kingsley O. Iwuozor1*, Ebuka Chizitere Emenike1, Chukwunonso O. Aniagor2, Felicitas U.

Iwuchukwu2, Enoch Mayowa Ibitogbe3, Okikiola Boluwape Temitayo4, Patrick E. Omuku1,
Adewale George Adeniyi5**
1
Department of Pure and Industrial Chemistry, Nnamdi Azikiwe University, P. M. B. 5025, Awka,
Nigeria.
2
Department of Chemical Engineering, Nnamdi Azikiwe University, P. M. B. 5025, Awka, Nigeria
3
Department of Civil Engineering, Landmark University, Omu-Aran, Kwara state, Nigeria.
4
Department of Animal Production, Landmark University, Omu-Aran, Kwara state, Nigeria.

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Department of Chemical Engineering, University of Ilorin, P. M. B. 1515, Ilorin, Nigeria

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*Corresponding author 1, Email address: kingsleyiwuozor5@gmail.com

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**Corresponding author 2, Email address: adeniyi.ag@unilorin.edu.ng
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Abstract
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An ideal adsorbent must be relatively cheap, abundant, easily undergo modification, and
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exhibit better removal efficiency. Animal wastes are much better adsorbents in comparison with
activated carbon adsorbents with respect to being cost-effective and their zero regeneration
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process factor. The review aims to report the efficiency of utilized cow-dung based adsorbents
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for the sequestration of a wide spectrum of pollutants from aqueous media. It discusses the
potential of utilizing cow dung as a cheap and effective adsorbent. It was observed that cow
dung-based adsorbents were efficient for the removal of dyes, heavy metals, and other pollutants
from aqueous solutions. The maximum reported uptake capacity of dyes and heavy metals was
501 mg/g and 625.26 mg/g for Methylene blue and lead, respectively, which were both for cow
dung activated carbon. The Langmuir and Freundlich isotherm models emerged as the best-fit
models for almost all studies. Based on the review outcome, a pseudo-second-order model was
reported as the kinetic model of best fit in all cases. Other adsorption studies such as adsorption
mechanism, thermodynamic modelling, desorption, column adsorption, and competitive
adsorption were also included in this study. Finally, the study identified some knowledge gaps
that could aid future investigation in this research field. Summarily, it can be deduced that cow

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dung-based adsorbent has exhibited good potential as an adsorbent for the mitigation of
pollutants from water.

Graphical Abstract

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Keywords: adsorption, cow dung, dyes, equilibrum modelling, heavy metals, pollutants
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1. Introduction
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Industrialization is the major cause of pollution in the hydrosphere, and this is of great
concern to environmentalists as pollution poses a great danger to plants, animals, and the
environment [1]. In addition, hazardous metal compounds on the surface of the earth, pollute
water bodies like seas, ponds, reservoirs, and lakes as well as underground water leaked out in
small quantities from the soil after rain [2, 3]. These activities and more lead to the pollution of
the environment by various pollutants. Examples of some of these pollutants are heavy metals
(such as Chromium [4], Cobalt [5], Strontium [6], Cadmium [7], and Lead [8]) and dyes. Some
of these pollutants are non-biodegradable and further accumulate in the food chain [6, 9]. The
pollutants churned out by some industries, such as textiles, rubber, plastic, pulp, and paint
industries, are mostly dyes [10]. Dyes are very toxic compounds used in these industries, and
their effluents are discharged into the water bodies and ecosystems [11, 12]. They form

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carcinogenic compounds when they undergo anaerobic degradation and, in intense situations,
can obstruct sunlight and oxygen penetration [13].

To reduce the pollution load on the hydrosphere, several scientists have undergone
various studies by utilizing various techniques for the removal of such pollutants. These
techniques are majorly sub-divided into three categories: biological techniques, which involve
the use of enzymes or micro-organisms such as the activated sludge process; physical techniques
such as coagulation/flocculation, adsorption, and membrane filtration; and chemical techniques
such as ozonation, ion exchange, chemical precipitation, and advanced oxidation [14-16]. A
large body of literature exists that supports the utilization of adsorption over other techniques due

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to its relatively simplicity of design and operation, environmental friendliness, energy efficiency,

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and low cost [17, 18]. Adsorption is very important in the treatment of effluent [19]. Properties
of the adsorbents can be highlighted based on the adsorbent material. Carbon nanotubes, for

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example, have good mechanical properties, large activated surface area, chemical stability [20-
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22], azo dyes stability and resistance due to the presence of aromatic groups [19]. Various
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adsorbents have been utilized in the removal of pollutants from aqueous solutions. Activated
carbon (AC) is one of the most popular adsorbents commonly used for the adsorption of
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pollutants from water, but due to its high cost, poor removal, and recyclability properties, the
need to obtain better alternatives has been widely considered and studied [23]. An ideal
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adsorbent must be relatively cheap, abundant, easily undergo modification, and exhibit better
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removal efficiency [6]. In developing countries, dumping animal waste products as solid trash in
the environment without processing or composting, or simply washing them into water canals,
has dangerous health consequences for humans and other living species. If these animal wastes
are disposed off carelessly, the prospect of utilizing them for a positive purpose is gone [24].
Some studies have focused on the use of these animal waste products as a low-cost, readily
available adsorbent for heavy metal removal from wastewater. Animal wastes such as fish bones
[25-27], pig bones [28, 29], egg shells [30-32], crab shells [33-35], and poultry litter [36-38]
have been studied as possible adsorbents for pollutants' removal. Activated carbon is also
prepared from animal wastes such as goat dung. Research carried out on the adsorption of lead
on goat dung activated carbon showed its dependency on factors like pH, dosage of adsorbent,
concentration of the metal and temperature, and contact time [39]. The adsorption rate was

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directly proportional to the increasing biosorbent dosage and inversely proportional to increasing
lead concentration, optimium pH of 4.5 and activated carbon equilibrium time of 60 minutes.

One of the fastest growing global industries is dairy farming. According to Ananno,
Masud, Mahjabeen and Dabnichki [40], the world's cattle population reached 987.51 million
head in 2020. Furthermore, the estimated global dairy market value is 673.8 billion dollars,
which is predicted to surpass one trillion dollars by 2024 [40]. As a result, it is clear that the
increase in cattle farming as well as the cattle population will not be reduced in the foreseeable
future. As the cattle population grows, so does the amount of dung produced, resulting in
unavoidable waste management issues. Livestock dung is a major public health and

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environmental problem because it emits hazardous germs, toxic gases, and odors [41]. Cow dung

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may be described as the undigested residue obtained from food materials excreted by
herbivorous animal species (cattle). It contains urine and faeces in a 3:1 ratio, with lignin,

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cellulose, and hemicellulose as its main components [42]. Valorization of cow-dung is an
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important solid waste management practice that can help solve environmental problems created
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by the dung as well as provide value-added products that can be of great benefit to mankind.
Cow dung has been used for the production of bio-fertilizer [43, 44], as a source of solid fuel and
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energy [45-47], as reinforcement of friction composites [48, 49], as vermicompost [50, 51]. It is
an animal by-product with great adsorbent potential for pollutant removal from wastewater [52].
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Cow dung consists of 12.5% CaO, 0.9% MgO, 0.3% CaSO4, 20% Al2O3, 20% FeO, and 61%
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SiO2. The high percentage of silica accounts for its high affinity for metal ions. It can be used as
an adsorbent in its unmodified (UCD) form or converted into biochar (CDC) or activated carbon
(CDAC). Sometimes, sodium carbonate is used to treat cow dung before it is incinerated. This
process reduces the pungent odour emanating from the dung and can act as a chemical activator
to the adsorbent [53, 54].

