Water Air Soil Pollut (2021) 232: 429

https://doi.org/10.1007/s11270-021-05378-8

Synthesis Strategies, Mechanisms, and Potential Risks

of Biomass‑Based Adsorbents (BAs) for Heavy Metal
Removal from Aqueous Environment: a Review
Wei Liu · Yingbo Dong · Hai Lin · Yuanyuan Shi

Received: 6 April 2021 / Accepted: 30 September 2021 / Published online: 9 October 2021
© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2021

Abstract Biomass-based adsorbents (BAs) have
been widely used for heavy metal (HM) removal from
wastewater, owing to its large specific surface area,
extraordinary pore capacity, biodegradability, and
low cost. However, the internal reaction processes are
still unclear due to the much different structure, group
types, element composition, as well as charge charac-
teristics of different BAs. Over the years, studies have
found that the adsorbed HMs tend to release again with
the change of water characteristics such as pH, redox
condition, and coexisting ions and then threaten the
safety and health of ecology and human beings. This
article aims to review the advanced development and
mechanism in the use of BAs for HM removal from
aqueous environment, including the physicochemical
properties, synthesis methods, influencing factors, and
microorganism-combined mobilization technologies.
Moreover, we propose the potential risks on the eco-
logical environment and life heath on the BA synthesis,
remediation, and migration processes. The key issues
for the development of high-performance BAs and
prospects for imminent are also highlighted.
Highlights
• Biomass-based adsorbents (BAs) for heavy metal
(HM) removal in water environment.
• The synthesis methods, physicochemical proper-
ties, and removal mechanisms of BAs were sum-
marized.
• Potential risks on life heath during the application
of BAs were assessed.
• Challenges and future directions of BAs in envi-
ronmental applications were discussed.
Keywords Biomass adsorbents · HM removal ·
Reaction mechanism · Affecting factors · Potential
risks · Aqueous environment

W. Liu · Y. Dong · H. Lin

School of Energy and Environmental Engineering,
University of Science and Technology, Beijing, 1 Introduction
Beijing 100083, China
Water, as the source of life, plays a major role in
Y. Dong (*) · H. Lin
the metabolic activities of human bodies, animals,
Beijing Key Laboratory On Resource-Oriented Treatment
of Industrial Pollutants, Beijing 100083, China and plants. However, the water environment on
e-mail: ybdong@ustb.edu.cn surface and underground has been threatened by
various modalities of heavy metals (HMs) over the
Y. Shi
past decades and is getting deteriorating duo to the
Beijing Municipal Research Institute of Environmental
Protection, Beijing 100037, China remained metal ions (Amen et al., 2018; Janette

