Journal of Environmental Chemical Engineering 10 (2022) 106502

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Adsorption of cadmium and lead from aqueous solution using modified

biochar: A review
Tianqi Liu a, Yelly Lawluvy a, Yang Shi b, Joshua O. Ighalo c, d, Yide He e, Yongjun Zhang e,
Pow-Seng Yap a, *
a
Department of Civil Engineering, Xi’an Jiaotong-Liverpool University, Suzhou 215123, China
b
Department of Architecture and Design, Xi’an Jiaotong-Liverpool University, Suzhou 215123, China
c
Department of Chemical Engineering, Nnamdi Azikiwe University, P. M. B. 5025, Awka, Nigeria
d
Department of Chemical Engineering, University of Ilorin, P. M. B. 1515, Ilorin, Nigeria
e
School of Environmental Science and Engineering, Nanjing Tech University, Jiangsu 211816, China

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

Editor: Teik Thye Lim Cadmium (Cd) and lead (Pb) contaminations are disturbing environmental issues, which cause serious harm to
aqueous systems and human health. Therefore, removing them from aqueous solution is essential to prevent their
Keywords: damage to the environment. Environmental adsorption research as one solution is promising and has been
Modified biochar getting a lot of attention in the recent years. Using modified biochar has proved to be more suitable for the
Cadmium
adsorption of cadmium and lead. In this review, the sources of cadmium and lead in the environment and their
Lead
hazards have been elucidated. In addition, the preparation methods of modified biochar to remove Cd and Pb
Adsorption kinetic models
Adsorption isotherm models have been discussed. This review also presents the adsorption kinetics and isotherms results for the adsorption of
Regeneration Cd and Pb from aqueous solution using modified biochar. The effect of experimental parameters and adsorption
mechanisms are also discussed in order to understand the adsorption performances of modified biochar in great
detail. The adsorption mechanisms were surface precipitation, surface complexation, ion exchange, chelation,
electrostatic attraction, inner sphere complexation, redox and physical adsorption. The adsorption was mainly
endothermic and spontaneous. Additionally, the results on the regeneration of modified biochar are presented to
provide a direction for sustainable improvement. Finally, this review article also provides the challenges,
prospects and future perspectives of adsorption of cadmium and lead from aqueous solutions using the modified
biochar.

1. Introduction
Over 2.1 billion people lack access to safe drinking water [1]. This
water scarcity is further exacerbated by the continuous increase in the
spread of various contaminants in the Earth’s water resources [2].
Heavy metals are one of the major contaminants and they are originated
from both natural and anthropogenic activities [3–5]. Heavy metals,
which have polluted about 40% of the Earth’s lakes and rivers [6], are
not metabolized upon ingestion and accumulate in soft tissues thereby
harming human health [2,4,7,8]. Ailments arising from heavy metal
accumulation in humans range from headaches to vomiting and could
result in death [9]. Aside from the harm to humans, heavy metals in
water bodies destroy marine habitats, and causes harm across the food
chain when contaminated water is absorbed by plants [8].
Cadmium (Cd) and lead (Pb) are amongst the most toxic heavy
metals that are extremely harmful to human health even at low con­
centrations [10,11]. When accumulated in the human body, cadmium
and lead can cause severe damage to the nerves and kidneys [10].
Furthermore, these elements can result in the creation of free radicals in
the human body, which harm proteins, lipids, and DNA [12]. It is
therefore essential that these toxic elements should be removed from the
aqueous environment [9,13]. Numerous technologies have been rec­
ommended for the removal of cadmium and lead from aqueous solutions
[2,4,13,14]. The common treatment processes are physiochemical pro­
cesses such as adsorption, advanced oxidation processes such as pho­
tocatalysis, and electrochemical processes such as electrodeionization
[2].
Adsorption has been a well-proven technology for the removal of

* Corresponding author.
E-mail address: PowSeng.Yap@xjtlu.edu.cn (P.-S. Yap).

https://doi.org/10.1016/j.jece.2021.106502
Received 3 August 2021; Received in revised form 30 September 2021; Accepted 2 October 2021
Available online 7 October 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
T. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 106502

many types of heavy metals [2,11,13]. In addition, adsorption has been
touted as an economical and efficient approach to contaminant removal
from aqueous solutions [11,15,16]. Additional benefits of the adsorption
process include its simplicity, flexibility, resilience, lack of toxic
byproducts, smooth operation, environmental friendliness, versatility,
and ease of regeneration [5,11,17,18]. Numerous adsorbents, including
activated carbon (AC), graphene oxide (GO), bentonite, and biochar,
have been employed in the removal of contaminants from aqueous so­
lutions [13]. Traditional adsorbent such as AC may not be favorable due
to its high production costs and regeneration costs [19,20]. Biochar, on
the other hand, has been found as a feasible alternative for contaminant
removal [21–23].
Biochar is a carbon-rich solid product produced by the pyrolysis of
biomass. It has been widely employed in the removal of contaminants
from aqueous solutions due to its affordability, environmental friendli­
ness, versatility, and high stability [13, 24–28]. In its pristine state,
biochar may have a lesser adsorption capacity than traditional adsor­
bents [26]. To enhance its adsorption capacity, chemical or biological
modifications are typically undertaken [13, 59]. These modifications
range from chemical oxidation, to the deposition of nanotechnologies to
modify biochar surfaces [4,13,14]. Research on biochar modification
techniques is however still an emerging field of study [26]. However,
given the potential environmental and economic benefits of
better-performing modification solutions, it becomes critical for the
further advancement of this research field [4,14]. Although Zhang et al.
[29] had recently published a review paper on the removal of heavy
metals and metalloids using modified biochar, it did not cover adsorp­
tion kinetics and adsorption thermodynamics in detail and the scope was
not specifically on cadmium and lead. Thus, the novelty of our review
article is that we have comprehensively covered the state-of-the-art
progress on the adsorption of cadmium and lead and we have
reviewed in detail the recent developments in all aspects of the
adsorption process (i.e. kinetics, isotherms, thermodynamics, and
regeneration). All the relevant experimental findings were comprehen­
sively summarized in our current review paper. Thus, our paper aims to
address the current research gap on the adsorption of cadmium and lead
from aqueous solutions using various types of modified biochar. As such,
this review article aims to consolidate and highlight the scholarly ad­
vancements in this research field, so as to provide a stepping stone for
further research. To the best of our knowledge, this is the first and
comprehensive review paper on the application of modified biochar to
adsorb cadmium and lead from aqueous solution, which thus serves as
the novelty of our review article.
eruptions, the industrial activities as highlighted in Table 1 contribute
significantly to the cadmium and lead contamination of the aqueous
environment. Upon contaminating the aqueous environment, as illus­
trated in Fig. 1, cadmium and lead contaminants will then enter the food
chain where they are finally consumed by humans, resulting in adverse
effects as liver and kidney problems.
The speciation of Cd and Pb in water is highly dependent on the
solution pH. The adsorption of Cd can be affected by pH values. It had
been elucidated that when pH value is lower than 7.0, Cd2+ mainly
dominates; when pH value is slightly less than 9.0, Cd can be precipi­
tated out as Cd(OH)2; when pH value is 8.0, the species distribution is
about 90% Cd2+ and 10% Cd(OH+), which signifies all species present at
pH 8.0 and below have a positive charge, Cd2+ or Cd(OH)+ [30].
Meanwhile, for Pb, when pH values are from 3.0 to 5.0, the main Pb
species are Pb2+, PbNO3+ and aqueous Pb(NO3)2; when pH value is 6.0,
their concentrations begin to change; when pH value is 6.3, solid Pb
(OH)2 is formed; and the formations of soluble hydroxides aqueous
namely Pb(OH)2, PbOH+ and PbOH3− start after pH 7.0 [31]. Therefore,
Cd and Pb speciation play an important role in adsorption through
surface chemistry.
2.1. Characteristics and hazards of cadmium
Naturally, cadmium occurs through volcanic eruptions, and erosion/
abrasion of rocks and soils [34]. Artificially, it is mainly found as a
byproduct of mining but is also present in waste from industries such as
steel and engineering [32,34]. Cadmium is amongst the most toxic
heavy metals due to its high mobility and bioaccumulative ability that
set it apart from other heavy metals [35]. Cadmium is non-degradable,
persistent and highly toxic to humans, plants, and animals [14,34,36]. In
the human body, cadmium can last between 10 and 35 years upon
exposure which occurs chiefly through oral ingestion, inhalation, and
dermal absorption of cadmium containing water, food, or dust [37].
The recommended limit for cadmium in drinking water by the World
Health Organization is 0.005 mg/L [34]. When this limit is exceeded,
cadmium poisoning arises which leads to such health hazards as hy­
pertension, liver disease, lung disease, kidney disease, and abnormal
physiological development [11,38].

2. Cadmium and lead in the aqueous environment

Aside from natural sources such as weathering rocks and volcano

Table 1
Common anthropogenic sources of cadmium and lead.
Industry Cadmium (Cd) Lead (Pb)

Paper mills ✓ ✓
Organic chemistry ✓ ✓
Allies, Chlorine ✓ ✓
Fertilizers ✓ ✓
Petroleum refinery ✓ ✓
Steel works ✓ ✓
Pharmaceutical ✓ ✓
Engineering ✓ ✓
Fine chemicals ✓ ✓
Dyes ✓ ✓
Pesticides ✓ ✓
Aircraft ✓
Welding ✓
Electroplating ✓
Nuclear fission ✓
Fig. 1. Hazards of cadmium and lead and their cycle in the environment
Source: Adapted from [32]. Adapted from [33].

2
T. Liu et al.
2.2. Characteristics and hazards of lead
Lead is one of the first metals discovered by humans. Due to such
unique properties as resistance to corrosion, low melting point, high
malleability, and softness, lead has been widely used in many industries
[39]. The many uses of lead have resulted it to be one of the most
widespread heavy metals in natural water [16,40]. Lead typically occurs
through such industrial sources as lead smelting, battery recycling, and
coal combustion [39]. From such sources, lead may enter the human
system through ingestion, inhalation, or skin contact [39–41].
The recommended limit for lead in drinking water by the World
Health Organization is 0.01 mg/L [32]. When this limit is exceeded, the
lead in the human system can affect almost all organs in the body [16,
40]. Though the nervous system is typically the most affected by lead,
lead can also cause serious and lethal harm to the hematopoietic system,
the reproductive system, the skeletal system, and the lungs [32, 39–41].
The hazardous nature of lead is further demonstrated by the over 500,
000 deaths caused by lead exposure each year [42].
3. Preparation of modified biochar
In this section, chemical and biological modifications are discussed
to give a comprehensive understanding about how to prepare modified
biochars (summarized in Table 2). There are three important factors that
are type of biomass, pyrolysis conditions, and modification agents.
Biochar is a carbon-rich substance that can be prepared from a variety of
biomass or feedstock such as corncob, crayfish shell, cow bone meal
powder, corn stalk, and etc. Pyrolysis conditions conduct temperature,
atmosphere, duration, and heating rate, which play an important role
during the preparation of modified biochar. Normally, the range of
temperature is from 350 ℃ to 750 ℃. Nitrogen is used to provide an
absence of oxygen surrounding. Duration time is commonly 1-2 h.
Generally, heating rate range is 5-20 ℃ min-1. Different modification
methods are developed according to different environmental application
fields [43–52]. Based on the summary in Table 2, chemical modification
agents mainly involve MgCl2, Fe(NO3)3, KMnO4, Fe2(SO4)3, FeSO4,
iminodiacetic acid, Fe3O4, NaOH, acrylonitrile, KOH, Na2HPO4, MgO,
H2O2, chitosan, ethylenediaminetetraacetic acid (EDTA), and FeCl3.
Shrimp bran and digestive system of cow as biological modifications can
transform fresh corn straw to a modified biochars [57, 59]. After shrimp
bran modification, pore structure distribution, surface functionalities,
surface morphology, chemical composition, and pHpzc are changed
[57]. Additionally, digestive system of cow can improve oxygen-­
containing functional group, surface area, and mineral components,
which can achieve a higher sorption capacity for cadmium [59].
In summary, it was observed that acids, bases, metal ions and oxi­
dants are among the most prominent techniques for the modification of
biochar for adsorbing cadmium and lead from aqueous media. These
techniques affect the biochar in a variety of ways that can lead to its
improved performance. Firstly, there is the addition of more functional
group that can introduce other types of physico-chemical interactions
with the heavy metals. The physical nature of the biochar can also be
transformed making it more hydrophilic. Modification is also able to
adjust the biochars’ isoelectric point and induce a stronger electrostatic
interaction for the uptake of cadmium and lead. In future studies, we
predict that researchers will endeavour to investigate even more intri­
cate techniques for biochar modification so as to push the threshold of
cadmium and lead adsorptive uptake performance to be even higher.
4. Adsorption performances of modified biochar for the
adsorption of cadmium and lead from water
4.1. Adsorption kinetics
Adsorption kinetics can demonstrate the relationship between the
amounts of metal ions adsorbent adsorbed onto biochar with time. The
3
Journal of Environmental Chemical Engineering 10 (2022) 106502
relationship can reveal the basic kinetics theory in the adsorption study
of cadmium and lead from aqueous solution. The types of kinetic models
mainly include pseudo-first-order (PFO) model, pseudo-second-order
(PSO) model, Elovich model, Avrami fractional-order model, intra­
particle diffusion (IPD) model, and liquid film diffusion model [13,63,
65,67,69–73]. It is also noteworthy that there are other models which
are beneficial for adsorption or adsorption-diffusion modeling,
including nonlinear film transfer model, branched pore diffusion model,
parabolic diffusion model, second-order reversible reaction model,
two-site nonequilibrium model, hyperbolic model, and mixed-order rate
equation model [63, 74–79].
There are many factors that might influence the performance of
adsorption kinetics, such as experimental parameters, adsorbate types,
and adsorbents [53,55,56]. Additionally, the adsorption kinetics model
should ideally describe the internal kinetics, which is the chemical ki­
netics of adsorbent surfaces with no migration restrictions [63]. Deng
et al. [89] report that the kinetics model can be used to describe the
adsorption process of modified corn straw biochar and peanut shell
biochar. Additionally, a suitable kinetics model type might be selected to
reflect the adsorption kinetics of lead ions on modified biochar [91-93].
Table 3 shows the experimental details of adsorption kinetics for the
removal of cadmium and lead.
4.1.1. Pseudo-first-order model
Largergren in 1898 presented the PFO equation for the adsorption of
malonic acid and oxalic acid by charcoal [94]. The PFO model is an
adsorption-reaction model. The original equation and linearized form of
PFO are shown as below [94]:
dq/dt = k1 (qe − q) (1)
ln(qe /(qe − q)) = k1 t (2)
where q (mg/g) and qe (mg/g) are adsorption capacity at time t and
equilibrium; k1 (min− 1) is the rate constant; t (min) is contact time. This
function with a slope k1 is a straight line passing the origin point. The
rate constant k1 as a function of the process conditions depends on initial
bulk concentration [95–98]. They are further reported that the rate
constant is decreased when the initial bulk concentration is increased.
1/k1 can be regarded as the time scale during the equilibrium process. If
the initial concentration is larger, the time for the process to reach
equilibrium will be longer. The rate constant k1 can be regarded as the
reaction rate constant. Additionally, some researchers report that k1 is
independent of the initial concentration [99,100]. The PFO is one of the
most widespread models in the study of environmental adsorption ki­
netics, and while PFO fits better at high intial concentrations [101],
there are some exceptions [102–104]. From Table 3, it was noticed that
initial concentrations of around 100 mg/L (for Cd) and 120 mg/L (for
Pb) are commonly employed in the experiments. Additionally, the
equilibrium behavior is influenced by pH and experimental tempera­
ture. The solution pH was mainly 5.0–7.0 and the adsorption was
commonly conducted in room temperature . The PFO model is consid­
ered to be valid when the system is at the initial adsorption stage and
reaching the equilibrium [63,105,106]. The experimental results can be
affected by adsorbent dosage and concentration range. These high var­
iabilities of experimental conditions cause there is no consensus on
standard operating conditions [107,108]. Adsorption efficiency also
depends on the surface cover and experimental conditions. Therefore,
the validity of the model is limited to a certain range of operations.
4.1.2. Pseudo-second-order model
The uptake rate of PSO model is assumed as second order, which is
relative to the effective surface position [63]. The PSO model is an
adsorption-reaction model. There are other available linearized forms,
whereas the frequently used original equation and linearized form of
PSO are shown as below [109,110]:
T. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 106502

