Mechanisms and Adsorption Capacities of Biochar For The Removal of Organic and Inorganic Pollutants From Industrial Wastewater

International Journal of Environmental Science and Technology (2021) 18:3273–3294
https://doi.org/10.1007/s13762-020-03060-w
REVIEW
Mechanisms and adsorption capacities of biochar for the removal

of organic and inorganic pollutants from industrial wastewater
T. G. Ambaye1,2 · M. Vaccari1 · E. D. van Hullebusch3 · A. Amrane4 · S. Rtimi5
Received: 7 August 2020 / Revised: 1 November 2020 / Accepted: 4 December 2020 / Published online: 26 December 2020
© The Author(s) 2020
Abstract
Currently, due to the rapid growth of urbanization and industrialization in developing countries, a large volume of wastewa-
ter is produced from industries that contain chemicals generating high environmental risks affecting human health and the
economy if not treated properly. Consequently, the development of a sustainable low-cost wastewater treatment approach has
attracted more attention of policymakers and scientists. The present review highlights the recent applications of biochar in
removing organic and inorganic pollutants present in industrial effluents. The recent modes of preparation, physicochemical
properties and adsorption mechanisms of biochar in removing organic and inorganic industrial pollutants are also reviewed
comprehensively. Biochar showed high adsorption of industrial dyes up to 80%. It also discusses the recent application and
mechanism of biochar-supported photocatalytic materials for the degradation of organic contaminants in wastewater. We
reviewed also the possible optimizations (such as the pyrolysis temperature, solution pH) allowing the increase of the adsorp-
tion capabilities of biochar leading to organic contaminants removal. Besides, increasing the pyrolysis temperature of the
biochar was seen to lead to an increase in its surface area, while it decreases their amount of oxygen-containing functional
groups, consequently leading to a decrease in the adsorption of metal (loid) ions present in the medium. Finally, the review
suggests that more research should be carried out to optimize the main parameters involved in biochar production and its
regeneration methods. Future efforts should be also carried out towards process engineering to improve its adsorption capac-
ity to increase the economic benefits of its implementation.
Keywords Adsorption · Biochar-supported photocatalysts · Inorganic/organic pollutants · Industrial wastewater
Introduction
A large amount of wastewater is generated every day from

industry (coal and steel industry, non-metallic minerals indus-
Editorial responsibility: Samareh Mirkia. try and industries for the surface processing of metals like iron
picking and electroplating), which has a huge effect on the
* S. Rtimi environment (Inyang et al. 2012). For this reason, different
[email protected]
approaches were applied to treat the industrial wastewater such
1
Department of Civil, Environmental, Architectural as advanced oxidation processes (AOPs), reverse osmosis,
Engineering and Mathematics, University of Brescia, Via adsorption, ion exchange, ozonation, precipitation, filtration
Branze 43, 25123 Brescia, Italy with coagulation and coagulation process (Park et al. 2011).
2
Department of Chemistry, Mekelle University, Mekelle, However, most of these processes require high operational and
Ethiopia capital costs. This has been considered as the main obstacle
3
Institut de Physique du Globe de Paris, CNRS, Université de that restricts their application for the abatement/removal of
Paris, 75005 Paris, France potentially toxic contaminants from polluted waters in devel-
4
Ecole Nationale Supérieure de Chimie de Rennes, CNRS, oped and developing countries (Giannakis et al. 2017; Ville-
ISCR – UMR6226, University of Rennes, 35000 Rennes, gas- Guzman et al. 2017; Lou et al. 2017; Ambaye et al. 2020).
France
Biochar, a solid formed from the pyrolysis of biomass
5
Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne, at a temperature below 700 °C under low or in the absence
Switzerland
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3274 International Journal of Environmental Science and Technology (2021) 18:3273–3294
of oxygen (Park et al. 2011). The resulting solid is rich in investigated by Bhatnagar and Jain (2014). Cao and Harris
carbon and presents a promising adsorption ability allow- (2010) showed that a very low dyes’ adsorption performance
ing it to remove organic and inorganic contaminants from was observed for adsorbents prepared from blast furnace
wastewater. Different waste materials such as straw, faces, sludge, dust and slag. These adsorbents were seen to exhibit
sludge have been tested as raw materials for biochar pro- a low surface area associated with a poor porosity. How-
duction. Park et al. (2016) proved that different methods ever, chemical activation using metal hydroxide reagents
such as pyrolysis, hydrothermal carbonization, gasification (e.g. KOH) is the most effective technique for producing
can be used to produce biochar. One can conclude that the high (> 1800 m 2/g) surface area of sludge-based adsorbents
performance of biochar can be affected by (i) the type of (Van Zwieten et al. 2010). In recent reports, high efficiency
the organic materials feedstock, the preparation tempera- removal of organic pollutants from industrial effluents was
ture, modification approaches, among others. Adsorption observed for biochar; however, the physicochemical proper-
ability of biochar has been used to manage waste resources ties of biochar may play as limiting factors (Rajapaksha et al.
(Park et al. 2011), improve soil performance (Liu and Zhang 2015; Peiris et al. 2017; Bielská et al. 2018; Zhang et al.
2009), mitigate the climate change and as renewable biofuels 2018). The disposal of organics and inorganics has become
(Kołodyńska et al. 2012). a serious environmental problem, and due to this, there have
Many scientists studied the feasibility of biochar pre- been stringent regulations for such wastes. Recent research
pared from animal manure, plant residues and biosolids for articles showed that technology-based on biochar adsorp-
the adsorption of pesticides, pharmaceuticals, hormones and tion is effective in removing heavy metals from wastewa-
potentially toxic metals (Downie et al. 2009; Joseph et al. ter (Inyang et al. 2016; Rizwan et al. 2016; O’Connor et al.
2010; Sun et al.; 2014). They showed that biochar exhibited 2018; Wei et al. 2018). This material has good adsorption
high efficiency for adsorbing pollutants when compared to capacity for typical industrial wastewater pollutants such
activated carbons. Similar results were reported by Özçi- as potentially toxic metals, organic pollutants, phosphorus
men and Karaosmanoğlu (2004) and Hossain et al. (2011) and nitrogen compounds. Biochar can be used as a release
in their studies to remove endocrine disrupting organic com- controlling agent in fertilizers thanks to its good adsorption
pounds from aqueous solutions using biochar prepared from capacity for phosphorus and nitrogen as previously reported
plant biomass. They showed that biochar was able to remove (Chen et al. 2011a, b; Yao et al. 2011a, b 2013a, b; Zhang
up to 60% of organic pollutants such as triazine herbicide, et al. 2013a, b). Because biochar is an environmentally
α-ethinylestradiol, atrazine and bisphenol. They concluded that friendly absorbent, the knowledge of its physicochemical
the absorption ability of biochar to remove pollutants depends properties and a systematic understanding of the adsorption
upon the preparation feedstock and physiochemical properties mechanisms is a matter of topical interest.
of both the biochar and the pollutant. Rice husk was used for The adsorption mechanism of biochar to remove organic
the removal of two dyes, namely safranin and methylene blue and inorganic pollutants can be based on electrostatic inter-
(Inyang et al. 2014). The adsorption constants showed values action, ion exchange, pore filling and precipitation. This
of 838 and 312 mg/g for the two dyes, respectively (Peng et al. depends upon the physiochemical characteristics of biochar
2011). such as dosage, pyrolysis temperature, pH of the medium/
Sawdust is an agricultural waste material that can be used effluent (Pellera et al. 2012; Ahmad et al. 2014; Lam et al.
for the abatement of many dyes, toxic metals and salts from 2016; Mubarak et al. 2016; Vithanage et al. 2016; Younis
wastewater (Peng et al. 2011). This material contains many et al. 2016; Rehman et al. 2017; Qayyum et al. 2017). How-
compounds (such as cellulose, lignin and hemicellulose) and ever, due to rapidly growing urbanization and industrializa-
polyphenolic groups, which play a vital role in binding to tion in developing countries, a large volume of wastewater
organic compounds through various mechanisms including is generated, which contains chemicals generating high
ion exchange, complexation and hydrogen bonding (Thies environmental risks which could affect health and socio-
and Rillig 2009). economic activities. Consequently, understanding the appli-
The adsorption capacity of orange peel leading to dyes cation of biochar in wastewater treatment and water purifica-
removal from industrial and domestic effluents was exten- tion gets increasing attention even if there is a lack of data
sively studied. The effect of some physicochemical param- dealing with adsorbents for industrial wastewater treatment.
eters that may affect the absorption performance such as In this paper, we review various forms of biochar sorb-
the biochar dosage, the medium acidity, the reaction time ing materials for the abatement of pollutants from industrial
and the dyes concentration was studied. Adsorption capaci- wastewater. The preparation methods, the biochar characteri-
ties of 10.72 and 21.05 mg/g were found for direct red 23 zation, and the different mechanisms involved during pollut-
and 80 within the first 15 min at initial pH 2 (Fuertes et al. ant adsorption are discussed, as well as biochar regeneration.