Apart from the large amounts of cow dung that are readily available to be used as an
adsorbent, lots of studies have been carried out within the last decade utilizing cow dung as an
adsorbent for the mitigation of pollutants. This informed our choice of cow dung as an adsorbent
in this study. Ojedokun and Bello [55] reviewed the use of cow dung as an adsorbent for the
removal of heavy metals from aqueous solutions. Although the review was comprehensive, lots
of other studies have been published in this field. In addition, their study didn’t cover the entire

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spectrum of pollutants that have been mitigated from aqueous solutions using cow dung-based
adsorbents. In view of this, this study was aimed at discussing the utilization and conversion of
cow dung as an adsorbent. The novelty of this study is that it is a review of studies that have
utilized cow dung-based adsorbents for the sequestration of a wide range of pollutants from
aqueous media. The study discusses the preparation and adsorption performance of cow dung-
based adsorbents. Kinetic and isotherm studies, thermodynamic studies, mechanism studies,
regeneration studies, and competitive adsorption studies were also reviewed.

2. Cow dung-based adsorbent preparation

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Due to their availability throughout several continents, cow dung-based adsorbents have

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been explored for the removal of various types of pollutants from aqueous media. For ease and

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clarity, the discussion in the subsequent subsections is presented in terms of the adsorbents'
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broad groupings, namely, cow dung biochar (CDC), cow dung activated carbon (CDAC) and
unmodified cow dung (UCD) as shown in Figure 1.
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Cow dung-based
adsorbents
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Unmodified cow Cow dung activated

Cow dung biochar
dung carbon

Figure 1: Classification of cow dung-based adsorbents

2.1. Unmodified cow dung adsorbent

UCD can be generally obtained by drying cow-dung cakes in the presence of sunlight or
in a furnace to evaporate its moisture and increase the number of active sites for the adsorption
process to give the cow dung ash [56, 57]. Bhatt and Bagla [58] reported that fresh samples were
collected from the respective sampling locations, sundried for several days before grinding them
to the required particle size. Conversely, Chen, Qin, Sun, Cheng and Shen [59] and Garba, Abd

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Samsuri, Othman and Hamdani [23] air-dried the fresh cow dung sample before milling to the
required particle size. However, Bhatt and Bagla [58] highlighted the need for proper drying
before use, especially when dealing with acidic effluent or those with alcohol functional groups.
According to the author, proper sample drying will prevent the oxidation of the cow dung
adsorbent. It has also been reported that after the initial drying, it was necessary to wash the cow
dung ash with distilled water and then dry again to remove some impurities on its surface [60].
After drying, the cow dung ash could then be sieved to obtain fine particles with a larger surface
area.

2.2. Cow dung biochar

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Generally, biochars are carbonized biomass that is devoid of any form of chemical or

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physicochemical activation [61]. According to Wan, Wu, Liu, Zhao, Fu and Xiao [52], the
biochar production process is a revolutionary approach to curbing global climate change, as CO2

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release due to open burning of biomass is mitigated. Consequently, cow dung biochar (CDC) is
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the refractory product of cow dung pyrolysis under intense hypoxic conditions. The majority of
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the authors prepared the cow dung biochar in a Pyrolysis reactor maintained either at 500 °C for
3 h [10, 61] or 700 °C for 2 h [52, 62] with temperature ramping at the rate of 5 °C/min as shown
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in table 1. During the biochar production in the reactor, nitrogen gas is sometimes supplied to
the material in a bid to prevent the formation of ash as well as to sustain the inert condition in the
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reactor [10]. It was also observed that the yield as well as the specific surface area (SSA) of CDC
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are dependent on the pyrolysis operating conditions. Chen, Wang, Tian, Liu, Ma, Liu and Li [7]
adopted both slow and fast pyrolysis approaches. In the procedure, the collected cow dung was
pulverized and subsequently oven-dried at 105 °C overnight. The oven-dried cow dung was
further subjected to slow pyrolysis in a tubular furnace (OTF-1200X) with a nitrogen purge gas
at a flow of 50 mL/min. The pyrolysis temperature was initially raised to 500 °C (at a heating
rate of 4 °C/min) and the temperature was maintained for 2 h. After cooling to room temperature,
the obtained biochar was ground with KOH at a mass ratio of 1:2 for 5 min, and re-heated in a
tubular furnace at 700 °C (with a heating rate of 2 °C/min) and kept at this temperature for 1 h.
Afterwards, the mixture was soaked in 60 % HF solution for 6 h. Finally, the resulting solid was
washed with distilled water three times and dried at 105 °C overnight.
2.3. Cow dung activated carbon adsorbent

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CDAC can be obtained from the chemical activation of UCD. In addition, Peng, Gao, Chu, Pan,
Peng and Xing [63] believe in the need to further functionalize/activate the CDC for optimum
sorption performance. Therefore, cow dung activated carbon (CDAC) can also be obtained upon
further activation of the biochar analogue. The CDAC and CDC have similar application
characteristics except for slight morphological variations, which are mostly related to porosity. It
is believed that the treatment of biochar via chemical or physical activation further enhances its
porosity [64]. During the synthesis, all authors adopted a pre-carbonization activation approach.
Thus, the cow dung samples were chemically activated before carbonization. Meanwhile, the
author gave no reason for the choice of synthesis protocol. According to the reviewed literature,

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fresh cow dung were collected, sun-dried, grinded and sieved to the desired particle size before
chemical activation. Elaigwu, Usman, Awolola, Adebayo and Ajayi [8] and Das, Mahapatra,

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Pradhan, Das and Thakur [4] used sulphuric acid as the activating agent while Rajkumar2019

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used 0.05 M CaCl2 and 0.05 M FeCl3. During the chemical activation process, a known mass of
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the dried and size-reduced cow dung sample contained in a beaker was contacted with a certain
volume of the activating agent(s) that is enough to form a slurry. After stirring for about 5 min,
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the set-up was left to stand undisturbed for 24 hours. Afterwards, the activated cow dung sample
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is obtained as filtration residue from the mixture and oven-dried at 100 oC for 3 hours. The
impregnated and dried cow dung residue was carbonized in a muffle furnace at different
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temperatures (300 oC, 500 oC or 700 oC) for 2 hours to produce the desired cow dung activated
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carbon. Elaigwu, Usman, Awolola, Adebayo and Ajayi [8] noted that chemical activation at
moderate temperatures produces a high surface area and a high degree of microporosity. Using a
similar approach, Hayder, Hussain, Ahmad, Jahanzaib and Ullah [65] and [66] synthesized cow
dung activated carbon using potassium hydroxide (KOH) and hydrochloric acid (HCl).
Various studies have been performed to optimize the functionality of CDAC and CDC,
such as the determination of the effect of different bases on the functionality of CDAC [67], the
effect of pyrolysis temperature on CDC’s yield [68], the effect of different chemical activators
on the yield and properties of CDAC [66], and the effect of different activators and impregnation
ratio on the functionality of CDAC [69]. Various characterization techniques, as shown in table
1, have been employed to study the properties of cow dung-based adsorbents, such as FTIR,
SEM, BET, TGA, XRF, ICP-OES, elemental analyzer, and Boehm titration. Fourier transform
infrared (FTIR) was used to determine the functional groups inherent in the adsorbent [70, 71];

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 Brunauer-Emmet-Teller (BET) was used to determine the specific surface area [72, 73]; X-ray
fluorescence (XRF) was used to examine the cow dung-based adsorbent at optimal modification
conditions in order to determine the elemental compositions of the adsorbent [74, 75]; Scanning
electron microscopy (SEM) was used to study the morphology of the adsorbent [76, 77]; X-ray
diffraction (XRD) was used to evaluate the crystallinity and material purity tests of the prepared
product [78, 79]; Thermogravimetric analysis (TGA) is used to evaluate the thermal stability of
the prepared adsorbent [80, 81]; Boehm titration was used to determine the concentration of
oxygenated surface functional groups on the adsorbent [82, 83]; and Inductively coupled plasma
optical emission spectrometry (ICP-OES) was used to analyze the metal content in the adsorbent

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[84, 85].
Table 1. Summary of methodology for the preparation of cow dung-based adsorbents

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Adsorben Modification/Activation Carbonization Characterization BET Yield Refs.