Table 2
Modification method/condition of biochar to remove Cd and Pb.
Type of modified biochar Type of Pyrolysis conditions Modification agents Heavy References
biomass metals
Temperature Atmosphere Duration Heating
(℃) (h) rate (℃
min-1)

15%Mg-Biochar (15%Mg-BC) Corncob 450 N2 1 10 MgCl2⋅6H2O Cd and [53]

Pb
MgCl2 modified biochar Crayfish shell 600 N2 2 - MgCl2 Cd [54]
(MgC600)
FeOx- modified bone biochar Cow bone 450 N2 2 10 Fe(NO3)3 Cd and [55]
pyrolyzed at 450 oC (FO-BC- meal powder Pb
450)
MnOx- modified bone biochar Cow bone 600 N2 2 10 KMnO4 Cd and [55]
pyrolyzed at 600 oC (MO-BC- meal powder Pb
600)
Magnetically modified water Water 700 N2 2 - Fe2(SO4)3 and FeSO4 Cd [56]
hyacinth biochar pyrolyzed at hyacinth
700 oC (MBC7)
Biochar modified with shrimp Typha 600 N2 1 20 Shrimp bran Cd [57]
bran (BCS) orientalis
Manganese-modified biochar Corn stalk 500 N2 2 - KMnO4 Cd [58]
pyrolyzed at 500 oC with 5:1
modification ratio (MBC2-500-
5:1)
Transabdominal transformation Fresh corn 600 N2 2 5 Digestive system of cow Cd [59]
modified biochar pyrolyzed at straw
600 oC (TCB600)
Iminodiacetic acid modified Palm fiber 400 N2 2 10 Iminodiacetic acid and Fe3O4 Cd [24]
magnetic biochar (MBCI)
KMnO4 impregnation treatment Rape straw 600 N2 1 10 KMnO4 Cd [60]
of modified biochar (BC-MnOx)
Alkaline treatment of modified Rape straw 600 N2 1 10 NaOH Cd [60]
biochar (BC-NaOH)
Acrylonitrile modified biochar Raw corncobs 350 N2 2 15 Acrylonitrile Cd [61]
pyrolyzed at 350 oC (MBC350)
KOH-modified biochar (ABC) Rice straw 500 Absence of 2 20 KOH Cd [62]
oxygen
Phosphate-modified activated Bamboo 750 - 2 - Na2HPO4 Cd [45]
bamboo biochar pyrolyzed at
750 oC (pm-BC3c)
Oxide–rice husk biochar Rice husk 350 N2 4 5 MgO Cd [64]
composite (MgO–BCR)
H2O2 modified biochar (HP-BC) Watermelon 350 N2 0.25 - H2O2 Pb [20]
seeds
Chitosan and Peanut shell 500 N2 2 5 Chitosan, Pb [66]
ethylenediaminetetraacetic ethylenediaminetetraacetic
acid modified magnetic biochar acid (EDTA), and FeCl3
(E-CMBC)
Chitosan-modified pine wood Pine wood 425 - 0.006- - Chitosan Pb [52]
biochar (CMBC) chips 0.008
Mn oxide-modified pine biochar Loblolly pine 600 N2 1 10 MnCl2⋅4H2O Pb [68]
(MPB) (Pinus taeda)
wood
Birnessite-modified pine biochar Loblolly pine 600 N2 1 10 KMnO4 Pb [68]
(BPB) (Pinus taeda)
wood

dq/dt = k2 (qe − q)2
/
t/q = 1 (k2 q2e ) + t/qe
where k2qe2 and t/q are the initial rate of adsorption and a straight line
for PSO model, respectively. 1/qe is the slope and 1/ k2qe2 is the inter­
cept. The rate constant k2 as a time scale is similar to k1 of PFO, which is
decrease with the increase of q value [111]. Furthermore, the rate
constant k2 (gmg− 1/min) can be regarded as the reaction rate constant.
The calculated values of q are generally approximate but less than the
experimental values. Therefore, it is recommended that the experi­
mental values can contribute to a check on the calculated values. The
PSO model can well simulate most of the environmental adsorption ki­
netic models, showing that it is superior to other models such as PFO
(3) [63]. Temperature and pH could affect the constant k2, which should be
further studied. Furthermore, the shape of the equilibrium isotherm
(4) might also have an effect on the constant k2. An adsorption-diffusion
model based on Langmuir surface reaction and pore diffusion are re­
ported by Douven et al. [112], which can be used to fit PSO kinetics.
Meanwhile, reaction control and the amount of adsorption should be
meet the experimental conditions. If particle swarm dynamics cannot be
simulated by the PSO model, they might be controlled by other mech­
anisms. The PSO model can also correlate the board spectrum dynamics
for almost all liquid adsorption systems [113–115].
From Table 3, the solution pH was mainly slightly acidic or near
neutral while the adsorbent mass was noticed to be mainly 0.10 g for Cd
and Pb experimental tests. The values of qe obtained from PSO model are
usually quite different from those obtained from the PFO model [115,

4
T. Liu et al.
116]. The random errors of qe values in the process of linearization of
PSO model may vary greatly than that of PFO model which may be
indicated by R2. When the R2 in PSO model is higher than that of PFO
model, the adsorption mechanism of heavy metal ions might include
chemisorption. In most adsorption research, it is generally assumed that
the adsorption process is carried out in a reaction-controlled state and it
is not clear whether any efforts have been made to eliminate migration
effects [63]. A lumped analysis is necessary whether it is a batch or
continuous system design [117,118]. The rate constant k1 and k2 under
specific experimental conditions might be lumped constants of the
combination of diffusion effects and reaction. These lumped constants
are merely empirical constants without physico-chemical significance
according to the underlying adsorption mechanism. Meanwhile, the
mixed reaction-diffusion rate constant is difficult to address the mech­
anism of the intrinsic kinetics. If the obtained rate constant is not the
mixed reaction-diffusion rate constant but the reaction rate constant,
then the adsorption activation energy can be elucidated using the
Arrhenius equation [119–121]. Both PSO and PFO models are related to
surface reaction control systems [104,122,123] although PFO model
also can be derived through hypothetical film diffusion control [124]. In
a study from Plazinski et al. [125], they indicated that the PSO and PFO
models are not only the exemplification of surface reaction-controlled
kinetics but also highly flexible formulas that combine diverse control­
ling mechanisms and models. Improved data fit and experimental con­
ditions could provide an appropriately controlled regime [126].
Furthermore, the limitation of PSO and PFO is that they are lacking a
theoretical basis because they are not derived from presupposed reac­
tion mechanisms [127].
4.1.3. Elovich model
The Elovich equation is originally proposed by Zeldovich and
Roginsky in 1934 to adsorb CO by using manganese dioxide [128]. The
more popular applied equations are the original equation and linearized
form, which are expressed as below [128]:
dq/dt = αe− βq
(5)
q = (ln(αβ))/β + (lnt)/β (6)
where one assumption is αβt >> 1; 1/β and ln(αβ)/ β are the slope and
intercept, respectively; α (mg/g) is the initial constant adsorption rate; β
(g/mg) is a desorption constant related to chemisorption activation
energy and surface coverage. The Elovich model can describe chemi­
sorption well [129]. The model has also been applied in the liquid phase
kinetics modelling. Moreover, Largitte and Pasquier [130] claimed that
the Elovich model was most suitable for the adsorption of lead by acti­
vated carbon. A study from Ramola et al. [131] indicates that the
regression parameters of lead adsorption can be analyzed by the Elovich
model. The constant α and β in a physical sense can increase along with
the growth of the initial dye concentration. With the increase of the
solution temperature, the value of constant α aggrandizes, while the
value of constant β reduces [132]. Theoretically, the Elovich model can
forecast an infinite q over a long period of time, which applies to kinetics
far from equilibrium when there is no desorption due to low surface
coverage. According to a theoretical basis of the Elovich linearized form,
it is assumed that the surface of the adsorbent is highly heterogeneous
[133].
4.1.4. Avrami fractional-order model
The adsorption rate coefficient might be time-dependent during the
adsorption process [134]. Avrami fractional-order model can be used to
describe this kinetic behaviour. The original equation and linearized
form of Avrami fractional-order model as shown as below [135–137]:
dq/dt = k1 ∙n∙tn− 1 (qe − q) (7)
ln(ln(qe /(qe − q)) ) = n∙lnk1 + n∙lnt (8)
5
Journal of Environmental Chemical Engineering 10 (2022) 106502
where k1 (min− 1) is the Avrami kinetic constant; n is the constant for the
adsorption mechanism. The constant k1 and n can be calculated from the
intercept and slope by plotting the relationship ln(ln(qe/(qe-q))) and lnt.
The straight lines can be found to obtain these two values. Furthermore,
the kinetics of fractional orders should be taken into account in this
model. Normally, the general order model can remedy the deficiencies
of PFO and PSO by presupposing the order of integral reaction [138].
The reaction order n of the general order should be decided by an
experiment. Considering fractional orders, the Avrami equation should
be transferred into the integral form. The equation is:
q = qe − qe e− k1 t n
(9)
where n can be changed to a fraction or integer. When n = 1, the result is
the same as the integral form of PFO equation.
4.1.5. Intraparticle diffusion model (IPD)
IPD is first proposed for adsorption kinetics by Weber and Morris in
1963 [139]. This model is also named as Weber-Morris model. The
linearized equation of IPD can be expressed as below [139]:
√̅
q = kid t + C (10)
where kid is the rate constant (mg/(g•min0.5)) in the adsorption kinetics
model. C is the initial adsorption (mg/g). These two parameters kid and
C are the slope and intercept, respectively. When the initial adsorptive
concentration increases, generally the values of kid may increase
[140–142], as the results can be inferred that the rate constant might
change the state of ion exchange leading to adsorption capacity change.
Furthermore, the behaviour of an IPD can be simulated by the PSO
model according to the study [125]. If the kinetics model is completely
controlled by IPD, this plot should go through the original point (C=0)
[143–145]. Nevertheless, in most studies, a better fit plot can be ob­
tained if the line is not forced through the original point (C>0) and
multiple linearity is displayed throughout the adsorption period
[146–148]. Generally, multiple linearity refers to the multiple mecha­
nisms that control the procedure [149]. Each line segment can represent
one control mechanical system or more simultaneous control mechani­
cal systems. The whole process begins with the surface adsorption or
instantaneous adsorption until the system equilibrium. Adsorption be­
comes slow when the surface cover approaches saturation and pore
diffusion rate constant reduces, thereby the role of IPD is abate [150].
Each line segment is arbitrary in the time period according to the kinetic
data. The large value of C can make the greater film diffusion resistance.
Meanwhile, the higher liquid concentration can improve the IPD rate
constant [151]. In the whole adsorption process, the time of film
diffusion is very short, which can rule out the model derivation [112].
The combined influences of surface reaction control and film diffusion
can be demonstrated by IPD [152]. This model is previously used to
investigate batch processes [153]. However, the initial adsorption sit­
uation (t = 0) has rarely been studied.
4.1.6. Liquid film diffusion model
In a system dominated by membrane diffusion, when the cumulative
amount of adsorption on the surface of the adsorbent is equal to the
adsorption diffusion rate through the liquid film (bound layer), the
concentration of absorbed body fluid phase can be expressed as below
[154]:
dC/dt = − kf (C − Cs ) (11)
where kf is the film diffusion coefficient (min− 1); Cs is the adsorbate
concentration of the liquid-solid interface (mg/L). The value Cs is
insignificantly small at short times. The equation is one type of
adsorption-diffusion model. Additionally, Eq. (11) can be integrated
shown as below:
 T. Liu et al.
Table 3
Adsorption kinetics for the removal of Cd and Pb.
Heavy Adsorption Experimental details Types of modified biochar References
metals kinetic
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g speed time (h)
pollutant (mg (mL) L− 1) or mass (rpm)
L− 1 ) (g)

K1 (min-1) qe, calculated R2

(mg g¡1)
1
Cd PFO 100 298.15 – 50 1.00 g L− 160 24 0.0037 27.38 0.9010 Hydroxyapatite synthesized with [72]
sludge-based biochar (HAP-SSBC)
1
Cd PFO 300 298.15 5.00 ± 0.05 – 0.50 g L− 100 48 0.0297 153.61 0.7300 Mg-coated biochar (MgBC400) [13]
Cd PFO 50 298.15 5.0 * 50 0.01 g 180 24 2.2810 77.86 0.6175 15%Mg-Biochar (15%Mg-BC) [53]
1
Cd PFO 50 298.00 5.0 200 0.50 g L− 160 12 0.0490 20.86 0.9720 FeOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (FO-BC-300)
1
Cd PFO 50 298.00 5.0 200 0.50 g L− 160 12 0.0750 39.28 0.9840 FeOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (FO-BC-450)
1
Cd PFO 50 298.00 5.0 200 0.50 g L− 160 12 0.0740 35.51 0.9940 FeOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (FO-BC-600)
− 1
Cd PFO 50 298.00 5.0 200 0.50 g L 160 12 0.1000 23.70 0.9830 MnOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (MO-BC-300)
− 1
Cd PFO 50 298.00 5.0 200 0.50 g L 160 12 0.1020 35.08 0.9850 MnOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (MO-BC-450)
1
Cd PFO 50 298.00 5.0 200 0.50 g L− 160 12 0.0610 51.71 0.9870 MnOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (MO-BC-600)
Cd PFO 400 298.00 – – 0.05 g 150 24 0.0161 5.73 0.6294 Modified rice straw [80]
6

308.00 0.0212 9.51 0.6846

318.00 0.0239 18.61 0.4961
Cd PFO 100 298.15 4.0 ± 0.1 10 0.01 g 120 24 0.0600 ± 0.0150 5.35 ± 0.26 0.8730 Goethite modified biochar [81]
pyrolyzed at 600 ℃ with 1 mass
ratio of Fe/BC (GMB-600–1)
1
Cd PFO 120 298.00 5.5 50 0.50 g L− 220 24 0.2500 53.71 0.4471 Modified vermicompost biochar [82]
(MVBC)
1
Cd PFO 72 293.00 2.5–6.9 100 0.10 g L− 180 12 0.0241 58.48 0.9838 Modified rice straw-derived [73]
303.00 0.0470 63.38 0.9797 biochar with -NH2 groups (BC-

Journal of Environmental Chemical Engineering 10 (2022) 106502

313.00 0.0538 67.61 0.9611 NH2)
Cd PFO 100 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0382 41.49 0.8750 Transabdominal transformation [59]
modified biochar pyrolyzed at
300 ℃ (TCB300)
Cd PFO 100 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0359 43.89 0.8870 Transabdominal transformation [59]
modified biochar pyrolyzed at
400 ℃ (TCB400)
Cd PFO 100 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0205 58.25 0.8630 Transabdominal transformation [59]
modified biochar pyrolyzed at
500 ℃ (TCB500)
Cd PFO 100 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0153 78.48 0.9480 Transabdominal transformation [59]
modified biochar pyrolyzed at
600 ℃ (TCB600)
Cd PFO 100 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0158 81.98 0.9550 Transabdominal transformation [59]
modified biochar pyrolyzed at
700 ℃ (TCB700)
(continued on next page)
 T. Liu et al.
Table 3 (continued )
Heavy Adsorption Experimental details Types of modified biochar References
metals kinetic
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g speed time (h)
pollutant (mg (mL) L− 1) or mass (rpm)
L− 1 ) (g)

