Biochar-Based Engineered Composites For Sorptive Decontamination of Water

Accepted Manuscript
Biochar-Based Engineered Composites for Sorptive Decontamination of Water:

A Review
K.S.D. Premarathna, Anushka Upamali Rajapaksha, Binoy Sarkar, Eilhann E.

Kwon, Amit Bhatnagar, Yong Sik Ok, Meththika Vithanage
PII: S1385-8947(19)30875-7
DOI: https://doi.org/10.1016/j.cej.2019.04.097
Reference: CEJ 21517
To appear in: Chemical Engineering Journal
Received Date: 24 January 2019

Revised Date: 6 April 2019
Accepted Date: 14 April 2019
Please cite this article as: K.S.D. Premarathna, A. Upamali Rajapaksha, B. Sarkar, E.E. Kwon, A. Bhatnagar, Y.
Sik Ok, M. Vithanage, Biochar-Based Engineered Composites for Sorptive Decontamination of Water: A Review,
Chemical Engineering Journal (2019), doi: https://doi.org/10.1016/j.cej.2019.04.097
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Biochar-Based Engineered Composites for Sorptive Decontamination of Water: A
Review
K. S. D. Premarathna1, Anushka Upamali Rajapaksha1, Binoy Sarkar2, Eilhann E. Kwon3, Amit
Bhatnagar4, Yong Sik Ok5*, Meththika Vithanage1,6**
1Ecosphere Resilience Research Center, Faculty of Applied Sciences, University of Sri
Jayewardenepura, Nugegoda, 10250, Sri Lanka

2Department of Animal and Plant Sciences, The University of Sheffield, Sheffield, S10 2TN, UK
3Department of Environment and Energy, Sejong University, 98 Gunja-Don, Republic of Korea

4Department of Environmental and Biological Sciences, University of Eastern Finland, P.O. Box 1627,
FI-70211, Kuopio, Finland

5Korea Biochar Research Center, O-Jeong Eco-Resilience Institute (OJERI) & Division of
Environmental Science and Ecological Engineering, Korea University, Seoul 02841, Republic of Korea
6Molecular Microbiology and Human Diseases Project, National Institute of Fundamental Studies,
Kandy, Sri Lanka
1
**Corresponding Author
Dr. Meththika Vithanage
Email: meththika@sjp.ac.lk
Co-Corresponding Author
Prof. Yong Sik Ok
Email: yongsikok@korea.ac.kr
2
Abstract
Biochar (BC) exhibits a great potential as an adsorbent in decontamination of water. To
improve the adsorption capabilities and impart the particular functionalities of BC, various
methods (chemical modification, physical modification, impregnation with different materials,
and magnetic modification) have been developed. As compared to surface modifications, BC-
based composites provide various technical and environmental benefits because they require
fewer chemicals, lesser energy, and confer enhanced removal capacity. Therefore, this review
focuses on BC composites prepared by the combination of BC with different additives
including metals, metal oxides, clay minerals, and carbonaceous materials, which greatly alter
the physicochemical properties of BC and broaden its adsorption potential for a wide range of
aquatic contaminants. Techniques for the preparation of BC composites, their adsorption
potentials for a variety of inorganic and organic environmental contaminants, factors affecting
BC properties and the adsorption process, and the mechanisms involved in adsorption are also
discussed. Modification typically alters the surface properties and functionalities of BC
composites including surface area, pore volume, pore size, surface charge, and surface
functional groups. Hence, modification typically enhances the adsorption capacity of BC for
most organic and inorganic compounds. Nevertheless, some modifications negatively affect the
adsorption of certain contaminants because of various factors including obstruction of pores
due to over coating and development of same charge as contaminant on surface of BC.
However, the use of BC composites in environmental remediation is still in its infancy, and
further research and development is needed to reach scalability and commercialization of the
new technology.
Keywords
3
Adsorption; Water pollution; Trace metals; Antibiotics; Biochar; Nutrients; Clay minerals
1. Introduction
Biochars (BCs) is defined as a carbon-rich material obtained by the thermal treatment of
carbon neutral carbonaceous materials such as wood, manure, or leaves under an oxygen free
environment [1]. It have garnered attention due to their genuine physico-chemical properties
and diverse applications in many sectors, including agriculture, climate change mitigation,
energy production, and environmental remediation [2]. The addition of BC to soil improves
soil fertility, enhances agricultural productivity, increases soil nutrient levels and water holding
capacity, and reduces emissions of greenhouse gases due to its intrinsic carbon negativity [1].
However, the use of BC as a sustainable medium in such applications has only been studied
scientifically in the last decade [3]. Recent uses of BC involve as a carbon precursor for
catalysts and contaminant adsorbents, as a gas adsorbent, as an energy source in fuel cell
systems, and as a raw material in supercapacitor and activated carbon production [3-4]. These
4
high value applications are still in their early stages, and further research and development is
needed to achieve their scalability and commercialization.
Biochar can be produced using various carbonaceous feedstocks, many of which are
considered organic wastes, thereby indirectly supporting waste management. Because of its
low production cost and feasibility in many contexts [5], it has been used in wastewater
treatment as a low-cost adsorbent alternative to activated carbon (AC) for the removal of
various contaminants from water such as nutrients, trace metals, pharmaceuticals, pesticides,
dyes, metal(loids), volatile organic compounds and polycyclic aromatic hydrocarbons [6-11].
The methods for producing BC from carbonaceous materials (mostly biomass) are pyrolysis,
and hydrothermal carbonization [2]. The yield of BC from these processes differs based on
operational conditions, types of biomass, and reaction media [3]. The most frequently used
method is pyrolysis, which can be categorized into slow and fast pyrolysis depending on the
pyrolysis temperature, heating rate, and residence time employed; each operation parameters
impart different characteristics to the final BC products (Table 1) [12-13].
Table 1: Pathways for thermal conversion of biomass to biochar.
Thermal Temperature Heating rate Residence Biochar
conversion range (°C) time yield
process %
Slow pyrolysis 350–800 Slow, Hours–Days 35
(<10 °C min-1)
Fast pyrolysis 400–600 Very fast Seconds 10–15
(1000 °C s-1)
Hydrothermal 180–250 Slow Hours 30–60
carbonization (<10 °C min-1)
5
Recent consideration for BC research was due to its close similarities in performance
capacity to AC in many uses. Generally AC has greater Brunauer–Emmett–Teller (BET)
surface area, surface activity, porosity, and physicochemical stability than BC [14]. The BET
surface areas of AC produced from mill and forest residues via steam activation in a rotary
calciner at 815 °C (1283.0 m2 g−1 and 575.9 m2 g−1, respectively) were significantly higher
than those of BC produced using the same feedstocks using gasification system designed by
Tucker Engineering Associates (TEA) (15.0 m2 g−1 and 11.8 m2 g−1, respectively) [15]. Similar
trend was shown regarding pore volume and total porosity. As a result of this, AC is being
studied as the most prominent environmental media for the removal of different environmental
contaminants via adsorption (Figure 1).
(Adsorption+ Activated Carbon / Adsorption + Biochar)