Vol.:(0123456789)
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429 Page 2 of 22
et al., 2016; Xu et al., 2016). It is known to all that
the HMs such as Zn, Cd, Cr(VI), As, Pb, Ni, Cu,
and so forth are widely produced from nonferrous
metal mining, electroplating, metallurgy, indus-
trial manufacturing, electronic material bleach-
ing, printing and dyeing, dye production, and other
industries (Azimi et al., 2017; Bandara et al., 2020;
Gupta et al., 2008; Hsu et al., 2016; Phoungthong &
Suwunwong, 2020; Thevenon et al., 2011). Because
of their nondegradability, they exist in the form
of ions, oxidized species, or sediments in aqueous
environment while the solution conditions changed
(Liu et al., 2019; Song et al., 2020). The critical
adverse influences of HM contamination have been
focused all over the world where the concentration
in natural water bodies is generally higher than that
of World Health Organization (WHO) safety limi-
tation in drinking water (Nikaido et al., 2010), and
detection these HM pollutants is ignored (Varotsos
et al., 2019). This truth is making destroyed influ-
ences on plant growth (root poisoning), microbial
metabolic activities (cell necrosis), and human
health (comprehensive effects on the immune sys-
tem, blood circulation, and respiratory system)
(Galal & Shehata, 2015; Niu et al., 2009; Ranjbar
et al., 2017; Singh & Kumar, 2017).
To date, various technologies have been applied to
remove HMs from water environment such as coagu-
lation, sedimentation, oxidation–reduction, adsorp-
tion, plant uptake, microbial mineralization, and so
on (Ma et al., 2016; Rezania et al., 2016; Sdiri et al.,
2011). Among these methods, adsorption was con-
sidered as the most preferable strategy for HM sepa-
ration from water environment. Recently, the adsor-
bents produced from biomass substances have aroused
wide attention in the water treatment field (Iqbal et al.,
2002; Lin et al., 2018; Schiewer & Patil, 2008; Wang
et al., 2018a, b, 2019a, b). The biomass substances, as
a production of plant wastes (Abdelhadi et al., 2017;
Bishay, 2010; Stavi, 2013) (corn stalk, rice straw,
cotton, various wood materials, etc.), peel (Albarelli
et al., 2011; Pavan et al., 2006) (citrus peel, coco-
nut shell, etc.), and even fermentation products (Bao
et al., 2013; Chen et al., 2014) (sludge composting
and domestic waste incineration products, etc.), can
be attained easily and widely distributed in the natu-
ral environment. Due to its large specific surface area,
extraordinary pore capacity, biodegradability, and low
cost, the BAs were prepared for HM removal.
13
Water Air Soil Pollut (2021) 232: 429
To obtain a considerable HM removal capacity, the
BAs usually need to be pyrolyzed from solid waste
materials with limited oxygen supply under 250 to
750 ℃ (Sohi, 2012) or be modified with certain modi-
fiers. The physicochemical properties of BAs are eas-
ily changed in these pyrolysis processes because the
production is sensitive to ambient conditions, such as
oxygen content, heating area, and size of feedstock.
As a result, these BAs used in adsorption batch exper-
iments had an overall distinction for HM removal effi-
ciency. It is maneuverable to select functional modifi-
ers by referring to the property of the target pollutant.
Besides, reports showed that some BA materials had
redox capacity because of the persistent radicals on
BAs’ structure (Zeng-Hui et al., 2018). Further-
more, BAs in conjunction with microbes applied in
water recovery are becoming another novel hot spot
due to the existence of an excellent synergistic effect
between BAs and microbial communities (Daboor,
2014; Huang et al., 2017a, b). The complex interac-
tion mechanisms attract researchers paying more
attention to associated various technologies with BAs.
Based on the previous research, the deep and precise
removal mechanism of HMs is still lack of excavation
(Zhao et al., 2019). Although some adsorption behav-
iors were proposed to explain the interaction between
different HMs and microorganisms on biomass adsor-
bents (Guo et al., 2017; Lin et al., 2017a, b), proposi-
tions are unable to reveal the exact process from a
molecular level while using BAs and BA-based adsorp-
tion for HMs. Also, functional distinctions of BAs
derived from different raw biomasses are not clear.
A significant issue has been ignored during the
adsorption activities which undergoes potential risks
on natural water environment (Zdravka et al., 2018).
Usually, as more and more BAs are used to solve the
HM pollution, though the reports claim that the adsor-
bents can be collected for reuse (Du et al., 2016),
actually most of the used adsorbents with adsorbing
saturated HMs are discharged into the environment
without proper disposal or disposed as hazardous
waste. Subsequently, HMs in the saturated adsorbent
will be released out slowly and migrate into water bod-
ies under the action of surface runoff and underground
seepage (Chatterjee & Abraham, 2019). Moreover, the
HMs may convert into other compounds which repre-
sented higher toxicity than that of the initial state dur-
ing the migration process (especially of Cr and As)
(Fan et al., 2019; Koski et al. 2020).
Water Air Soil Pollut (2021) 232: 429
Overall review of the application of BAs from syn-
thesis procedure, physicochemical properties, mecha-
nisms, and potential risks in water environment is of
vital importance for guiding the subsequent investi-
gation. Importantly, information gaps exist in focus-
ing on monitoring the potential risks of HM-contain-
ing BAs which migrate into the water environment.
Therefore, in this review, we critically discuss (i) the
synthesis and modification methods of BAs, (ii) the
capacity of pristine and modified BAs for the removal
of constant/variable valence HMs in aqueous environ-
ment, (iii) the key influencing factors on HM removal,
(iv) the mechanism of the interaction between HMs
and functional BAs, (v) potential risks of waste BAs
on life health, and (vi) challenges and future direction
of BA practical application.
2 The Sources, Synthesis Methods, and Properties
of BAs
2.1 Sources of BA Materials
Biomass substances have been extensively used as the
feedstock of BA preparation. In this article, we classify
it into three types from the raw biomass property of
component, structure, and physicochemical characters.
The first one is agricultural and forestry wastes (rice
husk, straw, livestock, heat straw, wood chips, sugar-
cane, bagasse, etc.) (Abdelhadi et al., 2017; Bishay,
2010; Eldemerdash, 2011; Lim et al., 2015), which
usually contain flourishing cellulose and lignin system
in their bodies, as well as high density from the inter-
nal microstructure; thus, they may form more complex
network structure after being pyrolyzed. The second is
urban organic wastes (e.g., sludge, kitchen waste, fruit
peel, poultry manure) (Oguntade et al., 2019; Othman
et al., 2013), which contain abundant organic fraction
and high moisture content and are easily be fermented;
as a result, the components in these wastes become
more complicated. The third is other biomass types
(algae, wetland plants) (Stavi, 2013), owing to their
special growing environment causing their bodies to
be full of nitrogen, phosphorus, and potassium. Thus, it
may perform more complicated interaction with HMs
than that of normal plants, and these also show the
potential for application in certain adsorption of con-
taminants and water, and soil remediation.
Page 3 of 22 429
2.2 Comprehensive Properties of BAs
The HM removal efficiency by using BAs is closely