2010). The adsorption capacity of wastes from steel and Its economic and environmental benefit is also analysed,
fertilizer industries for the adsorption of cationic dyes was especially regarding its application on a large scale. The
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International Journal of Environmental Science and Technology (2021) 18:3273–3294 3275
review also highlights the future research directions, espe- products and are typically used to produce bio-oil or gaseous
cially regarding environmental applications of biochar. materials (Hossain et al. 2011). For example, the gasification
method has a yield of about 85% for the gas product. The
content of gaseous products increases by the increase of the
Preparation and characteristics of biochar temperature.
Preparation methods of biochar

Characteristics
Different methods were used for the preparation of biochar.
Table 1 summarises some of the preparation methods, prepa- The physicochemical properties of biochar are highly influ-
ration conditions and the absorption yield of recently available enced by the biomass origin and the preparation conditions.
biochars. Pyrolysis appears to be a major method for the prep- Different biomass presenting different physical, chemical
aration of biochar. Pyrolysis is a decomposition taking place at and structural properties can be used to produce biochar.
high temperature in the absence of oxygen. It can be qualified Theoretically, biochar can be prepared from any type of bio-
as rapid, slow or “flash” pyrolysis based on the temperature mass. Various types of feedstock could be used to prepare
and the reaction time (Downie et al. 2009; Sun et al. 2014). biochar such as agricultural, aquatic or forest crops (Sun
Solid products can be formed due to slower heating rates and et al. 2014). Biochar can also be produced by transform-
lower pyrolysis temperatures. As shown in Table 1, the yield ing/or processing different biowastes such as husks, saw-
of solid product in the slow pyrolysis is usually 35%, and dust, shells and hulls. Other sources of biomass including
this reveals that slow pyrolysis can be assumed as the main manures, municipal solid wastes, sewage sludge (Zhang
preparation method of biochar among the three-pyrolysis tech- et al. 2017) are shown in Fig. 1.
niques (Özçimen and Karaosmanoğlu 2004). Many factors can affect the physicochemical properties
Hydrothermal carbonization (HTC) is another major tech- of biochar. One of the parameters that affect the properties
nique for the preparation of biochar. The biochar formed of biochar is the types of the raw material and the size of the
by HTC is more favourable for adsorption of pollutants in substrate. The pyrolysis type (slow, rapid or flash), the tem-
aqueous media. Harmful substances are not produced by this perature, the heating rate, the duration of pyrolysis can also
process. However, the main limitations associated with this affect drastically the quality of the resulting biochar (Downie
method are related to the high-pressure requirement con- et al. 2009; Peng et al. 2011; Thies and Rillig 2009). Biochar
comitant to high temperature, and the cost of the reactor as presents an abundant number of surface functional groups
reported by Van Zwieten et al. (2010); however, it may be such as hydroxyl, methyl, carbonyl and carboxyl (Fuertes
time-consuming which leads to high cost (Van Zwieten et al. et al. 2010). Many factors can affect its structure such as the
2010) delaying its practical application. However, recent high carbon content, oxygen-containing aromatic functional
studies showed that treating sewage sludges and digestate groups and its high porosity. Its porosity, stable molecular
using HTC can overpass its limitation in energy compared structure and its surface area favour the pollutants’ adsorp-
to other thermochemical processes. The hydrochar that can tion on its surface (Chen et al. 2014). Some of the above-
be produced from this process was seen to be more stable mentioned factors that affect the removal of contaminants
(Parmar and Ross 2019). For this reason, hydrochar from from industrial wastewater are discussed below.
HTC can improve the biogas production and soil amend-
ment/remediation. There is a need of more research for cou- Biochar’s properties influencing its activity
pling HTC with anaerobic digestion of process waters in the
future for large-scale applications (Parmar and Ross 2019). The properties of biochar depend upon the pyrolysis tem-
In addition to slow pyrolysis and HTC, other methods perature, the residence time, the considered feedstock and
include rapid pyrolysis, “flash” pyrolysis, gasification and the thermal conversion technology as mentioned earlier.
drying. However, such methods have a small yield of solid These factors also affect the removal efficiency of various
Table 1 Conventional Preparation methods Temperature (°C) Heating rate Reaction time Yield (%)
techniques used to prepare
biochar (Downie et al. 2009; Solid Liquid Gas
Novak et al. 2009; Sun et al.
2014) Slow pyrolysis < 700 Slow Hours 35 30 35
Fast pyrolysis < 1000 Fast Seconds 10 70 20
Flash pyrolysis 775–1025 Faster SECONDS 10–15 70–80 5–20
Hydro-carbonization < 350 Slow Minutes–hours 50–80 – –
Gasification 700–1500 Faster Seconds–minutes 10 5 85
13
Fig. 1 Classification of biochar

( Adapted from Dai et al. 2019)
contaminants (Chen et al. 2012). The adsorption of organic The latter contributed to the reduction of Cr(VI) to Cr(III).
contaminants using biochar prepared from pine needles at This reduction reaction is a serious environmental prob-
temperatures going from 100 to 700 °C was studied by lem because it is pH dependent. Ludwig et al. (2007) tried
Chen and Chen (2009). They showed that the pore size and the in situ reduction of Cr(VI) using ferrous sulphate and
the specific surface areas of biochar increase proportion- sodium dithionite. The reduction kinetics were very slow
ally with the pyrolysis temperature. Chen et al. (2012) as delaying the practical application of this method.
well as Ahmad et al. (2012) proposed that the presence of Thus, it has been reported that increasing the biochar’s
carbonized matter, surface area, pores and hydrophobicity pyrolysis temperature increases the biochar’s surface area,
of biochar increased when the temperature was increased, while it decreases the amount of oxygen-containing func-
which in turn led to increase the adsorption yield of naph- tional groups on its surface. This latter leads to decrease the
thalene. Also, the existence of more carbonized matter in adsorption of toxic metals in aqueous media as shown in
biochar favours the removal of organic contaminants having Fig. 2. These observations were in consistency with those
a functional group of oxygen and hydrogen (Ahmad et al. of Inyang et al. (2011). Inyang et al. (2011) observed that
2012). Moreover, the adsorption of potentially toxic metals the Pb adsorption on biochar decreased from 21 mg/L as the
on biochar can also be enhanced by optimizing the pyroly- pyrolysis temperature increased from 250 to 600 °C using
sis temperature. Kim et al. (2012) studied the effects of bagasse biochar. They attributed this to the decrease in the
pyrolysis temperature greater than 500 °C on the biochar’s number of oxygen-containing groups at high temperature.
pH and surface area. They applied their biochar to the Another parameter affecting the adsorption properties of
adsorption of Cd in aqueous media. In contrast, O’Connor biochar is the composition of the feedstock (Sun et al. 2014).
et al. (2018) showed that the increase of the pyrolysis tem- Indeed, the presence and absence of mineral-like C O32−,
3−
perature led to the decrease in the removal of Cr(VI) in PO4 in the feedstock affect the adsorption capacity of the
aqueous medium using biochar produced from coconut. obtained biochar, since these minerals can contribute to
13
d2+, Cu2+, Hg2+, Pb2+,

Fig. 2 Mechanisms of metal cations (e.g. C ature (< 450 °C) (Reproduced with permission from Sizmur et al.