30000
2000
Number of Publications "Adsorption"
Adsorption
25000
Adsorption + Activated Carbon
Adsorption + Biochar
1500
20000
Number of Publications
15000
1000
10000
500
5000
0 0
1990 1995 2000 2005 2010 2015
Published Year
Figure 1: Science Citation Indexed publications on adsorption and adsorption related to
activated carbon and biochar in SCOPUS (Accessed on 2018.01.10).
Despite the fact that AC is a successful adsorbent, one of the demerits for being used as
adsorbent is its high production cost and difficulties with regeneration [16]. According to the
literature, the estimated cost for BC and AC are USD 246 t-1, and USD 1500 t-1, respectively,
6
which means that BC is approximately 1/6 less expensive than AC [17], and the choice of the
initial feedstock for biochar production is more flexible than that of AC. In these respects, BC
has been vital as a low-cost adsorbent alternative to AC [16]. However, compared to AC, it has
not been promising in the context of sorptive removal of contaminants because of its relatively
low surface area and the influence of abiotic and/or biotic processes on its properties and
adsorption capacity for contaminants [15]. Therefore, a great deal of researches has focused on
enhancing the surface area and mechanical properties of BC through diverse modification
methods, i.e. chemical, physical and magnetic modification and impregnation with mineral
sorbents [18].
Engineered BCs prepared via impregnation with minerals are referred to as BC composites.
These composites can be prepared by incorporating BC with metal oxides, clay minerals,
organic compounds, or carbonaceous materials such as graphene oxide (GO), polysaccharides,
and carbon nanotubes (CNT), all of which greatly alter the surface functionalities of the BC
[19-20]. In these composites, BC acts as a porous structure to support the distribution of
modifier particles/compounds within its matrix and enhances the adsorption capacity for a wide
range of contaminants [21]. In some instances, the unwanted functionalities were imparted
during the fabrication of BC composites such as reduction of adsorption capacity via
obstruction of pores [22-23]. Hence, it is desirable to evaluate both the positive and negative
impacts of BC modification on adsorption of target adsorbates.
Production of BCs and the characterization of their properties and adsorption capacities for
various contaminants have been thoroughly reviewed [5, 12, 24-26]. Although numerous
studies have been published on the adsorption efficiencies of BCs, attention to
engineered/“designer” BCs for contaminant remediation has not been fully matured [2, 18-19,
27] (Table 2). Most reviews have focused on the removal capacities, while less (or no)
attention was given to a mechanistic understanding of the removal, despite this being of equal
7
importance since adsorption is a micro-molecular level process. Therefore, the overarching
objective of this review is to compensate the knowledge gap surrounding pristine and
engineered/designer BCs and their properties and uses, by revisiting the literature published
within the last decade (2007 to 2018). This review provides a comprehensive summary of the
environmental applications of various BC composites and important factors that influence the
characteristics of BCs, as well as discusses the factors influencing adsorption and mechanisms
involved in the adsorption process.
8
Table 2: Reviews published based on the applications of biochar in the removal of different types of contaminants available in aqueous media.
Title of review Anions Cations Pharmaceuticals Dyes PAHs VOCs Agrochemicals Reference
Interaction of arsenic with biochar in soil and √ Vithanage et
water: A critical review al., [28]
Biochar-based removal of antibiotic √ Peiris et al.,
sulfonamides and tetracyclines in aquatic [25]
environments: A critical review
Biochar adsorption treatment for typical √ √ √ √ √ Deng et al.,
pollutants removal in livestock wastewater: [29]
A review
Environmental application of biochar: √ √ √ √ √ Oliveira et al., [30]
Current status and perspectives
Biochar as a low-cost adsorbent for heavy √ Patra et al.,
metal removal: A review [31]
9
A review of biochar as a low-cost adsorbent √ Inyang et
for aqueous heavy metal removal al., [24]
Application of biochar for the removal of √ √ √ Tan et al.,
pollutants from aqueous solutions [32]
Characteristics and applications of biochar √ √ √ Xie et al.,
for environmental remediation: A review [33]
Biochar preparation, characterization, and √ √ √ Nartey and
adsorptive capacity and its effect on Zhao [34]
bioavailability of contaminants: An overview
Organic and inorganic contaminants removal √ √ √ √ √ Mohan et
from water with biochar, a renewable, low- al., [12]
cost and sustainable adsorbent – A critical
review
Biochar as a sorbent for contaminant √ √ √ √ Ahmad et
management in soil and water: A review al., [5]
10
Characterization and adsorption capacities of √ √ Gisi and
low-cost sorbents for waste water treatment – Notarnicola
A review [35]
A review: Utilization of biochar for waste √ √ √ √ √ Zhang et al.,
water treatment [36]
The potential role of biochar in the removal √ √ √ √ Inyang and
of organic and microbial contaminants from Dickenson
potable and reuse water: A review [37]
Challenges and recent advances in biochar as √ √ √ √ Rosales et
low-cost biosorbent: From batch assays to al., [38]
continuous-flow systems
11
2. Pristine biochar: State-of-the-art adsorbent
Biochar is a carbon-rich material obtained by the thermal treatment of carbon neutral
carbonaceous materials such as wood, manure, or leaves under an oxygen free environment
Biochar is produced through the dry carbonization or pyrolysis of biomass, differing from
both charcoal (complete carbonization) and hydrochar (which is produced as slurry in water
via hydrothermal carbonization of biomass under pressure). Feedstocks used for the
production of BC can be divided into two categories: produced biomass and its by products,
and waste biomass [39-40]. Animal manure, municipal solid waste (MSW), woody biomass,
and crop residues are commonly employed as waste feedstocks [5]. Waste materials are a very
cost-effective feedstock because they are abundant and easily collectable, and further
indirectly support waste management and carbon neutrality in urban/rural areas.
2.1 Factors influencing properties of biochar
The characteristics of BC are highly contingent on the types of feedstock, pyrolytic
temperature, heating rate, reaction media, and residence time [19]. Biochar from animal litter
and solid waste result in high yields and ash contents compared to those produced from crop
residues and wood [41], because of the high content of inorganic constituents [5, 42]. The
presence of various innate metals in animal litter also increases the BC yield by preventing the
loss of volatile material through changing the bond dissociation energies of organic and
inorganic carbon bonds [43]. Ash content is also affected by the composition of the feedstock;
high ash contents were found in animal manure and waste BCs owing to the high labile and
volatile C contents in these biomasses [41]. For example, BC from chicken manure contains
more than 17.5 wt.% of ash content [44]. Animal manure-derived BC has a higher mineral
content than that derived from plant matter [41]. Even at high pyrolysis temperatures (> 700
°C), BC produced from animal excreta and solid waste exhibit relatively lower surface areas
12
than those produced from crop residues and woods [5]. This is due to the extensive cross-
linking that results from the lower C contents and high molar ratios of H/C and O/C in crop
residues and wood feedstocks [45]. Moreover, the collapse of structural matrix of
lignocellulose biomass via the digestion system (i.e., acidic conditions and biological
fermentation) is one of the factors lowering the surface area of BC [46].
In general, the yield of BC decreases with increasing pyrolysis temperature, which is likely
due to the degree of carbonization [47]. At 400 °C, BC produced from wheat straw (WS-BC),
corn straw (CS-BC), and peanut shell (PS-BC) achieved yields of 32.4, 35.5, and 36.8 wt.%,
respectively; upon increasing the temperature to 700 °C, these yields decreased to 22.8, 24.9,
and 25.8%, respectively [48]. The yield of BC produced from vermicompost (VM-BC) also
achieved higher yield at 400 °C (91.56 wt.%) than at 700 °C (71.81 wt.%) [49]. This was
mainly due to the destruction of cellulose and hemicellulose as well as the thermolysis of
organic materials at high pyrolysis temperatures [50]. At higher pyrolysis temperatures, C and
ash contents significantly increase due to thermal cracking of volatile fraction in biomass and
its subsequent carbonization [51-52]. Ash content of bamboo based BC (BB-BC) increased
from 14.38 to 26.34 wt.% on increasing the temperature from 250 to 550 °C, and VM-BC
exhibited a 18.23 wt.% increase in ash content when the temperature was increased from 300
to 700 °C [49, 52].
The low H/C molar ratio obtained at higher pyrolysis temperatures is likely due to the
aromaticity, which makes BC more chemically and biologically stable [51]. The VM-BC and
pine needle derived BC (PN-BC) produced at 300 °C contained higher H/C molar ratios (0.13
and 0.62, respectively) than at 700 °C (0.03 and 0.08, respectively) [49, 51]. Polarity and
surface oxygen functional group density are indicated by the O/C and (O+N)/C molar ratios
[53]. The low O/C and (O+N)/C molar ratios obtained at high pyrolysis temperatures reduced
the polarity of BC surfaces because they contained fewer surface oxygenated functional
13
groups [49]. The highest O/C and (O+N)/C molar ratios (0.46 and 0.55, respectively) in VM-
BC were obtained at 300 °C, and the lowest (0.02 and 0.07, respectively) at 700 °C; for PN-
BC, the highest O/C molar ratio (0.07) was also obtained at 700 °C [49, 51]. An increase in
pH occurs at higher pyrolysis temperatures due to the retention of a higher number of alkaline
groups, the separation of alkali salts (K, Na, Ca, and Mg) from organic compounds, and the
removal of acidic functional groups [54-55]. For example, the pH of VM-BC increased from
7.37 to 11.31 upon an increase in temperature from 300 to 700 °C [49].
Surface area and pore volume also increase with increasing temperature [49, 56] because
of the recombination and crystallization of C during the carbonization step [57]. The surface
area of VM-BC increased 3-fold, and the pore volume also increased from 0.092 to 0.19 mL
g-1 when the temperature was increased from 300 to 700 °C [49]. The total pore volume of
PN-BC was eight times higher at 700 °C than that at 500 °C [51]. Further, the average pore
diameters in VM-BC produced at 300, 500, and 700 °C were 15.05, 13.91, and 9.94 nm,
respectively, which suggested that the micro-pores are dominantly formed during the
carbonization step at temperature higher than 550 °C [49].
2.2. Adsorption properties of biochar
Biochars produced at higher pyrolysis temperatures (700 °C) exhibit higher adsorption
capacities for antibiotics as compared to those produced at lower pyrolysis temperatures,
however, in some cases, even trace metals adsorption have shown high at high temperature
biochars [7, 54]. High aromaticity of the high temperature BCs lead to increase the removal
capacities of antibiotics, at the same time decrease in polarity supports at high temperatures
support the same [54]. Adsorption of trichloroethylene (TCE) mainly occurred via a pore-
14
filling and hydrophobic partitioning mechanisms [51]. Adsorption of TCE was prevented by
the oxygenated functional groups left intact in BCs produced at lower pyrolysis temperatures,
which instead adsorbed water through hydrogen bonding [58]. Pharmaceuticals typically
interact with BC via Van der Waals interactions, electrostatic interactions, and hydrogen
bonding [59]. Functional group density is higher in BC produced at low pyrolysis
temperatures, of which mechanisms for adsorption are mainly explained by electrostatic
interactions and hydrogen bonding between BC and the functional groups of target
compounds [32]. Biochar produced at higher pyrolysis temperatures has been shown to retain
a higher quantity of anionic dyes and a lower quantity of cationic dyes [49]. Adsorption of
cationic and anionic dyes occurred via cation exchange and π–π interactions, respectively
[49]. Adsorption capacity for pesticides was also increased with increasing pyrolysis
temperature [56]. Pesticides interact with BC via strong π–π electron-donor–acceptor (EDA)
interactions, acid-base interactions, amide bond formation, electrophilic addition, covalent
bond, ionic and hydrogen bonding, van der Waals forces and hydrophobic interactions [56].
Adsorption of both organic and inorganic compounds on BC is pH-dependent, because the
BC surface charge varies according to the point zero charge (pHpzc) of BC. At pH <pHpzc, the
surface is negatively charged, which expedites adsorption of positively charged contaminants
due to the electrostatic interactions. At pH>pHpzc, the surface is positively charged which
prevents adsorption of positively charged compounds due to the electrostatic repulsion [60].
Antibiotics, pesticides and many organic compounds exhibit different pKa values, and thus,
depending on the pH of a given medium, the antibiotic can predominantly exist in its cationic,
anionic, or neutral forms [61-62]. At higher pH values, anionic species become the dominant
form of some antibiotics such as tetracycline, sulfamethazine, ciprofloxacin etc. The
electrostatic repulsion between the negatively charged BC surface and anionic species of
antibiotics would thus increase, resulting in decreased adsorption at higher pH values [63].
15
However, high pH also facilitates weaker π–π EDA interactions between the antibiotic and
BC surface [63]. At lower pH conditions, anionic dye adsorption mainly occurs via
electrostatic interactions between the negatively charged anionic dye and protonated hydroxyl
and carboxylic acid groups of BC [64]. However, adsorption of cationic dyes decreases due to
repulsive forces occurring between cationic dyes and positively charged functional groups of
BC [49]. At higher pH, protonated functional groups of BC gradually deprotonated, as a result
electrostatic interaction weakens, leading to a decrease in the adsorption of anionic dyes but
an increase in the adsorption capacity for cationic dyes [49].
3. Engineered biochar composites: Preparation methods/synthesis
This section mainly focuses on the production processes of several key BC composites
(Figure 2).
Figure 2: Engineered biochar composites preparation pathways.
3.1 Biochar composites prepared with clay minerals
In recent years, clay minerals have been widely employed in medicine, pharmacy,
agriculture, and the manufacturing of cosmetics, paint, and ink [65]. Due to their lamellar
16
structures, high surface area, and high ion-exchange capacities, clay minerals have been
effectively used as adsorbents for the removal of different types of antibiotics, polymers, and
heavy metals/metalloids [66-70]. However, exclusive use of clays as adsorbents does not
appear to be prospective due to the regeneration issues as well as the volume of residue after
adsorption. Clay-BC composites prepared by mixing of small amount of clay with BC has
demonstrated promising results and high sorption capacities in removing different
contaminants [21]. Although various methods have been used to produce clay–BC
composites, the most common ones involve the preparation of a clay–BC slurry for pyrolysis
[21-22]. In brief, the feedstock is dipped in a stable clay suspension which is prepared by
adding the powdered material to deionized (DI) water or another suitable solvent and
pyrolyzed under oxygen-limited conditions in a muffle furnace at the relevant temperature
[21]. Alternatively, BC can also directly be soaked in a slurry prepared with clay minerals,
deionized water, and acetic acid, stirred overnight, and then oven-dried at 60 °C for 24 h. The
most commonly used weight ratios of clay:biomass/BC for both procedures were 1:5, 1:4, 1:2,
and 1:1 [21-22, 71-73].
3.2 Biochar composites prepared with metals and metal oxides
In BC–metal/metal oxide composites, BC acts as a porous carbon platform upon which
metal oxides precipitate, thus increasing the surface area available for adsorption. Generally,
impregnation with metal oxides is performed by soaking BCs or their feedstocks in solutions
of metal nitrates or chlorides. The most frequently used impregnation agents described in the
literature are FeCl3, Fe2O3, Fe(NO3)3, and MgCl2 [74-76]. Preparation of metal oxide
composites of BC was done by two methods: pre-pyrolysis treatment, soaking of the biomass
followed by pyrolysis; or post-pyrolysis treatment, pyrolysis of the biomass followed by
soaking in metal ion solution [18]. In the pre-pyrolysis method, the feedstock is soaked in a
17
metal salt solution and then pyrolyzed under an oxygen-free environment [23]. In the post-
pyrolysis method, pyrolysed feedstock is soaked in a metal salt solution [74, 77].
3.3 Biochar composites prepared with carbonaceous materials
Biochar can be combined with carbonaceous materials that have functional groups capable
of creating strong bonds with both the BC surface and the pollutants present in aqueous
medium. Polysaccharides, amines, carbonaceous nanomaterials, and CNTs are the most
commonly used agents [78-80]. Such modification can be achieved either through simple
chemical reactions or by mixing BC with polymers rich in amino groups such as
polyethylenimine or chitosan [81]. Among bulk carbon materials, graphene (G) and carbon
nanotubes (CNT) are commonly used in composite synthesis due to their great binding
affinity through functionalization with –OH and –COOH groups via chemical oxidation
methods [82]. Since the porous structure and relatively high surface area of BCs, it can be
used as a host to distribute and stabilize carbon nano-materials and expand the range of
potential applications [26]. Modification can further enhance the adsorption capacities of BCs
for different toxic pollutants [73, 83]. .
4. Characteristics of biochar composites and their influencing factors
Biochar composites are prepared by combining the carbon neutral feedstock with different
types of materials. For the preparation of BC, different feedstocks from a range of agricultural
and carbonaceous materials have been used [1]. Characteristics of BC composites mainly
depend on characteristics of the feedstock, combining agents and pyrolysis conditions [19].
Table 3 summarizes the characteristics of BC composites produced from different feedstocks
under different pyrolysis conditions.
High BC yield may be related to a higher composition of inorganic constituents in
feedstock materials [5]. It is suggested that various metals present in animal litter may protect
18
against the loss of volatile material by changing the bond dissociation energies of organic and
inorganic carbon bonds [43]. For example, the enhanced dehydrogenation in the presence of
inorganic constituents (catalytic effects) generally expedites crystallization, thereby resulting
in the high yield of BC. Generally, biomass with high lignin content results in high BC yield
[42]. The yield and elemental contents of BC composites decrease with increasing pyrolysis
temperature due to greater loss of volatile components [52]. The yield of some BC is
generally increased up to a heating rate of 5 °C min-1, but further increases result in decreased
yields. With the increase of heating rate, production of bio-crude and bio-gas dominate,
resulting in low BC yield due to the breakdown of organic compounds [84]. An increase in
residence time slightly decreases BC yield due to greater volatilization during longer
pyrolysis conditions [84]. Therefore, clay minerals, metal/metal oxides and carbonaceous
modifiers have exhibited strong influence on the yield of BC [52, 79]. The ash content of BC
is proportional to the pyrolysis temperature [48, 83]. The ash content is also varied with the
types of biomass feedstocks. Hence, both metal oxide and clay modifications slightly increase
the ash content in BC composites compared to raw samples due to the thermal stability of
metal oxide and clay minerals [73, 75, 83].
A slight decrease in the C content of BC composites resulting from metal and clay
modification [74, 83] may occur due to the introduction of metallic elements. For instance,
some elements in modifiers may play a role of a catalyst that results in the different
contaminant degradation mechanisms. However, feedstock and temperature are the main
factors determining C content. At high pyrolysis temperature, C content increases [52] due to
high carbonization and dehydrogenation, and a high amount of C exists within aromatic
structures [85]. High C content in the feedstock produces BC composites with higher C
contents due to the insufficient amount of hydrogen in its structural matrix [86].
19
Table 3: Characteristics of BC composites produced from different feedstocks at different pyrolysis temperatures.
Feedstock Modifier Pyrolysis Yield pH C H O N S Fe Al Ca Na K Mg Ash Surface Pore Reference
Temp. % area volume
and Time m2g-1 cm3g-1
------------------------------------------------%-------------------------------------------------------------------
250°C
78.00 - 51.90 5.45 - 0.87 0.08 0.01 - 0.50 - 0.83 - 14.38 - 0.36
30 min
350 °C
60.00 - 71.50 4.02 - 1.11 0.07 0.01 - 0.08 - 1.40 - 28.08 - 1.05
30 min
Untreated
450 °C
35.00 - 75.00 3.42 - 1.38 0.12 0.02 0.01 0.10 - 1.40 - 19.10 - 0.77
30 min
Rawal et al.,
550°C
Bamboo 33.00 - 79.20 2.72 - 1.28 0.06 0.03 0.01 0.08 - 0.85 - 26.34 - 1.01 [52]
30 min
250 °C
86.00 - 48.70 5.15 - 0.50 1.00 2.00 0.03 0.05 - 0.74 - 15.43 - 0.73
30 min
350 °C
Iron-kaolinite 59.00 - 67.60 3.30 - 0.87 1.10 2.10 0.04 0.05 - 1.00 - 11.40 - 0.86
30 min
450 °C
48.00 - 62.90 2.82 - 1.45 1.10 2.90 0.09 0.07 - 1.20 - 35.60 - 0.56
30 min
20
550°C
38.00 - 63.60 1.72 - 1.39 0.52 2.30 0.16 0.05 - 0.64 - 14.61 - 0.16
30 min
250 °C
76.00 - 48.70 5.15 - 0.50 0.73 1.20 0.01 0.05 - 0.35 - 15.91 - 0.88
30 min
350 °C
63.00 - 57.20 3.51 - 0.80 1.40 2.50 0.03 0.12 - 0.82 - 24.14 - 0.77
30 min
Iron-bentonite
450 °C
42.00 - 61.00 2.79 - 0.84 1.30 2.50 0.03 0.12 - 0.63 - 56.87 - 0.73
30 min
550 °C
38.00 - 70.20 2.49 - 0.79 0.63 1.70 0.10 0.10 - 0.37 - 31.64 - 0.42
30 min
500 °C
Untreated 14.89 10.40 75.81 - 19.30 - - - 0.39 1.51 - - 1.49 24.67 99.43 0.08
6h
Potato stem
Natural 500 °C 0.12
30.71 9.93 59.75 - 30.92 - - - 1.15 2.13 - - 2.05 50.33 90.4
attapulgite 6h
Table 3 continued
Temp. % area volume
------------------------------------------------%-------------------------------------------------------------------
21
Bamboo - - 80.89 2.43 14.86 0.15 - 0.00 0.04 0.34 0.01 0.52 0.23 - 375.5 -
Bagasse 600 °C - - 76.45 2.93 18.32 0.79 - 0.05 0.11 0.91 - 0.15 0.21 - 388.3 -
Untreated
Hickory 1h
- - 81.81 2.17 14.02 0.73 - 0.01 0.01 0.82 0.24 0.13 - 401.0 -
chip
Bamboo - - 83.27 2.26 12.41 0.25 - 0.23 0.68 0.21 0.14 0.33 0.14 - 408.1 -
Bagasse Montmorillonite 600 °C - - 75.31 2.25 18.87 0.75 - 0.47 0.75 0.85 0.13 0.32 0.22 - 407.0 - Yao et al.,
Hickory (MMT) 1h [21]