related to their physicochemical properties and
depends on the condition if the BAs are suitable for
applying to practical water treatment. To make the
comprehensive properties of BAs clear and further
investigate the function of most HMs, it is undoubt-
edly significant to know the structure, morphology,
and intrinsic nature of BAs.
2.2.1 Physicochemical Properties
The property of BAs is mainly dependent on the
origin of the raw biomass materials because so
many research studies have suggested that differ-
ent effects were observed with different biomass
adsorbents for removing the same ions. Firstly, the
oxygen-containing functional groups such as –OH,
–COOH, –R–O, and –R–O–H (Adeniyi et al., 2019;
Lin et al., 2017a, b; Liu et al., 2018a, b; Yang et al.,
2020) can largely intensify the capacity and selec-
tivity of BAs on certain HMs. Significantly, the oxy-
genated functional groups on the surfaces of BAs
modify their surface structures, thus changing their
physicochemical nature. For example, Nakakubo
et al. (2019) synthesized three new dithiocarbamate
(DTC)-modified cellulose biomaterials (DMC-1,
DMC-2, and DMC-4) to investigate the adsorp-
tion capacity on As(III); amazingly, among the
two different inorganic species of As (arsenite(III)
and arsenate(V)), DMCs showed highly selective
adsorption on As(III) in the pH range 2–7. Sec-
ondly, the particle size of BAs directly influenced
the sorption capacity due to the specific surface
area, porosity volume, and irregular surface which
are closely related to the particle characteristics
(Karamia & Mohammadib, 2019). Thirdly, the
intensity of the internal force between BAs and ions
also depends on their adsorption stability; how-
ever, this stability can be attributed to the chemical
adsorption and physical adsorption which simulta-
neously happened on the BAs’ surface (Quinones
et al. 2017). Based on the adsorption–desorption
equilibrium in aqueous environment, the adsorbed
HMs and their compounds may detach off again as
the external condition changed, causing the second
pollution (Sutherland & Venkobachar, 2020).
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429 Page 4 of 22
In addition to another major function/property
of BAs, however, removing HMs according to their
adsorption is not always, but converting a toxic ion
to its nontoxic state by redox reaction of BAs. For
instance, some biochar with redox-active moieties
(RAMs, i.e., phenolic –OH, semiquinone-type per-
sistent free radicals (PFRs), and quinoid C = O) can
induce complex oxidation–reduction while in a cer-
tain pH condition and oxygen supply (Zhong et al.,
2019). There exist complicated processes on the BAs’
surface once the oxygen was activated by the func-
tional groups, and the Eh (reductive potential) values
of the ­H2O2/H2O and ·OH/H2O couples were much
higher than those of the As(V)/As(III) couples in the
pH range of 3.0 to 9.5. In this condition, both ­H2O2
and ·OH can directly oxidize As(III) to As(V). Fur-
thermore, studies are required urgently for mechani-
cal strength (Li et al., 2020a, b), biodegradability
(Wang et al., 2019a, b), and thermal stability (Chin
et al., 2020), which played major roles in the phys-
icochemical performance of BAs and as a tested cri-
terion to know if the material can be applied in practi-
cal wastewater treatment.
2.2.2 Biocompatibility
During the preparation, utilization, discarding, and
recovery processes, BAs will inevitably be released
and migrated into the environments. Due to the
hydrophilic properties, complicated components, and
size effects of BAs, they have an indefinite impact on
natural environments, especially on aquatic environ-
ments and living organisms (Sun et al., 2020). Thus,
Fig. 1  The concluded
synthesis technique path of
various BAs
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Water Air Soil Pollut (2021) 232: 429
the potential impact of BAs on the environment can-
not be ignored. For example, in previous reports (Lian
& Xing, 2017), the black carbon had an important
impact on the aqueous ecosystems according to the
release of contaminants (HMs, free radicals, organ-
ics), as a carrier of pollutants and toxicity to biota
(aquatic plants, microbes). Especially, the containing
substances (HMs, organics, or complexes) released
from adsorption-saturated BAs play an important
role in deterioration in water and soil environment.
However, the BA particles in water or soil can sup-
ply microenvironment for microorganisms and, as
a result, enhance their corresponding life activities.
Besides, some kinds of BAs can also supply nutrients
for plants and exhibited considerable biocompatibil-
ity. The detailed influence and comprehensive poten-
tial risks by amending BAs on ecosystem and life
health will be reviewed and proposed later (Zhong
et al., 2018).
2.3 Synthesis of BAs
Over the past decades, since the biomass materi-
als were gradually discovered by researchers for the
treatment of water pollution, a variety of techniques
followed by the application had been developed to
prepare BAs. Usually, the synthesis technology can
be classified into straight pyrolysis and functional
modification and can be seen in Fig. 1. In the “straight
pyrolysis” process, various raw biomass materials
were cut up and put into a furnace, then pyrolyzed
at different temperatures; usually, the fast pyroly-
sis (300–1000 ℃, anhydrous) and slow pyrolysis
Water Air Soil Pollut (2021) 232: 429
(350–550 ℃, oxygen-free) could realize a diversity
of structure and further influence the function and
capacity of adsorbent (De la Rosa et al., 2017; Zhu
et al., 2018). In the “functional modification” process,
the molecule with special function and nanoparticles
were induced to decorate the surface of raw biomass
materials or pyrolyzed biomass.
2.3.1 Straight Pyrolysis of Biomass Wastes
This part focused on introducing the consequences
of pyrolysis technology on BAs’ adsorption capacity
at different conditions and how it affects the sorption
property of HMs. Various factors including eventually
pyrolysis temperature, type of raw biomass substance,
humidity, and supplement of oxygen (Elnour et al.,
2019; Hassan et al., 2020; Li et al., 2019) can affect
the pyrolysis efficiency and subsequently change the
BAs’ productivity or physicochemical properties.
Firstly, the different pyrolysis temperatures
result in a distinct fraction of products in which
300–1000 ℃ is 12% of biochar, 350–550 ℃ is 25%
of biochar, and 300–380 ℃ with no oxygen supplying
is hydrochar (Amen et al., 2018). Furthermore, the
main element fraction (O/C, H/C, C/N) on the BAs’
surface is also impacted by the pyrolysis temperature
with the surface groups decreasing. For example, the
quantity of functional groups such as –OH, –COOH,
and R–C = O– tended to decrease with the increase
of pyrolysis temperature and the productivity lost
sharply at over high temperature (over 900–1000 ℃)
due to the organics which may be decomposed (Efika
et al., 2018; Kah et al., 2017; Lian & Xing, 2017),
then the fiber structure collapsed. This consequence
directly changed the surface morphology and pore
volume which played a vital role in HM adsorption.
Secondly, the types of biomass also played a crucial
role and led to distinctions in pyrolysis results. The
surface morphology of pyrolyzed BAs from different
types of agriculture and plant wastes, urban organic
wastes, and fermentation products was usually lay-
ered, needle-like, fibrous, and columnar structures
(Chen et al., 2020a, b; Jung et al., 2019; Lopi et al.,
