j.jwpe.2020.101561

Journal of Water Process Engineering 38 (2020) 101561
Contents lists available at ScienceDirect
Journal of Water Process Engineering

journal homepage: www.elsevier.com/locate/jwpe
Latest trends in heavy metal removal from wastewater by biochar

based sorbents
Sarthak Gupta a, S. Sireesha a, I. Sreedhar a, *, Chetan M. Patel b, K.L. Anitha c
a
Department of Chemical Engineering, BITS Pilani Hyderabad Campus, Shameerpet, Hyderabad, 500078, India
b
Department of Chemical Engineering, SVNIT Surat, Surat, Gujarat, 395007, India
c
R&D, H B L Power Systems Ltd., Shameerpet Hyderabad, 500078, India
A R T I C L E I N F O A B S T R A C T
Keywords: Biochar, a solid carbon-rich residue is derived from wide variety of abundantly available raw materials like forest
Biochar and agricultural waste, industrial by products and waste, and municipal solid waste through pyrolysis. Besides
Synthesis protocols enhancing soil fertility thereby agricultural productivity and reducing greenhouse gas emissions, biochar based
Heavy metal removal
sorbents are widely being employed in waste water treatment owing to their attributes viz., high porosity, large
Kinetics and isotherms
Modification
surface area, affinity towards metals, surface modifications, stability, recyclability and even safe disposal. In this
Mechanism comprehensive review, latest trends w.r.t. synthesis protocols, modifications, mechanisms, metal removal
Regeneration comparison, thermo-kinetics, mechanisms, regeneration and safe disposal methods have been presented and
discussed. Synthesis through slow pyrolysis (300− 700 ◦ C, 0.01− 2 ◦ C/s), nanoscale modifications with metal
oxides especially based on iron to magnetise the biochar, regeneration through acids and complexation agents
are found to be highly promising. While ion exchange and electrostatic interactions are found to be common
mechanisms of metal removal which in turn depends on nature of biomass, process conditions and metal, it is
found that modifications and mechanisms are strongly interrelated. From our studies, biochar based sorbents
gave heavy metal adsorption capacities in mg/g of 1217 (Ag), 560 (Pb), 288 (Cu), 216 (Cd), 204 (As), 130 (Cr),
58 (Ni), 48 (Hg) etc under optimal conditions. Though the nature of kinetic models and isotherms do depend on
the material and process conditions, pseudo kinetic models (first and second order) along with Langmuir and
Fruendlich isotherms were most widely reported. Disposal of spent biochar could be using it in construction
(cement and bricks) and electronic (super-capacitors) industries besides phytoremediation.
1. Introduction metals and exceeding these limits could prove to be fatal. Hence, the
removal of heavy metals from contaminated water is both important and
Biosorbents based on biomass have been widely employed in waste urgent [7]. For example, Cadmium is a prevalent heavy metal that
water treatment to remove harmful contaminants like fluorides and causes adverse effects in humans, such as nausea, diarrhoea, and liver
heavy metals [1–4]. Heavy metal pollution, which negatively affects damage, when ingested, inhaled, or absorbed by the skin. Another heavy
human health, is a major global concern. Heavy metals are metal that causes serious environmental and human health related
non-biodegradable and are transferred along the food chain through the problems is nickel, which also happens to be a carcinogen responsible
process of bioaccumulation. Heavy metals such as nickel, copper, lead, for lung and bone cancer in addition to triggering dermatitis and eczema
chromium, and arsenic pose a risk to both indigenous habitats and [8]. Copper, zinc, and mercury are some of the other metals commonly
human health [5] alike. Table 1 summarizes a list of heavy metals with found industrial effluents. Excess concentrations of these metals in the
current maximum permissible amounts of contaminants by Indian water stream can cause maladies related to liver, kidneys, as well as
Standards [6]. The human body requires only trace amounts of these affect the nervous, gastrointestinal, and hematopoietic systems [9]. Lead
Abbreviations: OC, organic compounds; Aq Soln, aqueous solution; Temp, temperature; SA, surface area; Eq, equilibrium; PV, pore volume; Ads, adsorption; NP,
nano particle; S, sulphur; O, oxygen; &, and; (+), positive; (-), negative; ↓, reduce/decrease; ↑, increase; DW, de-ionised water; Atm, atmosphere; PS, particle size; EC,
epichlorohydrin; EG, ethylene glycol; FO, first order; PFO, pseudo first order; SO, second order; PSO, pseudo second order; EM, elovich model; RO, ritchie nth order.