- - 80.93 2.21 15.14 0.28 - 0.15 0.32 0.57 0.04 0.11 0.19 - 376.1 -
chip
Bamboo - - 81.02 2.15 15.85 0.25 - 0.08 0.30 0.19 - 0.07 0.05 - 239.8 -
Bagasse Kaolinite 600 °C - - 70.20 2.44 24.44 0.74 - 0.46 0.53 0.88 - 0.06 0.16 - 328.6 -
Hickory (KLN) 1h
- - 78.08 2.11 18.12 0.33 - 0.07 0.51 0.52 - 0.05 0.18 - 224.5 -
chip
400 °C
Untreated
1h - 5.3 76.05 3.47 19.04 037 0.37 - - - - - - - 2.27 -
300 °C
70.00 6.60 - - - - - - - - - - - - 9.84 0.05 Chen et al.,
Bamboo 1h
Montmorillonite [73]
350 °C
64.00 6.90 - - - - - - - - - - - - 13.40 0.05
1h
400 °C 61.00 7.10 64.01 3.81 10.03 0.41 0.44 - - - - - - 21.3 19.93 0.06
22
1h
450 °C
58.30 7.40 - - - - - - - - - - - - 26.22 0.06
1h
500 °C
56.00 7.6 - - - - - - - - - - - - 18.05 0.05
1h
Pine wood Untreated 600 °C - - 85.70 2.10 11.4 0.30 - 0.02 0.04 0.19 - 0.05 0.12 - 209.60 - Wang et al.,
(PW) Natural Hematite 1h - - 51.70 1.40 43.1 0.20 - 2.95 0.24 0.10 - 0.04 0.14 - 193.10 - [87]
Bamboo
Table 3 (continued)
Temp. % area volume
------------------------------------------------%-------------------------------------------------------------------
Untreated Frišták et al.,

500 °C - 8.74 82.84 2.11 - 1.36 - - - - - - - 16.21 16.50 -
Corncob [74]
Fe(NO3)3 2h
- 3.38 74.56 1.61 - 2.42 - - - - - - - 14.18 6.19 -
Pistachio Untreated 400 °C 31.40 6.40 73.42 2.93 23.44 0.21 1.70 196.40 Komnitsas
shells (PI) KOH 1h - 6.10 78.24 3.07 17.95 0.74 - - - - - - - - 572.40 - and
23
FeCl3 - 5.70 75.4 2.95 20.94 0.71 - - - - - - - - 421.50 - Zaharaki,
Untreated 34.70 6.10 71.6 2.65 25.15 0.6 - - - - - - - 1.80 142.40 - [88]
Pecan shells 400 °C
KOH - 5.80 75.3 2.75 21.09 0.76 - - - - - - - - 397.30 -
(PC) 1h
FeCl3 - 5.60 72.8 2.63 23.85 0.72 - - - - - - - - 351.60 -
Untreated 17.70 4.80 65.2 2.08 32.4 0.32 - - - - - - - 1.70 48.7.0 -

Sawdust 400 °C
KOH - 4.60 72.9 2.19 24.52 0.39 - - - - - - - - 124.60 -
(SD) 1h
FeCl3 - 4.40 67.3 2.11 30.23 0.36 - - - - - - - - 110.80 -
Untreated 27.90 6.90 - - - - - - - - - - - 4.50 0.01
Graphene
600 °C 25.70 6.40 - - - - - - - - - - - - 10.90 0.03 Tang et al.,
Wheat straw (G)0.1%
1h [79]
G- 0.5% 27.70 6.70 - - - - - - - - - - - - 15.80 0.06
G - 1.0% 29.00 7.10 - - - - - - - - - - - - 17.30 0.12
Untreated - 8.46 - - - - - 0.30 - - - - - 36.20 174.00 40.00