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t class Reagent Process Temp Heating Time SSA (wt%)
(℃) rate (hrs.)
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(℃/min)
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UCD - - - - - XRF, CHNSO elemental - - [58]

analyzer, FTIR, FEG-SEM,
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EDS
UCD - - - - - FTIR, SEM, EDS - - [86]
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UCD - - - - - FTIR, SEM - - [60]

UCD - - 500 - - - - - [87]
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UCD - - - - - Elemental analyzer, SEM, BET, 9.731 - [23]

Boehm titration, ICP-OES
CDC - - 600 10 2 - - 49.40 [68]
CDC - Pyrolysis 600 10 - FESEM, FTIR, XRP, BET, 1.565 38.36 [88]
elemental analyzer
CDC - Pyrolysis 500 5 3 SEM, EDS, FTIR - - [10]
CDC - Pyrolysis 700 5 2 Zeta potential analyzer, XPS, 6.770 - [52]
FTIR, elemental analyzer,
Boehm titration, BET, SEM,
chromatograph system, ICP-
OES
CDC - Pyrolysis 700 5 2 SEM, EDS, BET, elemental 141.7 38.34 [62]
analyzer, XRD, FTIR

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CDC - Pyrolysis 500 5 3 SEM-EDS, FTIR - 29.80 [61]
CDAC NaOH Pyrolysis + 650 - 2 SEM, AAS 1072 - [67]
Base
activation
CDAC H2SO4 Acid - - - - - - [42]
activation
CDAC CaCl2 + Salt 500 - 3 SEM, EDS, XRD, elemental 19.20 - [89]
FeCl3 activation + analyzer, FTIR, Boehm’s
Pyrolysis titration
CDAC Na2CO3 Base 800 - FTIR, SEM-EDS - - [54]
activation +

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pyrolysis

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CDAC CH3COOH Acid - - - SEM - - [90]
activation

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CDAC H3PO4 Acid 900 - 4 XRD, FTIR, BET, SEM, 1585 - [91]
activation + particle size analyzer
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pyrolysis
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CDAC KOH Base - - - SEM, BET 1123 14.78 [65]

activation
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CDAC H2SO4 Acid - - - - - - [8]

activation
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CDAC KOH Base 700 - - BET, SEM, FTIR 1916 - [69]

activation
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CDAC KOH Pyrolysis + 500 4 2 FTIR, SEM, TG/DTA, 660.0 - [7]

Base elemental analyzer,
activation
CDAC FeCl3.6H2O Pyrolysis + 700 5 2 Zeta potential analyzer, XPS, 111.7 - [52]
salt FTIR, elemental analyzer,
modification Boehm titration, BET, SEM,
chromatograph system, ICP-
OES
CDAC H3PO4 Pyrolysis + 500 - 1 XRD, SEM-EDS, BET 236.1 - [92]
acid
activation
SEM – Scanning electron microscopy, BET – Brunauer-Emmet-Teller analysis, FTIR – Fourier transform infrared spectroscopy, FESEM –
Field electron scanning electron microscopy, EDS – Energy-dispersive X-ray spectroscopy, TGA – Thermo-gravimetric analysis, DTA –
Differential thermal analysis, XRD – X-ray diffractometry, XPS - X-ray photoelectron spectroscopy, AAS – Atomic absorbance spectroscopy,

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FEGSEM – Field emission gun scanning electron microscopy.

3. Adsorption performance

The adsorptive performance of a given adsorbent is a key indicator of its applicational

efficacy and effectiveness [93]. Generally, this factor is expressed either in terms of removal
efficiency (%) or maximum adsorption capacity, qmax (mg/g) [94, 95]. Meanwhile, qmax is
considered a more integrated approach to elucidating adsorbent performance (in preference to
removal efficiency), as it provides insight regarding the adsorbents’ intrinsic sorption properties

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[96]. The findings from the reviewed literature concerning the different adsorbents’ performance

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are presented in Table 2.
Cow dung is a readily available green resin, devoid of any form of foul odour or colouration

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to treated water. The rich presence of minerals, carbohydrates, proteins, and many important
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functional groups (like carboxyl, phenols, quinols, amides, etc.) in unmodified cow dung has also
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been reported [86]. These organic and chemical constituents of UCD are responsible for their
enhanced adsorptive performance. Barot and Bagla [6] reported the heterogeneous nature of the
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UCD. According to the report, the heterogeneity confers both positively and negatively charged
sorption sites originating from the proteins (enzymes) and acidic functional groups, respectively.
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Hence, the adsorptive capacity of the UCD can be readily tuned to the variation of the solution
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pH, especially for a pH-responsive system. From the reviewed literature, unmodified cow dung
was reported as an effective adsorbent for the sequestration of a varying range of pollutants.
During the study on the adsorptive removal of aqueous fluoride ions, the abundant inorganic
elements (such as calcium, magnesium, phosphorus, etc.) are renowned fluorophilic elements
[89]. Hence, they served as effective fluoride scavengers during water treatment. During the
uptake of heavy metals, the inactive dead biomasses (such as the aerobic heterotrophic bacteria
and petroleum utilizing bacteria) were reported to exhibit strong cationic concentration and
complexation abilities. Sr(II) ions were efficiently adsorbed onto UCD via electrostatic
interaction between the cation and the negative UCD surface charges [97]. As reported by Garba,
Abd Samsuri, Othman and Hamdani [23], the large surface area and porosity of UCD were
responsible for the high glyphosate and aminomethyl phoshonic acid removal.