* Corresponding author.
E-mail address: isreedhar@hyderabad.bits-pilani.ac.in (I. Sreedhar).
https://doi.org/10.1016/j.jwpe.2020.101561
Received 19 May 2020; Received in revised form 9 July 2020; Accepted 25 July 2020
Available online 18 October 2020
2214-7144/© 2020 Elsevier Ltd. All rights reserved.
S. Gupta et al. Journal of Water Process Engineering 38 (2020) 101561
Table 1 Similarly, other metals such as chromium, arsenic and silver have also
Heavy Metals and their Maximum Allowable Contaminant Level. been classified as extremely hazardous for the biosphere. Hence, effec
Heavy Metal Max. Contaminant Level by IS (mg/L) tive methods for remediating the contamination caused by these metals
is of utmost importance to the general well-being of the biosphere.
Cu 1.5
Fe 0.3 The ongoing worldwide trends indicate a stronger need to accom
Mn 0.1 plish better ecological norms with minimal utilization of resources for
Hg 0.001 the treatment of effluents. Cost-effectiveness and specialized pertinence
Cd 0.003 are the two vital criteria in the choice of effective adsorbents for the
As 0.05
Pb 0.01
removal of heavy metals. In the recent past, adsorption [11] technology
Zn 15 was found to be widely deployed in the treatment of wastewater.
Cr 0.05 Adsorption, owing to its various pros such as operation with green
Ni 0.02 sorbents, cost-effectiveness, higher efficiency, a wide selection of
established adsorbents derived from agricultural and industrial wastes,
easy regeneration, low energy requirements, etc., is highly popular.
(Pb) has long been one of the most recyclable and reusable heavy metals.
Adsorption [11] is the strategy of mass exchange by which the material
It is employed in the manufacture and recycling of batteries, particularly
is moved from the fluid stage to the surface of solid and bound by
in the automotive, paint, pipe, and petrol industries. Lead adversely
chemical & physical interactions. Traditional methods such as adsorp
affects the nervous system, gastrointestinal tract, the lungs, and repro
tion [12–15], chemical precipitation [16–19], membrane filtration [20],
ductive system, and induces neurobehavioral deficiencies [10].
ion-exchange [21–25] and electrochemical treatment technologies [26]
Fig. 1. Mechanisms of heavy metal removal by biochar based sorbents [5,46].
Fig. 2. Advantages of deploying Biochar based sorbents.
2
Fig. 3. Comparison of metal removal performance of different sorbents [45,51–57].
Table 2
Overview of synthesis of biochar based sorbents.
Sr Synthesis Method Process Summary Merits Demerits Ref
No.
Equal proportion of liquid,

solid & gas products.
Longer residence time of biomass at relatively low temp. carried Large PS, higher ash & lignin [5,
1 Slow Pyrolysis Highly endothermic
out at atmospheric pressure. contents. 75–79]
Low-cost, robust & simple
process.
Non-condensable gasses as
product.
Less production of [5,
2 Fast Pyrolysis Rapid heating rate with less residence time Bio-oil produced can be used as
biochar quantity 80–82]
a feed material to produce
energy.