Paper and 750 °C
Chaukura et
paper sludge Fe2O3 2h - 2.86 - - - - - 22.60 - - - - - 49.30 15.30 3.50
al., [75]
24
The pH of the BC composite can be varied according to the acidity or basicity of the
combining material as well as the pyrolysis temperature [75, 89]. Depending on the level of O in
the clay minerals, clay modification of BC can alter the O content and may introduce additional
oxygen-containing functional groups to the BC surface [83]. However, chemical modification
results in slight decrease in the H, O, and N contents [88]. Furthermore, surface functional
groups determine the surface acidity/basicity, which is a crucial factor affecting the adsorption
capacities and selectivity of clay–BC composites. Most of the clay minerals used in BC
composites mainly consist of metals such as Ca, Na, Al, Mg, Fe, Zn, and Si [90]. As such, metal
concentrations are higher in clay BC composites than in pristine BC [21, 77, 83].
The electrical conductivity (EC) of BC significantly increases when it is pyrolyzed at high
temperatures [43, 48, 83], due to the loss of volatile material at high temperatures and the
different crystalline structural matrix of C. Modification with metal oxides increases the soluble
salt content within composites, thus increasing the EC of BC composites [75]. However,
modification with metals otherwise reduces the EC of modified BC [74].
Clay-modified BC exhibits comparable thermal stability to that of unmodified BC [21].
Conversely, BCs modified using carbonaceous materials exhibit higher thermal stability than
unmodified BC [78-79]. If the modifying agent has magnetic properties, the composite may
exhibit permanent magnetic properties after pyrolysis [78].
Upon chemical modification, the surface of BC becomes rough as a result of adherence of
fine particles of the modifier [77]. Scanning electron microscopy (SEM) allows the clear
visualization of fine particles adhered on BC surfaces [74, 79, 83], which mostly act to increase
surface area as well as adsorption capacity. However, the surface area can be decreased if pores
are clogged as a result of excessive coating [74]. Increases in pyrolysis temperature and
25
residence time also increase specific surface area, pore volume, and pore size of BCs due to the
thermal destruction of H and oxygen-containing functional groups including aliphatic alkyl,
ester, and phenolic groups.
5. Sorptive removal of inorganic contaminants by biochar composites
5.1 Nutrients
The release of nutrients such as nitrate, ammonia, and phosphate to the natural ecosystem
increases the level of growth-limiting nutrients in natural water bodies, and promotes the growth
of photosynthetic organisms, which can ultimately lead to eutrophication of aquatic ecosystems.
Although phosphate can be removed by many adsorbents, the parallel process for nitrate is rather
difficult. However, BC is able to remove phosphate, nitrates, and ammonium from aqueous
media [91]. In some instances, BC is unable to remove nitrate, and some BC itself releases
nitrate and phosphate into the solution [48]. At high pH values, phosphate adsorption capacity
decreases because the surface of BC is negatively charged.
Nevertheless, compared to raw BC, modified BCs have demonstrated high potential in
removing nutrients from aquatic systems. Table 4 summarizes the applications of modified BCs
in the removal of contaminants present in water. In some cases, modifications of BC can cause
differential adsorption effects for the same contaminant, possibly due to the influence of
feedstocks [23]. The SBT-BC has shown a very low phosphate removal rate (approximately
10%) [91] compared to SBT-MgO-BC (66.7%), which is explained by the strong affinity of
MgO for phosphate in aqueous medium due to its high general affinity for anions through mono-,
bi-, and tri-nuclear complexation [92]. However, the complexation mechanism depends on the
amount and distribution of MgO particles on the BC surface as well as the size of MgO particles.
26
Interestingly, PW-MgO-BC achieved a much lower phosphate removal rate (0.5%) [23].
Electrostatic repulsions between the BC surface and phosphate in solution was the reason for the
low adsorption of phosphate by PW-MgO-BC [93]. Nitrate removal by PS-MgO-BC and SBT-
MgO-BC was found to be 11.7% and 3.6%, respectively [23], which might be due to differences
in the adsorption mechanisms involved.
Chitosan-modified BC had not achieved promising results in the removal of phosphate from
solution because of net negative charge of the modified BC surface [78]. In contrast, zerovalent
iron (ZVI)-modified BC removed high concentrations of phosphate, and removal efficiency was
found to increase from 56% with increasing amount of Fe. The pH of the medium (5.7) was
lower than the pHpzc (7.7) of ZVI, and thus, the cationic form predominantly existing in this
solution might have promoted the binding of phosphate [94].
The enhanced adsorption capacities exhibited by BB-MMT-BC composite for ammonium and
phosphate were due to enhanced surface area of BC and increased number of binding sites
resulted from the clay modification [73]. Adsorption of phosphate and ammonium on the BB-
MMT-BC composite at low concentrations was mainly controlled by monolayer adsorption
(chemical adsorption), while at higher concentrations both chemical and physical adsorption
were involved, although multilayer adsorption also played an important role [73].
5.2 Trace metals
Presence of elevated trace metals concentrations in natural ecosystem potentially leads to
severe environmental concerns [37]. Most commonly found trace metals in aquatic ecosystem
are Pb, Hg, Cr, As, Cd, Zn and Cu. The United States Environmental Protection Agency (EPA)
has set the maximum allowable limit of above metals in drinking water and waste water.
27
Therefore, various methods were developed, such as chemical precipitation, reverse osmosis, ion
exchange, solvent extraction, electro-dialysis and adsorption for removing trace metals from
contaminated water. Due to relative expensiveness adsorption is considered as economically
feasible method for the removal of trace metals from aqueous media (Table 4).
The adsorption capacities of bentonite–BC composites for Cr(VI) and Zn(II) were lower than
that was achieved with raw BC and bentonite [22], and it was suggested that the binding of
anionic functional groups of the BC with the cationic compounds of the bentonite (and vice
versa) may have reduce the available adsorption sites.
The adsorption of As(V) onto the hematite-modified BC was roughly double than that of the
pristine BC at all concentrations, further suggesting that iron oxide particles served as adsorption
sites with a higher affinity than the unmodified BC for As in aqueous solution [87]. The
adsorption of As(V) onto a solid surface is mainly controlled by As speciation and the charge of
the sorbent surface [95].
Among three BC composites prepared by combining with different weight percentages of Mn,
the highest adsorption efficiency for Pb(II) (98.9%) was shown by BC composite loaded with
3.65 % Mn. However, BC composite coated with excessively high amount of Mn exhibited low
Pb(II) adsorption efficiency because of coating leading to reduction of surface area via blockage
of pores [77]. Solution pH influenced both Pb(II) species and net surface charges on the BC
composite, which directly influenced Pb(II) adsorption [77].
Removal of mercury increased with an increase in G content from 0.1 to 1.0% in a WS-G–BC
composite [79]. The removal of Hg was facilitated by the large surface area, allowing surface
complexation between Hg and the increased oxygen-containing functional groups (–OH, O=C–
O) and C=C groups on the surface of the composite containing 1% G [96].
28
Table 4: Applications of modified BCs for the removal of toxic contaminants in water.
Feedstock Modifier Pyrolysis Contaminant Enhancement Mechanism Reference
Conditions
Potato stem Natural 500 °C Norfloxacin Maximum adsorption capacity was The SiO2 particles and oxygen- Li et al., [83]
attapulgite 6h 1.7 times higher than raw PSt-BC. containing surface functional
More than 80.1% of NOR was groups serve as sorption sites for
removed in a wide range of pH adsorption. Electrostatic interaction
values (2.0–11.0). is the main mechanism involved.
Sweet Bentonite 400 °C Malachite green MG adsorption capacity of the Net negative charge of the BC- Fosso-Kankeu et
sorghum 1h (MG) composite was higher than that of composite is improved the al., [97]
bagasse pristine BC. attraction of cationic dyes via
(SSB) electrostatic interactions.
Bamboo Montmorillonite 600 °C Methylene blue The MB removal rate of BG–MMT- The superior ion-exchange capacity Yao et al., [21]
Bagasse 1h (MB) BC and HC–MMT-BC composites of MMT clay improved the
Hickory chip has been improved compared to raw adsorption capacity of BC
BCs but decrease the MB composites.
adsorption capacity of BB–MMT-
BC composite than raw BC.
Bamboo Kaolinite 600 °C MB The MB removal rate of BG-KLN-
29
Bagasse 1h BC and HC-KLN-BC was slightly
Hickory chip improved compared to raw BCs and
removal rate of MB by BB-KLN-
BC decreased compared to raw BC.
Table 4 (continued)
Conditions
Sweet Bentonite 400 °C Zn(II) Adsorption capacity of the The anionic functional groups on Fosso-Kankeu et
sorghum composite was lower for Zn(II) the BC that partially bind with the al., [22]
bagasse compared to bentonite and raw BC. cationic compounds in bentonite
and obstruct pores.
Cr(VI) Adsorption capacity of Cr(VI) by
composite is higher than bentonite
and slightly higher than raw BC.
Pine wood Natural 600 °C As(V) These γ-Fe2O3 particles act as BC Composite has exhibited Wang et al., [87]
Hematite 1h sorption sites for As(V) and magnetic properties due to
increase adsorption capacity of conversion of natural hematite into
30
As(V). γ-Fe2O3 particles with magnetic
properties. Electrostatic interactions
involved in adsorption.
Bamboo Montmorillonite 400 °C Phosphate Adsorption capacity for phosphate Adsorption of P was resulted via Chen et al., [73]
1h Ammonium is 8.4 times higher than ammonium. electrostatic attraction or ionic
bonds between P and cations in the
BC composite.
The adsorption of ammonium was
occurred via surface adsorption
onto the MMT, BC and
intercalation into the gallery of
MMT.
Table 4 (continued)
Conditions
Bamboo Zerovalent iron 600 °C MB Among all the iron-modified BCs, Zhou et al., [78]
1h the BC composite with the highest
weight ratio of Fe (3 times of BC
31
mass) achieved the highest MB
removal rate.
Pb(II) More than 93% of Pb(II) was The ZVI can remove heavy metal
removed. cations; Pb(II), Cr(VI) and As(V)
Cr(VI) The removal of Cr(VI) increased from aqueous solution through both
with the amount of ZVI in the adsorption and reduction processes.
samples when the mass ratios of the
other components were constant.
As(V) Removal rate of As(V) by BB-ZVI- Electrostatic attractions between the
BC composite increased from 72%. anions and the ZVI particles on the
Phosphate Phosphate removal increased from composite surface.
56%.
Rice husk Ca2+ 300 °C As(V) Percentage removal of As(V) Due to alkaline nature of solution Agrafioti et al.,
(RH) 1h increased from about 70% calcium oxide removed As via [98]
17 °C min-1 compared to raw BC. precipitation.
Cr(VI) Percentage removal of Cr (VI) High pH of BC composite solutions
slightly increased with deprotonate their functional groups
modification. and repel negatively charged
Cr(VI).
32
Table 4 (continued)
Conditions
Rice husk Fe0 300 °C As(V) Percentage removal of As(V) The close to neutral nature and Agrafioti et al.,
1h significantly increased with the alkaline nature of their arsenic [98]
Solid waste 17 °C min-1 modification and with the increase solutions respectively, indicated
of percentage amount of Fe0 that As(V) was possibly removed
removal percentage further by co-precipitation when Fe(OH)3
increased. was formed.
Percentage removal of As(V) from
40% and not changed with the
percentage amount of Fe0 available
in BC composite.
Cr(VI) Percentage removal of Cr(VI) was High pH of RH-Fe0 and SW-Fe0 BC
slightly increased when the composite solutions deprotonate
percentage amount of Fe0 in their functional groups and repel
composite high. negatively charged Cr(VI).
Percentage removal of Cr(VI) was
33
significantly decreased with the
modification and further increase of
percentage amount of Fe0 in BC
composite further decreased
percentage removal.
Table 4 (continued)
Conditions
Rice husk Fe3+ 300 °C As(V) Percentage removal of As(V) by Highly acidic nature of solution Agrafioti et al.,
Solid waste 1h RH-Fe3+ composite increased from promotes electrostatic interactions [98]
17 °C min-1 47% compared to raw BC and it between positively charged BC
further increase with the Fe3+ surface and negatively charged
amount in composite As(V) species.
Percentage removal of As(V) by
SW-Fe3+ increased from about 40%,
but it was not depend on percentage
amount of Fe3+ in BC composite.
34
Cr(VI) Percentage removal of Cr(VI) by Strongly acidic conditions cause an
RH-Fe3+ composite increased with impact on the solubility of Fe3+ and
the decrease of Fe3+amount in the which is negatively affected Cr(VI)
composite. adsorption on BCs.
Percentage removal of Cr(VI) was
high when percentage amount of
Fe3+ in BC composite is high.
Reed straw TiO2 500 °C Sulfamethoxazole As an adsorbent, the removal The composite TiO2-BC structure Zhang et al., [99]
6h (SMX) efficiency was less than that of strengthened the photocatalytic
unmodified BC. As a photocatalyst, activity of TiO2.
degradation of SMX was higher
than that of TiO2.
Table 4 (continued)
Conditions
Pine wood MnO2 100 °C Pb Biochar impregnated with 3.65% High hydroxyl group density Wang et al., [77]
1 h, then Mn exhibited the highest Pb(II) resulted in a lower pHpzc value,
700 °C adsorption efficiency (98.9%). which favored the removal of
35
3h Pb(II).
Corncob Fe(NO3)3 500 °C Eu Modification has no significant Adsorption mainly occurred via Frišták et al., [74]
2h impact on adsorption of Eu. chemisorption
As Modified BC exhibit more than 20
times increase of adsorption for As
compared to raw BC.
Sugar beet MgO 600 °C Phosphate and nitrate Phosphate removal rate was 66.7%. MgO has strong affinity for Zhang et al., [23]
tailings 1h Nitrate removal rate was 3.6%. phosphate in aqueous medium due
Nitrate removal rate was 11.7%. to its high general affinity for
Peanut shell Phosphate removal rate was anions through mono-, bi-, and tri-
Cottonwoods approximately 40%. nuclear complexation. However, the
(CW) Nitrate removal rate was complexation mechanism depends
approximately 5.0%. on the amount and distribution of
MgO particles on the BC surface as
well as the size of MgO particles.
Pine wood Phosphate removal rate was 0.5%. Electrostatic repulsions between the
Nitrate removal rate was BC surface and phosphate in
approximately 5.0%. solution results low adsorption of
phosphate by PW-MgO-BC.
36
Table 4 (continued)
Conditions
Wheat straw Graphene 600 °C Phenanthrene, Removal efficiency of phenanthrene Modified BC surface exhibited Tang et al., [79]
1h mercury and mercury increased with the more oxygen-containing functional
increase in G from 0.1 to 1.0%. groups and was negatively charged,
which improved adsorption of
phenanthrene and mercury.
Bamboo Chitosan 600 °C Pb(II), Removal of Pb(II) enhanced from Amine functional groups of the Zhou et al., [78]
1h 35.7% relative to unmodified BC. chitosan have strong affiliation to
Cr(VI) Removal of Cr(VI) enhanced from cationic metal ions in aqueous
27.8%, compared to unmodified solution.
BC.