Zn2+) and oxyanions (e.g. PO43−, AsO43−) sorption to biochar pre- (2017), Bioresource Technology 246 (2017) 34–47)
pared by pyrolysis at high temperature (> 450 °C) and low temper-
the formation of additional active sorption site, enhancing involved in the adsorption process include: (a) physical
adsorption of potentially toxic metals from wastewater (Cao adsorption in which the adsorbate settles on the adsorbent’s
et al. 2009). From another side, biochar produced by hydro- surface; (b) precipitation and complexation in which the
thermal carbonization (HTC) can produce a higher number adsorbate deposits on the adsorbent’s surface; and (c) pore
of oxygen-containing functional groups (Liu et al. 2010). filling in which the adsorbate is condensed into the pore
Similar conclusions were drawn by Kumar et al. (2017) who of the adsorbent (Fagbohungbe et al. 2017). This process
examined the removal of copper from wastewater using bio- occurs in three stages qualifying three zones: the first is
char produced by HTC and pyrolysis. the stage in which no adsorption takes place; it is called
the clean zone. The second stage is called the mass transfer
zone in which the adsorption is in progress. The last step is
Pollutants’ removal mechanisms the stage in which equilibrium is achieved; it is called the
exhausted zone (de Ridder et al. 2012). The saturated or
Mechanisms of biochar adsorption exhausted zone increases, while the clean zone decreases
during the process. The mass transfer zone is affected if the
In adsorption, the adsorbate is associated with the adsor- adsorbate’s concentration is increased; otherwise, it is not
bent’s surface until equilibrium is achieved. The steps affected. Such a trend continues until the breakthrough point,
13
a point where the adsorbent is saturated (Moreno-Castilla Cation/ion exchange capacity

2004).
The exchange of protons and ionized cations with dissolved
Mechanism of the adsorption of toxic metals salts on the biochar’s surface is the main principle of this
mechanism. Its adsorption capacity to remove heavy metals
The different mechanisms involved in the toxic metals’ depends upon the contaminated size and surface functional
removal are surface sorption, ion exchange, electrostatic group of the biochar (Rizwan et al. 2016). Ali et al. (2017)
interaction, precipitation and complexation. reported that the higher the cation exchange capacity of the
biochar means the higher adsorption of metals. However, the
Surface sorption cation exchange capacity is decreasing with pyrolysis tem-
peratures greater than 350 °C. El-Shafey (2010) investigated
It is a physical process that involves the formation of chemi- the removal of Hg2+ and Zn2+ from polluted water using
cal bonds through the diffusion of the metal ions in the pores biochar prepared from rice husk at pyrolysis temperature of
of the sorbent. The pores’ volume and the surface area of the 180 °C. They showed that high adsorption of Hg ions was
sorbent (biochar) depend upon the carbonization tempera- achieved compared to Zn ions. Trakal et al. (2016) investi-
ture. Kumar et al. (2017) studied the uranium adsorption gated the removal of Cd and Pb using biochar prepared from
onto biochar prepared from pinewood at a temperature of different feedstocks such as wheat straw, graph stalk, grape
300 and 700 °C. Their results showed that biochar prepared husk, plum stone and nutshell. The authors showed higher
at a high temperature can completely remove uranium than Pb and Cd removal efficiency for the feedstocks containing
the one prepared at low temperature. They attributed this to iron oxides. The presence of iron in the biochar feedstock
the fact that high carbonization enhances the surface area was seen to enhance the cation exchange capacity of the
and pores volume of the biochar. Another research reported biochar.
by Wang et al. (2015) aimed to investigate the adsorption
of toxic metals on biochar prepared from hickory wood and Precipitation
treated with KMnO4. Their results showed that the biochar
that they prepared exhibited 153.1 mg g−1adsorption of Pb, It is one of the main mechanisms that can be used for the
34.2 mg g−1 adsorption of Cu and 28.1 mg g−1 adsorption removal of inorganic pollutant onto biochar. It involves the
of Cd. This difference in the adsorption may be due to the formation of mineral precipitates into the solution or onto
affinity of these metals, presenting different valence towards the surface of the sorbing material, especially for biochar
the biochar. which is produced from the degradation of cellulose and
hemicelluloses material through pyrolysis temperature
Electrostatic interaction of metals on biochar greater than of 300 °C and having alkaline property (Cao and
Harris 2010). Puga et al. (2016) reported that biochar that
This mechanism involves the electrostatic interaction can be prepared from sugarcane and straw dust can enhance
between the charged biochar and metals ions to limit the the precipitation of Cd and Zn. However, they claimed that
mobilization of potentially toxic metals (Mukherjee et al. the efficiency of surface precipitation of the biochar depends
2011). For instance, according to the Qiu et al. (2009) the on the pyrolysis temperature so that more research needs in
removal of Pb from the aqueous solution using biochar pre- the future in the optimization of the pyrolysis temperature.
pared from rice and wheat shows high removal of Pb due to
the attraction of the positively charged Pb and negatively Complexation
charged of the biochar. In addition to this, they claimed that
increasing the pyrolysis temperature greater than 400 °C This mechanism of metal complexation includes the arrange-
can enhance the carbonization of the biochar and leads to ment of multi-atom formation through the interaction of spe-
an increase in the electrostatic interaction of the biochar to cific metal ligands to form complex. The biochar produced
adsorb the pollutant. The same result also reported by Keilu- at low temperature can bind with heavy metals thanks to the
weit et al. (2009), Dong et al. (2011), Agrafioti et al. (2014) functional groups which contain oxygen in their structure
and Igalavithana et al. (2017) who reported that electrostatic such as phenolic, lactonic and carboxyl. This oxygen con-
interaction is the main mechanism involved in the removal tent can increase surface oxidation of the biochar leading to
potentially toxic metals. However, this immobilization pro- enhance the metal complexation (Mohan and Pittman 2007;
cess depends upon the pH of the solution and point of zero Liu and Zhang 2009). It has been shown that biochar prepared
charge of biochar. from vegetal biomass has high efficiency in the binding of
potentially metals such as Cu, Cd, Ni and Pb to form metal
complexes with carboxylic and phenolic functional groups
13
when compared with biochar prepared from animals such Electrostatic interaction
as dairy manure and poultry litter (Cao et al. 2009; Zhang
et al. 2017). They concluded that plant-derived biochar dis- This is the most important mechanism which involves the
plays high surface complexation and ion exchange capaci- adsorption of ionizable organic compounds to the positively
ties. However, more research is needed in order to determine charged surface of the biochar through electrostatic interac-
the biochar metal complexes’ formation using sophisticated tion. Its efficiency to attract or to repel pollutants depends
spectroscopic techniques such as X-ray photoelectron spec- upon the pH and ionic strength of the aqueous solution
troscopy (XPS) and Fourier transform infrared spectroscopy (Ahmad et al. 2014; Zheng et al. 2013). Mukherjee et al.
(Zhou et al. 2014). (2011) investigated the effect of pH on the electrostatic inter-
action between organic contaminants and biochar surface
The mechanism involved in the adsorption showed positive charge at low pH value, whereas when the
of organic pollutants pH of the aqueous solution is high, it holds a negative charge.
This indicates that the net charge of the surface of the biochar
The different mechanism involved in the organic pollutants’ is controlled by the pH of the solution/effluent. The electro-
adsorption is pore filling, hydrophobic interaction, partition- static interaction of the organic contaminants with biochar is
ing, electrostatic interaction and electron donor–acceptor also affected by the ionic strength of the aqueous solution.
(EDA) interaction. Inyang et al. (2014) in their experiment related to removal of
methylene blue by biochar prepared from bagasse composite
Partitioning with carbon nanotubes (CNT) showed that an increase of the
ionic strength of the sorbate solution from 0.01 to 0.1 M NaCl
In this process, the adsorbate material diffuses into the pores led to decrease the adsorption of the methylene blue from 4.5
of the non-carbonized portion of the biochar. This portion to 3 mg g−1. This was attributed to an increase of the repulsive
can easily interact with the organic adsorbate leading to electrostatic interaction between the sorbent and the sorbate.
its sorption. However, the adsorption of organic pollutant
compounds depends upon the characteristics of the non-car-
Electron donor and acceptor interaction
bonized biochar (crystalline or amorphous carbon) and of
carbonized crystalline and graphene fractions of the biochar.