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 Based on the data presented in Table 2, some adsorptive studies on the use of CDC for the
uptake of different aqueous pollutants were reported. Notably, such successful application is
related to its (CDC) low-cost, physicochemical characteristics (such as improved porosity,
surface area, and carbon content) and other associated environmental benefits [98]. A CDC BET
surface area, pore volume and pore diameter in the range of 66.0 – 141.72 m2/g, 0.09–0.81 cm2/g
and 2.20–6.55 nm, respectively, were reported [7, 52, 62]. Similarly, the immense contribution
of the CDC surface functional groups has been previously studied. According to Chen, Wang,
Tian, Liu, Ma, Liu and Li [7], the abundant oxygen, aromatic, heterocyclic, and anhydride
groups of CDC provide veritable sorption sites for a varying range of pollutants. During the

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adsorption of Metolachlor onto CDC, Liu and Dai [62] reported a slight decrease in the –OH
vibration peak intensity (from 3430.46 to 3421.45 cm−1) due to the associated hydrogen and π–π

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bonds interactions. In a separate study, Wan, Wu, Liu, Zhao, Fu and Xiao [52] quantified the

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amounts of the three predominant functional groups that are responsible for CDC adsorptive
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performance. The hydroxyl groups (-OH), with a dose of 5.38 mmol/g were found to be the
greatest, while significant doses of carboxyl (1.78 mmol/g) and ester, -COOR (0.81 mmol/g)
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were also recorded. Apart from the contribution of the surface functional groups, the CDC
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surface morphology is also worthy of mention. The presence of surface wrinkles and the stacked
structure of uneven pore distribution aids in the formation of complex pore network linkages on
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the CDC surface. According to Rajkumar, Murugesh, Sivasankar, Darchen, Msagati and
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Chaabane [89], the Energy Dispersion X-ray (EDX) result of raw cow dung shows the presence
of abundant elements, which include carbon (67.00%), oxygen (24.86%), silicon (3.18%),
calcium (1.69%), phosphorus (0.75%), potassium (0.67%), sodium (0.62%), magnesium
(0.56%), aluminum (0.34%) and chlorine (0.32%). Meanwhile, only calcium, carbon, oxygen,
and phosphorus were detected on CDC after carbonization, due to the separation of some metal
compounds as oxides, carbonates, and chlorides from the carbon surface.
Despite the abundant inherent rich functional groups on CDC, as stated above, Peng, Gao,
Chu, Pan, Peng and Xing [63] believe that further functionalization/activation of the CDC is
required for optimum sorption performance. The CDAC and CDC have similar applicational
characteristics except for slight morphological variations, which are mostly related to porosity. It
is believed that the treatment of biochar via chemical or physical activation further enhances its
porosity [64]. The CDAC SEM image obtained by Rajkumar, Murugesh, Sivasankar, Darchen,

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 Msagati and Chaabane [89] showed a little surface distortion, with well-developed structures
composed of cracks and voids as compared to those of CDC. Also, a higher degree of surface
heterogeneous pores was observed. Just as in the case of typical activated carbon, CDAC has
improved porosity and surface area [54]. According to Li, Yang, Sun and Liu [66], the successful
conversion of cow dung into portent activated carbon adsorbent is not only useful in water
treatment but also provides a unique approach to achieving cleaner production in dairy farms.
Regarding the most effective activation method, a particular preference was made for chemical
activation (at minimal carbonization temperature) as opposed to the physical activation mode.
This is due to the morphological similarities between cow dung and sawdust (soft biomass)

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rather than coal or nut shell-like material (hard biomass).
Table 2: Adsorption performance of cow dung adsorbents for pollutant uptake

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Pollutants Adsorbent Highest 𝒒𝒎𝒂𝒙 pH Temp. Method of 𝒒𝒎𝒂𝒙 Refs.

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class RE% (mg/g) (ºC) determination
Lead(II) CDAC 99.98 625.26 2.0 - Experimental [8]
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Methylene Blue CDAC - 501.00 - - Experimental [66]
Phosphorus CDC - 345.00 - - Experimental [59]
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Fluoride CDAC - 111.11 - 25.0 Langmuir [89]

Green B CDAC - 75.600 5.15 - Experimental [99]
Acidoll yellow 2GNL CDAC - 54.200 2.35 - Experimental [100]
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Acid violet 17 UCD - 50.300 8.5 20.0 Langmuir [101]

Chromium(VI) CDAC 94.00 47.800 12.0 - Experimental [67]
Methylene Blue UCD - 43.900 - - Experimental [66]
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Eosin YWS CDAC - 39.600 4.12 - Experimental [99]

Reactive blue 221 CDAC - 38.800 10.05 - Experimental [100]
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Metolachlor CDC - 37.880 - - Langmuir [62]

Cadmium(II) CDAC 65.40 33.440 12.0 - Experimental [67]
N Blue RGB CDAC - 29.200 8.01 Experimental [99]
Chromium(VI) UCD 100.0 29.100 - 30.0 Langmuir [102]
Olive BGL CDAC - 18.300 3.32 - Experimental [100]
Congo red CDC 98.84 12.460 7.0 - Langmuir [61]
Nickel(II) CDAC 16.30 8.7200 12.0 - Experimental [67]
Cadmium(II) CDC - 5.8800 - - Langmuir [68]
Chromium(VI) UCD - 5.8700 2.0 30.0 Langmuir [103]
Chromium(VI) UCD - 5.7481 1.0 - Langmuir [60]
Basic green 4 CDAC - 4.9800 3.33 - Experimental [104]
Acid green 20 CDAC - 4.8050 10.20 - Experimental [105]
Acid blue 92 CDAC - 4.7700 4.95 - Experimental [106]
Perchlorate CDC - 1.7870 - 30.0 Langmuir [52]
Acid blue 193 CDAC - 1.6500 3.60 - Experimental [107]
Direct red 12 B UCD 100.0 - 2.7 30.0 Experimental [108]
Chromium(VI) CDAC 99.98 - 8.0 - Experimental [42]
Methylene Blue CDC 99.00 - - - Experimental [10]

12
Glyphosate UCD 95.00 - - - Experimental [23]
90
Strontium UCD 90.00 - 6.0 25.0 Experimental [6]
Chromium(VI) CDAC 90.00 - 3.42 30.0 Experimental [4]
Carbofuran CDAC 89.18 - - - Experimental [65]
Chromium(III) UCD 89.00 - 2.5 30.0 Experimental [109]
Cadmium(II) UCD 85.00 - 3.0 25.0 Experimental [97]
Mercury(II) UCD 85.00 - 3.0 30.0 Experimental [58]
Lead(II) UCD 81.00 - 4.0 - Experimental [54]
Chromium(III) UCD 75.00 - 6.0 25.0 Experimental [97]
Chromium(VI) UCD 75.00 - 1.0 25.0 Experimental [97]
Chromium(VI) UCD 75.00 - 1.0 25.0 Experimental [86]
Lead(II) CDAC 69.90 - 4.0 - Experimental [54]
Aminomethylphosphonic UCD 67.00 - - - Experimental [23]
acid
UCD – unmodified cow dung; CDC - cow dung biochar (CDC); CDAC - cow dung activated carbon;

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RE% - Percentage of removal efficiency; qmax – maximum adsorption capacity

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4. Adsorption isotherm and kinetic analyses

-p
Adsorption equilibrium data which is expressed as isotherms gives the definite solute
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distribution that is adsorbed onto the adsorbent and those in the bulk fluid phase at a given
lP

temperature [110]. Adsorption isotherm helps predict the performance of an adsorption system
and also makes for better adsorbent selectivity [111]. Several equations exist for isotherm
na

modelling. However, the effectiveness and validity of a given model equation is a function of its
basic assumptions, since there are no universally acceptable models for every adsorption system.
ur

The isotherm model of best fit and their associated parameters are collated and compiled
Jo

in Table 3. The Langmuir and Freundlich models emerged as the model of best fit in most of the
reviewed articles, except in a study [67] where Redlich-Peterson and Freundlich jointly emerge
as the best fit. Since the validity of an isotherm model for a given adsorption system is a function
of their fundamental assumptions, it is plausible to express the basic assumption of the two
predominant isotherm models. The Langmuir model assumes a homogenous distribution of
solutes on the adsorbent surface with negligible lateral interactions [112]. The linear and
nonlinear form of the equation is presented in Equations (1) and (2), respectively. Furthermore,
Langmuir’s dimensionless constant (separation factor) which expresses adsorption
unfavourability (when RL > 1), linearity (when RL = 1) and favourability (when 0 < RL < 1) and
irreversibility (when RL = 0) is expressed as Equation (3).
𝐶𝑒 1 𝐶
=𝑞 + 𝑞𝑒 (1)
𝑞𝑒 𝑚 𝐾𝐿 𝑚