Cd PFO 100 293.15 5.0 50 0.05 g 150 24 0.0051 14.44 0.6010 Titanium-modified ultrasonic [83]
biochar (BCTD)
Cd PFO 100 298.15 – 100 0.10 g 140 8 0.0080 ± 0.0010 35.08 ± 0.59 0.9850 Modified biochar added 0.25 g [84]
cystamine (C0.25)
Cd PFO 100 298.15 – 100 0.10 g 140 8 0.0070 ± 0.0010 60.30 ± 1.00 0.9870 Modified biochar added 0.50 g [84]
cystamine (C0.50)
Cd PFO 100 298.15 – 100 0.10 g 140 8 0.0070 ± 0.0010 75.28 ± 1.16 0.9780 Modified biochar added 0.75 g [84]
cystamine (C0.75)
Cd PFO 100 298.15 – 100 0.10 g 140 8 0.0090 ± 0.0010 25.10 ± 0.60 0.9640 Modified biochar added 0.10 g [84]
cystamine (C0.10)
Cd PFO 100 298.15 – 100 0.10 g 140 8 0.0060 ± 0.0010 2.86 ± 0.07 0.9760 Modified biochar added 1.25 g [84]
cystamine (C1.25)
Cd PFO 5 298.15 – 50 0.10 g 180 2 0.0006 – 0.9930 Modified reed biochar (MRBC) [85]
308.15 0.0007 0.9960
318.15 0.0007 0.9990
1
Cd PFO 100 293.00 6.0 – 1.00 g L− – 12 0.0072 50.50 0.9470 Magnetic modified oxidized [24]
biochar (MBCO)
1
Cd PFO 100 293.00 6.0 – 1.00 g L− – 12 0.0073 68.12 0.9160 Iminodiacetic acid modified [24]
magnetic biochar (MBCI)
Cd PFO 20 298.15 – 40 0.05 g 200 24 0.3455 6.99 0.9760 KMnO4 impregnation treatment of [60]
modified biochar (BC-MnOx)
Cd PFO 20 298.15 – 40 0.05 g 200 24 0.3447 6.92 0.9410 Alkaline treatment of modified [60]
7

biochar (BC-NaOH)
Cd PFO 100 298.15 6.8 ± 0.2* 25 0.05 g 180 24 0.0050 4.18 0.6160 Acrylonitrile modified biochar [61]
pyrolyzed at 350 ℃ (MBC350)
Cd PFO 100 298.15 6.8 ± 0.2* 25 0.05 g 180 24 0.0047 6.21 0.7560 Acrylonitrile modified biochar [61]
pyrolyzed at 450 ℃ (MBC450)
Cd PFO 100 298.15 6.8 ± 0.2* 25 0.05 g 180 24 0.0048 7.16 0.8190 Acrylonitrile modified biochar [61]
pyrolyzed at 550 ℃ (MBC550)
− 1
Cd PFO 210 298.15 7.2 – 1.00 g L 120 24 0.0352 202.28 0.9600 Phosphate-modified activated [45]
bamboo biochar pyrolyzed at
750 ℃ (pm-BC3c)

Journal of Environmental Chemical Engineering 10 (2022) 106502

Cd PFO 550 298.15 6.0 20 0.10 g 180 24 0.1230 81.13 0.9519 Modified rice straw-derived [86]
biochar (BCM)

K2 (g mg¡1 qe, calculated R2

min¡1) (mg g¡1)
1
Cd PSO 100 298.15 – 50 1.00 g L− 160 5.552 × 10-− 4
94.16 0.9998 Hydroxyapatite synthesized with [72]
sludge-based biochar (HAP-SSBC)
1
Cd PSO 300 298.15 5.00 ± 0.05 – 0.50 g L− 100 48 6.333 × 10-− 5
191.20 0.9900 Mg-coated biochar (MgBC400) [13]
Cd PSO 50 298.15 5.0 * 50 0.01 g 180 24 0.0434 83.49 0.7544 15%Mg-Biochar (15%Mg-BC) [53]
1
Cd PSO 50 298.00 5.0 200 0.50 g L− 160 12 0.0148 21.08 0.9980 FeOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (FO-BC-300)
1
Cd PSO 50 298.00 5.0 200 0.50 g L− 160 12 0.0032 40.73 0.9990 FeOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (FO-BC-450)
1
Cd PSO 50 298.00 5.0 200 0.50 g L− 160 12 0.0079 36.02 0.9990 FeOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (FO-BC-600)
1
Cd PSO 50 298.00 5.0 200 0.50 g L− 160 12 0.0020 23.22 0.9980 MnOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (MO-BC-300)
− 1
Cd PSO 50 298.00 5.0 200 0.50 g L 160 12 0.0028 37.34 0.9990 MnOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (MO-BC-450)
(continued on next page)
 Table 3 (continued )

T. Liu et al.
Heavy Adsorption Experimental details Types of modified biochar References
metals kinetic
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g speed time (h)
pollutant (mg (mL) L− 1) or mass (rpm)
L− 1 ) (g)
1
Cd PSO 50 298.00 5.0 200 0.50 g L− 160 12 0.0065 52.25 0.9990 MnOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (MO-BC-600)
Cd PSO 100 298.15 7.0 25 0.02 g 200 24 0.0150 38.00 0.9800 Enteromorpha prolifera biochar [87]
modified by KMnO4 (KBC)
Cd PSO 22.82 298.15 6.0–7.5 300 0.05 g 100 24 0.0263 119.18 0.9900 Biochar-supported nanoscale [88]
zerovalent iron (BC-nZVI)
Cd PSO 400 298.00 – – 0.05 g 150 24 0.0031 6.44 0.7537 Modified rice straw [80]
308.00 0.0036 10.13 0.7831
318.00 0.0023 19.62 0.6240
Cd PSO 100 298.15 4.0 ± 0.1 10 0.01 g 120 24 0.0230 ± 0.0090 5.49 ± 0.28 0.8860 Goethite modified biochar [81]
pyrolyzed at 600 ℃ with 1 mass
ratio of Fe/BC (GMB-600–1)
1
Cd PSO 120 298.00 5.5 50 0.50 g L− 220 24 0.0060 56.27 0.6809 Modified vermicompost biochar [82]
(MVBC)
Cd PSO 72 293.00 2.5–6.9 100 0.10 g 180 12 0.0006 62.22 0.9699 Modified rice straw-derived [73]
303.00 0.0011 66.54 0.9763 biochar with -NH2 groups (BC-
313.00 0.0012 70.81 0.9717 NH2)
Cd PSO 100 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0014 44.39 0.9420 Transabdominal transformation [59]
modified biochar pyrolyzed at
300 ℃ (TCB300)
Cd PSO 100 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0013 46.91 0.9360 Transabdominal transformation [59]
modified biochar pyrolyzed at
400 ℃ (TCB400)
Cd PSO 100 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0005 62.40 0.9350 Transabdominal transformation [59]
modified biochar pyrolyzed at
8

500 ℃ (TCB500)
Cd PSO 100 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0003 85.22 0.9490 Transabdominal transformation [59]
modified biochar pyrolyzed at
600 ℃ (TCB600)
Cd PSO 100 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0003 88.76 0.9470 Transabdominal transformation [59]
modified biochar pyrolyzed at
700 ℃ (TCB700)
Cd PSO 100 293.15 5.0 50 0.05 g 150 24 0.0009 72.05 0.9990 Titanium-modified ultrasonic [83]
biochar (BCTD)

Journal of Environmental Chemical Engineering 10 (2022) 106502

Cd PSO 100 298.15 – 100 0.10 g 140 8 0.0003 39.03 ± 0.01 0.9850 Modified biochar added 0.25 g [84]
cystamine (C0.25)
Cd PSO 100 298.15 – 100 0.10 g 140 8 0.0001 68.31 ± 0.13 0.9870 Modified biochar added 0.50 g [84]
cystamine (C0.50)
Cd PSO 100 298.15 – 100 0.10 g 140 8 0.0001 85.41 ± 0.43 0.9780 Modified biochar added 0.75 g [84]
cystamine (C0.75)
Cd PSO 100 298.15 – 100 0.10 g 140 8 0.0004 27.73 ± 0.36 0.9640 Modified biochar added 0.10 g [84]
cystamine (C0.10)
Cd PSO 100 298.15 – 100 0.10 g 140 8 0.0021 3.31 ± 0.05 0.9760 Modified biochar added 1.25 g [84]
cystamine (C1.25)
Cd PSO 5 298.15 7.0 50 0.10 g 180 2 0.0003 – 0.9660 Modified reed biochar (MRBC) [85]
308.15 0.0004 0.9760
318.15 0.0004 0.9840
1
Cd PSO 100 293.00 6.0 – 1.00 g L− – 12 0.0001 62.98 0.9960 Magnetic modified oxidized [24]
biochar (MBCO)
− 1
Cd PSO 100 293.00 6.0 – 1.00 g L – 12 0.00003 92.04 0.9970 Iminodiacetic acid modified [24]
magnetic biochar (MBCI)
Cd PSO 20 298.15 – 40 0.05 g 200 24 0.2410 7.288 0.9970 KMnO4 impregnation treatment of [60]
modified biochar (BC-MnOx)
(continued on next page)
 Table 3 (continued )

T. Liu et al.
Heavy Adsorption Experimental details Types of modified biochar References
metals kinetic
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g speed time (h)
pollutant (mg (mL) L− 1) or mass (rpm)
L− 1 ) (g)

Cd PSO 20 298.15 – 40 0.05 g 200 24 0.2369 7.239 0.9980 Alkaline treatment of modified [60]
biochar (BC-NaOH)
Cd PSO 100 298.15 6.8 ± 0.2* 25 0.05 g 180 24 0.0057 45.52 0.9990 Acrylonitrile modified biochar [61]
pyrolyzed at 350 ℃ (MBC350)
Cd PSO 100 298.15 6.8 ± 0.2* 25 0.05 g 180 24 0.0050 34.55 0.9990 Acrylonitrile modified biochar [61]
pyrolyzed at 450 ℃ (MBC450)
Cd PSO 100 298.15 6.8 ± 0.2* 25 0.05 g 180 24 0.0037 23.35 0.9990 Acrylonitrile modified biochar [61]
pyrolyzed at 550 ℃ (MBC550)
1
Cd PSO 210 298.15 7.2 – 1.00 g L− 120 24 0.0002 224.34 0.9000 Phosphate-modified activated [45]
bamboo biochar pyrolyzed at
750 ℃ (pm-BC3c)
Cd PSO 550 298.15 6.0 20 0.10 g 180 24 0.0022 85.83 0.9894 Modified rice straw-derived [86]
biochar (BCM)

α (mg g¡1 β (g mg¡1) R2

min¡1)
1
Cd Elovich 300 298.15 5.00 ± 0.05 – 0.50 g L− 100 48 – – 0.9400 Mg-coated biochar (MgBC400) [13]

Ki1 (mg g¡1 Ki2 (mg Ki3 (mg C (mg g¡1) R2

min¡0.5) g¡1 g¡1
min¡0.5) min¡0.5)
1
Cd IPD 100 298.15 – 50 1.00 g L− 160 24 3.4720 0.8299 0.2592 43.22 0.9349 Hydroxyapatite synthesized with [72]
sludge-based biochar (HAP-SSBC)
− 1
Cd IPD 300 298.15 5.00 ± 0.05 0.50 g L 100 48 0.77–0.88 Mg-coated biochar (MgBC400) [13]
9

– – – – –
Cd IPD 50 298.15 5.0 * 50 0.01 g 180 24 13.0719 – – 47.37 0.9555 15%Mg-Biochar (15%Mg-BC) [53]
1
Cd IPD 120 298.00 5.5 50 0.50 g L− 220 24 3.2100 - – 27.81 0.9416 Modified vermicompost biochar [82]
- 3.2000 21.86 0.9482 (MVBC)
1
Cd IPD 100 293.00 6.0 – 1.00 g L− – 12 5.6990 - - -5.10 0.9968 Magnetic modified oxidized [24]
- 1.7910 - -29.97 0.9690 biochar (MBCO)
- - 0.0220 -57.08 0.9089
1
Cd IPD 100 293.00 6.0 – 1.00 g L− – 12 9.3480 - - -9.47 0.9951 Iminodiacetic acid modified [24]
- 2.1470 - -50.57 0.9963 magnetic biochar (MBCI)
- - 0.4860 -79.99 0.9812

Journal of Environmental Chemical Engineering 10 (2022) 106502

Cd IPD 20 298.15 – 40 0.05 g 200 24 0.0307 – – – 0.7040 KMnO4 impregnation treatment of [60]
modified biochar (BC-MnOx)
Cd IPD 20 298.15 – 40 0.05 g 200 24 0.3239 – – – 0.7120 Alkaline treatment of modified [60]
biochar (BC-NaOH)
− 1
Cd IPD 210 298.15 7.2 – 1.00 g L 120 24 6.6899 – – 87.13 0.3700 Phosphate-modified activated [45]
bamboo biochar pyrolyzed at
750 ℃ (pm-BC3c)

Kfd (min¡1) R2
− 1
Cd Liquid film 100 298.15 – 50 1.00 g L 160 24 0.0037 0.9010 Hydroxyapatite synthesized with [72]
diffusion sludge-based biochar (HAP-SSBC)

K1 (min-1) qe, calculated R2

(mg g-1)
1
Pb PFO 300 298.15 5.00 ± 0.05 – 0.50 g L− 100 48 0.0867 412.34 0.8900 Mg-coated biochar (MgBC400) [13]
Pb PFO 100 298.15 5.0 * 50 0.01 g 180 24 0.5546 278.93 0.9121 15%Mg-Biochar (15%Mg-BC) [53]
1
Pb PFO 120 298.00 5.0 200 0.50 g L− 160 12 0.1100 125.02 0.9970 FeOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (FO-BC-300)
1
Pb PFO 120 298.00 5.0 200 0.50 g L− 160 12 0.1400 173.74 0.9970 FeOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (FO-BC-450)
(continued on next page)
 T. Liu et al.
Table 3 (continued )
Heavy Adsorption Experimental details Types of modified biochar References
metals kinetic
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g speed time (h)
pollutant (mg (mL) L− 1) or mass (rpm)
L− 1 ) (g)
1
Pb PFO 120 298.00 5.0 200 0.50 g L− 160 12 0.1280 150.92 0.9960 FeOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (FO-BC-600)
1
Pb PFO 120 298.00 5.0 200 0.50 g L− 160 12 0.1730 156.35 0.9880 MnOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (MO-BC-300)
1
Pb PFO 120 298.00 5.0 200 0.50 g L− 160 12 0.2090 174.56 0.9860 MnOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (MO-BC-450)
− 1
Pb PFO 120 298.00 5.0 200 0.50 g L 160 12 0.2030 208.73 0.9940 MnOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (MO-BC-600)
Pb PFO 50 298.15 7.0 50 0.10 g 180 2 0.0019 – 0.9360 Modified reed biochar (MRBC) [85]
308.15 0.0024 0.9560
318.15 0.0022 0.9580
Pb PFO 100 298.15 5.0 30 – 200 24 0.0053 19.78 0.9400 H2O2 modified biochar (HP-BC) [20]
1
Pb PFO 100 293.15 5.5 100 0.05 g L− – 2 0.6659 142.96 0.9563 MW-assisted one-pot synthesis of [90]
β-CD modified biochar (BCMW-
β-CD)
1
Pb PFO 200 298.00 3.0 25 1.00 g L− 150 48 0.0890 149.78 0.6800 Chitosan and [66]
ethylenediaminetetraacetic acid
modified magnetic biochar (E-
CMBC)
Pb PFO 50 295.15 5.5 * 20 0.05 g 40 48 0.0137 3.79 0.8900 Mn oxide-modified pine biochar [68]
(MPB)
Pb PFO 50 295.15 5.5 * 20 0.05 g 40 48 0.0111 16.26 0.9840 Birnessite-modified pine biochar [68]
10

(BPB)

K2 (g mg¡1 qe, calculated R2

min¡1) (mg g¡1)
1
Pb PSO 300 298.15 5.00 ± 0.05 – 0.50 g L− 100 48 1.1333 × 10-− 4
452.49 0.9900 Mg-coated biochar (MgBC400) [13]
Pb PSO 100 298.15 5.0 * 50 0.01 g 180 24 0.0025 308.23 0.9499 15%Mg-Biochar (15%Mg-BC) [53]
1
Pb PSO 120 298.00 5.0 200 0.50 g L− 160 12 0.0017 128.21 0.9990 FeOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (FO-BC-300)
1
Pb PSO 120 298.00 5.0 200 0.50 g L− 160 12 0.0012 179.21 0.9990 FeOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (FO-BC-450)

Journal of Environmental Chemical Engineering 10 (2022) 106502

1
Pb PSO 120 298.00 5.0 200 0.50 g L− 160 12 0.0012 156.25 0.9990 FeOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (FO-BC-600)
− 1
Pb PSO 120 298.00 5.0 200 0.50 g L 160 12 0.0020 160.77 0.9990 MnOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (MO-BC-300)
1
Pb PSO 120 298.00 5.0 200 0.50 g L− 160 12 0.0014 180.18 0.9990 MnOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (MO-BC-450)
1
Pb PSO 120 298.00 5.0 200 0.50 g L− 160 12 0.0016 213.68 0.9990 MnOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (MO-BC-600)
− 1
Pb PSO 50 298.15 7.0 50 0.50 g L 180 2 0.0002 – 0.9760 Modified reed biochar (MRBC) [85]
308.15 0.0003 0.9830
318.15 0.0002 0.9870
Pb PSO 100 298.15 5.0 30 – 200 24 0.0008 44.53 0.9900 H2O2 modified biochar (HP-BC) [20]
1
Pb PSO 100 293.15 5.5 100 0.05 g L− – 2 0.0069 153.48 0.9946 MW-assisted one-pot synthesis of [90]
β-CD modified biochar (BCMW-
β-CD)
1
Pb PSO 200 298.00 3.0 25 1.00 g L− 150 48 0.0010 155.43 0.9500 Chitosan and [66]
ethylenediaminetetraacetic acid
modified magnetic biochar (E-
CMBC)
(continued on next page)
 T. Liu et al.
Table 3 (continued )
Heavy Adsorption Experimental details Types of modified biochar References
metals kinetic
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g speed time (h)
pollutant (mg (mL) L− 1) or mass (rpm)
L− 1 ) (g)