Cost of the raw materials
High Ads. efficiency
0.5 mol of citric acid mixed with 0.5 M Al(NO3)3.9H2O soln→ is high
3 Sol-gel method [8,68]
stirred at 180 rpm for 2h→ heated from 60− 80 ◦ C to form gel Higher SA & active site Large volume shrinkage
Increase of thermal stability & cracking during drying
Greater SA Produces crystal defects
3.30 g biochar, 330 g agate spheres & 60 g DW were added to the
Heavy equipment
agate jars→ stirred at 300 rpm for 12 h & direction of rotation
4 Ball milling method Loud noise & strong [83–85]
changed every 3h→ centrifugation for 5 min at 9000 rpm→ The Larger PV
vibration during its
solid biochar was collected, oven dried at 80℃ for 12 h
working process
suspension obtained by immersing biochar in a mixed solution Efficient adsorbent Time consuming
of MgCl2 & AlCl3 (molar ratio of 3:1)→ stirring for 12 h→ soln &
suspension were dropwise added to a vessel & stirring speed at Some impurities get [74,
5 Co-precipitation method
400 rpm→ stabilization under 60 ◦ C for 12 h→ filtration & Promotes surface adsorption precipitated with the 86–88]
washing with ultrapure water & dried. Biochar is carbonized. product
Cooled to room temp
Soln A→ 0.01 mol Fe(NO3)3 & 0.02 mol Mg(NO3)2 were Production of high capacity
Expensive
dissolved in 50 mL DW adsorbent
Soln B→ 30 mL aqueous solution including 0.01 mol Na2CO3 &
0.03 mol NaOH.
Hydrothermalsynthesis
6 2 g magnetic biochar & soln B were added to soln A under stirring [89]
method Unable to see the
for 0.5h→ mixture slurry was transferred into Teflon-lined high- Good magnetic properties
growing crystals
pressure reaction kettle & aged at 120℃ for 6 h in oven. Final
product was collected, filtered & washed in DW & dried at 70 ℃
for 8 h.
FeCl3.6H2O, sodium acetate (NaAC) & polyethylene glycol 4000 Uniformly dispersed magnetic
(PEG4000) were added into 80 mL of ethylene glycol (EG) & NPs with controllable particle Expensive
stirred for 30 m in. BC was then added & stirred for 4 h to obtain size synthesised
7 Solvothermal method [90–92]
a precursor mixture→ soln treated in an autoclave at 200 ◦ C for 8
Unable to see the
h→ cooled down & the black ppt collected using magnet→ High product purity
growing crystals
washing with ethanol & DW→ vacuum dried
5 g BC was added to 500 mL of xylene, 14 mL of trimethylamine
& 10 g of succinic anhydride→
Production of efficient Low stability at high
8 Succinylation mixture was heated at a temp greater than 119 ◦ C for 8 h for [93]
biosorbent temperatures
succinylation→ filtered using a 0.45-μm pore filter paper &
washed with acetone to remove the residual xylene.
3
elimination of heavy metals relies on the concentration of the pollutants,

and the chemical properties of the adsorbent surface [39]. The varia
tions in organic composition, electrical properties, and functional
groups of biochar based sorbents provide significant explanations for the
difference in the observed adsorption mechanisms [40]. Fig. 1 demon
strates the general mechanism for adsorption. Approaches to the alter
ation of biochar based sorbents, including chemical modification,
impregnation of mineral sorbents, steam activation, and magnetic
modification have been widely studied [41–43]. Harikishore Kumar
Reddy & Lee, 2014 [44] used pine bark waste loaded with Cobalt and
Iron to remove heavy metal from metal industry effluent. Pine bark,
after modification, showed excellent results in the removal of Cd(II) and
Fe(II) ions. Similarly, a study was done by Xiao et al., 2020 [45] on cow
bone modified with the ball milling technique showed good results in
the removal of Cu(II), Pb(II) and Cd(II) ions.