The electron donor and acceptor interaction mechanism is
Cao et al. (2009) and Zhang et al. (2013a, b) reported that
mostly applied to the adsorption of aromatic compounds on
biochar prepared from swine and dairy manure at pyrolysis
biochar presenting a graphene-like structure. To have a com-
temperature of 200 and 350 °C shows high sorbate partition-
plete graphitization, a temperature greater than 1100 °C should
ing of atrazine pollutant using organic carbon (OC) fractions
be reached during the biochar preparation (Spokas 2010). How-
of biochar. Similar results were found by Sun et al. (2011)
ever, the electron density of the biochar to generate deficient or
showing that organic fractions of biochar prepared from
enriched π–electron depends upon the pyrolysis temperature
wood and grass can enhance the adsorption of norflurazon
of the biochar, that is if the temperature of the biochar is below
and fluridone by partitioning. In general, the partitioning
500 °C, the system of the biochar π aromatic acts as electron
mechanism is more visible and highly efficient when the
acceptor, while if the temperature is above 500 °C, the biochar
biochar has high volatile matter content and at high con-
acts as a donor (Sun et al. 2014; Zheng et al. 2013). Zheng
centration of organic contaminants (Keiluweit et al. 2010).
et al. (2013) tried to adsorb sulfamethoxazole using biochar
produced from reed and enriched on its surface with π–electron
Pore filling
graphene. A high sorption was observed between the aniline-
protonated rings of sulfamethoxazole and the graphene surface
This is a process in which the organic contaminants are at
of the biochar. Besides they claimed that the π-electron donor/
the surface of biochar having mesopores (2–50 nm) and
acceptor interaction between the electron-withdrawing substitu-
micropores (< 2 nm). The pore filing mechanism depends
ent of chlorine and aromatic carbon on the surface of biochar
upon nature, type of the biochar, as well as the polarity of
enhances the adsorption of atrazine compound.
the organic contaminant. Kasozi et al. (2010) reported that
biochar prepared from gamma grass, oak and loblolly for the
Hydrophobic interaction
sorption of catechol using micropore filling mechanism is
more dominant than other adsorption mechanisms. In gen-
This mechanism can be used for the adsorption of hydro-
eral, to have high efficiency of this pore filling process, the
phobic and neutral organic compounds through parti-
biochar must contain a small amount of volatile matter and
tioning and hydrophobic interaction processes. When
occur at low concentration of organic contaminants.
compared to the partitioning process, the hydrophobic
13
interaction mechanism requires less energy. Moreover, the in Fig. 3. Functional groups (hydroxyl, carboxyl, carbonyl,
main process for the adsorption of organic pollutants on amine) favour the affinity of organic molecules and their
the surface of the graphene structure is the hydrophobic adsorption on the biochar’s surface. Such adsorption mecha-
interaction (Zhu et al. 2005). Similar results were reported nism is an electron donor/acceptor type based on the uneven
by Li et al. (2018) who showed that hydrophobic interac- electrons’ distribution between the organic compound and
tion is the main mechanism involved in the adsorption of the adsorbent (biochar) functional groups. At this level, it is
ionizable organic pollutants such as benzoic acid, o-chlo- worth mentioning that the interaction between organic com-
robenzene acid and p-chlorobenzene acid. Chen et al. pounds presenting nitro- and chloro-substituent groups and
(2011a, b) investigated the perfluoro octane sulfonate sorp- the adsorbent is highly reduced. This leads to an increase in
tion on biochar produced from maize straw. The removal the electrostatic interaction between the organic compound
took place via the hydrophobic interaction due to high and the biochar (Mu’azu et al. 2017) as it is related to the
hydrophobic nature of the organic pollutant. The adsorp- strong electron acceptor nature of the substituent group in
tion of perfluoro octane sulfonate molecules increased the compound (Atkinson et al. 2010).
with the increase in the pyrolytic temperature. This was
attributed to the decrease in the number of polar groups on Factors affecting contaminants’ sorption
the biochar surface caused by the pyrolysis temperature. onto the biochar
The mechanisms of removal of organic and inorganic
adsorbates involving the sorption onto biochar are shown Effect of the pH of the medium
in Fig. 3. Metals adsorption on biochar occurs principally
through precipitation, ion exchange and electrostatic attrac- It has been reported that the pH of the aqueous solution affects
tion onto the adsorbent’s surface, while the adsorption the sorption of contaminants onto biochar. This is related
mechanisms for organic molecules are van der Waals forces, to the oxygen-containing functional groups, which are pH
hydrogen bonding and hydrophobic interactions as shown dependent. Consequently, the surface charge and ionization
Fig. 3 Different biochar adsorp-

tion mechanisms for organic
and inorganic contaminants.
(Adapted from Ahmad et al.
2014)
13
at the surface of the biochar are pH-dependent leading to dif- efficiency of the toxic metals when the concentration of the
ferentiate adsorption capacity to remove contaminants (Zhang biochar increased from 0.5 to 5 g/L. It was attributed to
et al. 2013a, b). A deprotonation of the functional groups hap- an increase in the number of active sites and surface area
pens when the pH of the aqueous solution increases. This by increasing the amount of biochar. This observation is in
leads to the increase of the sorption capacity of biochar agreement with the reports of Lalhruaitluanga et al. (2010),
towards cationic metals. However, if the pH decreases, it Tsai and Chen (2013) and recently by Lu et al. (2017). More-
leads to increase the electrostatic repulsion forces between over, Sun et al. (2013a, b) reported that increasing the dose
the protons and metal ions in the aqueous solution. Conse- of biochar (prepared from swine manure) from 1 to 8 g/L
quently, a competition between cations for the adsorption sites las to increase the active sites available to adsorb methylene
of the biochar can occur leading to decrease the capacity of blue. Wang et al. (2018) found similar results by increasing
the adsorbent material for metal ions (Lu et al. 2012). the biochar amount for the adsorption of organic pollutants.
In their study to adsorb metals like copper, zinc and lead A high concentration of biochar has a positive impact on
using biochar produced from hardwood and corn straw, Chen the adsorption of organic pollutants and potentially toxic
et al. (2011a, b) showed that an increase of the pH from elements. It would be therefore useful to find the optimum
2.0 to 5.0 led to an increase in the adsorption capacity of dose, which is a key factor to minimize the biochar produc-
the metallic cations. A pH above 5.0 led to decrease the tion costs in view of its industrial application.
adsorption capacity due to hydroxide complex formation.