Pb PSO 50 295.15 5.5 * 20 0.05 g 40 48 0.0051 4.07 0.9560 Mn oxide-modified pine biochar [68]
(MPB)
Pb PSO 50 295.15 5.5 * 20 0.05 g 40 48 0.0009 17.50 0.9890 Birnessite-modified pine biochar [68]
(BPB)

α (mg g¡1 β (g mg¡1) R2

min¡1)
1
Pb Elovich 300 298.15 5.00 ± 0.05 – 0.50 g L− 100 48 – – 0.9300 Mg-coated biochar (MgBC400) [13]
Pb Elovich 50 295.15 5.5 * 20 0.05 g 40 48 0.6885 1.86 0.9800 Mn oxide-modified pine biochar [68]
(MPB)
Pb Elovich 50 295.15 5.5 * 20 0.05 g 40 48 1.5515 0.40 0.9390 Birnessite-modified pine biochar [68]
(BPB)
11

Ki1 (mg g¡1 Ki2 (mg Ki3 (mg C (mg g¡1) R2

min¡0.5) g¡1 g¡1
min¡0.5) min¡0.5)

Pb IPD 100 298.15 5.0 * 50 0.01 g 180 24 43.1468 125.9125 – 15%Mg-Biochar (15%Mg-BC) [53]
K1 (min¡1) SD n qe, calculated R2
(mg g¡1)
1
Pb Avrami 100 293.15 5.5 100 0.05 g L− – 2 0.6439 1.3537 0.5088 151.15 0.9983 MW-assisted one-pot synthesis of [90]
fractional- β-CD modified biochar (BCMW-
order β-CD)

Journal of Environmental Chemical Engineering 10 (2022) 106502

1
200 298.00 3.0 25 1.00 g L− 150 48 0.0960 5.5600 – 156.63 0.9900 Chitosan and [66]
ethylenediaminetetraacetic acid
modified magnetic biochar (E-
CMBC)

Note: * means initial solution pH.

T. Liu et al.
C/C0 = e(− kf t)
(12)
The value of kf can be estimated from the plotting of ln(C/C0) against
with t.
4.2. Adsorption isotherms
The adsorption isotherm model considering adsorption equilibrium
data and adsorption characteristics are used to describe the interaction
mechanism between contaminants and adsorbents. The isometric heat is
regarded as one basic method to study adsorption [155]. The impor­
tance of information associated with heat release in kinetic research is
that heat release is caused by adsorption. The result is that some of the
energy released is absorbed by the solid adsorbent, and some dissipate
into the surrounding area. The adsorption part of the solid adsorbent
increases the temperature of the particles, causing the slowdown of the
adsorption kinetics. This can be attributed to mass adsorption, which is
controlled by the cooling rate of particles during the adsorption process.
Generally, three basic approaches had been elucidated for several
isotherm models including Freundlich model, Langmuir model,
Dubinin-Radushkevich (D-R) model, Temkin model, and Sips model.
The first basic approach reflects the kinetics when the adsorption rate
and desorption rate are equal and defines the adsorption equilibrium as
the dynamic equilibrium state [156]. The second basic approach, based
on thermodynamics, provides a framework to derive various forms of
adsorption isotherm models. The third basic approach can produce the
characteristic curve [157]. Much effort has been made to model
adsorption isotherms in the literature. Meanwhile, adsorption isotherms
for the removal of cadmium and lead are shown in Table 4. There are
other adsorption isotherms models such as Henry model, Toth model,
and Jovanovich model. According to collected literatures, proposed by
Ross and Olivier [158], Freundlich model, Sips model, and Jovanovich
model conform to the homotattic patch dividing the heterogeneous
adsorbent surface into homogeneous patches of small size, in which the
energy distribution of the adsorption potential is identified. Langmuir
model, Henry model, and Toth model are ineffective at high pressures
[157,159,160]. However, the performance of Dubinin-Radushkevich
(D-R) model displays well at high-pressure experiment but fails at
low-pressure experiment [156].
4.2.1. Freundlich model
The Freundlich model can be used to demonstrate the non-ideal and
reversible adsorption phenomenon, which is suitable for systems with
heterogeneous surfaces. The equation of this model is an empirical
equation and is originally created for animal charcoal adsorption [156].
The linearized form of its equation can be expressed as below
[163–165]:
logqe = logKF + (logCe )/n (13)
where KF ((mg/g)(L/mg)1/n) is the rate constant in the Freundlich
model, which is dependent on temperature; Ce (mg/g) refers to the
concentration of the adsorption in equilibrium; n can indicate the type of
the isotherm, which is also changed by temperature; 1/n indicates the
surface heterogeneity or adsorption strength, and represents the
adsorption site heterogeneity and relative energy distribution. Further­
more, when 0 < 1/n < 1, the adsorption process is favourable; when 1/
n > 1, the adsorption process is unfavourable; when 1/n = 1, the
adsorption is irreversible. The irreversibility of the isotherms can ascribe
a situation that the concentration or pressure should be greatly reduced
to lower values before the adsorbate molecules are desorbed from the
surface [163,164]. Meanwhile, 1/n and log (KF) are the slope and
intercept in the straight line. The isosteric heat of this model is a linear
function of the logarithm of the adsorption capacity.
The Freundlich model is not limited to the monolayer formation in
which its equation to the multilayer adsorption is applicable. Adsorption
heat is not necessary to equally distribute on heterogeneous surfaces in
12
Journal of Environmental Chemical Engineering 10 (2022) 106502
the Freundlich model. The exponential distribution of active sites en­
ergies and active sites are defined as well as the nonuniformity of the
surface in this model. The surface topography is patchwise that signifies
one patch can contain all sites having the same adsorption energy.
Simultaneously, each patch is independent and does not interact with
each other. Currently, the Freundlich model is widely used in hetero­
geneous adsorption systems such as highly interacting species on mo­
lecular sieves or organic compounds. Because the isotherm model does
not comply with Henry’s law at low pressure, this model contributes to a
narrow pressure range [156,163]. If the pressure is sufficiently great,
there is no limit for this model. From Table 4, the values of the initial
concentration of pollutions are not fixed. Normally, the values are be­
tween 0 and 300 mg/L. It can be inferred that room temperature and
mild acidity or near neutral pH solutions (pH 5.0–7.0) are conducive to
interact with target heavy metal ions. Moreover, the results of the cor­
relation coefficient (R2) showed that Freundlich model fitted the
adsorption data of cadmium and lead well for all samples.
4.2.2. Langmuir model
The Langmuir isotherm as an empirical model is first proposed to
expound the adsorption of gases on solid adsorbents such as activated
carbon [157]. The linear equation of the Langmuir model for
aqueous-phase adsorption and the separation factor (RL) are shown as
below [166–169]:
Ce /qe = (1/Qmax )Ce + 1/(Qmax KL ) (14)
RL = 1/(1 + KL C0 ) (15)
where Ce (mg/L) is the adsorbate equilibrium concentration; qe (mg/g)
is denoted to the amount of adsorbate uptake at equilibrium; Qmax (mg/
g) means the maximum saturated monolayer adsorption capacity of an
adsorbent; KL (L/mg) refers to the constant related to the affinity be­
tween an adsorbent and adsorbate; RL is the separation factor; C0 (mg/L)
is the initial concentration of the adsorbate. The adsorption area and
porosity of the adsorbent are related to the KL constant, indicating that
larger surface area and pore volume can produce larger adsorption ca­
pacity. The separation factor can indicate the adsorption properties
containing linear (RL =1), favorable (0 <RL <1), unfavorable (RL >1),
and irreversible (RL =0). The Langmuir model is assumed as the
monolayer adsorption, which means that the adsorption layer thickness
is one molecule. Another assumption is that the adsorption is homoge­
neous and each molecule has an adsorption activation energy and a
constant enthalpy. All sites and adsorbate have the same affinity. There
is no adsorbate migration on the surface plane [170]. The adsorption
process on the adsorbent surface follows the kinetic principle and takes
place at the same or equivalent localized location. From Table 4, the
Langmuir model fits well for most adsorption mechanisms. Lateral in­
teractions and steric hindrance between adsorbed molecules are inex­
istent, even at adjacent sites [171]. The adsorption and desorption rates
should be equal. The Langmuir isotherm equation can be simplified to
Henry’s law isotherm during low concentration and low pressure [163].
With the increase of pressure, the adsorption capacity increases linearly.
When the pressure is sufficiently high, the adsorption capacity reaches
saturation capacity, thereby the monolayer is covered. Moreover, rela­
tive to the correlation coefficient (R2) studied by Xiao et al. [55], the
fitting effect of most Langmuir isotherms (R2 =0.9920–0.9900) is better
than that of Freundlich (R2 = 0.9690 ~ 0.9830), indicating that phys­
ical adsorption may be an important mechanism of the adsorbents.
Additionally, the theoretical background of IPD established on
Langmuir surface kinetics are derived by Douven et al. [112]. Tradi­
tionally, the Langmuir isotherm model has been used to quantify and
compare various biological adsorption rates. Its adsorption classifica­
tions are different depending on the structural geometry and surface
chemical diversity of solid adsorbents [172]. These adsorption classifi­
cations consist of single-site Langmuir adsorption, multisite Langmuir
 T. Liu et al.
Table 4
Adsorption isotherms for the removal of Cd and Pb.
Heavy Adsorption Experimental details Types of modified biochar References
metals isotherm
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g L− 1) speed time (h)
pollutant (mg (mL) or mass (g) (rpm)
L− 1)

KF (mg g¡1) (L 1/n R2

mg¡1)1/n
1
Cd Freundlich 20–150 288.15 – 50 1.00 g L− 160 24 288.15 K: 50.79 288.15 K: 288.15 K: Hydroxyapatite synthesized with [72]
298.15 298.15 K: 52.25 0.1710 0.7972 sludge-based biochar (HAP-SSBC)
308.15 308.15 K: 67.73 298.15 K: 298.15 K:
318.15 318.15 K: 70.29 0.2180 0.8630
308.15 K: 308.15 K:
0.1910 0.9512
318.15 K: 318.15 K:
0.2310 0.9553
1
Cd Freundlich 0–300 298.15 5.00 ± 0.05 – 0.50 g L− 100 48 50.29 3.5714 0.9200 Mg-coated biochar (MgBC400) [13]
Cd Freundlich 10–100 298.15 5.0 * 50 0.01 g 180 24 67.9147 4.1959 0.9991 15%Mg-Biochar (15%Mg-BC) [53]
1
Cd Freundlich 5–200 298 5.0 200 0.50 g L− 160 12 3.2400 1.7668 0.9690 FeOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (FO-BC-300)
1
Cd Freundlich 5–200 298 5.0 200 0.50 g L− 160 12 6.0500 1.6835 0.9670 FeOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (FO-BC-450)
1
Cd Freundlich 5–200 298 5.0 200 0.50 g L− 160 12 5.9800 1.7794 0.9480 FeOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (FO-BC-600)
− 1
Cd Freundlich 5–200 298 5.0 200 0.50 g L 160 12 3.3300 1.6529 0.9670 MnOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (MO-BC-300)
1
Cd Freundlich 5–200 298 5.0 200 0.50 g L− 160 12 5.7600 1.7606 0.9620 MnOx- modified bone biochar [55]
13

pyrolyzed at 450 ℃ (MO-BC-450)

1
Cd Freundlich 5–200 298 5.0 200 0.50 g L− 160 12 10.4000 1.8762 0.9830 MnOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (MO-BC-600)
Cd Freundlich 20–200 297.15 6.0 50 0.10 g 120 24 2.61 ± 0.02 0.49 ± 0.05 0.9590 Magnetically modified water [56]
hyacinth biochar pyrolyzed at
500 ℃ (MBC5)
Cd Freundlich 20–200 297.15 6.0 50 0.10 g 120 24 2.31 ± 0.03 0.52 ± 0.02 0.9630 Magnetically modified water [56]
hyacinth biochar pyrolyzed at
700 ℃ (MBC7)
1
Cd Freundlich 5–100 298.15 7.0 20 0.10 g L− – 0.5 0.46 1.5625 0.9800 Magnetically modified spent coffee [161]

Journal of Environmental Chemical Engineering 10 (2022) 106502

ground biochar (MBC)
Cd Freundlich 0–800 298.00 – – 0.05 g 150 24 1.1217 0.2985 0.9495 Modified rice straw [80]
308.00 1.7636 0.2346 0.9666
318.00 0.6307 0.4895 0.9622
Cd Freundlich 1–200 298.15 5.0 20 0.05 g – 6 11.1026 0.7521 0.9988 Manganese-modified biochar [58]
pyrolyzed at 500 ℃ with 5:1
modification ratio (MBC2-500–5:1)
Cd Freundlich 0.1–100 298.15 4.0 ± 0.1 10 0.01 g 120 24 6.5230 ± 0.8000 2.4390 ± 0.2069 0.9800 Goethite modified biochar [81]
pyrolyzed at 600 ℃ with 1 mass
ratio of Fe/BC (GMB-600–1)
1
Cd Freundlich 5–200 298.00 5.5 50 0.50 g L− 220 24 26.8700 5.5556 0.9234 Modified vermicompost biochar [82]
308.00 33.9700 5.8824 0.9117 (MVBC)
318.00 40.3300 4.1667 0.9661
Cd Freundlich 10–120 293.00 2.5–6.9 100 0.10 g 180 12 8.8736 0.4569 0.9338 Modified rice straw-derived biochar [73]
303.00 12.7280 0.4360 0.8924 with -NH2 groups (BC-NH2)
313.00 15.0725 0.4091 0.8887
Cd Freundlich 20–400 298.15 6.00 ± 0.05* 30 0.03 g 180 24 6.6900 1.7241 0.9500 Transabdominal transformation [59]
modified biochar pyrolyzed at
300 ℃ (TCB300)
(continued on next page)
 Table 4 (continued )

T. Liu et al.
Heavy Adsorption Experimental details Types of modified biochar References
metals isotherm
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g L− 1) speed time (h)
pollutant (mg (mL) or mass (g) (rpm)
L− 1)

Cd Freundlich 20–400 298.15 6.00 ± 0.05* 30 0.03 g 180 24 11.1400 1.8868 0.9290 Transabdominal transformation [59]
modified biochar pyrolyzed at
400 ℃ (TCB400)
Cd Freundlich 20–400 298.15 6.00 ± 0.05* 30 0.03 g 180 24 14.0300 1.8868 0.9080 Transabdominal transformation [59]
modified biochar pyrolyzed at
500 ℃ (TCB500)
Cd Freundlich 20–400 298.15 6.00 ± 0.05* 30 0.03 g 180 24 15.9200 1.8182 0.8890 Transabdominal transformation [59]
modified biochar pyrolyzed at
600 ℃ (TCB600)
Cd Freundlich 20–400 298.15 6.00 ± 0.05* 30 0.03 g 180 24 16.6400 1.8182 0.9050 Transabdominal transformation [59]
modified biochar pyrolyzed at
700 ℃ (TCB700)
Cd Freundlich 50–300 293.15 5.0 50 0.05 g 150 8 3.7330 0.1111 0.8410 Titanium-modified ultrasonic [83]
biochar (BCTD)
Cd Freundlich 10–100 298.15 – 100 0.10 g 140 8 3.0310 0.4737 0.9950 Modified biochar added 0.25 g [84]
cystamine (C0.25)
Cd Freundlich 10–100 298.15 – 100 0.10 g 140 8 3.3650 0.5624 0.9900 Modified biochar added 0.50 g [84]
cystamine (C0.50)
Cd Freundlich 10–100 298.15 – 100 0.10 g 140 8 3.6640 0.5764 0.9870 Modified biochar added 0.75 g [84]
cystamine (C0.75)
Cd Freundlich 10–100 298.15 – 100 0.10 g 140 8 0.7350 0.6911 0.9970 Modified biochar added 0.10 g [84]
cystamine (C0.10)
Cd Freundlich 10–100 298.15 – 100 0.10 g 140 8 0.8510 0.2995 0.9950 Modified biochar added 1.25 g [84]
cystamine (C1.25)
14