2016; Zhao et al., 2019). These morphologies and
special structures were straightly attributed to the
intrinsic property of the pristine biomass. For exam-
ple, plant biomass, such as ditch reed and straw, with
high content of fiber, but the bone biomass usually
consists of inorganic, which results in the former
Page 5 of 22 429
looks like groovy and the latter looks like porous.
Thirdly, the oxygen supply can affect the physico-
chemical nature of BAs; according to a combination
with most of the elements on the BAs, a high tem-
perature may cause incomplete pyrolysis and, subse-
quently, the number of pores decreased obviously and
the pore size increased (Banik et al., 2018). Lastly,
other conditions such as biomass moisture content,
intrinsic ions, and contact area during pyrolysis can
also cause the change of BAs’ properties. The water
in BAs can occupy a volume when pyrolysis reaction
occurred, and further change its pore size (Udayanga
et al., 2019). Intrinsic ions played an important role
in ion exchange behavior of HMs, and its content or
type can affect sorption capacity (Wu et al., 2020).
For example, the ­Ca2+, ­Mg2+, and ­K+ usually con-
trol ion exchange reaction in most of cationic HMs,
but the ­PO42−, [Al(H2O)x(OH)y]n captured HMs from
other paths such as sedimentation or complexation
(Gupta et al., 2020).
Besides, the pH of solution and BAs have the same
obvious impact on adsorption capacity, owing to the
homoion effect on the surface of BAs (Huang et al.,
2017a, b). The pH of BAs is closely related to that of
surface groups and intrinsic ions. Based on these con-
siderations, Bandara et al. (2020) prepared six bio-
char samples from six types of agricultural wastes via
a slow pyrolysis batch technology at a ramp rate of
2 ℃/min, to a holding temperature of approximately
550 ℃. Seven types of HMs were selected to test the
sorption capacity, and as a result, the surface char-
acters may partly depend on their functional groups
during the pyrolysis process.
2.3.2 Functional Modification
Pristine biomass often exhibits poor adsorption per-
formance on contaminants due to its limited surface
area, pore volume, and active sorption sites. Thus,
present modification methods involving acid–alkali
treatment, surface group decoration, and composite
doping were induced to prepare various BAs.
Firstly, chemical treatment (acid or alkali) of bio-
mass is applied to increase its porosity and surface
area by extracting soluble organics, destroying some
sensitive groups, and profiting to eliminate coloration
of the treated water (Ngah & Hanafiah, 2008). The
cellulose was isolated from corncob and treated with
7% NaOH and 12% urea solution, then subsequently
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429 Page 6 of 22
grafted with acrylic acid and polyacrylamide as was
reported by Wichaita et al. (2015). From this study,
the modified adsorbent was used for Cu(II) and Ni(II)
removal from aquatic solution and the adsorption
capacity was up to 52–99% in the concentration range
of 8–12 mg/g. However, it is laborious to control the
concentration of acid or alkali as well as to deter-
mine how long the reaction spent can obtain the opti-
mal treatment effect to avoid BAs excessively being
destroyed by the solution. Furthermore, the pretreat-
ment conditions will change when different raw bio-
masses were treated. Moreover, though in most situ-
ations this treatment method can roughen the surface
of biomass and further efforts for increasing specific
surface area are needed, the low social acceptability
of a large amount of acid/alkali solution emission is
often inevitable (Chen et al., 2020a, b).
Subsequently, adsorbing HMs on BAs is a compli-
cated process because it involves physical and chemi-
cal interaction. In this case, decoration of surface
functional groups is of vital importance to reinforce
the comprehensive capacity of BAs. These decora-
tive methods involve roughing, grafting, and opti-
mizing structure. Duan et al. (2019) prepared a sur-
face-functionalized biosorbent (CSDTC) by grafting
macromolecular and converting the surface charge
into negative (C–S−), and the network structure of
surface group supplied a large area for ion complex-
ation. Not only that, recently, more and more novel
methods, of complex biomass material modification,
have been explored to harmonize the diverse capac-
ity on different ions as well as enhance the selectivity
of certain HMs in a multiple contamination aquatic
environment.
Furthermore, doping metallic oxide on the sur-
face of BAs is another powerful strategy to reinforce
its performance. Usually, the objective of doping is
closely related to the characteristics of the target pol-
lutant because the HMs can form precipitation with
doping metallic oxide on the BAs’ surface. Typically,
the metallic oxides, such as F ­ e3O4, ZnO, and M ­ nOx,
and aluminum oxides are widely induced to improve
the performance of BAs (Tariq et al., 2020). The main
interaction can be concluded as coprecipitation, elec-
trostatic adsorption, complexation, and formation of
new metal covalent bond. Recently, an investigation
of Zhong and his colleagues (2018) suggested that
magnetic biochar (MBC) conducted PFRs through the
presence of active F ­ e3O4 and carbon-centered PFRs
13
Water Air Soil Pollut (2021) 232: 429
in the porous and graphitic MBC. Subsequently, the
radicals can convert Cr(VI) to Cr(III).
Table 1 concludes the recent attention on synthesis
methods and other related characteristics of BAs in
performing HM separation. The synthesis/modifica-
tion method and influencing factors of BAs on HM
removal were analyzed and are discussed as follows.
3 The HM Removal Behavior of BAs
3.1 Applications of BAs on Typical Constant
Valence HM Removal
In the past decades, rapid industrial activities and
technical developments have made HM pollution
a problem, both in China and worldwide. Espe-
cially, in the mining process, wastewaters contain-
ing Cu, Zn, Pb, Cd, Ni, etc., were largely produced
along with the washing effluent (Jimenez & Ulbricht,
2019; Peiyu et al., 2020). These metals with the same
electrical characteristics and their valence states are
hardly changed in ordinary condition. Importantly,
these HMs cannot be degraded in water even with
the action of redox effect and finally cause biotoxicity
even at low concentration.
To separate these constant-valence HMs from
aquatic environment, techniques mentioned before
including sedimentation, coagulation, complexa-
tion, membrane separation, reverse osmosis, and
adsorption have been used (Cao et al., 2011; Ling
et al., 2017; Zhong et al., 2018). The BA materials
such as biochar, modified biomass, and dry sludge
or cells exhibited excellent performance, owing to
their being environmentally friendly, low cost, and
social acceptability. To date, most studies of the
use of BAs to remedy such divalent metals mainly
focused on improving sorption capacity or investi-
gating the dominant influencing factors. Corn stalk
(Li et al., 2020a, b), rice straw (Deng et al., 2020),
bamboo (Lin et al., 2012), lignin fiber, and other bio-
mass after pyrolyzing or modifying have achieved a
removal effect of 284 mg/g of ­Ni2+ and 48.6 mg/g
for ­Cd2+. However, in coexisted ion system, the BAs
obtain a very distinct sorption effect on a component.
For example, a biosorbent was carried out to treat a
mixture containing Cd, Cu, and Zn and the adsorp-
tion capacity followed the order Cd (90.7 mg/g) > Zn
(74.6 mg/g) > Cu (57.3 mg/g) from the adsorption
Water Air Soil Pollut (2021) 232: 429 Page 7 of 22 429