Similar results were reported by Tong et al. (2011) and Lu Management and regeneration of exhausted biochar
et al. (2012). However, Zhang et al. (2013a, b) proposed that
decreasing the pH of the solution leads to an increase in the During the regeneration of biochar, the adsorbate can be
adsorption capacity of anions such as Cr (VI) metals ions. recovered using the principle of decomposition and des-
This is due to electrostatic interactions between the nega- orption (Jia et al. 2013; Wang et al. 2015). Adsorbents for
tive charges of the chromate ion with the positive charge of the removal and degradation of pharmaceutical compounds
the biochar functional group at low pH. In contrast, by the were prepared by ball milling. Hybrid activated carbon and
removal of Cr (VI), increasing the pH was reported to lead biochar functionalized with Fe3O4 showed that magnetically
to a decrease in the Cr adsorption on the biochar surface. separable biochar degraded 97% of tetracycline in water
This was attributed to the OH—competition with Cr (VI) compared to the low adsorption of this compound on acti-
species to bind to the active/charged sites at the biochar’s vated carbon. The regeneration of this adsorbent depended
surface. Thus, the removal of Cr(VI) was dictated by the pH on the adsorbents’ origin, method of regeneration as well as
as reported by Shang et al. (2017). the dose of the adsorbents. Similar results were also reported
The pH of the solution also affects the adsorption capacity by Wang et al. (2015) who prepared magnetic biochar from
of organic contaminants of industrial wastewater. The adsorp- leaves residues of eucalyptus for the degradation of organic
tion of textile dyes in wastewater using biochar produced from pollutant. They showed that there is no change in band shift
food waste was investigated by Parshetti et al. (2013). They of the Fourier transform infrared spectroscopy spectra until
observed that an alkaline pH enhanced the adsorption of dyes. 6 cycles. This was attributed to an increase in the ash content
It was attributed to the high interaction between the nega- of the biochar as well as to the non-significant change in the
tively charged sites on the biochar’s surface with the positively functional groups present on its surface. Regenerated mag-
charged dyes. In contrast, at pH 3, its efficiency to adsorb netic biochar presented similar surface area and pore sizes
organic dye decreased because of the existence of extra H+ as the as-prepared biochar allowing high adsorption and/or
that compete with the positive charges of the dye. Tsai and separation rates. The regeneration of the adsorbent makes the
Chen (2013) and Xu et al. (2011) reported similar observa- adsorption process economic. However, the use of water for
tions on the effect of the pH on the adsorption capacity of regeneration is not an efficient method. Chemical regeneration
biochar. Thus, the pH of the solution affects the adsorption should be considered. It involves reagents such as NaOH. It
capacity of organic compounds and inorganic pollutants from can also be carried out by a change of the adsorbent’s pH in
industrial wastewater on biochar by altering the charged sites. order to desorb the non-reactive chemicals like aniline and
dyes (Fagbohungbe et al. 2017). Some the chemical reagents
Amount of biochar used for regeneration are costly and may pollute the environ-
ment to a high extent. For this reason, the process disposal of
The adsorption capacity is also affected by the amount the digestate is a key factor in the management of biochar. The
of biochar. Chen et al. (2011a, b) studied the removal of graphical representation of biochar to adsorb contaminants
potentially toxic metals (Cd, Cu, Pb and Zn) from indus- from wastewater, the regeneration of biochar, and other treat-
trial wastewater using biochar prepared from hardwood and ment processes, are shown in Fig. 4.
corn straw. They observed an improvement of the adsorption
13
One of the best methods for the regeneration of biochar on large scale due to the high cost of the material equipment,
is thermal regeneration. It allows the formation of small high-pressure resistance and its complexity.
pore sizes compared to the original pores of the used bio- In conclusion, from all methods for management and
char, especially when it is applied at high temperatures. The regeneration of biochar, thermal regeneration is seen to be
authors observed also that the efficiency of the regenera- the more mature regeneration process with low cost and high
tion increases with increasing the temperature. Qiao et al. economic applicability. However, a high carbon loss was
(2018) compared the adsorption rates of organic compounds, observed compared with other regeneration methods. More
such as pyrene and benzopyrene, using Enteromorpha pro- research should be carried out in the future focusing on the
lifera biochar. They observed that the adsorption efficiency economic aspect of the biochar uses.
increased by 35.0%, 45.0% and 48.0% for pyrene and by
31.0%, 41.0% and 40.0% for benzopyrene after regenera-
tion at 80 °C, 150 °C and 200 °C, respectively. Also, they Treatment of typical pollutants
observed that biochar regeneration using the thermal method
can also reduce the dissolved organic carbon. Due to its capacity to adsorb pollutants in the liquid phase
Microwave (MW) irradiation was also used for biochar (Chen et al. 2011a, b), biochar has been extensively explored
regeneration. It was shown that it allows a fast regeneration of for water/wastewater treatment. As summarized by Chen
biochars. Furthermore, using this method, the operating temper- et al. (2011a, b), it is mostly used for the adsorption of
ature can be easily controlled. MW irradiation was also seen to potentially toxic metals (46%) and organic pollutants (39%).
induce polar molecules in the biochar producing dipole/polariza- It can also be used for the adsorption of phosphorus and
tion. However, this method remains at laboratory scale and in nitrogen (13%). The remaining 2% is for adsorption of other
the experimental stage and is not currently applied on large scale pollutants because of its large specific surface area, porous
(Ania et al. 2005; Jia et al. 2013; Li et al. 2018). Otherwise, Dai structure and surface functional groups.
et al. (2019) investigate biochar regeneration by adjusting the
operating pressure using supercritical fluid. The author showed
high volatile organic compounds (VOCs) adsorption without Adsorption isotherm
changing the chemical and physical properties of the biochar.
This operation was shown to fulfil low biochar loss, low oper- The discharge of organic and inorganic pollutants in indus-
ating temperatures and a short operating cycle. However, this trial effluents is becoming a universal problem. Scientists
method remains also in the experimental stage and not applied applied biochar to remove these toxic pollutants from aque-
ous solution. Table 2 summarizes the use of biochar for the
Fig. 4 The graphical representation of wastewater contaminants’ adsorption on biochar and the possible ways of its regeneration (Adapted from
Mubarak et al. 2016)
13
adsorption of pollutants in water. Thus, it is necessary to results were reported by Tong et al. (2011). They compared
quantify and optimize the interaction between the adsorp- the fit of models such as Freundlich, Langmuir as well as
tion capacity of the biochar with the adsorbates through the Temkin for the adsorption of Cu2+ using three different
adsorption isotherms at constant ambient temperature (Fan biochar materials. They showed that the Langmuir model
et al. 2017; Goh et al. 2008; Kołodyńska et al. 2012). Dif- exhibited the highest fit of the data when compared to the
ferent empirical equilibrium models such as Temkin equa- other models, Freundlich and Temkin. Recently, the dynamic
tions, Langmuir–Freundlich, Freundlich and Langmuir were adsorption of heavy metals using biochar showed that the
applied to describe the equilibrium of organic and inorganic Freundlich model showed the highest fit than Langmuir
pollutants adsorption to biochar. The results showed that the isotherm (Kołodyńska et al. 2012; Lu et al. 2012; Xu et al.
adsorption equilibrium isotherms depend upon the binding 2013; Zhang et al. 2013a, b). According to Freundlich iso-
affinity of the pollutants on the surface of the biochar. Fre- therm, the model assumed one molecule with multiple types
undlich and Langmuir isotherm models showed the best fit of sites during the affinity of the adsorbate on the adsorbent.
models than other models during the quantification of the In another study, Zhang et al. (2013a, b) studied the adsorp-
adsorption of inorganic pollutants on biochar. These models tion of Pb2+ and Cr3+ using biochar prepared from wastewa-
consider only one layer of the adsorption of the adsorbate ter sludge. This biochar showed that the adsorption of P b2+
on the homogeneous surface of adsorbent during the binds fitted the Langmuir model, whereas the adsorption of C r3+
(Aydın and Aksoy 2009). Chen et al. (2011a, b) investi- fitted the Freundlich model. This result indicates that Freun-
gated the Langmuir–Freundlich model for the adsorption dlich isotherm has multiple sites as well as it is not restricted
of Cu2+ and Z n2+ at different concentrations. The results to one site like Langmuir for the adsorption pollutants.
showed that the Langmuir model fitted the experimental Biochar has a high affinity towards organic pollutants.