Cd Freundlich 0–40 298.15 – 50 0.10 g 180 8 0.2670 0.7174 0.8020 Modified reed biochar (MRBC) [85]
308.15 0.3330 0.6649 0.7960
318.15 0.3970 0.6540 0.8120
Cd Freundlich 2–200 298.15 5.5* 40 0.05 g 200 12 8.9530 1.8215 0.9850 KMnO4 impregnation treatment of [60]
modified biochar (BC-MnOx)
Cd Freundlich 2–200 298.15 5.5 * 40 0.05 g 200 12 9.7280 1.8692 0.9780 Alkaline treatment of modified [60]
biochar (BC-NaOH)
Cd Freundlich 20–200 298.15 6.8 ± 0.2* 25 0.05 g 180 24 2.6274 1.7527 0.9690 Acrylonitrile modified biochar [61]
pyrolyzed at 350 ℃ (MBC350)

Journal of Environmental Chemical Engineering 10 (2022) 106502

Cd Freundlich 20–200 298.15 6.8 ± 0.2* 25 0.05 g 180 24 1.8040 0.6369 0.8330 Acrylonitrile modified biochar [61]
pyrolyzed at 450 ℃ (MBC450)
Cd Freundlich 20–200 298.15 6.8 ± 0.2* 25 0.05 g 180 24 3.2871 0.4386 0.7940 Acrylonitrile modified biochar [61]
pyrolyzed at 550 ℃ (MBC550)
Cd Freundlich 0–20 298.15 4.5 25 0.10 g 4000 24 0.4500 – 0.9500 KOH-modified biochar (ABC) [62]
5.5 0.4600 0.9500
6.5 0.5200 0.9500
1
Cd Freundlich 10–500 298.15 7.0 – 1.00 g L− 120 24 20.5700 0.2400 0.8900 Phosphate-modified activated [45]
bamboo biochar pyrolyzed at 750 ℃
(pm-BC3c)
Cd Freundlich 10–550 298.15 6.0 20 0.10 g 180 12 12.1060 0.4610 0.9978 Modified rice straw-derived biochar [86]
(BCM)

KL (L mg¡1) Qmax (mg g¡1) RL R2

1
Cd Langmuir 20–150 288.15 – 50 1.00 g L− 160 24 288.15 K: 0.643 288.15 K: 94.79 – 288.15 K: Hydroxyapatite synthesized with [72]
298.15 298.15 K: 0.474 298.15 K: 0.9972 sludge-based biochar (HAP-SSBC)
308.15 308.15 K: 0.960 114.68 298.15 K:
318.15 318.15 K: 0.806 308.15 K: 0.9994
308.15 K:
(continued on next page)
 T. Liu et al.
Table 4 (continued )
Heavy Adsorption Experimental details Types of modified biochar References
metals isotherm
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g L− 1) speed time (h)
pollutant (mg (mL) or mass (g) (rpm)
L− 1)

127.55 0.9995
318.15 K: 318.15 K:
147.06 0.9990
Cd Langmuir 10–100 298.15 5.0 * 50 0.01 g 180 24 0.0275 178.97 – 0.9788 15%Mg-Biochar (15%Mg-BC) [53]
1
Cd Langmuir 5–200 298 5.0 200 0.50 g L− 160 12 0.0104 69.50 – 0.9820 FeOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (FO-BC-300)
1
Cd Langmuir 5–200 298 5.0 200 0.50 g L− 160 12 0.0111 151.30 – 0.9900 FeOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (FO-BC-450)
1
Cd Langmuir 5–200 298 5.0 200 0.50 g L− 160 12 0.0119 130.70 – 0.9700 FeOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (FO-BC-600)
− 1
Cd Langmuir 5–200 298 5.0 200 0.50 g L 160 12 0.0201 91.40 – 0.9870 MnOx- modified bone biochar [55]
pyrolyzed at 300 ◦ C (MO-BC-300)
1
Cd Langmuir 5–200 298 5.0 200 0.50 g L− 160 12 0.0169 125.20 – 0.9860 MnOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (MO-BC-450)
1
Cd Langmuir 5–200 298 5.0 200 0.50 g L− 160 12 0.0207 163.40 – 0.9920 MnOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (MO-BC-600)
Cd Langmuir 2.5–110 298.15 6.0–7.5 300 0.05 g 100 24 0.5740 223.62 – 0.9600 Biochar-supported nanoscale [88]
zerovalent iron (BC-nZVI)
Cd Langmuir 0–800 298.00 – – 0.05 g 150 24 0.0142 8.14 – 0.9403 Modified rice straw [80]
308.00 0.0324 7.75 0.8407
318.00 0.0045 19.32 0.9759
Cd Langmuir 1–200 298.15 5.0 20 0.05 g 6 0.0500 191.94 0.9940 Manganese-modified biochar [58]
15

– –
pyrolyzed at 500 ℃ with 5:1
modification ratio (MBC2-500–5:1)
Cd Langmuir 0.1–100 298.15 4.0 ± 0.1 10 0.01 g 120 24 0.1620 ± 0.0180 31.89 ± 1.00 – 0.9950 Goethite modified biochar [81]
pyrolyzed at 600 ℃ with 1 mass
ratio of Fe/BC (GMB-600–1)
1
Cd Langmuir 5–200 298.00 5.5 50 0.50 g L− 220 24 0.7500 60.23 – 0.9429 Modified vermicompost biochar [82]
308.00 0.9700 78.20 0.9655 (MVBC)
318.00 0.2300 123.69 0.9746
Cd Langmuir 10–120 293.00 2.5–6.9 100 0.10 g 180 12 0.0549 72.50 – 0.9838 Modified rice straw-derived biochar [73]

Journal of Environmental Chemical Engineering 10 (2022) 106502

303.00 0.0869 77.97 0.9797 with -NH2 groups (BC-NH2)
313.00 3.2301 84.27 0.1024
Cd Langmuir 20–400 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.1400 76.92 – 0.9840 Transabdominal transformation [59]
modified biochar pyrolyzed at
300 ℃ (TCB300)
Cd Langmuir 20–400 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0600 90.91 – 0.9730 Transabdominal transformation [59]
modified biochar pyrolyzed at
400 ℃ (TCB400)
Cd Langmuir 20–400 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0700 125.00 – 0.9870 Transabdominal transformation [59]
modified biochar pyrolyzed at
500 ℃ (TCB500)
Cd Langmuir 20–400 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0600 161.29 – 0.9890 Transabdominal transformation [59]
modified biochar pyrolyzed at
600 ℃ (TCB600)
Cd Langmuir 20–400 298.15 6.00 ± 0.05* 30 0.03 g 180 24 0.0500 175.44 – 0.9900 Transabdominal transformation [59]
modified biochar pyrolyzed at
700 ℃ (TCB700)
Cd Langmuir 50–300 293.15 5.0 50 0.05 g 150 8 0.3730 72.62 – 1.0000 Titanium-modified ultrasonic [83]
biochar (BCTD)
(continued on next page)
 T. Liu et al.
Table 4 (continued )
Heavy Adsorption Experimental details Types of modified biochar References
metals isotherm
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g L− 1) speed time (h)
pollutant (mg (mL) or mass (g) (rpm)
L− 1)

Cd Langmuir 10–100 298.15 – 100 0.10 g 140 8 0.0260 ± 0.0020 35.82 ± 0.95 – 0.9950 Modified biochar added 0.25 g [84]
cystamine (C0.25)
Cd Langmuir 10–100 298.15 – 100 0.10 g 140 8 0.0180 ± 0.0020 67.84 ± 3.82 – 0.9900 Modified biochar added 0.50 g [84]
cystamine (C0.50)
Cd Langmuir 10–100 298.15 – 100 0.10 g 140 8 0.0160 ± 0.0020 81.02 ± 5.35 – 0.9870 Modified biochar added 0.75 g [84]
cystamine (C0.75)
Cd Langmuir 10–100 298.15 – 100 0.10 g 140 8 0.0090 ± 0.0080 36.18 ± 2.01 – 0.9970 Modified biochar added 0.10 g [84]
cystamine (C0.10)
Cd Langmuir 10–100 298.15 – 100 0.10 g 140 8 0.0630 ± 0.0030 3.77 ± 0.05 – 0.9950 Modified biochar added 1.25 g [84]
cystamine (C1.25)
Cd Langmuir 0–40 298.15 – 50 0.10 g 180 8 0.2480 2.40 – 0.9640 Modified reed biochar (MRBC) [85]
308.15 0.2600 2.56 0.9760
318.15 0.2490 2.97 0.9850
1
Cd Langmuir 25–200 293.00 6.0 – 1.00 g L− – 12 0.0700 175.29 0.0670–0.3640 0.9992 Iminodiacetic acid modified [24]
303.00 0.0750 187.12 0.0630–0.3480 0.9991 magnetic biochar (MBCI)
313.00 0.0940 191.41 0.0510–0.2990 0.9995
323.00 0.1140 197.96 0.0420–0.2600 0.9994
Cd Langmuir 2–200 298.15 5.5 * 40 0.05 g 200 12 0.0900 81.10 – 0.9940 KMnO4 impregnation treatment of [60]
modified biochar (BC-MnOx)
Cd Langmuir 2–200 298.15 5.5 * 40 0.05 g 200 12 0.1020 72.37 – 0.9930 Alkaline treatment of modified [60]
biochar (BC-NaOH)
Cd Langmuir 20–200 298.15 6.8 ± 0.2* 25 0.05 g 180 24 0.0100 144.09 – 0.7320 Acrylonitrile modified biochar [61]
16

pyrolyzed at 350 ℃ (MBC350)

Cd Langmuir 20–200 298.15 6.8 ± 0.2* 25 0.05 g 180 24 0.0400 39.83 – 0.9790 Acrylonitrile modified biochar [61]
pyrolyzed at 450 ℃ (MBC450)
Cd Langmuir 20–200 298.15 6.8 ± 0.2* 25 0.05 g 180 24 0.0800 26.99 – 0.9940 Acrylonitrile modified biochar [61]
pyrolyzed at 550 ℃ (MBC550)
Cd Langmuir 0–20 298.15 4.5 25 0.10 g 4000 24 5.5000 15.50 – 0.9800 KOH-modified biochar (ABC) [62]
5.5 5.8900 24.70 0.9700
6.5 5.7400 41.90 0.9700
1
Cd Langmuir 10–500 298.15 7.0 – 1.00 g L− 120 24 0.0900 202.55 – 0.9720 Phosphate-modified activated [45]
bamboo biochar pyrolyzed at 750 ℃

Journal of Environmental Chemical Engineering 10 (2022) 106502

(pm-BC3c)
Cd Langmuir 10–550 298.15 6.0 20 0.10 g 180 12 0.0380 117.98 – 0.9660 Modified rice straw-derived biochar [86]
(BCM)

qe (mg g¡1) KDR (mol2 kJ¡2) E (kJ mol¡1) R2

Cd D-R 20–200 298.15 6.8 ± 0.2* 25 0.05 g 180 24 – -10930000 6.76 0.9580 Acrylonitrile modified biochar [61]
pyrolyzed at 350 ℃ (MBC350)
Cd D-R 20–200 298.15 6.8 ± 0.2* 25 0.05 g 180 24 – -6140000 9.03 0.8150 Acrylonitrile modified biochar [61]
pyrolyzed at 450 ℃ (MBC450)
Cd D-R 20–200 298.15 6.8 ± 0.2* 25 0.05 g 180 24 – -4230000 10.87 0.7810 Acrylonitrile modified biochar [61]
pyrolyzed at 550 ℃ (MBC550)

AT (L mg¡1) BT (kJ mol¡1) R2

− 1
Cd Temkin 20–150 288.15 – 50 1gL 160 24 288.15 K: 39.43 288.15 K: 288.15 K: Hydroxyapatite synthesized with [72]
298.15 298.15 K: 13.68 186.51 0.8187 sludge-based biochar (HAP-SSBC)
308.15 308.15 K: 58.57 298.15 K: 298.15 K:
318.15 318.15 K: 25.93 137.31 0.9083
308.15 K: 308.15 K:
(continued on next page)
 T. Liu et al.
Table 4 (continued )
Heavy Adsorption Experimental details Types of modified biochar References
metals isotherm
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g L− 1) speed time (h)
pollutant (mg (mL) or mass (g) (rpm)
L− 1 )

152.12 0.9755
318.15 K: 318.15 K:
120.65 0.9910
1
Cd Temkin 0–300 298.15 5.00 ± 0.05 – 0.5 g L− 100 48 – – 0.97 Mg-coated biochar (MgBC400) [13]
Cd Temkin 0–800 298.00 – – 0.05 g 150 24 0.2873 1.4242 0.9699 Modified rice straw [80]
308.00 1.1084 1.1773 0.9763
318.00 0.0938 3.2710 0.9245

KF (mg g¡1) (L 1/n R2

mg¡1)1/n

Pb Freundlich 50–150 298.15 5.0 * 50 0.01 g 180 24 266.5197 4.7548 0.9974 15%Mg-Biochar (15%Mg-BC) [53]
1
Pb Freundlich 5–400 298 5.0 200 0.50 g L− 160 12 26.3000 3.0769 0.8480 FeOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (FO-BC-300)
1
Pb Freundlich 5–400 298 5.0 200 0.50 g L− 160 12 58.2000 3.7879 0.8780 FeOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (FO-BC-450)
− 1
Pb Freundlich 5–400 298 5.0 200 0.50 g L 160 12 48.5000 3.8760 0.7400 FeOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (FO-BC-600)
1
Pb Freundlich 5–400 298 5.0 200 0.50 g L− 160 12 53.7000 3.8760 0.8420 MnOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (MO-BC-300)
1
Pb Freundlich 5–400 298 5.0 200 0.50 g L− 160 12 53.5000 2.9762 0.9180 MnOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (MO-BC-450)
17

− 1
Pb Freundlich 5–400 298 5.0 200 0.50 g L 160 12 64.4000 2.8653 0.9600 MnOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (MO-BC-600)
Pb Freundlich 0–160 298.15 – 50 0.10 g 180 8 6.0350 0.1657 0.8630 Modified reed biochar (MRBC) [85]
308.15 7.0030 0.1645 0.8390
318.15 7.8220 0.1648 0.9390
Pb Freundlich 20–300 298.15 5.0 30 – 200 24 16.9900 3.1250 0.8300 H2O2 modified biochar (HP-BC) [20]
1
Pb Freundlich 10–300 278.15 5.5 100 0.05 g L− – 2 16.7700 0.3390 0.9101 MW-assisted one-pot synthesis of [90]
293.15 31.8400 0.2994 0.8327 β-CD modified biochar (BCMW-
308.15 62.6300 0.2500 0.7768 β-CD)
1
Pb Freundlich 20–500 298.00 3.0 25 1.00 g L− 150 24 108.8000 0.0796 0.73300 Chitosan and [66]

Journal of Environmental Chemical Engineering 10 (2022) 106502

308.00 110.1300 0.0789 0.7300 ethylenediaminetetraacetic acid
318.00 111.4400 0.0808 0.7400 modified magnetic biochar (E-
CMBC)
1
Pb Freundlich 150–230 298.00 5.0 25 2.00 g L− 200 24 13.5000 0.2618 0.9990 Chitosan-modified pine wood [52]
308.00 6.5800 0.4785 0.9960 biochar (CMBC)
318.00 6.3300 0.5181 0.9940
Pb Freundlich 1–300 295.15 5.5 * 20 0.05 g 40 24 1.4850 3.5971 0.9900 Mn oxide-modified pine biochar [68]
(MPB)
Pb Freundlich 1–300 295.15 5.5 * 20 0.05 g 40 24 16.8000 4.4843 0.8080 Birnessite-modified pine biochar [68]
(BPB)

KL (L mg¡1) Qmax (mg g ¡1) RL R2

Pb Langmuir 50–150 298.15 5.0 * 50 0.01 g 180 24 0.0078 526.20 – 0.8860 15%Mg-Biochar (15%Mg-BC) [53]
1
Pb Langmuir 5–400 298 5.0 200 0.50 g L− 160 12 0.0313 173.90 – 0.9760 FeOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (FO-BC-300)
1
Pb Langmuir 5–400 298 5.0 200 0.50 g L− 160 12 0.0916 271.90 – 0.9530 FeOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (FO-BC-450)
− 1
Pb Langmuir 5–400 298 5.0 200 0.50 g L 160 12 0.0871 247.80 – 0.8750 [55]
(continued on next page)
 T. Liu et al.
Table 4 (continued )
Heavy Adsorption Experimental details Types of modified biochar References
metals isotherm
Initial Temperature Solution pH Solution Adsorbent Mixing Contact
model
concentration of (K) volume dosage (g L− 1) speed time (h)
pollutant (mg (mL) or mass (g) (rpm)
L− 1)