13
 𝑞𝑚𝑎𝑥 𝐾𝐿 𝐶𝑒
𝑞𝑒 = (2)
1+𝐾𝐿 𝐶𝑒
1
𝑅𝐿 = 1+𝐾 (3)
𝐿 𝐶0

Where Ce = equilibrium concentration of adsorbate (mg/L), qe = adsorbed adsorbate per

gram of the adsorbent at equilibrium (mg/g), q max = maximum adsorption capacity (mg/g), KL =
Langmuir isotherm constant (L/mg). Where Co = initial adsorbate concentration (mg/L). In
studies where Langmuir emerged as the best fit, very little adsorbate bulk condensation
tendency, with uniform adsorption energy is assumed. Thus, no significant adsorption occurs on
the adsorbent surface beyond the first adsorbed layer. This scenario is prevalent for
chemisorption [97]. The Freundlich model assumes simultaneous solute adsorption onto non-

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uniform adsorbent surfaces, which exhibits exponential distribution with the adsorption energy.

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The linear and nonlinear expression of the model is given by Equations (4) and (5). The isotherm

-p
data presented in Table 3. further showed that a given adsorbent type fulfilled the assumptions of
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more than one isotherm model. For instance, unmodified cow dung adsorbent were best fitted to
Langmuir model in some cases and then Freundlich model in other cases. Such variation in
lP

adsorbent features depends on the type of adsorbate being considered. The constant K f and nF are
the Freundlich capacity factor and intensity parameter, respectively.
na

q e = K f Ce1/n (4)
ur

1
log q e = log K f + log Ce (5)
n
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Considering the implication of the Langmuir parameter to the reviewed literature, the
maximum adsorption values (qmax) is a key indicator of the effectiveness of a given adsorption
system. From Table 2, reasonably large qmax values were generally recorded. Notably, the largest
qmax value of 1787 mg/g [52] was observed from the review. This large value was recorded
during the adsorption of perchlorate onto biochar. This observation is outstanding and suggests
the existence of great affinity between the adsorbent and adsorbate. An unmodified cow dung
adsorbent also depicted a large qmax value of 547.7 mg/g during the adsorption of basic green 4
dye [104]. For the studies where the Freundlich model emerged as the model of best fit, the
adsorption intensity constant (nF) was in all cases less than unity. This finding indictates the
occurrence of favourable adsorption. However, Olim, Afu, Adie and Akpa [113] recorded
negative nF-values, which implies unfavourable adsorption. This observation faults the
conclusion made by the author regarding the isotherm model of best fit.

14
 The adsorption kinetics describes the adsorbate variation in bulk solution as a function of
time. There exist several kinetic models for describing solute adsorption, with each having
perculiar assumptions. Based on the review outcome, the pseudo-second-order model was
reported as the kinetic model of best fit in all cases (Table 3), hence the need to elucidate its
basic assumptions. The model assumes a direct relationship between adsorption rate and active
sites on the adsorbent. As the best fit model, it is further believed that the respective sorption
process is predominantly chemisorption and exhibits high operational enthalpy. Furthermore, no
linear dependence was observed between the second-order model rate constant (k2) and the
initial adsorbate concentration. This observation was made despite the existing assertion that

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links it (k2) to the initial adsorbate concentration [114]. Consequently, k1 and k2 values recorded
in all the studies were all within the acceptable range (k >>>1), except for the k2-value of 1.95

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reported by Rajkumar, Murugesh, Sivasankar, Darchen, Msagati and Chaabane [89]. The linear

-p
and nonlinear mathematical expression of the PSO model is presented in Equations 6-7.
re
k ∗q2 ∗t
2 e
q t = (1+k (6)
∗t)2
lP

𝑡 1 𝑡
=𝐾 2 +𝑞 (7)
𝑞𝑡 2 𝑞𝑒 𝑒
na

Where 𝑘2 is the pseudo-second-order rate constant (mg-1min-1), 𝑞𝑒 and 𝑞𝑡 (mg/g) are the
amounts of adsorbate adsorbed onto the adsorbent at equilibrium and at any time t (min).
ur

Table 3. Best-fit isotherm and kinetic models for cow dung adsorbents.
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Pollutants Adsorbe Model Type Isotherm models Kinetic models

nt class Best fit Parameters of best fit models Parameters of best fit models
k nF qm R2 Best q K R2 Model Refs
fit Type .
Methylene CDC Linear Langmuir NS - NS 0.996 PSOb NS NS 0.994 Linear [10]
Blue
90Strontium UCD - - - - - - PSOb 9.00 0.011 0.999 Linear [6]
Chromium UCD - - - - - - PSOb 19.31 0.106 0.976 Linear [97]
(III)
Cadmium UCD - - - - - - PSOb 8.387 0.011 0.998 Linear [97]
(II)
Chromium UCD - - - - - - PSOb 10.20 0.012 0.997 Linear [97]
(VI)
Chromium UCD - - - - - - PSOb 10.20 0.012 0.997 Linear [86]
(VI)
Mercury (II) UCD - - - - - - PSOb 16.00 0.010 0.999 Linear [58]
Glyphosate UCD Nonlinear Freundlich 1.168 3.29 - 0.985 - - - - [23]
AmPAa UCD Nonlinear Freundlich 2.915 2.12 - 0.865 - - - - [23]
Congo red CDC Linear Langmuir NS - 12.46 0.902 - - - - [61]
Metolachlor CDC Linear Langmuir 0.455 - 37.88 0.996 PSOb 28.99 0.035 0.999 [62]
Lead(II) CDC Linear Freundlich 0.532 1.410 - 0.999 PSOb 7.576 0.003 0.935 Linear [54]
Lead(II) UCD Linear Freundlich 0.724 1.414 - 0.992 PSOb 8.333 0.006 0.981 Linear [54]
Copper(II) UCD Linear Freundlich 2.794 -10.55 - 0.999 - - - - - [113

15
 ]
Lead(II) UCD Linear Freundlich 4.105 -4.08 - 0.999 - - - - - [113
]
Zinc(II) UCD Linear Freundlich 2.758 -9.71 - 0.999 - - - - - [113
]
Chromium CDC Nonlinear Langmuir 0.44 - 5.81 0.990 PSOb 4.73 0.055 0.990 Linear [68]
(II)
Acid green UCD Linear Langmuir - - 8.26 0.999 - - - - - [105
20 ]
Acid blue UCD Linear Langmuir - - 13.0 0.999 - - - - - [106
92 ]
Basic green UCD Linear Langmuir - - 574.7 1.000 - - - - - [104
4 ]
Acid blue UCD Linear Langmuir - - 2.57 0.998 - - - - - [107
193 ]
Fluoride CDAC Linear Freundlich 36.14 1.45 - 0.977 PSOb 7.09 1.95 0.994 - [89]
Reactive UCD Linear Langmuir - - 67.80 0.996 - - - - - [100
blue ]

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Acidoll UCD Linear Langmuir - - 235.3 0.999 - - - - - [100
yellow ]

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Olive BGL UCD Linear Freundlich 0.761 1.31 -` 0.998 - - - - - [100
]
N Blue UCD Linear Langmuir - - 59.10 0.998 - - - - - [99]