data (R2 > 0.998) when compared to the Freundlich model Table 3 summarizes the high performance of biochar derived
(R2 were 0.86–0.94). This model considers one single site from biomass in removing organic pollutants such as pes-
of the adsorbate binds with one molecule of adsorbate in a ticides, antibiotics, herbicides and dyes. The adsorption
homogeneous surface during the binding affinity. Similar of the organic pollutants fitted the model of Langmuir and
Table 2 Adsorption capacities of different biochars for inorganic contaminants from industrial wastewater
Type of biochar pH Temp. (°C) Targeted species Con. range (mg/L) Langmuir adsorp- References
tion capacity
(mg/g)
Pinewood char 5 25 Pb2+ 2–1036 4.13 Mohan et al. (2011)

Celery 5 25 Pb2+ 270–305 Zhang et al. (2017)
Peanut straw char 4.5 25 Cu2+ 6–318 12.52 Mubarak et al. (2013a, b)
Soybean straw char 4.5 25 Cu2+ 158–954 33 Tong et al. (2011)
Rice husks 5 24 Cu2+ 1–20 3.49 Pellera et al. (2012)
Pig manure biochar 5 20 Zn2+ 0.065–0.2 62.13 Kołodyńska et al. (2012
Cow manure biochar 5 20 Zn2+ 0.06–0.2 58.11 Kołodyńska et al. (2012
Dairy manure biochar – – Cu2+ 0–318 48.11 Xu et al. (2013)
Dairy manure biochar – – Zn2+ 0–327 32.95 Xu et al. (2013)
Dairy manure biochar – – Cd2+ 0–6575 32.03 Xu et al. (2013)
Oak Wood char 2 25 Cr6+ 1–100 3.03 Mohan et al. (2014)
Sugar beet tailing biochar 2 22 Cr6+ 50–800 123 Dong et al. (2011)
Coconut coir derived char 3 25 Cr6+ 10–500 – Kim et al. (2012)
Pine needle biochar 6 25 U6+ 5–30 2.12 Park et al. (2011)
Corn straw 5 22 Hg2+ 0–139 – Wang et al. (2018)
Pinewood biochar 2 25 F− 1–100 7.66 Ahmad et al. (2012)
Digested sugar beet tailing biochar 7 22 PO43− 15–640 133.085 Yao et al. (2011a, b)
undigested sugar beet tailings 7 22 PO43− 61.5 – Yao et al. (2011a, b)
Orange peel biochar – 25 PO43− 0–12 0.007 Chen et al.a (2011)
Banana peels 5 25 Cu2+ 60–80 38.2 Ahmad and Gao (2018)
Banana peels 6 22 Pb2+ 70–250 87.5 Ahmed et al. (2018)
Corn straw 5 22 As3+ 0–7 – He et al. (2018)
Corn straw 5 22 Hg2+ 140 5.03 Wang et al. (2018)
13
Freundlich (Ahmed et al. 2016; Chen et al. 2012; Jung et al. mechanisms and chemical reaction involved in the adsorp-
2013; Kah et al. 2017; Li et al. 2018; Lima 2018). Ahmad tion process thorough the intra-particle diffusion model. Most
et al. (2012) reported on the removal of trichloroethylene from kinetic properties that were studied for the removal of pollut-
water using biochar derived from crop residues. They showed ants mediating biochar fitted a pseudo-second-order kinetic
that the experimental adsorption of the trichloroethylene fit- model due to a rate-limiting step involving chemical sorption
ted to the Langmuir model. Similar results were reported (Mohan et al. 2011). Biochar derived from sewage sludge
for the adsorption of methylene blue using biochar prepared was used by Lu et al. (2012) to adsorb P b2+ from water in
from different biomass (Sun et al. 2013a, b). In contrast, Yao the range of pH from 2 to 5. They showed that the kinetics
et al. (2013a, b) demonstrated that the adsorption of fluoro- fitted the pseudo-second-order model due to a chemisorption
quinolone antibiotics on biochar derived from the sludge of of the P b2+ on the biochar. Liu and Zhang (2009) studied the
wastewater fitted the Freundlich model. In general, the use of adsorption mechanism of P b2+ on biochar prepared from bio-
biochar as adsorbent for the removal of organic and inorganic mass of pinewood and rice husk. Their mechanism showed
pollutants from water showed high performance. Moreover, that their kinetics fitted the pseudo-second-order model
the binding affinity of the biochar with the contaminants because the chemical adsorption was considered as the rate-
depended on the physicochemical properties of the biochar. limiting step (Jia et al. 2013). Likewise, oxytetracycline and
methylene blue sorption on biochar produced from biomass
Adsorption kinetics of palm bark, maize straw and eucalyptus was seen to fit the
pseudo-second-order kinetic model (Sun et al. 2013a, b).
The chemical and physical properties of the biochar can dras-
tically affect the adsorption behaviour of biochar towards Heavy metal pollutants
organic and inorganic pollutant. These properties affect
the adsorption kinetics and mechanism involving chemi- Heavy metals are the most significant contaminants resulting
cal binding as well as mass transport (Boutsika et al. 2014; from industries, whereby the presence of very small amounts
Inyang et al. 2012; Xu et al. 2013). Reddy and Lee (2013) of heavy metals such as Cd, Cu, Zn and Pb in wastewater
reported that to apply biochar in large scale for the removal causes a significant effect on the environment. Adsorption of
of organic and inorganic pollutants from wastewater, it is nec- heavy metals on materials like biochar before discharging the
essary to clearly know the adsorbent surface area, diffusion treated water can reduce their concentration before reaching
Table 3 Adsorption capacities of different biochars towards organic contaminants from industrial wastewater
Type of biochar pH Temp. (°C) Targeted species Concentration Langmuir adsorp- References
range (mg/L) tion capacity
(mg/g)
P-(acrylamide)-wood biochar – 25 Phenol 5–50 23.14 Karakoyun et al. (2011)

Rice husk biochar – 40 Phenol 100–15,000 409.8 Liu et al. (2011)
Hardwood (Laurel oak, – – Humic acid 0–13 – Mukherjee and Zimmerman,
Quercus) (2013)
Orange peel biochar – 25 Naphthalene 18 – Zhou et al. (2014)
Wood char 7 25 Pyrene 0.002–0.12 – Peng et al. (2011)
Pine needle biochar – – m-dinitrobenzene 0.02–1.0 – Chen and Chen, (2009)
Peanut straw char 5–9 25 methyl violet 40–816 104.61 Xu et al. (2011)
kenaf fibre char 8.5 30 methylene blue 50–200 18.18 Xu et al. (2011)
Rice straw-derived char 5 30 Malachite green 25–300 128.14 Han et al. (2015)
Bamboo biochar 1 40 Acid black 172 50–500 358.14 Han et al. (2015)
Sewage sludge/ 2,4-Dichlorophenol 100% removal – Kalderis et al. (2017)
Corn straw 5 22 Bisphenol 500 – Zhao et al. (2017)
Dissolved black carbon biochar 5 25 Naphthalene 91 – Fu et al. (2018)
(DBC)
Miscanthus-derived biochar 5 30 Naphthalene 4–35 – Kim and Hyun (2018)
Bamboo hydrochars 1 35 Congo red 100 – Li et al. (2018)
Sugarcane bagasse biochar 7 25 Malachite green 3000 – Vyavahare et al. (2018)
Corn straw 5 22 Atrazine 70 – Zhang et al. (2018)
Macadamia nutshells 7 30 Phenanthrene 60 – Yang et al. (2018)
13
the environment. Biochar has a high ability to adsorb inor- the amount of volatile matter contained in the raw sludge.
ganic pollutants like heavy metals upon different interac- Similar results were reported by Bartoli et al. (2016) to pro-
tion mechanisms such as physical adsorption, precipitation, duce biochar from Arundo donax using microwave-assisted
ion exchange and electrostatic attraction. The mechanisms pyrolysis to adsorb sulfamethoxazole. They observed that
involved in the adsorption of heavy metals and their interac- increasing the pyrolysis temperature decreased the adsorp-
tion are described in Fig. 1a, and the adsorption capacities of tion capacity of biochar. It was reported that biochar has a
various biochar for heavy metals are given in Table 2. significant impact on the adsorption of organic pollutants,
Dong et al. (2011) studied the interaction mechanisms of such as phenols, compounds with high-chromatic content,
Cr(VI) with biochar produced from sugar beet leading to the herbicides (Inyang et al. 2011; Klasson et al. 2013).