The use of untreated biosorbents poses difficulties, such as a low
adsorption efficiency and high release of organic material, which
consequentially increases COD, BOD, and TOC. Pre-treatment is
Fig. 4. Synthesis Process for the production of biochar based sorbents. frequently advised to maintain adsorption efficiency. In most cases, it
increases removal efficiency and selectivity in comparison to unmodi
were found to be costly affairs and thus not beneficial for low concen fied biosorbents. This pre-treatment can enhance ion-exchange ability,
tration of heavy metals [27]. Precipitation produces large amounts of improve the formation of functional groups, and provide a greater
relatively low-quality sludge, which may pose problems with dewater number of binding sites, which in turn, favours metal uptake. It has been
ing and disposal [28]. Such processes were shown to be successful at found that pre-treatment modifications led to improved attributes in
experimental stages but not on an industrial scale. To overcome these biochar based sorbents and thereby enhancing its performance. Fig. 2
problems, studies are being conducted on biosorption. Biosorption is a shows these trends [11,47–49]. In a study by Ahmad et al., 2018 [50], a
process independent of energy, where heavy metals are adsorbed on the banana peel compost was given thermal treatment. It was observed that
cell surface or active site of an adsorbate. The main benefits of bio biochar based sorbents productivity was high due to the catalytic action
sorption are in its high efficiency in the removal of heavy metal ions, and of K during the pyrolytic conversion of the feedstock. Similarly, modi
the use of low-cost biosorbents. These methods are more suited for the fication of biochar based sorbents with nano zero-valent iron increased
treatment of dilute heavy metal wastewater [29]. Bio-sorbents are most
commonly produced through the simple carbonization of economical
and abundantly available biomass materials viz., bagasse, straw, shells
of different materials like peanuts, eggs, etc., besides microbes like
bacteria and algae [30].
Biochar is one such biosorbent derived from the pyrolysis of various
types of biomass materials mentioned above while bio sorbents also
include the adsorbents derived from biomass from various other
carbonization routes of the biomass including modifications [11,31–36].
Biochar, also known as pyrogenic black carbon (as it is produced
through pyrolysis) is nothing but a carbon-rich material with attractive
attributes like high permeability, good porosity, large surface area [5,
37,38]. Besides these attributes, its affinity towards different functional
groups makes it an attractive option to adsorb various heavy metals onto
its surface thereby leading to effective wastewater treatment. There
have been studies to utilize cottonwood, corn stalk, pinewood, chestnut
shell, clay, egg white, and other agricultural wastes. Modification of the
chemical structure of biochar-based sorbents is a promising and
Fig. 6. Comparison of various kinetic models at a glance.
attractive way to confer biochar specificity. The process for the
Fig. 5. Common kinetic models in metal removal by biosorbents [94].
4
Table 3
Comparison at a glance of various biochar-based sorbents w.r.t heavy metal removal, kinetics and Isotherms.
S. Gupta et al.
Sr No. Metal Source Biochar Modifications Synthesis Process Kinetics Isotherm %Removal- Merits Demerits Ref.
Ion Composition Parameter Adsorption
Capacity
Pyrolysis→ T: 25 ◦ C
Homogenisation→ AD: 0.25
sieving→ ultrasound g/L
As Nanoscale zero Redlich & Synergistic effects ↑ Low affinity for As
1 Aq Soln Corn Stalk (BC) → stirring soln→ Rotation: PSO 148.5 mg/g [124]
(III) valent iron (nZVI) Peterson Ads capacity (III)
washing with DW & 200 rpm
C2H5OH→ vacuum Time: 1h
freeze-drying pH: 4
T: 25 ◦ C High Ads with Mn Expensive
production of FMO
AD: 1 g/L SO2¡
4 & NO3- ↑ Ads
sorbents.