Table 1  The source of raw BAs and its application on the removal of various HMs
Raw materials Synthesis/modifica- Target pollutant Sorption efficiency Optimum pH Reference
tion methods

Pine wood char Mn oxide–modified Arsenate/Pb 47.05 g/kg & 4.91 g/ – (Shengsen et al. 2015)
kg
Rice husk char Pyrolyzed at 300 ℃ As(V) 2.59 µg/g 6.7–7.0 (Agrafioti et al.,
and modified by 2014a, b)
­Ca2+, ­Fe0, and
­Fe3+, respectively/
pyrolyzed at
300 ℃, oxygen-free
Activated sludge Dried at 60 °C to Cr(VI) 204 mg/g 1.0–4.0 (Wu et al., 2010)
constant weight,
HCl solution
(0.1 mol/L) treated
for 8 h
Activated sludge char Pyrolyzed at a maxi- As(III) 0.07 mg/g 3.0–3.5 (Tavares et al., 2012)
mum heating ramp
of 30 °C/min, from
room temperature
to a final tempera-
ture of 550 °C and
at an He flow rate
of 100 mL/min
Pine bark char Pyrolyzed at 300 ℃ As(III) 13 5.0 –
Eichhornia crassipes Oven-dried at 70 °C Cd2+/Zn2+/Cr(VI) 12.4/9.3/5.6 mg/g 5.0/6.0/2.0 (Shweta & Rai, 2010)
char for 48 h, ground,
and sieved through
a 2-mm sieve
Lignocellulosic char Modified with N-bro- Pb2+/Cd2+ 381.7/278.6 mg/g 5.0 (Lin et al. 2012)
from bamboo mosuccinimide and
epichlorohydrin
Sunflower char Sunflower powder Ni2+/Cd2+/Cr(VI) 0.45/0.32/0.28 mM/g – (Jain et al., 2015)
mixed with con-
centrated ­H2SO4
in the ratio of 2:1
­(H2SO4:sunflower,
v/w) and carbon-
ized at 150 °C in
a hot air oven for
24 h; finally soaked
in 2% ­NaHCO3
(w/v) overnight
Streptomyces rimosus – Zn2+ 80.0 mg/g 7.5 (Sahmoune & Nasser,
2018)
Sesame straw biochar Slow pyrolysis at Pb2+/Cd2+/Cr(VI)/ 102/86/65/55/34 mg/g – (Park et al., 2016)
700 °C and limited Cu2+/Zn2+
oxygen for 4 h in
a stainless airtight
container
Chicken bone Drive the internal Cu2+/Cd2+/Zn2+ 130/109/93 mg/g – (Park et al., 2015)
biomass chamber
temperature to
600 °C at a rate of
10 °C/min for 4 h