formation of Cr(III). They showed that positive charges of The mechanism of adsorption can be either physical or
the biochar are electrostatically attracted towards the negative chemical. It dependents mainly on the aromatic and/or special
charge of Cr(VI) species. Also, they showed that hydrogen functional groups and on the polarity of both the biochar and
ions coming from the biochar are involved in the reduction the organic pollutants. The nature of intermolecular gravitation
of Cr(VI) to Cr(III). The reduced Cr(III) reacts with the and electrostatic force between the biochar and the pollutants
functional groups of the biochar in aqueous solution to form is the determining factor for the physical adsorption, while the
a complex of Cr(III). Similar findings were reported by Lu chemical adsorption mainly depends on the chemical interactions
et al. (2012), who worked on the adsorption of Pb2+ from between the biochar and the organic pollutant, which can be π
wastewater using biochar prepared from sewage sludge; they bonds, hydrogen bonds and coordination bonds (Liu and Zhang
showed that the functional groups of the biochar are crucial 2009). Liu and Zhang (2009) prepared biochar from different
to forming a complex with Pb. Similar mechanism was also raw materials (cole, peanut and rapeseed straw) after pyrolyzing
shown by Kong et al. (2011) and Sun et al. (2014) in adsorb- at 350 °C. The methyl violet adsorption capacity of their biochar
ing Hg(II) using biochar derived from soybean stalk and was in the range of 123.5–195.4 mg/g. Rapeseed straw gave the
adsorption of Cd(II) using biochar produced from corn straw. highest adsorption at room temperature. The presence of electro-
Moreover, another parameter that affects the adsorption of static attraction between methyl violet and biochar was confirmed
heavy metals like Pb, Cu, Zn and Cd is the composition of the by zeta potential and FTIR analysis. The results revealed that
feedstock. Although prepared at the same pyrolysis tempera- the methyl violet was mainly adsorbed on the hydrophilic and—
ture, biochars obtained from different feedstocks exhibit dif- COO-sites. Mohan et al. (2014) obtained methyl blue removal
ferent adsorption capacity of heavy metals (Sun et al. 2014). efficiency of 99.5, 99.3 and 86.1% using biochar prepared from
It should be related to the presence and absence of minerals anaerobic digestion residue, palm bark and tree, respectively. The
like CO2−3
, PO3−
4 in the feedstock, which affects the adsorp- organic materials were pyrolysed at 400 °C for 30 min, and the
tion capacity of biochar. These minerals can contribute to the conditions during the treatment were pH 7, 40 °C and 4 mg/L of
formation of active sites that enhance the adsorption of heavy the dye. It was found that the pyrolysis temperature had a signifi-
metals from wastewater (Cao et al. 2009; Xu et al. 2013). cant effect on the treatment of methyl violet.
Mohn et al. (2014) prepared biochar from peanut shells
Treatment of organic pollutants and wheat straw and obtained a maximum adsorption capac-
ity of 58.82 and 20.61 mg/g, respectively. These organic
Organic pollutants such as phenols, antibiotics, herbicides materials were pyrolysed at 400 and 600 °C, respectively. The
can be highly adsorbed onto biochar (Chen et al. 2011a, b). adsorption capacity of biochar prepared from mixed wood
In livestock wastewater, similar organic contaminants and wastes, pyrolysed at 450 °C for 1 h, was investigated, and
pollutants are always found; as a result, biochar has become maximum adsorption capacities of 1066 and 1158 mg/g were
a major focus in agricultural resources and the environment. obtained for two herbicides, namely simazine and atrazine,
Table 3 summarizes the application of biochar in the adsorp- respectively (Qiu et al. 2009). The authors claimed that better
tion of organic pollutants, and the various mechanisms adsorption performances were obtained in acidic conditions.
involved are described in Fig. 3b.
Antibiotic substances such as a fluoroquinolone, sul- Treatment of nitrogen and phosphorus
famethoxazole can be adsorbed by biochar in their aque- contamination
ous phase mainly through hydrogen bonding, π–π electron
transition and cationic interactions. For example, the fluoro- Other than the above organic and heavy metal pollutants,
quinolone adsorption ability of biochar was investigated by biochar has been also tested to remove nitrogen and phos-
Hale et al. (2012). Their biochar was prepared using pyroly- phorus from industrial wastewater to reduce the impact of
sis of sludge at 500 °C for 1 h, and the maximum adsorp- eutrophication on the ecosystem. The digestate left after this
tion capacity was 19.8 ± 0.4 mg/g. It was also found that the process can be used as high-quality fertilizer (Zhang et al.
adsorption of fluoroquinolones was positively correlated with 2013a, b; Hale et al. 2012). Using biochar produced from
13
cow dung to remove PO4-P and NH4-N from wastewater. is removing organic pollutants from the wastewater. This
Wang et al. (2014) observed high adsorption capacity. They may be due to its high surface area and highly oxidative
also found that the biochar feedstock dictated the adsorption reactive species enhancing the adsorption capacity during
capabilities towards nitrogen and phosphorus. Therefore, the photodegradation process. As shown in Table 4, there
biochar has a high capacity to remove PO4-P and NH4-N are different types of biochar-supported photocatalysts,
allowing to release nutrients to increase soil fertility, which and many studies have been carried out in the past ten
contributes to increasing crops’ production. years for the removal of organic pollutants. The results
showed the high efficiency for the degradation of meth-
ylene blue, phenol and sulfamethoxazole. Its adsorption
Biochar‑supported catalysts for wastewater capacity is equal to 400 ppm, 50 ppm and 10 ppm, respec-
treatment tively, when compared with nanoparticles only. Accord-
ing to Lisowski et al. (2017), a reactor loaded with soft-
Biochar can be used as a support for catalytic nanoparticles wood pellets-TiO2 significantly mineralized methanol into
to take advantage of their exceptional properties such as high methyl formate and carbon dioxide due to the generation
electrical conductivity, chemical stability, having functional of highly reactive species such as OH and O2− and h+ as
groups that can easily be tuned and unique surface properties shown in Fig. 5. Moreover, they claimed that the biochar-
(Cuong et al. 2019; Liu et al. 2015; Xia and Larock 2010). supported TiO 2 can act also as electrodes as well as it
Kim and Kan (2016) investigated the degradation of sul- can act as the water splitting during hydrogen production.
famethoxazole from wastewater through biochar-supported J. Matos (2016) reported a comparison of the efficiency
TiO2 photocatalyst material. Results showed that the biochar of the biochar-supported Au-TiO2 for the degradation of
loaded with TiO2 has high adsorption efficiency towards organic pollutants. It showed that the biochar-supported
sulfamethoxazole when compared to the commercial nano- Au-TiO2 composite has higher efficiency for the degrada-
particles. This was attributed to the biochar’s electron con- tion of the organic pollutants than the nanoparticles by
ductivity decreasing the recombination of the electron/hole themselves. This can be attributed to the presence of the
pairs during the photocatalysis. Furthermore, this enhances oxygen-containing groups on the biochar surface leading
the charge balance at the surface of the biochar (functional to reduce the photo-generated charge recombination and
groups) to adsorb various contaminants from the wastewater. thus to enhance the pollutants’ degradation. Also, the bio-
For this reason, researches carried out synthesis of various char-supported photocatalytic material has high stability
biochar-supported photocatalysts such as T iO2 hybrid with when compared to the commercial nanoparticle.
Miscanthus straw pellets and softwood pellets, TiO2–corn The incorporation of nanoparticles onto the biochar can:
cob, TiO2–waste plum, T iO2–wheat husks, T iO2–chitosan,
TiO2–reed straw, T iO2–bamboo, graphitic carbon nitride/ • increase the physicochemical properties of the nanopar-
FeVO4–pine needles, graphitic carbon nitride–chestnut, ticles,
ZrO2–wheat husks, BiOX–biochar and T iO2–wood char- • increase their active sites,
coal. These combinations and others showed that these • shuttle electrons through a graphene-like skeleton,
biochar-supported photocatalytic nanoparticles exhibited • act as electron reservoir which conducts away the elec-
high efficiency for the degradation of different pollutants tron from the e− /h+,
under visible light radiation. Such hybrid materials have • reduce the bandgap energy by carbon or other non-metal
been reported with high chemical stability as well as high doping (impurities or dangling bonds) improving the
recollection ability (Colmenares et al. 2016; Kalaivani and charge separation when compared with bare catalytic
Suja 2016; Khataee et al. 2017a, 2017b; Kim and Kan 2016; nanoparticles.
Kumar et al. 2017; Li et al. 2016; Lisowski et al. 2017; Liu
et al. 2017; Luo et al. 2015; Matos et al. 2013a, 2013b; Pi For this reason, it has high performance in degradation
et al. 2015; Wu et al. 2015; Zhang et al. 2017). and absorption of the organic pollutants in aqueous solution.
However, there are some aspects to be further investigated
in the future for the development of highly efficient biochar-
Removal of organic pollutants supported photocatalysts such as:
from wastewater using biochar‑supported
catalysts • the use of different biomass and nanoparticles,
• the heating/operating conditions,
Biochar-supported photocatalytic materials can be used • the ratio of biomass to nanoparticles,
for different applications. One of the most promising • the use of other waste materials such as manure and sew-
applications of biochar-supported photocatalytic material age sludge composite with nanoparticles.