As(V) Did not remove anionic As(V) or Surface of both raw BC and
Phosphate phosphate from solution. chitosan modified BC negatively
MB MB removal rate was also high. charged.
37
Sweet gum Graphene oxide 600 °C Pb(II), Cd(II) Adsorption capacities for Pb(II) and Liu et al., [82]
wood (GO) 1h Cd(II) were higher than those of
Carbon pristine BC. The GO–BC composite
nanotubes showed higher adsorption of Pb(II)
and Cd(II) than the CNT–BC
composite.
38
In novel adsorbents prepared by combining BC with chitosan and ZVI, chitosan acted as a
dispersing and soldering agent to attach ZVI particles to the BC surface [78]. Chitosan-modified BC
increased the removal of Pb(II) compared to the unmodified BC because the amine functional groups
of chitosan had strong affinities to cationic metal ions in the aqueous solution [81]. The presence of
both ZVI and chitosan increased the removal of Pb(II) up to 93%, which is exempted from the
amount of ZVI present in the composite. However, removal of Cr(VI) increased with an increasing
amount of ZVI in the composite; the highest removal rates observed were 35 and 40% (for
BB:chitosan:ZVI 1:1:3 and 1:2:3, respectively), indicating that both chitosan and ZVI particles
conferred enhancement to the removal of cationic heavy metals [78]. Unmodified BC and chitosan-
modified BC did not achieve significant removal of anionic As(V) from solution [78], which might
have been due to their surfaces having net negative charges [81]. However, ZVI-modified BC
removed between 23 and 95% of As(V), and increasing the Fe level in the composite further
improved removal of As(V). The pHpzc of ZVI is reported around 7.7 [94]. As the pH of the medium
(5.7) was lower than the pHpzc, ZVI particles were positively charged and could have assisted the
adsorption of the anionic As(V).
Both Ca and Fe modified BCs exhibited high As(V) removal capacities (95%), except for that
produced using a RH feedstock impregnated with Fe0, which removed only 58%. However, the
Cr(VI) removal rate was not as high as expected; the highest removal rate (95%) was achieved by
RH-BC impregnated with Fe3+ [98].
Engineered BCs (EBC) produced using stillage residue collected from a biofuel pilot plant, which
manufactures ethanol, were used for the removal of Ag(I) from an aqueous medium. The removal
percentage of Ag(I) reached 97.4%. Adsorption of Ag(I) on EBC occurred via multilayer sorption,
and that the process could be governed by multiple mechanisms [100].
Both GO–BC and CNT–BC composites prepared from sweet gum feedstock achieved higher
adsorption capacities for Pb(II) and Cd(II) than the pristine BC. The GO–BC composite exhibited
39
higher adsorption of Pb(II) and Cd(II) than the CNT–BC composite [82]. Adsorption of both metals
could be governed via complexation with oxygen-containing functional groups of the carbon nano-
materials, electrostatic attractions, cation exchange, and surface adsorption onto the CNTs, GO, and
BC surfaces [101].
Pine bark waste was impregnated with CoFe2O4 has shown low removal percentage for both
Pb(II) and Cd(II), and removal was clearly pH-dependent, and removal percentage increased with
increase of pH from 2.0 to 8.0. At acidic pH due to the presence of high concentration of H+ on the
BC composite, BC surface was protonated and became positively charged. It therefore reduced the
adsorption of metal ions due to electrostatic repulsion. At high pH, BC composite surface charged
negatively, thus adsorption of metal ions increased.
The Cu(II) adsorption capacity of nano MnO2 BC composite enhanced with the increase of pH
between 3.0 to 6.0, and comparatively higher than that of nano MnO2. Formation of complexes
between Cu(II) and oxygen-containing functional groups present on BC composite surface was the
major mechanism involved in the metal adsorption [102].
Magnetic BC prepared via impregnating with different mass ratios of FeSO4 and NaBH4 was
showed affinity for Cu(II), and the adsorption affinity increased with the increase of molar ratio of
FeSO4 and NaBH4 in the BC composite. Sorption capacity increased with the long stirring time, and
decreased with the higher initial concentration of Cu(II) in the solution. Main functional groups
contributing to the coordination of Cu(II) on the BC surface were carboxyl, hydroxyl and phenolic
groups. Partial deprotonation of the functional groups under acidic conditions promoted the
adsorption of Cu(II) via exchanging Cu(II) with hydrogen ions [103].
Hydrogel BC composite was synthesized by embedding RH-BC into poly(acrylamide) hydrogel
with N.N’-methylenebisacrylamide (MBA) as cross linker. Removal of As increased with the
increase of pH from 4.0 - 6.0, and decreased beyond pH 6.0 - 10.0. High As adsorption at pH 6.0
facilitated by electrostatic interactions occurred between oxyanion species of As and positively
40
charged BC surface because at pH<pHPZC due to protonation of surface-active sites BC surface
became positively charged. At pH >pHPZC, BC surface was negatively charged, and decreased the
adsorption of As due to repulsive effect. Alternatively, increase of hydroxyl ions in the solution
competing with As species reduced the adsorption of As at high pH [104].
Higher removal efficiency of Pb(II) was demonstrated by magnetic ZnS-BC composite compared
to magnetic BC, however it was pH dependent and beyond pH 6.0 Pb(II) precipitated as hydroxide
[105]. The adsorption of Pb(II) was suggested as an endothermic and spontaneous process. In a
different study, adsorption of Pb(II) by MgO-BC composite was reported to be rapid, and reached
99.9% within 10 min. Adsorption capacities remained constant at the pH range of 3.0 to 7.0
dominated by ion-exchange between Pb2+ and Mg2+[106].
6. Sorptive removal of organic contaminants
The main organic contaminants in aqueous bodies are pesticides, pharmaceuticals, antibiotics, and
polycyclic aromatic hydrocarbons. For the adsorption of organic contaminants, modified BC has
been widely used. Attapulgite–BC composites derived from lotus stalk biomass and natural
attapulgite adsorbed more than 80.1% of NOR from aqueous solution over a wide range of pH values
(2.0–11.0), because pH had a major impact on the molecular form of NOR, and the surface charge of
the BCs [107]. The removal capacity of NOR by the composite was very high compared to that of
the unmodified BC. This might be due to the high adsorption capacity of attapulgite particles for
NOR [83].
Acid pretreated titanium dioxide (TiO2)-reed straw BC (TiO2-pBC) and acid pretreated reed straw
BC (pBC) were produced via a sol-gel method [99]. TiO2 particles covered the surface and filled
internal pores of the pBC, reducing the surface area of the adsorbent. Thus, the adsorption capacity of
TiO2-pBC produced at 300 °C for SMX was lower than that of pBC. The degradation of SMX was
significantly higher by TiO2-pBC produced at 300 °C compared to its degradation under simulated
41
sunlight and UV light. Furthermore, the SMX degradation efficiency of TiO2-pBC produced at 300
°C reached 91.27%, which was much higher than that achieved with pure TiO2 (58.4%). Therefore,
the composite TiO2-pBC structure strengthened the photocatalytic activity of TiO2 [108].
Liquid phase reduction method was used for the production of BC composite (Co/Fe/MB) under
anaerobic conditions. The BC composite was shown the highest cefotaxime removal efficiency of
82.48% and it decreased slightly with increased pH from 4.0 to 9.0, but significantly decreased at
neutral and alkaline conditions [109]. Electrostatic attraction supported the adsorption because of that
the surface of composites was positively charged below pH 6.0. The catalysis of produced atomic
hydrogen further enhanced the removal efficiency of cefotaxime (CFX). Nevertheless, the CFX
removal efficiencies were equal at pH 4.0 and 5.0, which indicated that the hydrogen ion
concentration was still enough for the formation of atomic hydrogen at pH 5. The CFX removal
efficiency decreased significantly with the increase of pH (alkaline and neutral conditions) as a result
of passivation of layers and less atomic hydrogen production on the surface of Co/Fe/MB [110-111].
Phenanthrene removal efficiency increased from 63.3 to 94.9% with an increase of G percentage
of BC from 0 to 1%. Adsorption occurred via partitioning, π–π interaction, surface adsorption, pore-
filling, and electrostatic attractions [48]. The coating of G on the surface of BC resulted in greater
surface area, pore size, pore volume, stronger vibration of C=C bonds, an increasing negative surface
charge, and more oxygen-containing groups. Therefore, G-modified BC more effectively removed
phenanthrene than raw WS-BC (Table 4).
Raw BG-BC, BB-BC, and HC-BC all demonstrated very low MB removal rates. Upon surface
modification with MMT and KLN, MB adsorption capacities increased. However, such modification
slightly reduced the removal of MB by the BB-MMT-BC and BB-KLN-BC, possibly due to
obstruction of pores by clay particles [21]. (Table 4).
Chitosan– and ZVI–BC composites achieved higher removal of MB from aqueous solution than
unmodified BC. Among all the iron-modified BCs, the BC composite with the highest amount of Fe
42
achieved the highest MB removal rate. This enhanced removal can be due to both surface adsorption
and chemical reduction mechanisms [112].
The adsorption efficiency of MO by ZVI-modified RH-BC was studied in composites prepared
with ZVI:BC ratios of 1:3, 1:5, and 1:7. The highest MO adsorption efficiency for ZVI–BC
composites was shown at 1:5 ratio (98.5 %), and further increase of ratio to 1:7 slightly decreased the
MO adsorption efficiency (95.2%) [113]. The MO is an anionic dye, and its adsorption was favored
by the positively charged ZVI particles, as its pHpzc was 8.0, which was higher than the pH of the
solution (5.6) [94].
Magnetic BC and activated BC were prepared using tannin BC and exhausted husk obtained by
black wattle. The adsorption capacities of activated BC and magnetic BC for thiacloprid (TCL) and
thiamethoxam (TMX) were 1.02, 0.97 mg g-1 and 0.73, 0.40 mg g-1, respectively. Adsorption of
pesticides on to activated BC mainly occurred via π–π EDA interactions due to the presence of
aromatic rings in BC, while magnetic BC had more polar groups (-OH).
7. Factors influencing adsorption
The factors governing the adsorption rate are the BC’s surface area, nature and initial
concentrations of adsorbate, solution pH, temperature, interfering substances, properties and amount
of adsorbent. Adsorption is proportional to the surface area available for adsorption in general
however, the magnitude differs [114]. Hence, materials with more pores and higher surface area
usually increase adsorption due to the enhanced mass transferring mechanisms, however, this
depends on various other factors such as chemical composition of the adsorbate, size and its
speciation. In case of a composite preparation, excess coating of a material may leads to obstruction
of pores, resulting in significant decrease in the pore volume, and hence it reduces the adsorption
capacity [22]. This was apparent in excessive hydrous manganese oxide incorporated BC [77].
43
The physicochemical nature of the adsorbent strongly impacts on adsorption rate and adsorption
capacity. Fine powder adsorbents have higher adsorption capacity than those consisting of large
particles due to the increase in surface area [115]. The presence of surface functional groups
promotes chemical interactions, and thus the adsorption capacity can be enhanced by increasing the
concentration of appropriate functional groups, however, this may influence negatively based on the
composition of the functional group. The presence of cations or anions on the surface of the
adsorbent may enhance its ion-exchange capacity, which is an important mechanism in the removal
of heavy metals.
Adsorption occurs within pores of the adsorbent, so molecular size of the adsorbate is also related
to adsorption rate and capacity. If the rate is controlled by intra-particle transport, adsorption rate will
increase with decreasing molecular weight of the adsorbate molecules [116].
Further, pH has a major impact on the adsorption process as it directly influences both the
chemical form of the contaminant and the surface charge as well as ionization or speciation of the
adsorbate [83]. Incorporation of a material in preparation of a composite may influence the change in
pHpzc [72].
Adsorption reactions are exothermic reactions; thus adsorption, is temperature dependent,
typically increases with increasing temperature. Furthermore, adsorption may be influenced
positively or negatively by the presence of interfering organic or inorganic compounds. At the same
time, the presence of natural organic matter may impact on adsorption which could be positive or
negative depending on the adsorbate properties. A study reported the influence of cadmium ions
(Cd2+) on the adsorption of SMX by Cd2+ neutralizing the surface of BC [117]. Competitive
adsorption between different chemicals generally occurs at the solid–water interface and can generate
an impact to the sorption characteristics and affinity of the adsorbent for each contaminant. The
presence of oxytetracycline (OTC) significantly inhibits the adsorption of carbaryl (CBL) on the
44
original BC (produced at 600 and 700 °C) indicating a competing effect between OTC and CBL
adsorption [56].
8. Mechanisms involved
Several mechanisms are responsible for the removal of contaminants from aqueous solutions
using BCs and modified BCs, including electrostatic interactions, ion-exchange, hydrogen bonding,
surface complexation, pore-filling mechanisms and π–π EDA interactions may occur simultaneously
[118]. Figure 3 illustrates the major mechanisms involved in adsorption of contaminants on modified
BC.
The surface of BC composites can be positively or negatively charged depending on the pH of the
medium. When pH is higher than pHpzc, the surface of the adsorbent is negatively charged, and when
pH is lower than pHpzc, the surface is positively charged [119]. This can facilitate electrostatic
attraction between the BC surface and the cationic or anionic forms of contaminants. Such
electrostatic attractions have been reported in many studies i.e. on the adsorption of NOR by PSt-
attapulgite–BC composite [83], adsorption of phosphate by a BB-MMT–BC composite produced at
400 °C [73], and adsorption of As by a magnetic BC composite prepared from PW and natural
hematite [87]. Positively charged metal ions attached to the BC surface also encourage adsorption of
anionic compounds via electrostatic interactions [73], and can further promote adsorption of metals
via ion-exchange mechanisms [19] Adsorption via ion-exchange mainly depend upon the size of
metal and the available functional groups on the BC surface [37]. Also the presence of a clay mineral
with a high ion-exchange capacity on the BC surface stimulates adsorption of contaminants such as
organic dyes and antibiotics via ion-exchange mechanisms [21]. In additional contaminants can
exchange with ions available in the interlayer spaces of combined clays, which is referred as
intercalation interactions [66].
45
Figure 3: Possible mechanisms of adsorption of inorganic and organic compounds on modified
biochar.
The presence of oxygen-containing functional groups promotes adsorption of toxic organic
compounds via hydrogen bonding and complexation between BC and the contaminant [107].
Meanwhile, cationic metals and anionic metals/metalloids can be bound by these oxygenated
functional groups via electrostatic attraction [19]. However, the presence of a large number of