FeOx- modified bone biochar

pyrolyzed at 600 ℃ (FO-BC-600)
− 1
Pb Langmuir 5–400 298 5.0 200 0.50 g L 160 12 0.1090 205.10 – 0.9590 MnOx- modified bone biochar [55]
pyrolyzed at 300 ℃ (MO-BC-300)
1
Pb Langmuir 5–400 298 5.0 200 0.50 g L− 160 12 0.0553 325.10 – 0.9650 MnOx- modified bone biochar [55]
pyrolyzed at 450 ℃ (MO-BC-450)
1
Pb Langmuir 5–400 298 5.0 200 0.50 g L− 160 12 0.0516 407.20 – 0.9480 MnOx- modified bone biochar [55]
pyrolyzed at 600 ℃ (MO-BC-600)
Pb Langmuir 0–160 298.15 – 50 0.10 g 180 8 0.1510 15.19 – 0.9990 Modified reed biochar (MRBC) [85]
308.15 0.1570 15.84 0.9980
318.15 0.1700 17.54 0.9990
Pb Langmuir 20–300 298.15 5.0 30 – 200 24 0.1100 60.87 – 0.9900 H2O2 modified biochar (HP-BC) [20]
1
Pb Langmuir 10–300 278.15 5.5 100 0.05 g L− – 2 0.0200 126.43 – 0.9931 MW-assisted one-pot synthesis of [90]
293.15 0.0400 174.81 0.9711 β-CD modified biochar (BCMW-
308.15 0.0900 240.13 0.9767 β-CD)
1
Pb Langmuir 20–500 298.00 3.0 25 1.00 g L− 150 24 10.0100 159.12 – 0.9900 Chitosan and [66]
308.00 11.1700 160.53 0.9900 ethylenediaminetetraacetic acid
318.00 11.8400 163.19 0.9900 modified magnetic biochar (E-
CMBC)
Pb Langmuir 25–100 298.00 5.5 50 0.02 g 130 2.5 0.0310 238.00 – 0.9600 Modified pine cone biochar by [162]
308.00 0.0390 268.00 0.9500 H3PO4 (AC1)
318.00 0.0420 283.00 0.9600
18

1
Pb Langmuir 150–230 298.00 5.0 25 2.00 g L− 200 24 0.0791 50.50 – 0.9960 Chitosan-modified pine wood [52]
308.00 0.0149 103.00 0.9940 biochar (CMBC)
318.00 0.0113 134.00 0.9880
Pb Langmuir 1–300 295.15 5.5 * 20 0.05 g 40 24 0.0002 4.91 – 0.9160 Mn oxide-modified pine biochar [68]
(MPB)
Pb Langmuir 1–300 295.15 5.5 * 20 0.05 g 40 24 0.0007 47.05 – 0.9230 Birnessite-modified pine biochar [68]
(BPB)

qe (mg g¡1) KDR (mol2 kJ¡2) E (kJ mol¡1) R2

Pb D-R 20–300 298.15 5.0 30 200 24 116.87 14.9200 0.9000 H2O2 modified biochar (HP-BC) [20]

Journal of Environmental Chemical Engineering 10 (2022) 106502

– –
2
AT (L mg )
¡1
BT (kJ mol¡1
) R
1
Pb Temkin 0–300 298.15 5.00 ± 0.05 – 0.5 g L− – 48 – – 0.8700 Mg-coated biochar (MgBC400) [13]
Ks (L mg¡1) as (L mg¡1) n R2
1
Pb Sips 10–300 278.15 5.5 100 0.05 g L− – 2 0.0024 0.0195 1.0500 0.9917 MW-assisted one-pot synthesis of [90]
293.15 0.0025 0.0154 1.3900 0.9474 β-CD modified biochar (BCMW-
308.15 0.0043 0.0194 1.9100 0.9327 β-CD)

Note: *Means initial solution pH.

T. Liu et al.
adsorption, generalized Langmuir adsorption, cooperative adsorption,
dissociative adsorption, and multilayer adsorption [172].
4.2.3. Dubinin-Radushkevich (D-R) model
The Dubinin-Radushkevich (D-R) model is usually used to distin­
guish between chemisorption and physical adsorption of metal ions. The
linearized form equation of the model is shown as below [173,174]:
ln(qe ) = ln(qs ) − KDR ε2 (16)
where qe (mg/g) is the amount of adsorbate in the adsorbent at equi­
librium; qs (mg/g) is the theoretical isotherm saturation capacity; KDR
(mol2/kJ2) is the Dubinin–Radushkevich isotherm constant; Ɛ = RTln
(ps/p), which is the Dubinin–Radushkevich isotherm constant (kJ/mol),
meanwhile, R (8.314 × 10-3 kJ/mol K), T (K), ps (atm.) and p (atm.) are
the universal gas constant, the absolute temperature, the saturation
vapor pressure and the equilibrium pressure of adsorbate molecules
[175]. The application precondition of D-R model is the accuracy of Ɛ
value. The D-R isotherm model can be extended to aqueous and gas
√̅̅̅̅̅̅̅̅̅̅̅̅
phase adsorption. Additionally, E = 1/ 2KDR , which is the mean free
energy (kJ/mol).
The D-R model assumes a multi-layer role, including Van der Waal’s
forces, which can be applied to physical adsorption processes [156]. The
model is a semi-empirical equation in which the adsorption of the model
is based on the pore-filling mechanism. It is usually used to represent the
adsorption mechanism of Gaussian energy distribution on heteroge­
neous surfaces [176]. This model is also applied to describe the
adsorption of steam and gas on activated carbon, zeolite and other
microporous adsorbents. The model successfully fits the range of high
active solute and medium adsorbate concentrations, which can be
attributed to the unrealistic asymptotic behaviour. The isotherms are
classified into three types based on their curvature and initial slope,
depending on the adsorbent’s affinity for the adsorbate. The shape of the
isotherm curve can be classified as three types by Giles et al. [177],
namely S-type, L-type and H-type. Adsorption isotherm shape is a key
feature of the adsorption mechanism, which can provide preliminary
information for the adsorption mechanism [175].
4.2.4. Temkin model
The Temkin empirical isotherm model is utilized to explain hydrogen
adsorption on a platinum electrode in an acidic solution, which is
regarded as a chemisorption process. The linear equation of the model is
presented as below [178,179]:
qe = (RT/BT )lnAT + (RT/BT )lnCe (17)
where AT and BT are constants in the adsorption isotherm model; R is the
ideal gas constant (8.314 × 10− 3 kJmol− 1K− 1); T (K) is the tempera­
ture. One assumption is that the heat of adsorption is a function of
temperature and that the heat of adsorption of all molecules present in
the layer decreases linearly rather than logarithmically because of an
increase in surface cover [178]. The binding energies might be homo­
genously distributed according to its equation. This Temkin model
considers the interaction between adsorbent and adsorbate, ignoring
both maximum and minimum concentrations. The model is only suitable
for the medium concentration range.
4.2.5. Sips model
The Sips model is the combination of the Langmuir and Freundlich
model, which predicts the heterogeneity of the adsorption system and
overcomes the limitations of the Freundlich model of increasing adsor­
bate concentration. This in turn leads to expressions with finite limits at
high concentrations. The linearized Sips equation is shown as below
[156,180]:
βS ln(Ce ) = − ln(Ks /qe ) + ln(aS ) (18)
where βs is the Sips isotherm model exponent; KS (L/mg) is the Sips
19
Journal of Environmental Chemical Engineering 10 (2022) 106502
isotherm model constant; aS (L/mg) is the Sips isotherm model constant.
Significantly, the Sips model is effective for adsorption localization in
the absence of adsorbent-adsorbate interaction. When the adsorbate
concentration is low, the model conforms to Henry’s law [163]. This
means that the monolayer adsorption characteristics of Langmuir model
are predicted at high adsorbate concentration. Changes in operating
conditions such as concentration, pH and temperature determine the
parameters of the equation. The limitation indicates that the Sips model
is difficult to provide the correct Henry’s low at low pressures, which is
similar to the Freundlich model.
4.3. Adsorption thermodynamics
The change in standard Gibbs free energy is shown in the equation as
below [156]:
(19)
◦ ◦ ◦
∆G = ∆H − T∆S
where ΔG◦ (kJ/mol) is the change in standard Gibbs free energy; ΔH◦
(kJ/mol) is the change in standard enthalpy; ΔS◦ (kJ/mol.K) is the
change in standard entropy; T (K) is the temperature. These parameters
had been determined from adsorption thermodynamics studies for the
removal of cadmium and lead, such as titanium-modified ultrasonic
biochar (BCTD) and biochar modified with sodium alginate (SA-CaRB)
in Table 5. In general, the positive change in standard enthalpy can be
observed for the removal of cadmium and lead using modified biochar.
Similarly, increasing the heat of adsorption leads to an increase in the
number of adsorbed molecules [181].
From Table 5, it can be observed that the adsorption of cadmium and
lead onto biochar is mainly an endothermic process. Furthermore, this
suggests that an increase in the temperature of the process will favor
uptake. It is therefore unsurprising that experimental values for tem­
perature for cadmium and lead (see Table 6) are always at ambient or
above-ambient conditions. Besides a few exceptions [20,82,90,93], the
magnitude of ΔH◦ was always below 50 kJ/mol. This suggests that
physical interaction mechanisms could be at play in most cases for the
adsorptive uptake of cadmium and lead by biochar.
Chemically-mediated adsorption usually expresses much greater
changes in thermal energy. The most values of ΔS◦ suggest the increase
of freedom at the solid-liquid interphase. It might be surmised from the
tables that the adsorptive uptake of cadmium and lead by biochar is
spontaneous.
4.4. Effect of experimental parameters
This depends on the type adsorbed, the adsorbate, the adsorbent and
various physical properties of the solution, including pH, ionic strength
and temperature. In general, the adsorption experiment is established
when the contact time between the adsorbate and the adsorbent is suf­
ficient, and the interface concentration should maintain a dynamic
balance with the concentration of the adsorbate in the volumetric so­
lution. These effects of experimental parameters are commonly used in
the design of industrial adsorption processes and the characterization of
porous solids. From Table 6, it can be observed that the cadmium and
lead concentration usually range from 0 to 500 mg/L. The initial con­
centration is quite important to the adsorption process because it pro­
vides the mass transfer driving force [182]. The adsorption process
involves mass transfer which (by principle) is affected by a concentra­
tion gradient. Following this, heavy metal adsorption can be quite rapid
at the onset due to higher initial concentrations. This rapidity gradually
tails us as equilibrium is achieved. Increasing the adsorbent mass usually
improves the adsorption of cadmium and lead. This is because it makes
more active sites and functional surfaces available for adsorption [183].
However, there can be an upper threshold where increased adsorbent
mass does not favour the uptake process. This is at high dosage where
agglomeration of the adsorbent particles begins to occur (thereby
T. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 106502

reducing the effective surface area).
The pH of the solution is another important parameter that affects
cadmium and lead adsorption. From Table 6, the pH of the solution for
the adsorption of cadmium and lead is generally kept between 4 and 7.
The values of pH in the alkaline region will lead to the precipitation of
the heavy metals out of the solution as they react with OH ions to form
insoluble hydroxides. On the other hand, pH values lesser than 4 also
affects cadmium and lead adsorption negatively because the high con­
centration of H+ in solution produces a strong competing effect with the
heavy metals. The pH also affects the adsorbents’ isoelectric point
thereby determining the pH regime for electrostatic attraction or
repulsion [184]. From Table 6, adsorption temperature is usually set at
ambient conditions and in some cases, above it. Though adsorption in­
volves comparatively little temperature change, it can be quite sensitive
to process temperature. The temperature can affect the kinetic energy of
species and help them cross the solid-liquid boundary layer more easily.
Usually, an important aspect of understanding temperature effects is via
thermodynamics modelling. The positive or negative value of the
change in enthalpy indicates the extent of its endothermic or exothermic
nature, respectively. As shown in Table 5, it is usually endothermic. The
magnitude of this change in enthalpy suggests the kinds of bonds/in­
teractions that are possible in the process [185]. Competing species is
also a factor that can affect cadmium and lead adsorption. Other ions in
the solution can have different ways of challenging the adsorption
process. For example, most salts ionize to produce cations like Na+, Mg+
and Ca2+. These cations can become direct competitors with cadmium
and lead in the aqueous phase. Furthermore, various competing species
can reduce the solubility of cadmium and lead. This drop-in solubility
(known as the salting-out effect) can negatively affect the adsorption
process [186].
Table 6 also presents the adsorption capacities of various modified
biochars for cadmium and lead, respectively. The adsorption capacity is
more representative of the adsorbent’s potential for uptake of cadmium
and lead and depends mainly on the factors affecting the solution
chemistry (pH and temperature). This is a better index for making a
comparison across various adsorbent types [187]. On the contrary, the
removal efficiency depends more on process parameters such as the
initial concentration and the dosage of the adsorbent [186]. It can be
seen from the tables that adsorption is an efficient technique for the
removal of heavy metals from an aqueous solution, albeit under care­
fully chosen process parameters.
High temperature can speed the reaction rate and ion exchange.
Appropriate contact time can allow the heavy metal solution to come
into full contact with the adsorbent. The functional groups on the
adsorbent surface such as amine and amide groups can present high
efficiency to remove heavy metal ion.
4.5. Adsorption mechanisms
This section examines the different physico-chemical interaction
mechanisms by which cadmium and lead are adsorbed from the aqueous
phase. Feedstock used in the synthesis of adsorbents are usually derived
from complex and diverse sources, so this means that heavy metal
adsorption can be promoted in different methods. Different adsorption
mechanisms can be classified by physical adsorption, ion exchange,
surface complexation or inner sphere complexation, chelation, and
surface precipitation [29,32,190]. The selected adsorbents have
different types of functional groups such as carbonyl, amine, amide,
imine, hydroxyl, phosphodiester, phenolic, phosphate thioether, and
sulfonate groups that can be used to entice metal ions to the biochar
surface [191–193]. The study on the adsorption mechanism is of great
significance for improving the understanding of the surface binding
between metal and biosorbent, controlling the removal of heavy metal,
and improving the adsorption efficiency of adsorbents. Adsorption
mechanism can be determined by characteristics of the binding site of
modified biochar such as type and availability [190]. Moreover, it has
been further reported that the affinity between metal and active site can
also affect the adsorption mechanism. The removal of heavy metals by

Table 5
Adsorption thermodynamics data for removal of Cd and Pb.
Heavy Types of modified biochar ΔH0 (kJ ΔS0 (kJ ΔG0 (kJ T (K) References
metals mol− 1) mol− 1K− 1) mol− 1)

Cd FeOx- modified bone biochar pyrolyzed at 450 ℃ (FO-BC-450) 13.47 0.1049 -17.79 298 [55]
Cd MnOx- modified bone biochar pyrolyzed at 600 ℃ (MO-BC-600) 13.64 0.1097 -19.06 298 [55]
Cd Biochar modified with shrimp bran (BCS) 18.84 0.19 − 39.64 303 [57]
– – − 41.5 313
Cd Modified vermicompost biochar (MVBC) – – -27.7 298.00 [82]
71.97 0.33 -30.79 308.00
– – -34.4 318.00
Cd Modified rice straw-derived biochar with -NH2 groups (BC-NH2) 37.37 0.199 -20.58 293.00 [73]
– – -23.39 303.00
– – -24.52 313.00
Cd Titanium-modified ultrasonic biochar (BCTD) 18.341 0.07 -1.73 293.15 [83]
– – -2.24 298.15
– – -2.42 303.15
Cd Iminodiacetic acid modified magnetic biochar (MBCI) 13.871 0.0002 -2.20 293.00 [24]
– – -2.75 303.00
– – -3.29 313.00
– – -3.84 323.00
Pb FeOx- modified bone biochar pyrolyzed at 450 ℃ (FO-BC-450) 5.55 0.0863 -20.17 298 [55]
Pb MnOx- modified bone biochar pyrolyzed at 600 ℃ (MO-BC-600) 14.55 0.1293 -23.97 298 [55]
Pb H2O2 modified biochar (HP-BC) 146.43 0.52 -4.02 283.00 [20]
– – -6.78 298.00
– – -19.46 313.00
Pb MW-assisted one-pot synthesis of β-CD modified biochar (BCMW-β-CD) 96.64 0.41 -19.55 278.15 [90]
– – -22.10 293.15
– – -30.67 308.15
Pb Chitosan and ethylenediaminetetraacetic acid modified magnetic biochar (E- 3.95 0.02 -3.12 298.00 [66]
CMBC) – – -3.37 308.00
– – -3.60 318.00
Pb Biochar modified with sodium alginate (SA-CaRB) 64.97 0.31 -26.24 298.00 [93]
– – -27.44 303.00
– – -29.29 308.00