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429 Page 8 of 22
Table 1  (continued)
Raw materials Synthesis/modifica- Target pollutant
tion methods
Walnut shell Slow pyrolysis Cu2+/Pb2+
at a nitrogen
flow of 900 mL/
min, following 2
temperature set-
tings (350 °C and
550 °C) for 2 h
with a heating rate
of 5 °C/min
equilibrium isotherm, but this study failed to explain
the mechanism and sorption behavior which occurred
in the process (Suzuki et al., 2005). In our previ-
ous study (Luo et al., 2018), the NaOH/CO(NH2)2/
acrylonitrile-modified biochar showed excellent
sorption capacity on C­ d2+ in laboratory batch experi-
ment; however, when the biochar was used for puri-
fying wastewater which contains C ­ d2+ and C­ a2+,
2−
­SO4 achieved poor capacity and will be invalid
for a short time. Though these BA materials have
achieved considerable removal performance in batch
experiment, the practical HM-containing wastewaters
with more complicated components and other con-
taminants may further restrain the adsorption process
and even cause the invalid of adsorbents (Fang et al.,
2020).
3.2 Applications of BAs on Variable Valence HM
Removal
It is different from most of the constant-valence
metal ions which are usually removed from solu-
tion by adsorption. The variable valence ions can be
converted to other valence states and may show high
toxicity in the water environment. Typically, arsenic
exists in the form of − 3, 0, + 3, and + 5 values and
chromium in the form of + 3 and + 6 values in solu-
tion with the change of redox conditions (Anand-
kumar et al., 2020). The conversion of highly toxic
metal ions into low toxicity state is also a strategy to
dispose the HM pollution. Investigations on oxida-
tion of As(III) (Zhong et al., 2019) and reduction of
Cr(VI) (Zhong et al., 2018) have been already carried
out for conversion of metal ions in previous reports,
such as Fenton oxidation, photocatalysis redox, ozone
and ­Fe0 reduction, and so forth (Jokai et al., 2020).
13
Water Air Soil Pollut (2021) 232: 429
Sorption efficiency Optimum pH Reference
2.4%/6.1% 7.89 (Wang & Liu, 2017)
However, these techniques often rely on external
energy or chemical reagents, and it inevitably caused
different second pollutions.
Developing an economical self-driving reaction
of BA technology is no doubt that can remove HMs
from aqueous ecology expediently. For example, the
oxidation removal process of As(III) by converting it
to As(V) was exhibited in Fig. 2. Amazingly, this oxi-
dation process is spontaneously induced on biochar
surface and relies on no external oxidant due to the
special oxygen-containing groups that can be stimu-
lated by oxygen and produce ·HO2 and ·OH radicals.
Another key information was the oxidation behavior
which is dependent on solution pH values. This may
be because the concentration of ­H+ controlled the tar-
get electron donor and thus changed the converting
pathways of active radicals. This discovery of biochar
with oxidative activity guides for further understand-
ing of the BAs’ properties especially the design of
functional groups. Though this behavior of oxygen-
containing group developed a new insight ignored
before, this conversion process just changed the for-
mation of HMs but failed to separate them from solu-
tion; thus, these low-toxicity ions may be converted to
toxic state (As(V)) again while the redox conditions
changed.
To remedy this gap, another strategy is to adsorb the
high toxicity ions and then change its valence by oxi-
dation or reduction. For instance, the core–shell Fe@
Fe2O3 nanowires can capture Cr(VI), at the first time,
the reduction of Cr(VI) followed by the surface-bound
Fe(II) besides the reduction of Cr(VI) adsorbed on the
iron oxide shell via the electrons transferred from the
iron core (Yi et al., 2015). The distinction between
redox and sorption-redox was that the latter not only
decreases the toxicity of HMs but also separates the
Water Air Soil Pollut (2021) 232: 429
Fig. 2  The spontaneous oxidation process on As conversion and removal on the surface of biochar (Zhong et al., 2019)
ions out of water along with the separation of sorb-
ents. From another point, it is also discrepant of con-
stant-valence HMs and variable-valence HM disposal.
The single ion system is often much easier to adsorb
by BAs than that of combined pollution, owing to
the BA materials which exhibited selectivity of vari-
ous valence ions. As a result, these different valence
states of the single ion cannot be separated completely
from the water environment. In summary, it is better to
simultaneously adsorb HMs and oxidate/reduce than
to only change their valence to decrease risks in water
environment, and the HM-combined pollution system
can affect the sorption capacity of BAs.
3.3 Impact of Solution pH on Adsorption
Performance of BAs
The formation of HM ions in aqueous environment
straightly depended upon the pH value of solution,
and usually, the HM element exists in ions with a
low pH value; on the contrary, the HM element will
tend to form precipitation, and when the pH value
is at around 7, the elements existed in both ion state
and precipitation state. The reason and process of
solution pH values for the interaction of ions and
adsorbents are extremely complicated based on
sorption–desorption equilibrium, ion competition,
surface charge of BAs, and other effects (Bandara
et al., 2020). For example, in the acid solution, H­ +
Page 9 of 22 429
will be first attracted by the active sites on BAs,
causing the decrease adsorption amount of ­ Cd2+
2+ +
and ­Cu ; in most cases, ­H is more possibly cap-
tured by adsorbents than by other cations. This phe-
nomenon might be ascribed to ­H+ having the lower
binding energy with other elements or it is more
instrumental in decreasing the chemical energy of
a reaction system. Besides, the pyrolyzed BAs must
be charged due to the ionization of surface group or
its intrinsic ions (e.g., ­Ca2+, ­Mg2+, ­K+, ­Na+, ­Fe2+,
­Fe3+, ­CO32−, ­OH−); in this way, it is favored to cap-
ture the HMs at a high pH value rather than at low
pH values (Wieszczycka et al., 2020). These com-
plicated interactions happened in solution and the
BAs’ surface, such as electronic interaction, ion
exchange, precipitation, and complexation, depend-
ing on the critical influences of pH value on the
removal of various HMs. Besides, the temperature
of the reaction system can also influence the inter-
action of HMs and BAs because the temperature of
the reaction system not only accelerates molecular
motion and changes solution pH indirectly, but also
affects the solubility of HMs.
3.4 Impact of Coexisting Ions on Adsorption
Performance of BAs
In the practical wastewaters discharged from indus-
tries, mine leaching, or in other natural waters, there
13
429 Page 10 of 22 Water Air Soil Pollut (2021) 232: 429

Table 2  Characteristics of groundwater samples (GW1 and related to the properties of water samples and the
GW2) collected from Vehari and Burewala that were used to different anions showed quite diversity in a mixture
quantify the impact of coexisting inorganic ions on the removal
of Pb(II) from contaminated water (Meseguer et al., 2016)
polluted by HMs. Besides, evidence proved that the
presence of ­SO42− ions significantly affected the sorp-
Characteristics Units GW1 (Burewala) GW2 (Vehari) tion potential of Cr(VI) by tea waste as compared to
Mg 2+
mg/L 60 ± 3.2 45 ± 2 ­PO43− and N ­ O3− (Khalil et al., 2018). Excavating the
Na+ mg/L 287 ± 7.3 50.3 ± 4 interaction of coexisting ions and biosorbent is neces-
K+ mg/L 19.5 ± 1.8 5 ± 0.25 sary to further understand the deep mechanism and to
Ca2+ mg/L 129 ± 6.3 34.9 ± 4 obtain a considerable treatment effect.
CO32− mg/L 98 ± 3.8 60 ± 4
HCO3− mg/L 183 ± 6 244 ± 8.4
Cl− mg/L 1416 ± 10 566.4 ± 8 3.5 Impact of Microorganism Inoculation on HM
Pb2+ µg/L 30 ± 3.6 18 ± 3.2 Removal