13
Table 4 Application of Type of biochar-nanoparticles catalysis Targeted species Concentration References

various biochar-supported range (mL–
photocatalysts mg/L)
Starbon-TiO2 Phenol 150–50 Colmenares et al. (2013)

Softwood pellets-TiO2 Phenol 150–50 Lisowski et al. (2017)
Pinewood-TiO2 Bisphenol 50–20 Luo et al. (2015)
Waste plum stones-N-TiO2 Methylene blue 125–25 Matos et al.(2013b)
Bamboo-TiO2 Methylene blue 200–30 Wu et al. (2015)
Chestnut leaf-g-C3N4 Methylene blue 20–4.8 Pi et al. (2015)
Sludge/wheat husks-TiO2 Reactive Blue 69 1–20 Khataee et al. (2017a)
Reed straw-TiO2 Sulfamethoxazole 160–10 Zhang et al. (2017)
Corn cob-TiO2 Sulfamethoxazole 100–10 Kumar et al. (2017)
USA from 23 biochar companies reported an average price

of 2512.00 US$/ton. Currently, the International Biochar Ini-
tiative and the European Biochar Certificate are establishing
a standards’ chart for the development of biochar as recently
reported by Dai et al. (2019).
In general, the application of biochars for the removal of
pollutants was discussed in detail in the past years. However,
the research on biochar market/price is in an early stage so
that more research must be carried out in the future to ana-
lyse the significant differences in the biochar prices and their
Fig. 5 Fundamentals of organic pollutant photodegradation by reac- economic benefits, to apply at large scale for the removal of
tive oxygen species pollutants.
The application of biochar to mitigate the impact of cli-
mate change and to enhance sustainable agricultural and
These trends can improve the performance of the biochar- environmental development is a new approach (Oliveira
supported photocatalysts for the degradation and removal et al. 2017). Currently, the world still faces the environmen-
of recalcitrant/emerging organic pollutants from aqueous tal impact of greenhouse gases and global warming (Wang
solution. et al. 2018). Environmental issues and the reduction of
greenhouse gases (GHG) are the driving forces for research
to develop new environmentally friendly mitigate materials
Economic and environmental benefit to immobilize carbon from the active cycle and return it to
analyses an inactive cycle using biochar. Liu et al. (2015) showed
that CO2 emission can be reduced in the range of 0.10–0.30
As seen from the above-reviewed literature, biochar has a billion tons/year using biochar. This shows that biochar can
huge application potential in the removal of industrial pol- contribute to reducing the concentration of atmospheric
lutants. However, prior large-scale application, some param- CO2, which leads to GHG’s emission reduction. Otherwise,
eters should be optimized to improve the economic viability Dai et al. (2019) reported that N 2O emissions could be
of the process, namely the type of biochar, local availability reduced by biochar-modified soil. Indeed, the greenhouse
of the source material, pyrolysis temperature, availability of effect of N2O is 310 times higher than that of CO2.
industrial-scale reactors, regeneration method and life span. In the last two decades, a lot of studies dealt with biochar
Given a maximum benefit for the users and a long-term applications related to soil amendment, waste management,
manufacturing for the industry, Dai et al. (2019) observed climate change and energy production as shown in Fig. 6.
that biochars produced using slow and fast pyrolysis condi- This technology involves 4 complementary and often syn-
tions have costs of 18.30 and 8.14 US$/ton, respectively. ergistic social and financial uses, namely:
Also, a survey made by the International Biochar Initiative
(IBI) in 2013 reported that the average price of biochar is • soil improvement (to improve productivity as well as to
globally in the range of 80.00 US$/ton to 13,480.00 US$/ton reduce pollution toxicity),
at sellers’ company. However, a recent survey made in the • climate change mitigation,
13
• energy production and biochar quality and physicochemical factors affecting the
• waste management. contaminants removal efficiency remain on an initial stage.
Therefore, the following research areas should be considered
However, the application of biochar to remove organic or in the near future:
inorganic contaminants and other environmental activates
depends upon the type of biochar used as shown in Fig. 7. 1. Establishing the model for a modified biochar adsorption
Based on the pyrolysis of biomass, biochar was reported mechanism. It is crucial to modify the surface function-
to sequester carbon in soil, to capture C O2 from the atmos- ality and the porosity according to the application. To
phere and to generate biogas. In order to achieve the do so, processes such as amination, sulfonation, surface
sequestration of carbon in the soil, biochar should be able oxidation and pores’ structure modification can bring new
to remain for long time in the soil. This longevity is princi- insights to the preparation of selective biochar materials.
pally related to the mineralization of the biochar over many 2. Developing modified methods to improve adsorption
years. It is worth to investigate the relationship between the efficiency. Many trials should be done to explore other
preparation method/conditions, the feedstock, the micro- modifiers or activators, which impact the efficiency of
structure and the biochar stability over decades. Many biochars to remove organic and inorganic pollutants.
techniques can be used to assess the biochar mineraliza- 3. It would be useful to find the optimum dose and method
tion over time such as infrared spectroscopy, biomarkers, for biochar production allowing it to rapidly remove
nuclear magnetic resonance among others (Weldon et al. various contaminants from wastewater. These are key
2019; Medyńska-Juraszek et al. 2020). However, one can- factors to apply for large-scale implementation in order
not omit the ecotoxicological effects that may arise from to minimize the biochar production and utilization costs.
the mineralization from the biochar itself. This specific 4. The economic visibility of biochar and its regeneration
point needs deep investigation. and standard operating methods in removing toxic pol-
lutants from industrial wastewater are needed today. Bio-
char’s pre-treatment for the removal of toxic compounds
Future perspectives and subsequent biological treatment need more investiga-
tion before possible implementation on a large scale.
It has been demonstrated that biochar is a promising mate- 5. Biochar activated with chemicals showed high adsorp-
rial for water treatment and agricultural soil fertility main- tion capacity to remove pollutants if compared to non-
tenance and remediation. However, studies dedicated to the activated ones. However, absorption mechanisms need
contribution of biochar to the removal of contaminants from further investigation.
wastewaters, the influence of different feedstock sources on
In general, only a few studies were conducted in these
areas, so that further research is required on topics related
to the relationship between raw materials, processing param-
eters, as well as on the biochar regeneration to avoid envi-
ronmental risks as shown in Fig. 8.
Conclusion
The review shows that biochar has broad prospects for the
removal of typical organic and inorganic pollutants pre-
sent in industrial wastewater. It is an interesting type of
adsorbent with high efficiency. It is an eco-friendly sorbing
material owing to its large surface area, charged surface
and functional groups. Biochar showed a great potential to
adsorb inorganic and organic pollutants involving various
mechanisms such as pore filling, electrostatic interactions,
ion exchange, precipitation and surface sorption, which are
dependent upon the physiochemical characteristics of bio-
char such as biochar dosage, pyrolysis temperature and the
Fig. 6 Social and financial involvements of biochar technology pH of the treated matrix. Also, biochar decreases the bio-
(adapted from Joseph et al. 2010) availability, toxicity and mobility of organic and inorganic
13
Fig. 7 Biochar characteristics and suitability for specific applications (adapted from Oliveira et al. 2017)
Fig. 8 Future proposed research mechanism for biochar application
pollutants and reported to be beneficial for the removal Funding Open Access funding provided by EPFL Lausanne.
of contaminants at high concentrations. This review sug-
gests that biochar might be used as an effective, low-cost Compliance with ethical standards
and environmentally friendly adsorbent for the removal
of organic and inorganic pollutants removal in industrial Conflict of interest The authors declare that they have no conflict of
interest arising from this work.
wastewater.
Open Access This article is licensed under a Creative Commons
Acknowledgments This study was supported by the Netherlands Fel- Attribution 4.0 International License, which permits use, sharing,
lowship Programmes (NFP) for capacity building. S.R. thanks EPFL.
13
adaptation, distribution and reproduction in any medium or format, organic compounds in biochar amended soils. Sci Total Environ
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Mechanisms and Adsorption Capacities of Biochar For The Removal of Organic and Inorganic Pollutants From Industrial Wastewater

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International Journal of Environmental Science and Technology (2021) 18:3273–3294