20
 Table 6

T. Liu et al.
Adsorption performance as influenced by experimental parameters for the removal of Cd and Pb.
Heavy Types of modified biochar Type of Initial Mass (g) or Solution Solution pH Temperature Adsorption Method of Cycles Main findings References
metals water concentration of dosage of volume (K) capacity (mg regeneration of reuse
pollutant (mg adsorbent (g (mL) g− 1)
L− 1) L− 1)
1
Cd Hydroxyapatite synthesized with Deionized 20–150 1 g L− 50 3.0–8.0 298.15 114.68 – – • The adsorption capacity of HAP-SSBS is [72]
sludge-based biochar (HAP-SSBC) (DI) water higher than that of raw slugebased bio­
char (SGBC) in the aqueous solution.
• Chemical adsorption manages the
adsorption rate and liquid film diffusion is
defined as the speed-limiting step.
Cd Mg-coated biochar (MgBC400) Deionized 0–300 0.50 g 100 5.00 ± 0.05 400 197.83 1 M NaOH 5 cycles • The adsorption capacity of MgBC400 is [13]
(DI) water increased by 30 times compared with
original biochar (BC400).
• Ion exchange and mineral precipitation
contribute to the adsorption of Cd by
MgBC400.
Cd 15%Mg-Biochar (15%Mg-BC) Deionized 10–100 0.01 g 50 5.0 298.15 178.97 – – • The adsorption capacity of 15%Mg-BC is [53]
(DI) water increased by 2.36–9.34 times compared
with original biochar.
• The solution initial pH can affect the
adsorption capacity.
• The adsorption kinetics of Cd2+ follows
the intraparticle diffusion model.
• The adsorption isotherms of Cd2+ follows
the Freundlich model.
Cd MgCl2 modified biochar (MgC600) Deionized 0–500 0.08 g 40 6.0 313.15 93.90 NaOH and 5 cycles • The adsorption capacity of MgC600 is [54]
(DI) water EDTA-2NaCa increased by twice compared with
original biochar.
21

• Reaction time, initial concentration and

solution pH can affect the adsorption
capacity.
• Physical adsorption and functional group
complexation are the main adsorption
mechanism.
• BJP model is more accurate for the fixed
bed filtration process.
Cd FeOx- modified bone biochar Deionized 5–200 0.005 g 200 5.0 298 151.31 KH2PO4 4 cycles • FO-BC-450 can realized high adsorption [55]

Journal of Environmental Chemical Engineering 10 (2022) 106502

pyrolyzed at 450 ℃ (FO-BC-450) (DI) water capacity for heavy metals.
• The pyrolysis temperature have an
influence on micropore creation,
functional groups, specific surface areas,
and heavy metal sorption capacities of
FO-BCs.
Cd MnOx- modified bone biochar Deionized 5–200 0.005 g 200 5.0 298 163.44 KH2PO4 4 cycles • MO-BC-600 can realized high adsorption [55]
pyrolyzed at 600 ℃ (MO-BC-600) (DI) water capacity for heavy metals.
• The pyrolysis temperature have an
influence on micropore creation,
functional groups, specific surface areas,
and heavy metal sorption capacities of
MO-BCs.
Cd Magnetically modified water Double- 20–200 0.10 g 50 – 310.15 45.8 – – • The maximum adsorption capacity is at a [56]
hyacinth biochar pyrolyzed at distilled solution 37 ℃ and a pH 6.
700 ℃ (MBC7) water • The Langmuir model is better then
Freundlich model to reach the maximum
adsorption capacity.
1
Cd 5–100 0.10 g L− 20 7 298.15 10.42 – – [161]
(continued on next page)
 T. Liu et al.
Table 6 (continued )
Heavy Types of modified biochar Type of Initial Mass (g) or Solution Solution pH Temperature Adsorption Method of Cycles Main findings References
metals water concentration of dosage of volume (K) capacity (mg regeneration of reuse
pollutant (mg adsorbent (g (mL) g− 1)
L− 1) L− 1 )

Magnetically modified spent coffee Distilled • Fe-C functional group contains a variety
ground biochar (MBC) water of oxygen-containing functional groups is
the reason to reach the high adsorption
efficiency of FeSO4-composite biochar for
Cd2+.
• The pseudo-second-order model fits well
for the magnetic modified biochar (MBC).
Cd Biochar-supported nanoscale Deionized 2.5–110 0.05 g 300 6.0–7.5 298.15 223.62 – – • The maximum adsorption capacity of BC- [88]
zerovalent iron (BC-nZVI) (DI) water nZVI is increased by 97%.
• The removal mechanism follows the
surface complexation and chemical
reduction, which fits the pseudo-second-
order and the Langmuir model.
1
Cd Poplar bark thiourea-modified Deionized 5–500 4.00 g L− 20 7.0 298.15 19.998 – – • The Langmuir model can explain [188]
biochar (TSBC-600) (DI) water chemical adsorption mechanism for
TSBC-600.
• Thiourea modified biochar can provide
high adsorption capacity and strong acid
resistance.
1
Cd Poplar sawdust thiourea-modified Deionized 5–500 5.00 g L− 20 7.0 298.15 9.63 – – • The Langmuir model can explain [188]
biochar (TMBC-600) (DI) water chemical adsorption mechanism for
TMBC-600.
• Thiourea modified biochar can provide
22

high adsorption capacity and strong acid

resistance.
Cd Modified rice straw Distilled 0–800 0.05 g – 5.5 318.00 19.32 – – • The methods in improving adsorption [80]
water capacity include raising up the initial
Cd2+ concentration, increasing the
contact time, enhancing the temperature,
boosting the initial pH, and decreasing
the ionic strength.
• The pseudo-second-order model fits well
for the adsorption mechanism.

Journal of Environmental Chemical Engineering 10 (2022) 106502

Cd Manganese-modified biochar Deionized 1–200 0.05 g 20 – 298.15 191.94 – – • MBC2 pyrolyzed at 500 ℃ with 5:1 [58]
pyrolyzed at 500 ℃ with 5:1 (DI) water modification ratio has the best adsorption
modification ratio (MBC2-500–5:1) capacity because of the higher degree of
aromatization and more active sorption
sites.
Cd Goethite modified biochar Ultrapure 0.1–100 0.01 g 10 4.0 ± 0.1 298.15 31.89 NaOH 4 cycles • GMB-600–1 has high adsorption for Cd2 + [81]
pyrolyzed at 600 ℃ with 1 mass water at high pH and the mass ratio of Fe/BC
ratio of Fe/BC (GMB-600–1) can control the goethite loading and pore
structure.
• The adsorption mechanism includes
specific adsorption (hydroxyl complex,
surface complexation, π-π interaction, ion
exchange, etc.), non-specific adsorption
(physical adsorption and electrostatic
interaction), and chemisorption.
1
Cd Modified vermicompost biochar Deionized 5–200 0.50 g L− 50 5.5 318.00 123.69 – – • Mineral precipitation is the most [82]
(MVBC) (DI) water important mechanism and the main
precipitate is CdCO3.
(continued on next page)
 Table 6 (continued )

T. Liu et al.
Heavy Types of modified biochar Type of Initial Mass (g) or Solution Solution pH Temperature Adsorption Method of Cycles Main findings References
metals water concentration of dosage of volume (K) capacity (mg regeneration of reuse
pollutant (mg adsorbent (g (mL) g− 1)
L− 1) L− 1)

Cd Modified rice straw-derived biochar Deionized 10–120 0.10 g 100 – 313.00 84.27 – – • The complexation action happens [73]
with -NH2 groups (BC-NH2) (DI) water between functional group -NH2 and Cd2+,
which increases the adsorption capacity by
72.1%.
Cd Transabdominal transformation Deionized 20–400 0.03 g 30 8.0 298.15 161.29 – – • The reason of high adsorption capacity for [59]
modified biochar pyrolyzed at (DI) water TCB is more O-containing surface
600 ℃ (TCB600) functional group, improved Brunauer-
Emmett-Teller specific surface area, and
the development of mineral components.
• The adsorption mechanism includes ion
exchange, precipitation, and adsorption-
complexation.
Cd Titanium-modified ultrasonic Deionized 50–300 0.05 g 50 5.3 293.15 72.62 – – • The adsorption mechanism includes [83]
biochar (BCTD) (DI) water complexation and ion exchange.
• Ultrasonically reacting improves the pore
volume and surface area of biochar and
TiO2 are added on the surface and inner
pores.
Cd Modified biochar added 0.75 g Deionized 10–100 0.10 g 100 7.0 298.15 81.02 1 M HCl 6 cycles • The surfaces of C0.75 with granular [84]
cystamine (C0.75) (DI) water nanopolymers of enough functional groups
of primary amine and disulfide linkage make
the biochar surface more conducive to
electrostatic attraction and surface
complexation.
Cd Modified reed biochar (MRBC) Deionized 0–40 0.10 g 50 7.0 318.15 2.97 • Fe from (NH4)2Fe(SO4)2 improve the [85]
23

– –
(DI) water microstructure surface area of MRBC to
make itself more reactive for Cd2+
adsorption.
1 1
Cd Iminodiacetic acid modified Milli-Q 25–200 1.00 g L− 50 8.0 323.00 197.96 0.1 mol L− 5 cycles • The Langmuir model fits well for the [24]
magnetic biochar (MBCI) water Na2EDTA adsorption mechanism.
• MBCI can be isolated from the solution
because of magnetic forces.
Cd KMnO4 impregnation treatment of Deionized 2–200 0.05 g 40 8.0 298.15 81.10 – – • The main adsorption mechanism for BC- [60]
modified biochar (BC-MnOx) (DI) water MnOx is cation-π bonding and cation

Journal of Environmental Chemical Engineering 10 (2022) 106502

exchange.
Cd Alkaline treatment of modified Deionized 2–200 0.05 g 40 8.0 298.15 72.37 – – • The main adsorption mechanism for BC- [60]
biochar (BC-NaOH) (DI) water NaOH includes surface complexation,
surface electrostatic attraction, and surface
precipitation.
Cd Acrylonitrile modified biochar Deionized 20–200 0.05 g 25 7.0 298.15 85.65 – – • The main adsorption mechanism is [61]
pyrolyzed at 350 ℃ (MBC350) (DI) water surface complexation and ion exchange.
• MBC350 can provide good acid resistance
and adsorption capacity.
Cd KOH-modified biochar (ABC) Distilled 0–20 0.10 g 25 6.5 298.15 41.90 – – • The Langmuir model fits well for the [62]
water adsorption mechanism.
• The surface functional groups and porous
structure are improved due to alkali-
activated biochar.
1
Cd Phosphate-modified activated Deionized 10–500 1.00 g L− – 7.0 298.15 202.55 – – • The adsorption capacity is increased by [45]
bamboo biochar pyrolyzed at 750 ℃ (DI) water 10 times due to the phosphate
(pm-BC3c) modification.
• The Langmuir model and pseudo-first-
order model fit well for the adsorption
mechanism.
(continued on next page)
 T. Liu et al.
Table 6 (continued )
Heavy Types of modified biochar Type of Initial Mass (g) or Solution Solution pH Temperature Adsorption Method of Cycles Main findings References
metals water concentration of dosage of volume (K) capacity (mg regeneration of reuse
pollutant (mg adsorbent (g (mL) g− 1)
L− 1) L− 1)

Cd Modified rice straw-derived biochar Deionized 10–550 0.10 g 20 – 298.15 117.98 – – • More adsorption sites are provided [86]
(BCM) (DI) water because of deprotonation of hydroxyl and
carboxylic groups.
• The electrostatic attraction is conducive
to the higher adsorption capacities.
Pb Mg-coated biochar (MgBC400) Deionized 300 0.50 g – 5.00 ± 400.00 433.17 1 M NaOH 5 cycles • The total adsorption capacity of MgBC400 [13]
(DI) water 0.05 is increased by 20 times compared with
original biochar (BC400).
• Ion exchange and mineral precipitation
contribute to the adsorption of Pb by
MgBC400.
Pb 15%Mg-Biochar (15%Mg-BC) Deionized 50–150 0.01 g 50 5.0 298.15 526.20 – – • The metal sorption capacity of 15%Mg-BC [53]
(DI) water is increased by 2.36–9.34 times compared
with original biochar.
• The solution initial pH can affect the
adsorption capacity.
• The adsorption kinetics of Pb2+ follows
the pseudo-second-order model.
• The adsorption isotherms of Pb2+ follows
the Freundlich model.
Pb FeOx- modified bone biochar Deionized 5–400 0.005 g 200 5.0 298.00 271.85 KH2PO4 4 cycles • FO-BC-450 can realized high adsorption [55]
pyrolyzed at 450 ℃ (FO-BC-450) (DI) wate capacity for heavy metals.
• The pyrolysis temperature have an
influence on micropore creation,
24

functional groups, specific surface areas,

and heavy metal sorption capacities of
FO-BCs.
Pb MnOx- modified bone biochar Deionized 5–400 0.005 g 200 5.0 298.00 407.23 KH2PO4 4 cycles • MO-BC-600 can realized high adsorption [55]
pyrolyzed at 600 ℃ (MO-BC-600) (DI) wate capacity for heavy metals.
• The pyrolysis temperature have an
influence on micropore creation,
functional groups, specific surface areas,
and heavy metal sorption capacities of
MO-BCs.

Journal of Environmental Chemical Engineering 10 (2022) 106502

Pb Modified reed biochar (MRBC) Deionized 0–160 0.10 g 50 7.0 318.15 17.54 – – • Fe from (NH4)2Fe(SO4)2 improve the [85]
(DI) water microstructure surface area of MRBC to
make itself more reactive for Pb2+
adsorption.
1
Pb H2O2 modified biochar (HP-BC) Deionized 20–300 – 30 5.0 298.15 60.87 1.0 mol L− 5 cycles • The Langmuir model fits well for the [20]
(DI) water HCl adsorption mechanism.
• The active adsorption sites are increased
due to H2O2 modification.
1
Pb MW-assisted one-pot synthesis of Distilled 10–300 0.50 g L− 100 5.5 308.15 240.13 HCl and 5 cycles • The adsorption mechanism includes [90]
β-CD modified biochar (BCMW- water ethanol electrostatic interactions and
β-CD) complexation.
• The Langmuir model can affect the Pb2+
adsorption.
1 1
Pb Chitosan and Deionized 20–500 1.00 g L− 25 5.0 298.00 159.12 0.1 mol L− 3 cycles • The Langmuir and Avrami fractional- [66]
ethylenediaminetetraacetic acid (DI) water Na2EDTA order model fit well for the adsorption
modified magnetic biochar (E- mechanism.
CMBC) • Strongly acidic conditions cannot affect
the adsorption of E-CMBC.
(continued on next page)
T. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 106502

modified biochar may occur through redox reactions, whereby lead ions
References
were reduced by the nanoscale zero valent iron when the hydrophilic
corn stalk biochar-supported nanoscale zero valent iron composite was

[189]

[52]

[68]

[68]
employed [194]. Moreover, the removal process for heavy metal also
contains redox reactions because of oxidation of oxygen-containing

• The adsorption capacity of BPB is better

• The pseudo-second-order and Langmuir

complexation, co-precipitation, and ion

functional groups [190]. Additionally, Cd and Pb speciation in water

managed by the coordination between

Pb2 + ions and chitosan amine groups.
• The Langmuir model fit well for the
• The adsorption mechanism is mostly
• The Langmuir model fit well for the

• The Langmuir model fit well for the

• The adsorption mechanism includes
might change the concentration of dissolved cations and solution pH;

than that of MPB due to birnessite

model fit well for the adsorption

thereby influence the adsorption process possibly because of surface

carboxylic acid sites on the modified biochar [52,195].
The summary of heavy metal adsorption mechanisms using biochar
adsorption mechanism.

adsorption mechanism.
adsorption mechanism.
adsorbent is shown in Fig. 2. The mechanisms involved in biosorption
for the removal of heavy metal are summarized in Table 7. Additionally,
it is helpful to acquire knowledge about the process mechanism in order
mechanism.
Main findings

exchange.

to select a suitable method for the regeneration of adsorbents.