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RGB
Green B UCD Linear Langmuir 139.9 0.999 - - - - - [99]
re
Eosin YWS UCD Linear Freundlich 0.981 1.613 - 0.990 - - - - - [99]
Nickel (II) CDAC Nonlinear Freundlich 0.51 2.33 - 0.990 - - - - - [67]
lP
R-P 96.78 - -
Cadmium CDAC Nonlinear Freundlich 0.57 1.75 - 1.000 - - - - - [67]
(II) R-P 186.4 - -
na

Chromium CDAC Nonlinear Freundlich 0.43 1.96 - 1.000 - - - - - [67]

(VI)
R-P 2 - - 0.996
× 106
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Chromium UCD Linear Langmuir 0.003 - 10.16 0.996 - - - - - [60]

(VI) 1
Perchlorate CDC Linear Langmuir 0.001 - 1787 0.961 PSOb 1031 0.000 0.966 [52]
Jo

49
UCD – unmodified cow dung; CDC - cow dung biochar (CDC); CDAC - cow dung activated carbon; AmPA- Aminomethylphosphonic acid; NS - not
specified; k - equilibrium constant (L/mg); nF – Freundlich exponent; qm - maximum adsorption capacity (mg/g); R2 - coefficient of determination; PSOb-
pseudo second order

5. Thermodynamic modelling of Cow-dung based adsorbents

Adsorption studies typically include thermodynamics studies to observe the effect of
temperature on the process and the feasibility of the adsorption process [115, 116]. Table 4
shows the change in standard enthalpy (∆Ho), standard Gibbs free energy (∆Go), as well as the
change in standard entropy (∆So) for each study at ambient (or near-ambient) conditions.
The ∆Hº parameter describes the adsorption process's responsiveness to variations in thermal
energy (temperature rise or decrease). From Table 4, both negative and positive values of ∆Ho
representing an endothermic process and an exothermic process, respectively, can be observed.
Hence, both scenarios play out in the use of cow dung as an adsorbent. Broadly speaking, the

16
 absolute value of ΔHº was less than 40 kJ/mol, which implies the dominant mechanism is
physical (which is attributed to weak van der Waal forces [117]), and not a chemical mechanism.
The nature of the sorption mechanism does have a significant impact on the thermal response of
adsorption processes. A negative Gibbs free energy (∆Go<0) value is indicative of the
spontaneity of the adsorption process. A combination of both spontaneous (∆Go<0) and non-
spontaneous (∆Go>0) reactions were observed (Table 4) for various classes of adsorbent and
absorbate types. The amount of the system's disorderliness at the solid-liquid interface
throughout the adsorption process is highlighted by changes in standard entropy (∆So). Upon
observation of the entropy values in Table 4, most of the studies recorded positive ΔS° which is

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indicative of increased randomness [117]. The values of ΔGº, ΔHº, and ΔSº in Table 4 might be
wrongly calculated, using incorrect constants as the thermodynamic equilibrium constant. A

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literature survey by Lima, Hosseini-Bandegharaei, Moreno-Piraján and Anastopoulos [118]

-p
explained that the van’t Hoff equation is used in different ways without any consideration of the
re
concept of physical-chemistry of equilibrium.
lP

Table 4. Summary of thermodynamics parameters for cow dung adsorbents

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Pollutants Adsorbent Thermodynamics Refs.

class Temp (K) ∆𝐆º ∆𝐇º ∆𝐒º
(kJ/mol) (kJ/mol) (J/mol.K)
ur

90
Strontium UCD 298 -3.281 -6.396 22.889 [6]
Chromium (VI) UCD 298 -2.007 -4.757 16.64 [86]
Jo

Mercury (II) UCD 298 -1.820 -10.42 35.67 [58]

Chromium (VI) CDAC 303 -23.504 9.39 108.59 [4]
Methylene blue CDC 278 -6.439 -16.169 82.49 [103]
Direct red 12 B UCD 303 1.686 11.795 32.818 [108]
Chromium (III) UCD 303 3.21 25.12 91.83 [109]
Lead (II) CDC 301 10.078 -8.688 -0.0623 [54]
Lead (II) UDC 301 9.115 -11.390 -0.0681 [54]
Fluoride CDAC 298 -9.139 -62.99 -182 [89]
∆𝐆º- change in Gibb’s free energy; ∆𝐇º - Enthalpy change; ∆𝐒º - Entropy change

6. Surface Chemistry and Mechanism of Pollutants adsorption by Cow Dung based

Adsorbents

According to Tran et al (2020), several mechanisms are at play during the adsorption of
organic and inorganic compounds onto different adsorbents. Notwithstanding, the primary

17
adsorption mechanisms are strongly influenced by the experimental conditions (pH,
thermodynamics, kinetics), the adsorbate characteristics (solubility, pKa, e.t.c.), and the
properties of the adsorbent (surface functional groups and surface area). Kinetics and isotherm
models of best fit assumptions can be used in some cases to identify the most likely mechanism
[119]. Most studies conform to the pseudo-second order kinetics that models chemisorption
(Table 3). Furthermore, by employing thermodynamic parameters, one can gain a better
understanding of the nature of adsorbent-adsorbate interactions and, as a result, the adsorption
process [96]. pH in the adsorption process has a significant impact on the magnitude of
electrostatic charges that the pollutant imparts. On the basis of pHzc, it is possible to explain the

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influence of the optimum pH of the solution. Point of zero charge (pHzc) occurs when the
adsorbent material surface is neutral. In other words, the net charge of the functional group

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charge is zero. The electrostatic effect becomes more pronounced as the pH of the solution rises,

-p
making the surface potential more negative. The surface charge becomes positive when pH is
re
lower than pHzc, making it difficult to adsorb positively charged metal ions. When pH exceeds
pHzc, the surface charge turns negative [120].
lP

The use of cow dung as a renewable cellulose-based material for adsorption is gaining
na

interest. Cow dung is a heterogeneous biological adsorbent which possesses many positively
charged sites owing to some proteins and enzymes [86], and negatively charged sites from acidic
ur

groups [58]. Cow dung usually includes a lot of labile organic and inorganic constituents,
Jo

resulting in a high-ash-content adsorbent which is proportional to the nutritional and chemical

composition of the biomass. Generally, the surface of cow dung adsorbent is enriched with many
functional groups, including carboxyl, phenols, quinols, amides, etc., which enhances its
adsorption properties. It also contains carbohydrates, aromatic and aliphatic species (humic
acids), and ash. According to Zhu, Yi, Yuan, Wu, Wang and Yan [121], the ash content aids
adsorption of organic pollutants. An overall 72% decrease in adsorption efficiency was observed
after de-ashing. Humic substances also aid metal adsorption. For instance, Singh and Kaur [122]
reported the existence of humic substances in vermicompost as chiefly responsible for metal
adsorption.