functional groups and mineral components on the surface can negatively affect this adsorption
mechanism by blocking the trajectories to pores on the BC surface [25, 120].
The porous structure of BC surfaces facilitates adsorption of organic compounds via a pore-filling
mechanism [51]. During modification, the deposition of modifying materials on the BC increases the
surface area of BC, thereby enhancing the number of adsorbates which can be adsorbed on the
surface [83].
In some cases, adsorption is based on physical bonding/intermolecular forces such as van der
Waals and dipole-dipole interactions. Ammonium adsorption onto BB-MMT–BC composite
46
produced at 400 °C was suggested to be primarily controlled by van der Waals forces and to a lesser
extent by a cation-exchange process [73].
Adsorption of organic pollutants can be further governed by π–π EDA interactions between
BC and aromatic groups of organic compounds. Removal efficiency of phenanthrene is dominated by
π–π EDA interactions as well as surface adsorption, partitioning, and electrostatic attractions [79].
Mostly, adsorption of trace metals occurs via surface complexation mechanism, i.e., via diffuse
double layers. Mercury adsorption occurs via surface complexation between mercury and the
oxygen-containing functional groups (–OH, O=C–O) and alkene (C=C) groups on the surface of a
BC composite containing 1% Graphene [96].
9. Future perspectives
This review highlighted the utilization of engineered BC for the management and removal of
frequently encountered inorganic and organic pollutants in the aquatic systems. Modification tailors
surface properties of BC (surface area, pore volume, pore size, surface charge, and surface functional
groups). A range of modifiers has been used combining with BC, such as clays, metals, metal oxides,
zero-valent ion and organic compounds (polymer, graphene, graphene oxide). Overall, the modifying
agents exert promising improvement in adsorption capacities, but sometimes show negative effects
on the adsorption capacity of target contaminants. Hence, further investigations require to identify
compatible modifiers for targeting specific contaminants. It can be done via changing the nature of
adsorbents including the physical and chemical properties. Environmental conditions can also be
altered to improve the adsorption efficiency including maintaining temperature and pressure. In
addition, high-end instruments such as HPLC and ICP can be used to achieve high detection limit of
contaminants.
Among modified BCs, role of clay–BC composites as adsorbents in waste water remediation has
not been extensively studied. Nevertheless, the limited published data offer adequate proof for the
47
effectiveness of clay–BC composites as adsorbents for the removal of nutrients, metals and dyes.
Even though surface area is often reduced due to blockage of pores, the combined effect of BC and
clay minerals improves the adsorption capacity of clay–BC composites significantly, especially when
layered clays are combined with BC. Hence, further studies will be essential to enhance the
knowledge regarding surface chemistry, adsorption mechanisms and the factors influencing the
adsorption capacities of clay–BC composites prepared by clay minerals. Furthermore, employing
waste clay materials such as red mud and steel slag with biochar application can be a desirable end
use.
Modification of BC with metals or metal oxides has been studied in relation to several
contaminants. Certain modifiers negatively impacted the adsorption of a given contaminant,
justifying further investigation. Neither pristine BC nor BC composites have been demonstrated to
improve adsorption of nutrients (phosphates and nitrates) which are the main compounds responsible
for polluting fresh water ecosystems and causing eutrophication. Thus, further research is necessary
to develop or identify a suitable adsorbent for the control of these nutrients.
Recently, functionalized biochar has been successfully applied for various applications.
Functionalization process of biochar allows tuning of its surface properties and functionality [26],
hence can be applied for various sustainable processes. Design of functionalized biochar based
composites is suggested in order to further enhance performance of different applications.
Most adsorption studies were conducted under laboratory conditions. However, the natural
environment often differs significantly from the laboratory environment, especially concerning
continuous fluctuations in pH and temperature, each of which exert substantial influence on the
adsorption of most adsorbents studied. Hence, pilot-scale testing will be essential for determining the
stability and efficacy of BCs and their composites in environmental remediation. Furthermore, long-
term investigations are mandatory to assess the stability of BC composites and ensure their
environmental friendliness. In addition, information regarding large-scale production of engineered
48
BC is limited and should be documented. A production cost analysis is another key undertaking that
will allow the estimation regarding the profitability of BC-based remediation compared to other
techniques available. The increasing quantity of municipal solid waste can be combined with
naturally abundant clay materials via simple pyrolysis process to make clay-BC composites. Bio-oil
and gases produced during the pyrolysis process can be utilized for the energy production.
In recent decades, the environment has been exposed to a diverse group of emerging contaminants
such as pharmaceuticals, personal care products, endocrine disrupters, hormones, and toxins, owing
to rapid industrialization and anthropogenic activities. Because BC composites have been used as
adsorbents for the elimination of both organic and inorganic contaminants, they should be considered
as candidate materials for use in efforts to mitigate the spread and effects of such emerging
contaminants.
Other than adsorption, removal of contaminants via degradation using metal oxide BC composite
was achieved. Therefore, the BC composites showed evidence of strengthening the photocatalytic
activity of catalysts. Thus, future research should focus on the generation of engineered BCs, which
can be used for complete and long-term removal of emerging contaminants.
References
[1] J. Lehmann, S. Joseph, Biochar for environmental management: Science and Technology,
Earthscan, UK., 2009.
[2] J.S. Cha, S.H. Park, S.-C. Jung, C. Ryu, J.-K. Jeon, M.-C. Shin, Y.-K. Park, Production and
utilization of biochar: A review, Journal of Industrial and Engineering Chemistry 40 (2016) 1-15.
[3] K. Qian, A. Kumar, H. Zhang, D. Bellmer, R. Huhnke, Recent advances in utilization of biochar,
Renewable and Sustainable Energy Reviews 42 (2015) 1055-1064.
49
[4] J. Lee, K.-H. Kim, E.E. Kwon, Biochar as a catalyst, Renewable and Sustainable Energy Reviews
77 (2017) 70-79.
[5] M. Ahmad, A.U. Rajapaksha, J.E. Lim, M. Zhang, N. Bolan, D. Mohan, M. Vithanage, S.S. Lee,
Y.S. Ok, Biochar as a sorbent for contaminant management in soil and water: A review,
Chemosphere 99 (2014) 19-33.
[6] Y. Yao, B. Gao, M. Zhang, M. Inyang, A.R. Zimmerman, Effect of biochar amendment on
sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil, Chemosphere 89 (2012)
1467–1471.
[7] Z. Shen, Y. Zhang, O. McMillan, F. Jin, A. Al-Tabbaa, Characteristics and mechanisms of nickel
adsorption on biochars produced from wheat straw pellets and rice husk, Environmental Science and
Pollution Research 24 (2017) 12809-12819.
[8] M. Vithanage, S.S. Mayakaduwa, I. Herath, Y.S. Ok, D. Mohan, Kinetics, thermodynamics and
mechanistic studies of carbofuran removal using biochars from tea waste and rice husks,
Chemosphere 150 (2016) 781-789.
[9] I. Herath, P. Kumarathilaka, M.I. Al-Wabel, A. Abduljabbar, M. Ahmad, A.R.A. Usman, M.
Vithanage, Mechanistic modeling of glyphosate interaction with rice husk derived engineered
biochar, Microporous and Mesoporous Materials 225 (2016) 280-288.
[10] S.S. Mayakaduwa, P. Kumarathilaka, I. Herath, M. Ahmad, M. Al-Wabel, Y.S. Ok, A. Usman,
A. Abduljabbar, M. Vithanage, Equilibrium and kinetic mechanisms of woody biochar on aqueous
glyphosate removal, Chemosphere 144 (2016) 2516-2521.
[11] A. Wathukarage, I. Herath, M.C.M. Iqbal, M. Vithanage, Mechanistic understanding of crystal
violet dye sorption by woody biochar: implications for wastewater treatment, Environ Geochem
Health (2017).
50
[12] D. Mohan, A. Sarswat, Y.S. Ok, C.U. Pittman, Organic and inorganic contaminants removal
from water with biochar, a renewable, low cost and sustainable adsorbent – A critical review,
Bioresource Technology 160 (2014) 191-202.
[13] C.E. Brewer, Biochar characterization and engineering, Iowa State University, 2012.
[14] M. Sevilla, R. Mokaya, Energy storage applications of activated carbons: supercapacitors and
hydrogen storage, Energy & Environmental Science 7 (2014) 1250-1280.
[15] N. Anderson, J.G. Jones, D. Page-Dumroese, D. McCollum, S. Baker, D. Loeffler, W. Chung, A
comparison of producer gas, biochar, and activated carbon from two distributed scale
thermochemical conversion systems used to process forest biomass, Energies 6 (2013).
[16] M. Ahmad, D.H. Moon, M. Vithanage, A. Koutsospyros, S.S. Lee, J.E. Yang, S.E. Lee, C.
Jeong, Y.S. Oka, Production and use of biochar from buffalo-weed (Ambrosia trifida L.) for
trichloroethylene removal from water, Journal of Chemical Technology and Biotechnology 89 (2013)
150-157.
[17] B.A. McCarl, C. Peacocke, R. Chrisman, C.C. Kung, R.D. Sands, Economics of biochar
production, utilization and greenhouse gas offsets, in: L. J., J. A.S. (Eds.) Biochar for Environmental
Management: Science and Technology, Earthscan, London, 2009, pp. 341–358.
[18] M.B. Ahmed, J.L. Zhou, H.H. Ngo, W. Guo, M. Chen, Progress in the preparation and
application of modified biochar for improved contaminant removal from water and wastewater,
[19] A.U. Rajapaksha, S.S. Chen, D.C.W. Tsang, M. Zhang, M. Vithanage, S. Mandal, B. Gao, N.S.
Bolan, Y.S. Ok, Engineered/designer biochar for contaminant removal/immobilization from soil and
water: Potential and implication of biochar modification, Chemosphere 148 (2016) 276-291.
[20] S. Mandal, B. Sarkar, N. Bolan, J. Novak, Y.S. Ok, L. Van Zwieten, B.P. Singh, M.B. Kirkham,
G. Choppala, K. Spokas, R. Naidu, Designing advanced biochar products for maximizing greenhouse
gas mitigation potential, Crit. Rev. Environ. Sci. Technol. 46 (2016) 1367-1401.
51
[21] Y. Yao, B. Gao, J. Fang, M. Zhang, H. Chen, Y. Zhou, A.E. Creamer, Y. Sun, L. Yang,
Characterization and environmental applications of clay–biochar composites, Chemical Engineering
Journal 242 (2014) 136-143.
[22] E. Fosso-Kankeu, F.B. Waanders, F.W. Steyn, The preparation and characterization of clay-
biochar composites for the removal of metal pollutants, 7th International Conference on Latest
Trends in Engineering & TechnologyIrene, Pretoria (South Africa), 2015.
[23] M. Zhang, B. Gao, Y. Yao, Y. Xue, M. Inyang, Synthesis of porous MgO-biochar
nanocomposites for removal of phosphate and nitrate from aqueous solutions, Chemical Engineering
Journal 210 (2012) 26-32.
[24] M.I. Inyang, B. Gao, Y. Yao, Y. Xue, A. Zimmerman, A. Mosa, P. Pullammanappallil, Y.S. Ok,
X. Cao, A review of biochar as a low-cost adsorbent for aqueous heavy metal removal, Critical
Reviews in Environmental Science and Technology 46 (2016) 406-433.
[25] C. Peiris, S.R. Gunatilake, T.E. Mlsna, D. Mohan, M. Vithanage, Biochar based removal of
antibiotic sulfonamides and tetracyclines in aquatic environments: A critical review, Bioresource
Technology 246 (2017) 150-159.
[26] W.-J. Liu, H. Jiang, H.-Q. Yu, Development of Biochar-Based Functional Materials: Toward a
Sustainable Platform Carbon Material, Chemical Reviews 115 (2015) 12251-12285.
[27] B. Wang, B. Gao, J. Fang, Recent advances in engineered biochar productions and applications,
Critical Reviews in Environmental Science and Technology 47 (2017) 2158-2207.
[28] M. Vithanage, I. Herath, S. Joseph, J. Bundschuh, N. Bolan, Y.S. Ok, M.B. Kirkham, J.
Rinklebe, Interaction of arsenic with biochar in soil and water: A critical review, Carbon 113 (2017)
219-230.
[29] Y. Deng, T. Zhang, Q. Wang, Biochar adsorption treatment for typical pollutants removal in
livestock wastewater: A review, in: W.-J. Huang (Ed.) Engineering Applications of Biochar, InTech,
Rijeka, 2017, pp. Ch. 05.
52
[30] F.R. Oliveira, A.K. Patel, D.P. Jaisi, S. Adhikari, H. Lu, S.K. Khanal, Environmental application
of biochar: Current status and perspectives, Bioresource Technology 246 (2017) 110-122.
[31] J.M. Patra, S.S. Panda, N.K. Dhal, Biochar as a low-cost adsorbent for heavy metal removal: a
review, International Journal of Research in BioSciences 5 (2016) 1-7.
[32] X.-f. Tan, Y.-g. Liu, Y.-l. Gu, Y. Xu, G.-m. Zeng, X.-j. Hu, S.-b. Liu, X. Wang, S.-m. Liu, J. Li,
Biochar-based nano-composites for the decontamination of wastewater: A review, Bioresource
Technology 212 (2016) 318-333.
[33] T. Xie, K. Reddy, C. Wang, E. Yargicoglu, K. Spokas, Characteristics and applications of
biochar for environmental remediation: A review, Critical Reviews in Environmental Science and
Technology 45 (2014) 939-969.
[34] O.D. Nartey, B. Zhao, Biochar preparation, characterization, and adsorptive capacity and Its
effect on bioavailability of contaminants: An overview, Advances in Materials Science and
Engineering 2014 (2014) 12.
[35] S.D. Gisi, M. Notarnicola, Characteristics and adsorption capacities of low-cost sorbents for
waste water treatment: A review, Sustainable Materials and Technologies 9 (2016) 10 - 40.
[36] H. Zhang, Z. Yu, Q. Huang, A review : Utilization of biochar for wastewater treatment, in: A.
Bhatnagar (Ed.) Application of adsorbents for water pollution control, Bentham science 2018, pp.
413-431.
[37] M. Inyang, E. Dickenson, The potential role of biochar in the removal of organic and microbial
contaminants from potable and reuse water: A review, Chemosphere 134 (2015) 232-240.
[38] E. Rosales, J. Meijide, M. Pazos, M.A. Sanromán, Challenges and recent advances in biochar as
low-cost biosorbent: From batch assays to continuous-flow systems, Bioresour. Technol. 246 (2017)
176-192.
[39] S. Brick, W. Madison, Biochar: Assessing the Promise and Risks To Guide U.S. Policy, in:
N.R.D. Council (Ed.), 2010.
53
[40] S. Brick, S. Lyutse, Biochar: Assessing the promise and risks to guide US policy, (2010).
[41] A. Enders, K. Hanley, T. Whitman, S. Joseph, J. Lehmann, Characterization of biochars to
evaluate recalcitrance and agronomic performance, Bioresource Technology 114 (2012) 644-653.
[42] S.P. Sohi, E. Krull, E. Lopez-Capel, R. Bol, Chapter 2 - A review of biochar and its use and
function in soil, Advances in Agronomy, Academic Press2010, pp. 47-82.
[43] K.B. Cantrell, P.G. Hunt, M. Uchimiya, J.M. Novak, K.S. Ro, Impact of pyrolysis temperature
and manure source on physicochemical characteristics of biochar, Bioresource Technology 107
(2012) 419-428.
[44] J. Lee, D. Choi, Y.S. Ok, S.-R. Lee, E.E. Kwon, Enhancement of energy recovery from chicken
manure by pyrolysis in carbon dioxide, Journal of Cleaner Production 164 (2017) 146-152.
[45] J. Bourke, M.M. Harris, C. Fushimi, T. Nunoura, M.J. Antal Jr., Do all carbonized charcoals
have the same chemical structure? 2. A model of the chemical structure of carbonized charcoal., Ind.
Eng. Chem. Res. 46, (2007) 5954–5967.
[46] S.-R. Lee, J. Lee, T. Lee, Y.F. Tsang, K.-H. Jeong, J.-I. Oh, E.E. Kwon, Strategic use of CO2 for
co-pyrolysis of swine manure and coal for energy recovery and waste disposal, Journal of CO2