The truth that HMs adsorbed on BAs will leach out

is usually not one type of HMs but coexisting various
types of ions in water environment, including a variety
of metal ions ­(Ca2+, ­Mg2+, and HMs), ­CO32−, ­HCO3−,
­PO42−, ­SO42−, ­NO3−, and ­Cl−. These coexisting ions
in water body play a crucial role in restraining the nat-
ural adsorption process of target HMs (Reddy et al.,
2011; Vilvanathan & Shanthakumar, 2015). For exam-
ple, in a study on Pb(II) removal by using a biosorbent
(Imran et al., 2019), the biosorption and removal rate
decline obviously with the increase of biosorbent dos-
age in treating two groundwater samples (the charac-
teristics of these two samples are shown in Table 2),
and the explanation causing this phenomenon may be
­ a+ and ­K+ ions with
attributed to the poor affinity of N
Pb(II) as compared with an affinity of C ­ a2+ and ­Mg2+
ions (Meseguer et al., 2016).
However, an opposite result demonstrated the
nonsignificant effects of cations on the biosorption
potential of modified Moringa oleifera for Cd, Ni,
and Cu using salt of the respective cations individu-
ally in each metal solution (Reddy et al., 2012). This
may suggest that the cations have different impacts
on various biomass materials in the presence of
some special groups and have the intrinsic nature in
conjunction with each ion. Subsequently, the anions
­(CO32−, ­HCO3−, ­Cl−) were also induced to inves-
tigate the influences on adsorption performance
of Moringa oleifera biosorbent. Distinctions were
observed in the two groundwater samples of which
the removal capacity on C ­ O32− is 98 ± 3.8 mg/L and
60 ± 4 mg/L, that on H ­ CO3− is 183 ± 6 mg/L and
244 ± 8.4 mg/L, and that on ­Cl− is 1416 ± 10 mg/L
and 566.4 ± 8 mg/L, respectively. This result reflected
that the impact of anions on removal was closely
into the solution constantly again and will threaten the
safety of the water environment has arisen as a world-
wide concern of researchers. Based on this defect,
there are two countermeasures. The first one is to sepa-
rate BAs from solution and take regeneration for recy-
cling. The second is inoculating microorganisms onto
BAs to intensify the accumulation capacity and even
achieve the mineralization of HMs adsorbed on BAs.
Recently, further investigation on the intensifica-
tion and stability of BAs has been carried out for HM
removal by inoculating certain ion-resistant micro-
organisms in an experimental study (Aftab et al.,
2020; Al-Hagar et al. 2020; Xue et al., 2020). Due
to the fast-generation, high survival rate, nutrient
substances can be obtained from water polluted by
HMs, and microorganisms such as bacteria, fungi,
yeast, and microalgae have been studied in the appli-
cation of stability and/or removal of HM ions from
the aqueous environment (Singh et al., 2016; Siva-
kumar, 2016; Vendruscolo et al., 2016). From the
report of Tu et al. (2020), the biochar was used as
a carrier for immobilizing the Cd–Cu-resistant strain
NT-2; subsequently, ­Cd2+ and C ­ u2+ compounds were
partly mineralized and converted into a more sta-
ble state. However, these reports lack investigation
by inoculating pure microorganisms for HM uptake
because they were hardly separated after contamina-
tion sorption and, also, the microbial cells were eas-
ily impacted by the shock resistance of wastewater.
From the above point of view, the key technology
of HM-polluted water remediation is to screen and
develop bacterial strain which can resist certain con-
centration of HM ions in aqueous or soil environment
and can be fixed on the carriers such as BAs. The

13
Water Air Soil Pollut (2021) 232: 429 Page 11 of 22 429

viable Bacillus bacteria immobilized onto different
biochars were used for C ­ d2+ removal. The biosorp-
tion by these immobilized cells was superior when
compared to cells in suspension (Bandara et al., 2020).
High biosorption capacity was the result of simulta-
neous adsorption from biochar and bacteria, in which
the bacterial cells contributed more than the biochar
matrix to total removal. Furthermore, the studies
based on pretreatment of biomass by functional bac-
terium were also carried out to prove the intensifica-
tion on BAs’ capacity. For instance in a study of Xue
et al. (2020), a cellulose-degrading bacterial strain was
used to modify the rice straw. As a result, this method
can obtain much rougher surface than raw BAs and
largely improve its specific surface area. The evidence
of this enhancement was proved and attributed to the
cellulase system secreted by strain FJ17 which disinte-
grated the epidermal structure of rice straw to expose
the vascular bundle and the parenchyma area. Finally,
Table 3 concludes the recent use of microorganisms
associated with BAs for HM separation or immobili-
zation from water media, and the corresponding fac-
tors including type of BAs, target HMs, amendment
dosage, and sorption capacity are listed, respectively.
4 Mechanisms
To attain further comprehension of HM removal behav-
ior by BAs and BA-based purification technologies, we
reviewed most of the concluded mechanisms from pre-
vious reports. The possible interaction between pollut-
ants and BAs typically includes surface complexation
and precipitation, electrostatic attraction, ion exchange,
and oxidation–reduction. The detailed processes are
shown in Fig. 3 and depicted as follows.
4.1 Complexation and Precipitation
Firstly, the complexation effect was divided into sur-
face complexation and inner-sphere complexation and
usually relies on functional groups of BAs; for exam-
ple, the functional groups (–OH, –COOH, –NH2,
–SO3H) in BAs provide binding sites and strongly
attract HMs combined with the certain element
(Adeniyi et al., 2019; Liu et al., 2018a, b; Yang et al.,
2020). Briefly, HMs or their complexes can form a
special bond with atoms or radicals on the surface of
BAs, resulting in the migration of ions from the solu-
tion to the BAs’ surface (Sun et al., 2011). This bind-
ing strength usually showed certain stability and was
affected by the type of HMs. For example, the bind-
ing energy of is 404.1 eV for Cd–O, 1021.7 eV for
Zn–O, 933.9 eV for Cu–O, and 137.5 eV for Pb–O,
on BAs (Ali, 2012). Secondly, HM ions may also
form precipitates with metal ions in BAs especially
for BAs of high mineral content, and this also can be
divided into direct precipitation and coprecipitation
with other metals (especially mineral ions). The direct
precipitation and coprecipitation can be attributed

Table 3  Influences of microorganism inoculation on HM removal efficiency

Name BAs Target HMs Initial con- Capacity (mg/g) Removal rate (%) Reference
centration
(mg/L)

Microbial Turmeric residue Cu2+ 120 13.12 40 (Hu et al., 2019)

Aspergillus aus- Chitosan/alginate Cu2+ 20 26.1 79 (Contreras-Cortés
tralensis et al., 2019)
Bacillus megaterium Wheat straw Cd2+ 2.5 – 84.5 (Xiao et al., 2021)
Phosphate-solubiliz- Rice husk Pb2+ 1000 12.17 60.85 (Chen et al., 2019)
ing bacteria
Bacillus subtilis Corn straw/pig Pb2+/Hg2+ 1040/1000 181.3/136.7 – (Wang et al., 2017)
manure
Enterobacter sp. Alkaline biochar/ Cd2+ 1000 – 78.9/30.2 (Chen et al., 2020a,
acidic biochar b)
Pseudomonas sp. Maize biochar Cd2+/Cu2+ 56/247 – – (Chen et al., 2020)
NT-2
Bacillus cereus NS4 Cinnamomum Ni2+ 50/100 – 74/46 (Zhang et al., 2019)
leaves