Rotation: Post-treatment
As Pristine Fe-Mn binary Langmuir &
2 Aq Soln Slow Pyrolysis with N2 2000 rpm PSO 8.25 mg/g not eco friendly [102]
(III) biochar oxide (FMO) Freundlich
Time: 50
capacit y. Ads ↓ as pH ↑
min
Removal ↓ when
pH: 3
PO3−
4 conc. ↑
Pyrolysis→ crushing & T: 25 ◦ C PSO Sips 5.49 mg/g Fast kinetics
sieving → washing AD: 2 g/L
As Difficulty in [125]
3 Aq Soln Douglas fir Magnetite loaded with DW→ oven Time: 1h Good magnetic
(III) desorption [126],
drying→ loading with properties
pH: 7
magnetite
T: 22 ◦ C Well-crystalline
Pyrolysis→ crushing &
AD: 0.1 g/
5
n AlOOH sieving → washing
4 As (V) Aq Sol Cottonwood L EM Freundlich 17.41 mg/g [127]
nanocomposite with DW→ oven AlOOH flakes observed
Rotation:
drying
200 rpm
T: 22 ◦ C ‫ץ‬-Fe2O3 ↑ SA
Pyrolysis→ crushing & AD: 0.1 g/
‫ץ‬-Fe2O3 sieving → washing L
5 As (V) Aq Soln Cottonwood FO Langmuir 3.147 mg/g Magnetic separation [128]
nanocomposite with DW→ oven Rotation:
used for MBC
drying 200 rpm
Time: 4 h
oven drying→ air T: 25 ◦ C PSO Freundlich 204.2 mg/g Highly magnetic.
cooling→ sieving→ AD: 0.15
ultrasound → g/L
Pine wood Fe3O4-loaded
6 As (V) Aq Soln centrifugal Rotation: Contact time was less Highly costly, [51]
sawdust activated carbon
separation→ 2000 rpm for Ads
Pyrolysis→ washing Time: 6 h
with DW pH: 8
Difficulty in
T: 25 ◦ C High SA,
desorption
AD: 0.4 g/ Strong magnetic
sieving→ Pyrolysis →
L property,
7 As (V) Aq Soln Chestnut shell Magnetic gelatin washing with DW→ PSO Langmuir 45.8 mg/g [129]
Rotation:
filtering→ drying Gelatin ↑ Ads capacity Low Ads capacity
150 rpm
Time: 4 h Ads capacity ↑ with ↑
pH: 4 (+) anions
PO3−
4 ↓ As
Fe-Mn-La T: 25 ◦ C
removal.
As
8 Aq Soln Corn Stem BC: Fe: Mn: La Slow Pyrolysis AD: 5 g/L PSO Langmuir 14.9 mg/g Mn, Fe & La atoms ↑ SA [130]
(III) As(III) Ads ↓ as pH
weight ratio of Rotation:
↑ from 3 to 7.
25:4:1:3 180 rpm
(continued on next page)
Table 3 (continued )
S. Gupta et al.

Capacity
Time: 6 h
pH: 6
crushing→ oven T: 22 ◦ C 124.5 mg/g nZVI aggregate.
drying → Pyrolysis→ AD: 0.1 g/
Desorption
washing with tap L
water & DW→ Rotation:
As Zero-valent iron Langmuir & Ads in anoxic condition
9 Aq Soln Pinewood sonication→ cooling 40 rpm PFO [131]
(III) NP (nZVI) Freundlich more Lower SA.
to room temp→ Time: 1h
98.2 %
vacuum filtering→
drying in vacuum pH: 4.1
oven
As (III) Mt-nZVI upon reacting
Montmorillonite- 59.9 mg/g with H2O & oxygen
As sieving→ Pyrolysis → PO3−
4 had an
supported zero- As (V) forms a number of Fe
10 (III) s Aq Soln Clay washing with DW→ inhibitory action [132]
valent iron NP 45.5 mg/g corrosion product &
(V) filtering→ drying on the Ads,
(Mt-nZVI) Desorption provides new Ads sites
50 % for As(III) & As(V).