Utilization 22 (2017) 110-116.
[47] X. Yang, H. Wang, J. Strong, S. Xu, S. Liu, K. Lu, K. Sheng, J. Guo, L. Che, L. He, Y.S. Ok, G.
Yuan, Y. Shen, X. Chen, Thermal properties of biochars derived from waste biomass generated by
agricultural and forestry sectors, 2017.
[48] X. Gai, H. Wang, J. Liu, L. Zhai, S. Liu, T. Ren, H. Liu, Effects of feedstock and pyrolysis
temperature on biochar adsorption of ammonium and nitrate, PLoS One 9 (2014) e113888.
[49] G. Yang, L. Wu, Q. Xian, F. Shen, J. Wu, Y. Zhang, Removal of congo red and methylene blue
from aqueous solutions by vermicompost-derived biochars, PLoS One 11 (2016) e0154562.
[50] X. Cao, W. Harris, Properties of dairy-manure-derived biochar pertinent to its potential use in
remediation, Bioresource Technology 101 (2010) 5222-5228.
54
[51] M. Ahmad, S.S. Lee, A.U. Rajapaksha, M. Vithanage, M. Zhang, J.S. Cho, S.-E. Lee, Y.S. Ok,
Trichloroethylene adsorption by pine needle biochars produced at various pyrolysis temperatures,
[52] A. Rawal, S.D. Joseph, J.M. Hook, C.H. Chia, P.R. Munroe, S. Donne, Y. Lin, D. Phelan,
D.R.G. Mitchell, B. Pace, J. Horvat, J.B.W. Webber, Mineral–biochar composites: molecular
structure and porosity, Environmental Science & Technology 50 (2016) 7706-7714.
[53] M.I. Al-Wabel, A. Al-Omran, A.H. El-Naggar, M. Nadeem, A.R.A. Usman, Pyrolysis
temperature induced changes in characteristics and chemical composition of biochar produced from
conocarpus wastes, Bioresource Technology 131 (2013) 374-379.
[54] A.U. Rajapaksha, M. Vithanage, M. Ahmad, D.-C. Seo, J.-S. Cho, S.-E. Lee, S.S. Lee, Y.S. Ok,
Enhanced sulfamethazine removal by steam-activated invasive plant-derived biochar, Journal of
Hazardous Materials 290 (2015) 43-50.
[55] J.-H. Yuan, R.-K. Xu, H. Zhang, The forms of alkalis in the biochar produced from crop
residues at different temperatures, Bioresource Technology 102 (2011) 3488-3497.
[56] M. Li, Z. Zhao, X. Wu, W. Zhou, L. Zhu, Impact of mineral components in cow manure
biochars on the adsorption and competitive adsorption of oxytetracycline and carbaryl, RSC
Advances 7 (2017) 2127-2136.
[57] B. Chen, Z. Chen, Sorption of naphthalene and 1-naphthol by biochars of orange peels with
different pyrolytic temperatures, Chemosphere 76 (2009) 127-133.
[58] B. Chen, D. Zhou, L. Zhu, Transitional adsorption and partition of nonpolar and polar aromatic
contaminants by biochars of pine needles with different pyrolytic temperatures, Environmental
Science & Technology 42 (2008) 5137-5143.
[59] A. Solanki, T.H. Boyer, Pharmaceutical removal in synthetic human urine using biochar,
Environmental Science: Water Research & Technology 3 (2017) 553-565.
55
[60] Y. Gao, Y. Li, L. Zhang, H. Huang, J. Hu, S.M. Shah, X. Su, Adsorption and removal of
tetracycline antibiotics from aqueous solution by graphene oxide, Journal of Colloid and Interface
Science 368 (2012) 540-546.
[61] P.H. Chang, Z. Li, J.S. Jean, W.T. Jiang, Q. Wu, C.Y. Kuo, J. Kraus, Desorption of tetracycline
from montmorillonite by aluminum, calcium, and sodium: an indication of intercalation stability,
International Journal of Environmental Science and Technology 11 (2014) 633-644.
[62] P.-H. Chang, W.-T. Jiang, Z. Li, C.-Y. Kuo, Q. Wu, J.-S. Jean, G. Lv, Interaction of
ciprofloxacin and probe compounds with palygorskite PFl-1, Journal of Hazardous Materials 303
(2016) 55-63.
[63] X. Han, C.-f. Liang, T.-q. Li, K. Wang, H.-g. Huang, X.-e. Yang, Simultaneous removal of
cadmium and sulfamethoxazole from aqueous solution by rice straw biochar, Journal of Zhejiang
University SCIENCE B 14 (2013) 640-649.
[64] V. Vimonses, S. Lei, B. Jin, C.W.K. Chow, C. Saint, Adsorption of congo red by three
Australian kaolins, Applied Clay Science 43 (2009) 465-472.
[65] R. Pusch, Bentonite cay: Environmental properties and applications, CRC Press, Boca Raton,
FL, USA., 2015.
[66] L. Aristilde, B. Lanson, J. Miéhé-Brendlé, C. Marichal, L. Charlet, Enhanced interlayer trapping
of a tetracycline antibiotic within montmorillonite layers in the presence of Ca and Mg, Journal of
Colloid and Interface Science 464 (2016) 153-159.
[67] A.U. Rajapaksha, M. Vithanage, L. Jayarathna, C.K. Kumara, Natural red earth as a low cost
material for arsenic removal: Kinetics and the effect of competing ions, Applied Geochemistry 26
(2011) 648-654.
[68] R. Donat, A. Akdogan, E. Erdem, H. Cetisli, Thermodynamics of Pb2+ and Ni2+ adsorption onto
natural bentonite from aqueous solutions, Journal of Colloid and Interface Science 286 (2005) 43-52.
56
[69] M.K. Uddin, A review on the adsorption of heavy metals by clay minerals, with special focus on
the past decade, Chemical Engineering Journal 308 (2017) 438-462.
[70] A.A. Adeyemo, I.O. Adeoye, O.S. Bello, Adsorption of dyes using different types of clay: a
review, Applied Water Science 7 (2017) 543-568.
[71] G. Dou, J.L. Goldfarb, In situ upgrading of pyrolysis biofuels by bentonite clay with
simultaneous production of heterogeneous adsorbents for water treatment, Fuel 195 (2017) 273-283.
[72] S. Ismadji, D.S. Tong, F.E. Soetaredjo, A. Ayucitra, W.H. Yu, C.H. Zhou, Bentonite hydrochar
composite for removal of ammonium from Koi fish tank, Applied Clay Science 119 (2016) 146-154.
[73] L. Chen, X.L. Chen, C.H. Zhou, H.M. Yang, S.F. Ji, D.S. Tong, Z.K. Zhong, W.H. Yu, M.Q.
Chu, Environmental-friendly montmorillonite-biochar composites: Facile production and tunable
adsorption-release of ammonium and phosphate, Journal of Cleaner Production 156 (2017) 648-659.
[74] V. Frišták, B. Micháleková-Richveisová, E. Víglašová, L. Ďuriška, M. Galamboš, E. Moreno-
Jimenéz, M. Pipíška, G. Soja, Sorption separation of Eu and As from single-component systems by
Fe-modified biochar: kinetic and equilibrium study, Journal of the Iranian Chemical Society 14
(2017) 521-530.
[75] N. Chaukura, E.C. Murimba, W. Gwenzi, Synthesis, characterisation and methyl orange
adsorption capacity of ferric oxide–biochar nano-composites derived from pulp and paper sludge,
Applied Water Science 7 (2017) 2175-2186.
[76] C.-H. Ooi, Y.-L. Sim, F.-Y. Yeoh, Urea adsorption by activated carbon prepared from palm
kernel shell, AIP Conference Proceedings 1865 (2017) 020009.
[77] M.C. Wang, G.D. Sheng, Y.P. Qiu, A novel manganese-oxide/biochar composite for efficient
removal of lead(II) from aqueous solutions, International Journal of Environmental Science and
Technology 12 (2015) 1719-1726.
57
[78] Y. Zhou, B. Gao, A.R. Zimmerman, H. Chen, M. Zhang, X. Cao, Biochar-supported zerovalent
iron for removal of various contaminants from aqueous solutions, Bioresource Technology 152
(2014) 538-542.
[79] J. Tang, H. Lv, Y. Gong, Y. Huang, Preparation and characterization of a novel
graphene/biochar composite for aqueous phenanthrene and mercury removal, Bioresource
Technology 196 (2015) 355-363.
[80] B. Sarkar, S. Mandal, Y.F. Tsang, P. Kumar, K.-H. Kim, Y.S. Ok, Designer carbon nanotubes
for contaminant removal in water and wastewater: A critical review, Sci. Total Environ. 612 (2018)
561-581.
[81] Y. Zhou, B. Gao, A.R. Zimmerman, J. Fang, Y. Sun, X. Cao, Sorption of heavy metals on
chitosan-modified biochars and its biological effects, Chemical Engineering Journal 231 (2013) 512-
518.
[82] T. Liu, B. Gao, J. Fang, B. Wang, X. Cao, Biochar-supported carbon nanotube and graphene
oxide nanocomposites for Pb(ii) and Cd(ii) removal, RSC Advances 6 (2016) 24314-24319.
[83] Y. Li, Z. Wang, X. Xie, J. Zhu, R. Li, T. Qin, Removal of Norfloxacin from aqueous solution by
clay-biochar composite prepared from potato stem and natural attapulgite, Colloids and Surfaces A:
Physicochemical and Engineering Aspects 514 (2017) 126-136.
[84] B. Zhao, D. O'Connor, J. Zhang, T. Peng, Z. Shen, D.C.W. Tsang, D. Hou, Effect of pyrolysis
temperature, heating rate, and residence time on rapeseed stem derived biochar, Journal of Cleaner
Production 174 (2018) 977-987.
[85] J.M. Novak, I. Lima, B. Xing, J.W. Gaskin, C. Steiner, K.C. Das, M. Ahmedna, D. Rehrah,
D.W. Watts, W.J. Busscher, H. Schomberg, Characterization of designer biochar produced at
different temperatures and their effects on a loamy sand, 3 (2009) 195-206.
58
[86] F. Lian, F. Huang, W. Chen, B. Xing, L. Zhu, Sorption of apolar and polar organic contaminants
by waste tire rubber and its chars in single- and bi-solute systems, Environmental Pollution 159
(2011) 850-857.
[87] S. Wang, B. Gao, A.R. Zimmerman, Y. Li, L. Ma, W.G. Harris, K.W. Migliaccio, Removal of
arsenic by magnetic biochar prepared from pinewood and natural hematite, Bioresource Technology
175 (2015) 391-395.
[88] K. Komnitsas, D. Zaharaki, Morphology of modified biochar and its potential for phenol
removal from aqueous solutions, Environmental Science & Technology 4 (2016).
[89] D. Angın, Effect of pyrolysis temperature and heating rate on biochar obtained from pyrolysis of
safflower seed press cake, Bioresource Technology 128 (2013) 593-597.
[90] M.S. Nazir, M.H. Mohamad Kassim, L. Mohapatra, M.A. Gilani, M.R. Raza, K. Majeed,
Characteristic properties of manoclays and characterization of nanoparticulates and nanocomposites,
in: M. Jawaid, A.e.K. Qaiss, R. Bouhfid (Eds.) Nanoclay Reinforced Polymer Composites:
Nanocomposites and Bionanocomposites, Springer Singapore, Singapore, 2016, pp. 35-55.
[91] Y. Yao, Sorption of phosphate and other contaminants on biochar and its environmental
implications, University of Florida, 2013.
[92] Y. Yao, B. Gao, M. Inyang, A.R. Zimmerman, X. Cao, P. Pullammanappallil, L. Yang,
Removal of phosphate from aqueous solution by biochar derived from anaerobically digested sugar
beet tailings, Journal of Hazardous Materials 190 (2011) 501-507.
[93] K. Lou, A.U. Rajapaksha, Y.S. Ok, S.X. Chang, Pyrolysis temperature and steam activation
effects on sorption of phosphate on pine sawdust biochars in aqueous solutions, Chemical Speciation
& Bioavailability 28 (2016) 42-50.
[94] T. Almeelbi, A. Bezbaruah, Aqueous phosphate removal using nanoscale zero-valent iron,
Journal of Nanoparticle Research 14 (2012) 900.
59
[95] T. Tuutijärvi, J. Lu, M. Sillanpää, G. Chen, As(V) adsorption on maghemite nanoparticles,
Journal of Hazardous Materials 166 (2009) 1415-1420.
[96] G. Li, B. Shen, F. Li, L. Tian, S. Singh, F. Wang, Elemental mercury removal using biochar
pyrolyzed from municipal solid waste, Fuel Processing Technology 133 (2015) 43-50.
[97] E. Fosso-Kankeu, F.B. Waanders, J. Potgieter, Enhanced adsorption capacity of sweet sorghum
derived biochar towards malachite green dye using bentonite clay, International Conference on
Advances in Science, Engineering, Technology and Natural ResourcesParys (South Africa), 2016.
[98] E. Agrafioti, D. Kalderis, E. Diamadopoulos, Ca and Fe modified biochars as adsorbents of
arsenic and chromium in aqueous solutions, Journal of Environmental Management 146 (2014) 444-
450.
[99] H. Zhang, Z. Wang, R. Li, J. Guo, Y. Li, J. Zhu, X. Xie, TiO2 supported on reed straw biochar
as an adsorptive and photocatalytic composite for the efficient degradation of sulfamethoxazole in
aqueous matrices, Chemosphere 185 (2017) 351-360.
[100] C. Gerente, V.K.C. Lee, P.L. Cloirec, G. McKay, Application of chitosan for the removal of
metals from wastewaters by adsorption—mechanisms and models review, Critical Reviews in
Environmental Science and Technology 37 (2007) 41-127.
[101] M. Inyang, B. Gao, A. Zimmerman, M. Zhang, H. Chen, Synthesis, characterization, and dye
sorption ability of carbon nanotube–biochar nanocomposites, Chemical Engineering Journal 236
(2014) 39-46.
[102] L. Zhou, Y. Huang, W. Qiu, Z. Sun, Z. Liu, Z. Song, Adsorption Properties of Nano-MnO2–
Biochar Composites for Copper in Aqueous Solution, Molecules 22 (2017) 173.
[103] D. Kołodyńska, J. Bąk, Use of three types of magnetic biochar in the removal of copper(II)
ions from wastewaters, Separation Science and Technology 53 (2018) 1045-1057.
[104] M.L. Sanyang, W.A.W.A.K. Ghani, A. Idris, M.B. Ahmad, Hydrogel biochar composite for
arsenic removal from wastewater, Desalination and Water Treatment 57 (2016) 3674-3688.
60
[105] L. Yan, L. Kong, Z. Qu, L. Li, G. Shen, Magnetic Biochar Decorated with ZnS Nanocrytals for
Pb (II) Removal, ACS Sustainable Chemistry & Engineering 3 (2015) 125-132.
[106] L.-L. Ling, W.-J. Liu, S. Zhang, H. Jiang, Magnesium Oxide Embedded Nitrogen Self-Doped
Biochar Composites: Fast and High-Efficiency Adsorption of Heavy Metals in an Aqueous Solution,
Environmental Science & Technology 51 (2017) 10081-10089.
[107] W. Liu, J. Zhang, C. Zhang, L. Ren, Sorption of norfloxacin by lotus stalk-based activated
carbon and iron-doped activated alumina: Mechanisms, isotherms and kinetics, Chemical
Engineering Journal 171 (2011) 431-438.
[108] A.G. Trovo, R.F. Nogueira, A. Aguera, C. Sirtori, A.R. Fernandez-Alba, Photodegradation of
sulfamethoxazole in various aqueous media: Persistence, toxicity and photoproducts assessment,
Chemosphere 77 (2009) 1292-1298.
[109] H. Wu, Q. Feng, P. Lu, M. Chen, H. Yang, Degradation mechanisms of cefotaxime using
biochar supported Co/Fe bimetallic nanoparticles, Environmental Science: Water Research &
Technology 4 (2018) 964-975.
[110] J. Farrell, M. Kason, N. Melitas, T. Li, Investigation of the Long-Term Performance of Zero-
Valent Iron for Reductive Dechlorination of Trichloroethylene, Environmental Science &
Technology 34 (2000) 514-521.
[111] X. Weng, Q. Sun, S. Lin, Z. Chen, M. Megharaj, R. Naidu, Enhancement of catalytic
degradation of amoxicillin in aqueous solution using clay supported bimetallic Fe/Ni nanoparticles,
Chemosphere 103 (2014) 80-85.
[112] K. Miyajima, C. Noubactep, Effects of mixing granular iron with sand on the efficiency of
methylene blue discoloration, Chemical Engineering Journal 200-202 (2012) 433-438.
[113] L. Han, S. Xue, S. Zhao, J. Yan, L. Qian, M. Chen, Biochar Supported Nanoscale Iron
Particles for the Efficient Removal of Methyl Orange Dye in Aqueous Solutions, PLOS ONE 10
(2015) e0132067.
61
[114] A. Naeem, P. Westerhoff, S. Mustafa, Vanadium removal by metal (hydr)oxide adsorbents,
Water Research 41 (2007) 1596-1602.
[115] S. Kara, C. Aydiner, E. Demirbas, M. Kobya, N. Dizge, Modeling the effects of adsorbent dose
and particle size on the adsorption of reactive textile dyes by fly ash, Desalination 212 (2007) 282-
293.
[116] H. Zhang, C.-H. Huang, Adsorption and oxidation of fluoroquinolone antibacterial agents and
structurally related amines with goethite, Chemosphere 66 (2007) 1502-1512.
[117] W. Wu, H. Wang, J. Xu, Z. Xie, Adsorption characteristic of bensulfuron-methyl at variable
added Pb2+ concentrations on paddy soils, Journal of Environmental Sciences 21 (2009) 1129-1134.
[118] B. Peng, L. Chen, C. Que, K. Yang, F. Deng, X. Deng, G. Shi, G. Xu, M. Wu, Adsorption of
antibiotics on graphene and biochar in aqueous solutions induced by π-π interactions, Scientific
report 31920, 2016.
[119] A.A. Bazrafshan, S. Hajati, M. Ghaedi, Synthesis of regenerable Zn(OH)2 nanoparticle-loaded
activated carbon for the ultrasound-assisted removal of malachite green: optimization, isotherm and
kinetics, RSC Advances 5 (2015) 79119-79128.
[120] T.H. Nguyen, H.-H. Cho, D.L. Poster, W.P. Ball, Evidence for a pore-filling mechanism in the
adsorption of aromatic hydrocarbons to a natural wood char, Environmental Science & Technology
41 (2007) 1212-1217.
62
63
 Biochar composites for improved water pollution abatement are reviewed
 Metals and metal oxides have been widely used in engineered biochar
 Modification typically alters the surface properties and functionalities of biochar
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Biochar-Based Engineered Composites For Sorptive Decontamination of Water