The majority of studies use FTIR to determine the active functional groups on the
adsorbent's surface, which aids in understanding their role in the adsorption mechanism [123].
Thus, FTIR analysis would aid in elucidating possible adsorption mechanisms in cow dung-

18
 based adsorbents. The FTIR of various studies is depicted in Table 5. Careful observation shows
that the hydroxyl groups, carboxyl groups, carbonyl groups, and amine groups were mostly
reported. Chemisorption, electrostatic attraction, and intra-particle diffusion were reported to be
the predominant mechanisms for Cr (VI) uptake by cow dung-based adsorbents. The difference
in these mechanisms could be due to the varied functional groups reported [4, 60, 67, 86].
Chemical properties at the surface and precipitation-inducing reactions often influence metal ion
adsorption. Chemisorption was the major adsorption mechanism reported for Hg (II) uptake [58].
This can be attributed to surface active carboxylic group (-COOH ligand) complexation. On the
other hand, for polar organic compounds such as Methylene Blue (MB), the sequestration

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mechanisms were electrostatic attraction, hydrogen bonding, n-π interaction (due to siloxane
groups) and cationic exchange [121]. In another study, Chen, Qin, Cheng, Huang, Sun, Chen and

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Shen [124] described the precipitation mechanism for phosphorus (P). Surface functional groups

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may be limited in their ability to give a full perspective of the adsorption mechanism taking
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place.
Table 5: Mechanism of Pollutants uptake by Cow dung based adsorbents
lP

Adsorb
ent Pollutants Functional groups Mechanisms ΔpHzc Refs.
na

Class

Electrostatic attraction (due to -

ur

Free phenols (-OH)

OH & carboxyl group),
Hydrogen bonding (due to -
Jo

Carboxylic groups (-COOH)

Methylene COOH & -OH)
CDC - [121]
blue n-π interaction (due to siloxane
Siloxane group (Si-O-Si)
groups)
Cationic & ion-exchange
(evolution of H+ ions)
Hydroxyl groups (-OH), Conjugate groups
Methylene
CDC (C=C), Siloxane group (Si-O-Si), Aldehyde - 7.8 [10]
blue
(C-H), Carboxylate (COO-)
Chromium Carboxylic groups (-COOH, C=O stretch)
UCD Chemisorption [97]
(VI) Amine group (N-H)
Carboxylic groups (-COOH, C=O strech)
Mercury Amine group (N-H) Chemisorption (due to
UCD - [58]
(II) Alkyl halide (C-Br, inorganic impurities) complexation with -COOH)
Conjugate groups (C=C)
Direct red
UCD - Complexation - [108]
12B
Chromium Electrostatic attraction (surface
CDAC - - [4]
(VI) protonation),

19
 Silica group (Si-O)
C-O conjugated strech
CDC Fluoride - 9.09 [89]
Carbonyl groups (C=C strech)
stretching vibration (=CO)
CDC Phosphorus - Precipitation - [59]
hydroxyl group (-OH)
Chromium Electrostatic attraction (due to
CDC Amine groups (-NH) - [60]
(VI) protonation),
Carbonyl groups (C=O)
Chromium
CDAC - Intra-particle diffusion - [67]
(VI)
Perchlorate Hydroxyl groups (-OH), Esters (COOR), Electrostatic attraction (due to 10 –
CDC [52]
(ClO4-) Carboxylic groups (-COOH) protonation), 10.5
Ion exchange (due to FeCl3),
FeCl3 Perchlorate Hydroxyl groups (-OH), Carboxylic groups

of
Hydrogen bonding (due to - 4 – 4.5 [52]
@ CDC (ClO4-) (-COOH), Esters (COOR)
COOH & -OH)

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-p
7. Desorption and Column Adsorption Studiesre
It is important that an adsorbent be regenerated for reuse or final disposal [92]. The
applicability of an adsorbent in real wastewater treatment largely depends on its ability to be
lP

regenerated and reused. Desorption studies help in understanding the pathway and fate of sorbed
na

ions after the adsorbent has been disposed into the environment [58], and in understanding the
mechanism of the adsorption process [109]. Few studies have investigated the potential of cow
ur

dung adsorbent to be desorbed and reused. The desorption of Hg(II) from cow dung powder was
Jo

studied by Bhatt and Bagla [58] using 0.1 M HCl, H2SO4 and HNO3 as eluents. It was found that
only 8-12% of the metal ion could be desorbed, while the use of water as eluent yielded no
tangible result. This may be as a result of the different chemisorption mechanisms, such as
chelation and complexation, involved in the Hg(II) sorption. Garba, Abd Samsuri, Othman and
Hamdani [23] investigated the desorption of glyphosate and aminomethylphoshonic acid from
cow dung. Desorption was found to decrease with increase in glyphosate concentration to the
extent that no data was obtained between the glyphosate initial concentration ranges of 150 mg/L
up to 300 mg/L, while the presence of animomethylphoshonic acid was not detected at any
concentration, thus indicating the strong adsorption of the pollutants on the cow dung adsorbent.
Namasivayam and Yamuna [109] studied the desorption of Cr(II) from a biogas residual slurry
fed with only cow dung. It was found that the regeneration of Cr(II) from the adsorbent increases
from 25% at pH 2.0 to 34.5% at pH 1.0. This is because at acidic pH, the adsorbent surface is

20
protonated, thereby replacing Cr(II) and leading to desorption. For the desorption of fluoride
anion from cow dung carbon, a composite prepared from natural cow dung and cow dung
impregnated by a solution of calcium, NaOH solution at various concentrations of 0.05, 0.1 and
0.2 M was used as the eluent [89]. The desorption percentage was found to be inversely
proportional to initial fluoride concentration. With 0.05 M of NaOH solution, the fluoride
desorption was 100% for initial fluoride concentration of 2 mg/L, 50% at 4 mg/L and 26% at 8
mg/L. Using 0.1 M NaOH solution, 100% of desorption was achieved at up to 4 mg/L but was
found to decrease to as high as that of 0.05 M NaOH solution for the initial fluoride
concentrations from 4 mg/L to 8 mg/L. Desorption percentage was 100% for all the initial

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fluoride concentrations using 0.2 M NaOH solution. These studies however, failed to conduct the
reusability study of the adsorbent.

ro
To evaluate the reusability of a cow dung-based biochar, metolachlor adsorbed to the pores

-p
on the surfaces of the adsorbent was desorbed by ultrasonic vibration [62]. The result showed
re
that after two cycles, the removal efficiency of the biochar decreased to 32.2%. However, a
lP

greater removal efficiency can be achieved by increasing the amount of the cheap biochar during
recycling. The reusability of iron-modified cow dung biochar on the removal of perchlorate was
na

also investigated by Wan, Wu, Liu, Zhao, Fu and Xiao [52] after being regenerated with FeCl3.
The adsorption efficiency remained at 77.4% even after three cycles of reuse, thus showing the
ur

excellent reusability of the bioadsorbent. In addition, to assess the reusability of cow dung
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biochar in the adsorption of methylene blue, different diluents (HCl, HNO3, H2SO4, NaOH and
H2O) at a concentration of 0.1 M were used to perform 3 cycles of adsorption/desorption [92].
The highest desorbed methylene blue was 4.59 mg/L with concentrated HNO3, while the lowest
desorbed was 0.68 mg/L when distilled water was used. The adsorbent was reused three times
using HNO3 as the regenerating solvent, with the adsorption capacity decreasing to 26.9% after
the 4th cycle.

Column adsorption helps in revealing the best adsorption parameters and the best fit
experimental data. Adsorption is easier to set up using continuous fixed-bed column than batch
operation system, and it’s preferred by industries [119, 125]. There exist a paucity of studies that
reported the usage of cow-dung based adsorbents in a column set-up. One study that studied this
was performed by Suárez‐Vázquez, Cruz‐López, Márquez‐Reyes, Flores Breceda and

21
García‐Gómez [92]. This was done in a bid to determine the model that best described the
characteristics of methylene blue in a fixed-bed adsorption onto cow dung biochar. The
experimental data was adjusted using 3 dynamic models. It was revealed that the application of
Thomas model with R2 value of 0.9702 best described the adsorption data than the Yoon-Nelson
model (R2 = 0.9649) and the Bohart-Adams model (R2 = 0.8485) [92].