particles.
Physical adsorption is principally decided by specific pore structure
and surface area. At higher pyrolysis temperature (773 K or 873 K) in
Tables 2 and 3, the microporous structure of modified biochar is well
of reuse

established and the interaction between adsorbate and surface can be

Cycles

realized by a weak Van der Waals force [196]. Micropores size and
–

distribution are determined by the feedstock cell structure. The growth

regeneration

of micropores is conducive to physical adsorption, while the growth of

Method of

mesoporous pores facilitates the diffusion of contaminants and thus

hasten the adsorption kinetics [197]. The pore adsorption process can
–

end up becoming the most important (rate-limiting) step in the

adsorption process if it is the slowest [198]. Furthermore, surface area of
capacity (mg
Adsorption

modified biochar and solution pH can basically influence this adsorption

99.95

47.05
4.91
134.00

process due to the weak binding [199,200]. Therefore, results can be

g− 1)

observed where the physical adsorption is a reversible process and might

be difficult to play the dominant mechanism for biosorption of metal
Solution pH Temperature

ions. Furthermore, most studies have claimed that physical adsorption is

298.15

318.00

295.15

295.15

not the only significant process mechanism for the removal of heavy
metal or metalloids [29,190]. Since kinetics can be faster for meso­
(K)

porous adsorbents, it is unsurprising that most of such adsorption pro­

cesses using them are controlled predominantly by other
physico-chemical interaction processes [201].
5.0

Chemical adsorption mainly consists of ion exchange, surface

–

complexation, inner sphere complexation, chelation, electrostatic

Solution

attraction and surface precipitation, which is presented in Fig. 2.

volume
(mL)

Generally, the adsorption mechanism of modified biochar prepared from

50

25

20

20

diverse feedstock on metal ions is very different. Harvey et al. [202]

adsorbent (g

suggest that the interaction between metal and adsorbent is depended

Mass (g) or

1
dosage of

on the soft-hard Lewis acid-base property of the adsorbent and surface

2.00 g L−
0.10 g

0.05 g

0.05 g

charge. For the oxygen-containing functional group biochar whose

L− 1)

surface is dominated by hard Lewis base (such as carboxylic acid and

deprotonated phenols), the metal is favorable for adsorption through
concentration of

cation exchange. Modified biochars whose functional groups are

pollutant (mg

mainly soft Lewis bases (such as aromatic structures and carbonyl),

150–230
50–800

the metal can be conducive to dipole-dipole interactions (such as cati­

1–300

1–300
Initial

L− 1)

onic-π bonds). It can be inferred from Table 7 that ion exchange is

suitable for most adsorption mechanisms of heavy metal removal from
(DI) water

(DI) water

(DI) water

(DI) water
Modified corn stalks pith biochar by Deionized

Deionized

Deionized

Deionized

aqueous solutions. Ion exchange occurs when ions are adsorbed on the
Type of
water

surface of adsorbent exchange with other ions in solution, which is

commonly a reversible process [203]. Ion exchange mechanism is
generally affected by metal ions and the number of acid sites on solid
Birnessite-modified pine biochar

surfaces [204–206]. Most studies report that ions exchange mechanism

Mn oxide-modified pine biochar
Chitosan-modified pine wood

provides the main impetus for the adsorption process [69,205,207,208].

polyethylene and potassium
Types of modified biochar

From Table 7, Ca2+, Mg2+ and Na+ ions in the aqueous solution are
Note: *means initial solution pH.

released, which indicates that the adsorption process experiences an

ion-exchange mechanism. In a study by Cho et al. [209], they had
hydroxide (SP3)

biochar (CMBC)

revealed that ion exchange between alkaline cations and heavy metal
Table 6 (continued )

might play an important role in removing contaminations. Furthermore,

ionic strength might be a key factor influencing the ion exchange
(MPB)

(BPB)

mechanism. In addition to ion exchange, complexation mechanism is

another important chemisorption mechanism. Complexation mecha­
metals
Heavy

nism refers to the combination of two or more substances to form

Pb

Pb

Pb

Pb

complexes including mononuclear or polynuclear formations [190]. The

25
T. Liu et al. Journal of Environmental Chemical Engineering 10 (2022) 106502

Fig. 2. The overview of heavy metal adsorption mechanisms on biochar.

Adapted from [29, 190].

type of complex depends on the number of metal ions bound by the utilized sawdust for adsorption of lead ions in accordance with Table 7,
ligand at the central location. Chemically, polydentate ligands are the biosorption experiments are conducted on sawdust modified by
favored over monodentate ligands because polydentate ligands contain MoS2. The results suggest that the adsorption of lead is obviously
multiple ligands and can attract multiple ions [210–212]. A study enhanced due to the complexation reaction between soft ligand groups

Table 7
The adsorption mechanism of Cd and Pb on modified biochar.
Type of modified biochar Heavy Mechanism References
metals

15%Mg-Biochar (15%Mg-BC) Cd and Pb Ion exchange, precipitation, surface complexation, and metal chelation [53]
MgCl2 modified biochar (MgC600) Cd Physical adsorption, functional group complexation, and ion exchange [54]
FeOx- modified bone biochar pyrolyzed at 450 ℃ (FO-BC-450) Cd and Pb Chemical complexation, cation-π bonds, ion exchange, and precipitation [55]
reaction
MnOx- modified bone biochar pyrolyzed at 600 ℃ (MO-BC-600) Cd and Pb Chemical complexation, cation-π bonds, ion exchange, and precipitation [55]
reaction
Magnetically modified water hyacinth biochar pyrolyzed at 700 ℃ (MBC7) Cd Ion exchange [56]
Magnetically modified spent coffee ground biochar (MBC) Cd Ion exchange, surface complexation, and cation attraction [161]
Poplar bark thiourea-modified biochar (TSBC-600) Cd Electron-electron pairs, ion exchange, and surface complexation [188]
Poplar sawdust thiourea-modified biochar (TMBC-600) Cd Electron-electron pairs, ion exchange, and surface complexation [188]
Biochar modified with shrimp bran (BCS) Cd Physical microporous filtration, surface complexation, ion exchange, and [57]
electrostatic attraction
Manganese-modified biochar pyrolyzed at 500 ℃ with 5:1 modification Cd Mainly surface complexes [58]
ratio (MBC2-500–5:1)
Transabdominal transformation modified biochar pyrolyzed at 600 ℃ Cd Precipitation, ion exchange, and complexation [59]
(TCB600)
Iminodiacetic acid modified magnetic biochar (MBCI) Cd Surface complexation [24]
KMnO4 impregnation treatment of modified biochar (BC-MnOx) Cd Mainly cation exchange and cation-π bonding [60]
Alkaline treatment of modified biochar (BC-NaOH) Cd Surface electrostatic attraction, surface complexation, and surface [60]
precipitation
Acrylonitrile modified biochar pyrolyzed at 350 ℃ (MBC350) Cd Ion exchange and complexation [61]
KOH-modified biochar (ABC) Cd Mainly surface precipitation and ion exchange [62]
Phosphate-modified activated bamboo biochar pyrolyzed at 750 ℃ (pm- Cd Complexation [45]
BC3c)
Rice straw-derived magnetic biochar Cd Chelation with hydroxyl and carbonyl functional groups, ion exchange, [63]
and cadmium adsorption
Oxide–rice husk biochar composite (MgO–BCR) Cd Precipitation, surface complexation, and electrostatic attraction [64]
H2O2 modified biochar (HP-BC) Pb Complexation [20]
Chitosan and ethylenediaminetetraacetic acid modified magnetic biochar Pb Complexation [66]
(E-CMBC)
Biochar modified with sodium alginate (SA-CaRB) Pb Complexation, ion exchange, and precipitation [93]
Mn oxide-modified pine biochar (MPB) Pb Strong interactions [68]
Birnessite-modified pine biochar (BPB) Pb Strong interactions [68]

26
T. Liu et al.
(sulphur containing groups) and soft acid groups (lead ions). Therefore,
according to Pearson acid-base theory, it can be deduced that sulphur
containing groups have a high affinity with lead ions, resulting in a
complexation reaction between the two groups which significantly im­
proves the adsorption of lead [70]. Table 7 indicates that the
oxygen-containing groups (such as phenol group, carboxyl group, and
hydroxyl group) can construct complexes with cadmium, lead and other
metals. Moreover, the solution pH and buffer capacity of biochar might
change the speciation of complexes, which can affect the mechanism of
heavy metal. For instance, under proper alkaline conditions at pH 8.0 or
higher, low soluble hydroxyl complexes can be formed [64,70,71,213].
Chelation has complex ring structures in which an electron-supplying
atom is simultaneously bound to a metal ion in multiple positions [71,
190]. The chelates are characterized by ring formation and their struc­
tural stability increases with the increase of ligand binding sites.
Commonly, chelates are more stable than complexes because poly­
dentate ligands participate in the reaction and metal ions promote the
formation of stable structures through multiple bonding [206]. Func­
tional groups such as NH3+, OH-, SO2- and RCOO- participate in the
chelation of metal ions [214–216]. These functional groups can be found
in Table 7 where they are used to increase metal removal efficiency.
Functional group NH3+ has been observed to be most effective in
eliminating heavy metals because electrostatic interactions and chela­
tion occur simultaneously in this case [217]. Under the chelating
mechanism, blocking carboxyl group by esterification reaction and
blocking hydroxyl group by methylation reaction can reduce the bio­
sorption efficiency, indicating that the chelating mechanism plays an
important role in the adsorption of metal ions to some extent [216].
Additionally, in accordance with Table 7, another vital chemical
adsorption mechanism is surface precipitation, defined as the formation
of insoluble hydroxides and metal oxides on the adsorbent surface
because of chemical reactions like oxidation-reduction reaction [64,
216, 218–220]. Typically, this mechanism can be observed when the
capacity of the adsorbent is lower than the metal concentration on the
surface of the adsorbent [199,216]. The surface precipitation in the
cadmium removal process might be formed during the proper alkaline
conditions [59,60,221]. The adsorption rate by surface precipitation is
much slower than other mechanisms.
5. Regeneration of modified biochar
Regeneration research is helpful to understand the recycling method
of biosorbents and reduce the demand for raw materials. It is also usu­
ally important when the raw materials for biosorbents are not readily
available or the synthesis method is costly and time-consuming. The
performance of biochar in multiple reuse cycles indicates the availability
of the adsorbent. From Table 6, an acid like HNO3 or HCl is usually
applied for the regeneration of modified biochar. Numerous hydronium
ions can be released into the aqueous solution, which thus results in the
effect of competing solutes for active sites. Meanwhile, the metal ions
are separated from the adsorbent surface, developing a complex with the
acid ions [48,222,223]. The results indicate that HNO3 acid solution is
the most effective for biochar regeneration according to Table 6. On the
other hand, alkali like NaOH or NH4OH can be added into the polluted
solution where the protonation degree of the modified biochar surface
can be reduced, thereby resulting in metal ions desorption. Recently, to
regenerate MnO2 modified biochar from deionized (DI) water, 0.3 M
HNO3 and 0.5 M NaOH are used. The results show that removal ca­
pacities achieved are individually more than 15 mg/g and 34 mg/g for
both cadmium and lead ions, even after five cycles reuse, which are still
keeping around 92% on cadmium ions and 80% on lead ions of the
initial adsorption capacities of virgin modified biosorbents [47]. Addi­
tionally, in order to desorb cadmium and lead from Mg-coated biochar
(MgBC400), 1.0 M NaOH is utilized to complete five cycles. The
adsorption abilities of modified biochar for cadmium and lead after
regeneration are about 92 mg/g and 272 mg/g, respectively [13]. Acidic
27
Journal of Environmental Chemical Engineering 10 (2022) 106502
are alkali products are common in many industries, which can be one
advantage for regeneration treatment. Thus, employing these waste
products during regeneration treatment can contribute to improve waste
utilization. Furthermore, metal salt e.g. CaCl2 was used when ion ex­
change was involved as the adsorption mechanism [224]. Moreover,
complexing agents such as EDTA [24] can also be another option to
regenerate biosorbents due to rich electron-donating groups. Therefore,
regeneration is an important process because it can make the biosorbent
reusable and enable metal recovery, thus reducing the overall operating
cost of the wastewater treatment plant.
6. Challenges, prospects and future perspectives
Modified biochar has been studied for the adsorption of heavy metals
in wastewater treatment in the last decade, but it still faces many
challenges. Due to different experimental conditions, such as feedstock
type, pyrolysis process, and specific operation methods, it is difficult to
address the adsorption capacity data and adsorption mechanism of
modified biochar at present, which means that the comparability of data
is insufficient. Modified biochar has great potential in wastewater
treatment, but studies on the transformation of toxic ingredients in the
pyrolysis process have not been reported. Additionally, it is not clear
whether chemical modifiers will produce secondary pollution during
modified biochar production. Whether these methods of treating heavy
metal-containing liquids are conducive to a virtuous cycle of environ­
mental systems is unclear. Compared with traditional biochar produc­
tion, modified biochar might employ more energy and resources, which
leads to upsurge product costs. Therefore, regarding the future per­
spectives, the following aspects should be paid attention to:
• The large-scale operation conditions should be conducted as close as
possible for the designed kinetics and isotherms experiments.
Empirical models are more descriptive instead of predictive. The
practical significance and ease of operation of these lumped kinetic
models might expound their continued popular acceptance in
aqueous adsorption kinetic models.
• The application of modified biochars faces hindrances in industrial
production. Techniques like plasma mass spectrometry and atomic
absorption spectrometry can only be used in laboratory experiments
and are not sufficient for industrial purposes that require continuous
monitoring of metal ion concentrations. Surface plasmon resonance
sensors and surface enhanced Raman scattering should be adopted
for industrial purposes.
• The use of modifiers and process methods will increase production
costs, and countermeasures must be considered to determine the
balance between cost and adsorption capacity before large-scale
production. It is necessary to set corresponding pyrolysis parame­
ters for different modification methods to obtain better removal
performance of target heavy metal ions and make modified biochars
have sustainable benefits.
• Modified biochars that have shown success in batch tests in the
laboratory may not be able to achieve industrial purposes. One of the
primary reasons is that metal ions complexity of real industrial
wastewater is much more than that of the laboratory. It is known that
metal ions and anions co-existing in an industrial wastewater may
compete s for the active sites on modified biochars, leading to the
overall reduction of the heavy metal removal efficiency of modified
biochar. Another reason is that some modified biochars have a ten­
dency to expand in the adsorption process, which may block the
liquid flow.
• The stability of modified biochars composites should be considered
to meet the requirements of long life and excellent adsorption ca­
pacity under water scouring and immersion.
• Chemical modification of biochars might increase potential envi­
ronmental risks. Additionally, in practical application, acid-base
treatment as a biochar regeneration method can lead to the
T. Liu et al.
prominent mass loss of modified biochars and corrosion of equip­
ment over time. Therefore, other chemical approaches such as metal
salt and complexing agents might be more suitable to regenerate
modified biochars for some situations. Future research should focus
on the recovery of pollutants and the reuse of modified biochars.
• As a new adsorbent, nanoparticles tend to aggregate in an aqueous
solution, which reduces the reactivity of particles. Recently, metal
oxide-biochar nanocomposites presents a promising solution since
they may demonstrate certain salient features of nanomaterials and
biochar, thus enabling them to have a good prospect in the field of
adsorption for water pollution control.
7. Conclusions
Modified biochars have been actively studied in the past ten years. In
order to improve the adsorption capacity of biochar for the removal of
heavy metals from water, various synthesis methods have been con­
ducted, using chemical or biological modifications to improve the sur­
face properties of biochar. The most commonly encountered adsorption
kinetic models for removal of cadmium and lead from aqueous solution
are pseudo-first-order kinetic model and pseudo-second-order kinetic
model. Meanwhile, the most frequently encountered adsorption
isotherm models are Freundlich isotherm model and Langmuir isotherm
model. Different experimental parameters, such as initial concentration
of pollutant, dosage of adsorbent, solution pH, and temperature, can
influence the performance of modified biochar for the adsorptive
removal of cadmium and lead from water. The adsorption mechanisms
for the removal of cadmium and lead from aqueous solution could be
surface precipitation, surface complexation, ion exchange, chelation,
electrostatic attraction, inner sphere complexation, redox and physical
adsorption. Acid solutions like HNO3 or HCl and alkali solutions like
NaOH or NH4OH are usually applied for the regeneration of modified
biochar. Although the application of modified methods in biochar is
increasing, its production and application are still in the laboratory
stage, and related research needs to be further carried out. Furthermore,
developing new technologies and methods to find a balance between
optimized performance and production costs is a future goal.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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