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Biochar-Based Engineered Composites for Sorptive Decontamination of Water:

K.S.D. Premarathna, Anushka Upamali Rajapaksha, Binoy Sarkar, Eilhann E.

To appear in: Chemical Engineering Journal

Received Date: 24 January 2019

K. S. D. Premarathna1, Anushka Upamali Rajapaksha1, Binoy Sarkar2, Eilhann E. Kwon3, Amit

Bhatnagar4, Yong Sik Ok5*, Meththika Vithanage1,6**

1Ecosphere Resilience Research Center, Faculty of Applied Sciences, University of Sri

Jayewardenepura, Nugegoda, 10250, Sri Lanka

3Department of Environment and Energy, Sejong University, 98 Gunja-Don, Republic of Korea

FI-70211, Kuopio, Finland

Kandy, Sri Lanka

Dr. Meththika Vithanage

Prof. Yong Sik Ok

Biochar (BC) exhibits a great potential as an adsorbent in decontamination of water. To

methods (chemical modification, physical modification, impregnation with different materials,

focuses on BC composites prepared by the combination of BC with different additives

aquatic contaminants. Techniques for the preparation of BC composites, their adsorption

discussed. Modification typically alters the surface properties and functionalities of BC

adsorption of certain contaminants because of various factors including obstruction of pores

Biochars (BCs) is defined as a carbon-rich material obtained by the thermal treatment of

needed to achieve their scalability and commercialization.

impart different characteristics to the final BC products (Table 1) [12-13].

Table 1: Pathways for thermal conversion of biomass to biochar.

Thermal Temperature Heating rate Residence Biochar

conversion range (°C) time yield

Slow pyrolysis 350–800 Slow, Hours–Days 35

Fast pyrolysis 400–600 Very fast Seconds 10–15

Hydrothermal 180–250 Slow Hours 30–60

carbonization (<10 °C min-1)

capacity to AC in many uses. Generally AC has greater Brunauer–Emmett–Teller (BET)

contaminants via adsorption (Figure 1).

(Adsorption+ Activated Carbon / Adsorption + Biochar)

Figure 1: Science Citation Indexed publications on adsorption and adsorption related to

activated carbon and biochar in SCOPUS (Accessed on 2018.01.10).

organic compounds, or carbonaceous materials such as graphene oxide (GO), polysaccharides,

[19-20]. In these composites, BC acts as a porous structure to support the distribution of

during the fabrication of BC composites such as reduction of adsorption capacity via

impacts of BC modification on adsorption of target adsorbates.

studies have been published on the adsorption efficiencies of BCs, attention to

involved in the adsorption process.

Interaction of arsenic with biochar in soil and √ Vithanage et

water: A critical review al., [28]

Biochar-based removal of antibiotic √ Peiris et al.,

sulfonamides and tetracyclines in aquatic [25]

environments: A critical review

Biochar adsorption treatment for typical √ √ √ √ √ Deng et al.,

pollutants removal in livestock wastewater: [29]

Environmental application of biochar: √ √ √ √ √ Oliveira et al., [30]

Current status and perspectives

Biochar as a low-cost adsorbent for heavy √ Patra et al.,

metal removal: A review [31]

for aqueous heavy metal removal al., [24]

Application of biochar for the removal of √ √ √ Tan et al.,

pollutants from aqueous solutions [32]

Characteristics and applications of biochar √ √ √ Xie et al.,

for environmental remediation: A review [33]

Biochar preparation, characterization, and √ √ √ Nartey and

adsorptive capacity and its effect on Zhao [34]