8. Competitive Adsorption and Ionic strength Effects

Competitive adsorption study reveals the affinity of an adsorbent to an adsorbate in the

of
presence of other competing species in solution [119]. In real wastewater treatment, the presence

ro
of metal ions and counter ions may increase or decrease the ionic strength, which may affect the
adsorption performance [62]. Notwithstanding, the presence of these competing species may also

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have no effect on the adsorption process. Barot and Bagla [97] investigated the effect of
re
competing salts on the percentage adsorption of Cr(III), Cr(VI) and Cd(II) on cow dung powder.
lP

Different organic and inorganic salts at varying concentrations of 10, 50 and 100 mg were used
for the study. It was observed that some salts were not interfering with the adsorption rate at 100
na

mg, some were enhancing the adsorption process, while some were suppressing the process even
at concentrations of 10 mg. All the 3 metal ions showed the same adsorption pattern, with salts
ur

such as tartarate, thiourea and thiosulphate decreasing the adsorption efficiency even at low
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concentrations. 23 different salts at various proportions (10, 25, 50 and 100 mg) were reported as
the competing species in the sorption of Hg(II) from wastewater [58]. Some salts were found to
decrease the adsorption at 10 mg while others did not affect the process even at 100 mg.

In the adsorption of metolachlor by cow dung-prepared biochar, Na+ was used to evaluate the
potential of the adsorbent ionic strength [62]. When the Na+ concentrations were 0, 0.01, 0.05
and 0.1 mol/L, the removal efficiency respectively corresponded to 52.91, 64.01, 62.54 and
60.31%. This increase in the ionic strength may be explained by the high hydrophobicity of
metolachlor which decreased its solubility, hence resulting in a salting-out effect [62]. The effect
of other anions on the adsorption of fluoride anion onto cow dung carbon was studied by
Rajkumar, Murugesh, Sivasankar, Darchen, Msagati and Chaabane [89] in the presence of 0.5 M
concentration of sodium salt of chloride, hydrogen carbonate, nitrite, nitrate and sulphate. The
completion for the adsorbents active sites with these species led to a decrease in the removal

22
efficiency of the fluoride from 80% to 40%, 50%, 54% and 55% for HCO3-, NO3-(and NO2-),
SO42- and Cl- ions respectively. Furthermore, Wan, Wu, Liu, Zhao, Fu and Xiao [52] studied the
effects of different coexisting anions (Cl-, NO3- and SO42-) on the adsorption of perchlorate,
ClO4-, onto iron-modified cow dung biochar. Compared to blank experiment, the three coexisting
anions all slightly reduced the perchlorate adsorption rate in the order: NO3- > SO42- > Cl-. After
6 hours, the adsorption capacity reduced from 1020 μg/g to 678, 859 and 938 μg/g respectively.
This was attributed to the high affinity of the competing ions for the modified cow dung
bioadsorbent.

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9. Recommendations and Future Outlook

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Based on this study, certain knowledge gaps have been identified, and some interesting new

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areas for future investigation have been proposed.
re
1. A probe into the body of literature revealed that cow-dung-based adsorbents are still
lP

underutilized for water treatment. Its usage for the mitigation of heavy metals such as
paladium and arsenic, and dyes such as methyl orange, pesticides, and other emerging
na

contaminants should be encouraged [126]. This needs to be studied so as to increase its

ur

application and enable its large-scale usage as an adsorbent.

2. There is a dearth of work on the column adsorption of pollutants using cow dung-based
Jo

adsorbents, with only one investigation on that till date [92]. Future work is therefore
recommended to conduct studies on this to establish the best column experimental model for
using cow dung-based adsorbents in mitigating pollutants.
3. Some authors have recorded a high microbial load in cow dung [127, 128]. Pre-treatment of
the adsorbent to reduce its microbial load as well as investigation into the microbial load of
treated water before and after adsorption treatment with cow dung should be encouraged.
4. The necessity of waste minimisation efforts and solid waste management is a major aspect in
the use of biomass for environmental applications [129]. In line with this, a lifecycle analysis
of adsorbent production and utilization from cow dung would be interesting to help
understand the adsorbent’s environmental impact.
5. It will also be necessary to undertake a cost study to establish the financial benefit of using
cow dung for adsorbent preparation and product utilization on a large and industrial scale.

23
 Researchers are also enjoined to carry out more studies on the reusability of this cheap
adsorbent and its application for the treatment of industrial wastewater. This will
undoubtedly help in determining the industrial feasibility of using cow dung-based
adsorbents as a low-cost adsorbent in removing pollutants from the environment.
6. There has been no research on the disposal of used cow-dung-based adsorbents following
pollutant adsorption. Similar concerns about a paucity of data on adsorbent disposal have
been noted in recent reviews using sugarcane bagasse and sunflower as adsorbents [23, 120].
Despite the fact that incineration is the most common method of adsorbent disposal [130],
other approaches proposed by Eletta, Adeniyi, Ighalo, Onifade and Ayandele [131] include

of
immobilization in a polymeric resin or a cementitious binder.
7. Finally, work on adsorption mechanisms to determine the best adsorption concentration,

ro
optimal conditions, and cow dung modification as adsorbents is still limited. Intensive work

-p
on the limited conditions will establish cow dung as a good and useful adsorbent.
re
lP

10. Conclusion
na

As much as it costs very little to obtain cow dung, there are insufficient records of its usage
in published literature. In this study, the application of cow dung-based adsorbent for the
ur

removal of pollutants from water was reviewed. The adsorbents were used in their unmodified
Jo

state, biochars, or activated carbon. It was observed that cow dung-based adsorbents were
efficient for the removal of dyes, heavy metals, and other pollutants from aqueous solutions. The
highest reported uptake capacities of dyes and heavy metals were 501 mg/g and 625.26 mg/g for
Methylene blue and lead, respectively, which were both for cow dung activated carbon. The
Langmuir and Freundlich isotherm models emerged as the best-fit models for almost all studies.
Based on the review outcome, the pseudo-second-order model was reported as the kinetic model
of best fit in all cases. Other adsorption studies, such as adsorption mechanism, thermodynamic
modelling, desorption, column adsorption, and competitive adsorption, were also included in this
study. Finally, the study identified some knowledge gaps that could aid future investigation in
this research field. From this study, it can be deduced that cow dung-based adsorbents have
exhibited good potential as an adsorbent for the mitigation of pollutants from water.

24
Disclosure statements
Conflict of Interest: The authors declare that there are no conflicts of interest.
Funding: There was no external funding for the study.
Compliance with Ethical Standards: This article does not contain any studies involving human
or animal subjects.

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Highlights

• This study was aimed at discussing the utilization and conversion of cow dung as an
adsorbent with special attention given to its adsorption performance.
• Kinetic and isotherm studies, thermodynamic studies, mechanism, regeneration studies,
and competitive adsorption studies were also reviewed.
• The maximum reported uptake capacity of dyes and heavy metals was 501 mg/g and 625.26
mg/g for Methylene blue and lead, respectively, which were both for cow dung activated
carbon.
• The Langmuir and Freundlich isotherm models emerged as the best-fit models for almost
all studies, and the pseudo-second-order model was reported as the kinetic model of best

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fit in all cases.

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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