13
429 Page 12 of 22
Fig. 3  Conceptual repre-
sentation of the potential
mechanisms for the immo-
bilization and removal of
HMs on BAs
to metal’s inherent interaction and sediment forma-
tion with –OH in BAs. These surface complexation
and precipitation interactions could be depicted by
observing alterations in the position of spectral bands
associated with functional groups after adsorption of
a toxic element. The XPS and FTIR spectra are usu-
ally induced to reflect the changes of used BAs from
pristine BAs, the deviation of binding energy and the
valence of element or special peak position, demon-
strating that contamination is adsorbed and combined
with materials.
4.2 Electrostatic Interaction
Most of the BAs are charged, owing to the internal
metal cations (e.g., ­Ca2+, ­Mg2+, ­K+, ­Na+, ­Al3+) and
surface groups. The valence and number of cations
and anions depend on its surface-charged property.
The HM cations can be captured when the surface
charge is negative, and in contrary, the HM anions
were adsorbed easily than cations. The zeta poten-
tial played an important role on charged particles
and can be used to reveal the surface potential of
BAs. Reports have illustrated that the high elec-
tronegativity of biochar improved the sorption
capacity of positively charged ions (Ahmad et al.,
2018). In addition, homoion effect can constrain
the adsorption of target HMs because the active
13
Water Air Soil Pollut (2021) 232: 429
sites were occupied by other ions in homogeneous
aqueous media (Wang & Harrell, 2005). For exam-
ple, the effect of ionic strength on Cd(II) sorption
was much more apparently caused by ­Ca2+ than
by ­K+ in ­CaCl2 solution, the higher valence state
of ­Ca2+ caused a stronger limit for Cd(II) removal,
and the surface charge of the BAs was changed by
increased ionic strength, especially in case of pH
close to ­pHpzc (R. et al. 1994). In another study
(Wang et al., 2015), it was revealed that the biochar
surface was positively charged at pH 7 due to pro-
tonation of the surface functional groups as pH was
lower than the ­pHpzc, indicating that the electro-
static interaction between As and biochar was the
main sorption mechanism. Another discovery dem-
onstrated the surface charges generated by surface
groups which became increasingly negative at high
pH values (Cho et al., 2010; Tong et al., 2011).
4.3 Ion Exchange
Ion exchange effect, as one of the major removal path-
ways from aqueous environment, can be divided into
anion exchange effect and cation exchange effect. The
ion exchange capacity of various BAs is attributed
to their intrinsic ions released and special functional
groups such as ­K+, ­Na+, ­Ca2+, ­Mg2+, –COO–Me,
O–H, and –R–O–Me (Guo et al., 2016). Especially,
Water Air Soil Pollut (2021) 232: 429
the cation exchange capacity (CEC) of BAs based
on groups was usually derived from plants and the
dominant CEC ascribed to ­Ca2+ or ­Mg2+ was mostly
obtained from animal bones (Sicong et al., 2018).
Both the two main strategies with high CEC can
improve the adsorption capacity for HMs (Tang et al.,
2013). The net amount of alkali metal ion released
from solution after HM adsorption on biochar was
measured in the study by Wu et al. (2019), and the
change of certain concentration of ions illustrated that
ion exchange effect occurred during the adsorption
process. Usually, the selection of ion exchange pro-
cess on different HM ions is depicted in Eq. (1).
1 1 1 1
A + A ⇔ A1 + A2 (1)
z1 1 z2 2 z1 z2
where A1 and A2 represent different ions, A1 and
A2 represent the counter ions, and Z1 and Z2 are
coefficients.
4.4 Oxidation–Reduction
Since all the HM ions cannot be degraded, they fell
low as persistent and toxic pollutants in the water
environment. Some of them can be oxidized or
reduced from one valence state to another, resulting
in a decrease of biotoxicity. Oxidation and reduction
were considered as another important method to solve
some certain HM pollution in the water environment.
The typical conversion of As(III) to As(V) and of
Cr(VI) to Cr(III) is considered as an effective path-
way for alleviating its toxicity (He et al., 2020a, b).
BA materials, with variable functional groups, mor-
phology, and property, especially the corresponding
RAMs (i.e., phenolic –OH, semiquinone-type PFRs,
and quinoid C = O), can release persistent radicals
(Zhong et al., 2019). These radicals exhibited differ-
ent behaviors such as reduction and oxidation while
being stimulated by different media, and this case can
also be seen in Fig. 2. In summary, the reduction and
oxidation properties of BAs were mainly attributed to
their fickle surface groups. However, the HMs with
low toxicity are not stable and can return to toxic state
when external condition changed, especially of pH
and radicals in water.
Page 13 of 22 429
5 Potential Risks of BAs in Water Environment
Until now, adsorption has developed to a power-
ful solution to separate HMs from wastewaters. As
diverse functional sorbents were prepared for immo-
bilizing HMs, however, another problem has been
ignored. The so-called recyclable materials from
experimental activities actually fail to regenerate for
reuse or to collect for reasonable disposal, and finally,
they could migrate into the environment, causing var-
ious negative impacts on surrounding ambient condi-
tions (Bat et al., 2018; Bundschuh et al., 2015). As a
result of threatening the human, animal, and plant life
safety, hence, it is necessary to make people know the
straight and indirect potential risks during BA reme-
diation in the environment.
5.1 The Risks on Ecological Environment
As there is certain regulation on HMs which can
be accepted by water or soil environment from the
WHO, the over emissions of HMs inevitably lead to
potential implication on the ecological environment.
Firstly, the HMs can easily migrate in natural water
bodies from straightly discharging and releasing sedi-
ment or HM carrier (BAs or other adsorbents). Stud-
ies on a migration model of various HMs in river flow
and soil body have been supplied to reflect the law of
pollution on ecological environment. Shunong (1988)
and Shunong and Yingming (1990) first advocated
the use of sediment to analyze river metal pollu-
tion, because under the chemical conditions of water
environment such as temperature, redox factors, and
pH values, the metals will be released from the sedi-
ment and will return to the dissolved phase, causing
second pollution. These sediments have the potential
to convert into other toxic species and accumulate in
aquatic animals (e.g., Mullus barbatus, Merlangius
merlangus, Scophthalmus maximus, Mugil cephalus,
Engraulis encrasicolus, Trachurus mediterraneus,
and Sarda sarda) and plants bodies or even cause
death (Bat et al., 2021). Secondly, the raw and modi-
fied BAs in water will release out other substances,
inducing a series of complicated chain reactions. For
example, reports suggested that the dissolved organic
matters (DOMs) originally from BAs tend to combine
with some certain metals, subsequently migrating in
the aqueous environment (Shiyi et al. 2016). Thirdly,
the amendment of BAs and their migration into water
13
429 Page 14 of 22
will further influence the activity of microorganisms.
Liu et al., (2018a, b) evaluated the potential nega-
tive impact of BAs on urease activity, and the results
showed that biochar inhibited urease activity (indi-
cated by the ­NH4+ generation). This observed inhi-
bition of urease activity may be the result of oxida-
tive reactions with free radicals on the BAs’ surface
or oxidative reactions with reactive oxygen species
promoted by free radicals. Finally, the report on soil
research indicated that biochar pyrolyzed at low tem-
perature demonstrated a higher bioavailability to bac-
teria compared to biochar prepared at high tempera-
ture after adsorbing contaminants (Wang et al., 2020).
Also, in soil environment, the high amendment of
low-density BAs can affect the comprehensive prop-
erties of soil, e.g., structure, content of mineral sub-
stances, moisture content, and nutrients, and as a
result, the soil community structure will be changed
(Mehmood et al., 2018; Yang et al., 2016).
5.2 The Direct Risks on Human Health
The mobility and bioavailability of HMs have aug-
mented concerns due to water/soil contamination,
food safety, and arising health risks. However, lit-
tle information is available on the assessment of the
potential risks for BA application and migrated into
the water environment. Investigating the potential
risk of applying BA materials is an advisable move
to be aware of threat for human health in advance and
take the proper countermeasures. The potential risk
on human from BAs or the waste BAs which have
migrated into the environment often originates from
three aspects. (1) As known for us, BA material is
usually at µm class and existing in powder state; these
fine particles are facile to convert to aerosol with the
action of external force and may be breathed in by
human, and the HM-containing aerosol will damage
the human physiological function (He et al., 2019;
Lee et al., 2004). It is suggested to decrease dust
exposure by spraying water to maintain soil ambient
moisture contents during biochar applications or pro-
duce biochar by pelleting or prilling (Li et al., 2018).
(2) The BA materials, such as HM-saturated biochar,
are usually regenerated with chemical method; how-
ever, the treated BAs still contain toxic substances
and lead to effluents (Duan et al., 2020). Some of
them are untreated and discharged into soil environ-
ment; subsequently, the pollutants may be mobilized
13
Water Air Soil Pollut (2021) 232: 429
by plants or microorganisms. As a result, the con-
taminated vegetation will harm human health through
the food chain. Especially, other toxic chemicals con-
tained in biochar could also induce human health
risks. For example, the PAHs in biochar produced
during pyrolysis in the absence of air led to their
accumulation in vegetables, resulting in increased
risks of human dietary exposure and thus cancer risk
(Wang et al., 2018a, b). (3) The BAs discharged or
migrated into the water environment, on the one hand,
may form sediment and mixed with substrate sludge
as a persistent pollutant. On the other hand, a part of
HMs will be released directly and captured by uptake
of fish, shrimp, or aquatic plant, and finally, it is also
harmful for human health through the food chain and
drinking water. The HM removal process by BAs and
the pollutants’ migration paths on the potential risk
on health are summarized in Fig. 4.
6 Challenges and Future Direction
Over the past decades, researches have focused on
investigating how the BAs and BA-based functional
composites can be applied for solving environmental
issues. The experimental results have also demonstrated
that BAs have considerable application prospects in
contaminant adsorption, degradation, HM mineraliza-
tion, redox, etc. However, knowledge gaps still exist in
our understanding of further studies on the exact selec-
tivity mechanism, practical implementation, and large-
scale commercial application of BAs; importantly, the
regeneration and disposal of waste BAs is also urgent
to be taken seriously. These may include the following:
A) Most of the researches are devoted to improve the
adsorption capacity of BAs by modifying them
with functional groups and grafting with certain
molecules. However, the adsorption capacity is
still constrained by a limited specific surface area
while using different biomass as the precursor. In
addition, BAs are usually difficult to use in the
simultaneously removal of various HMs from
wastewater. In this case, more efforts should be
focused on investigating the influencing factors
of BA synthesis process and properties of various
pristine biomass. Besides, the stability of BAs is
still needed to consider to further achieve practi-
cal application and commercial production.
Water Air Soil Pollut (2021) 232: 429
Fig. 4  The process of overall removal of HMs from aqueous environment by using BAs, and the pollutants’ migration paths on
potential risk on health
B) BAs and BA-based materials have opened up a
new strategy for the development of efficient and
economical water treatment techniques. How-
ever, some damages on ecological environment
by using BAs have been observed from previous
studies. These can be concluded as follows: (1) It
is difficult to separate them from water for recy-
cling in practical applications. (2) The extended
amendment of BAs in soil has illustrated that soil
properties can be changed which may also change
the local ecological environment, and the mobi-
lized HMs on BAs also show bioavailability for
bacterium or plants (Xu et al., 2019). (3) The BA
sorbents are often with fine diameter and are easy
to migrate as dust or aerosol in air, causing inhala-
tion by human. Meanwhile, the BAs widely used
in water purification will remain in the form of
persistent precipitation when they are discharged
into natural water body, causing long-term nega-
tive impact. From these cases, the post treatment
of wasting BAs is particularly important.
C) Mineralization of HMs is often associated with
inoculating microorganism technologies, and the
ions are mobilized in materials according to the
physiological and metabolic activities of bacte-
Page 15 of 22 429
ria, fungi, or protozoans on the surface of BAs.
The microbial community is easily influenced
by the turbulence of wastewater properties and
then loses their normal function; in contrary, the
BAs’ skeleton can supply a safe site for microbial
community from the negative impact of water
polluted by HMs. Therefore, in order to obtain a
deep understanding of the protection mechanism
of BAs on microorganisms, researchers should
pay attention on comparing the protection behav-
ior from different raw biomass–pyrolyzed BAs
and make the precise principle clear by some
more advanced visualization technologies.
D) The DOM, originated from BAs during the pyrol-
ysis process, is possible to dissolve into solution
again and forms complex compounds with HM
ions. Thus, a part of distributed HMs is pre-
vented from adsorbing onto BAs and transfer into
another transportable pollutants. Furthermore,
BAs distributed in the environment played a car-
rier role for most pollutants, as the environmental
condition changed, such as temperature varia-
tions, precipitation events, and microbial activi-
ties, causing drastic changes to the physicochemi-
cal properties and aging. In this field, studies on
13
429 Page 16 of 22
the aging and transformation behavior of BAs
are urgently carried out to eliminate the negative
impacts.
Author Contribution Wei Liu: conceptualization, literature
collection and arrangement, and writing the original draft;
Yingbo Dong: supervision and revision; Hai Lin: supervision;
Yuanyuan Shi: revision. All authors participated and approved
the final manuscript to be published.
Funding This study was funded by the National Natu-
ral Science Foundation of China (51874018), the National
Key R&D Program of China (2019YFC1805002), and the
Fundamental Research Funds for the Central Universities
(FRF-TP-19-014B1).
Data Availability All data generated or analyzed during this
study were included in this published article.
Declarations
Ethics Approval All authors followed the ethical responsi-
bilities of this journal.
Conflict of Interest The authors declare no competing inter-
ests.
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