Slow Pyrolysis→
Red Oak (RO) Zero-valent Fe T: 21.5 ◦ C PSO Langmu RO
sieving → Exhausted ZVI-
As sorption intensity ↑
As crushing→ 26.12 mg/g biochar complexes
11 Drinking Water with ↓ loading of ZVI [133]
(III) Switchgrass sonication→ oven SG are hazardous
Time: 48 h ir biochars
(SG) drying→ purging with waste.
14.21 mg/g
N2
Low energy
6
T: 23 ◦ C
consumption
Pyrolysis → washing AD: 2 g/L Langmuir- Eco-friendly
12 Ag (I) Aq Soln Pomelo peel PSO 137.4 mg/g [134]
with DW→ drying Rotation: Freundlich
40 rpm Highly efficient
Time: 24 h
Pyrolysis→ T: 22 ◦ C High Ads capacity
Homogenisation→
sieving→ ultrasound
Nanoscale zero
13 Ag (I) Aq Soln Pinewood → stirring soln→ 1217 mg/g PS ↓ Ads capacity [52]
valent iron (nZVI) AD: 0.04 g Cheap biochar
washing with DW &
C2H5OH→ vacuum
freeze-drying
Sludge (SB)
T: 25 ◦ C PSO
Cow Dung (DB) Pulverization→ slow
Corn Stalk (CB) pyrolysis→ cooling→ AD: 0.0 8g
Cd Freundlich & CB > DB >
14 Aq Soln KOH as activator adding KOH→ Rotation: High SA of CB Low SA of SB [135]
(II) Langmuir WB > SB
Willow washing wth DW→ 200 rpm
Branches (WB) drying Time: 12 h
pH: 7
Higher thermal
T: 28 ◦ C 87 %
stability
AD: 0.5 g
Cd Oil Palm Alumina
15 Aq Soln Sol-gel method Rotation: Ads ↓ as PS ↑ [8]
(II) Bagasse (OPB) nanoparticle 13.2− 17.4
200 rpm Higher SA
mg/g
Time: 2h
pH: 6
Pine Tree washing with DW→
Cd T: 25 ◦ C C content ↑ as temp ↑. SA ↓ as pyrolysis
16 Aq Soln Residue (PRB) drying→ Pyrolysis→ PSO Langmuir 85.8 mg/g [136]
(II) temp ↑
crushing→ sieving O & H ↓ as temp ↑
S. Gupta et al.

Capacity
Pine bark AD: 1.2 g/

(PBB) L
Pine cones Rotation: More carbonisation at
(PCB) 4000 rpm higher temp
Pine needle Time: 2h PBB (85.5 mg/g) > M-
(PNB) PRB
pH: 6 (62.9 mg/g) > PNB
(53.8 mg/g) > PCB
(40.8 mg/g).
mycelial pellet MP good for long term
oven drying→ crushi T: 25 ◦ C PSO Langmuir 57.66 %
(MP) use.
ng→ sieving→ AD: 2 g/L
MP has low
Pyrolysis→
Cd Industrial mechanical
17 Rice Husk (RH) sonication→ Rotation: [137]
(II) Waste Water biochar colloids 102.04 mg/ strength & poor
culturing→ washing 160 rpm & Temkin Higher SA
(BC) g stability.
with
Time: 2h
DW
pH: 6− 7
T: 28 ◦ C 95.6 % High C content
Cd Orange Peel Al2O3
18 Aq Soln Sol-gel method AD: 0.5 g Less contribution of PS Effect of pH [138]
(II) (OP) nanoparticle
pH: 4− 6 on removal
T: 25 ◦ C 91 % Carboxyl, hydroxyl & Effect of pH.
amide groups ↑ Ads
Cd Corn Cob Al2O3 AD: 5 g/L PS 0.5mm
19 Aq Soln Sol-gel method process s. [139]
7
(II) Residue (CCD) nanoparticle Small effect of PS.
Lignocellulosic nature
pH: 6
of CCD
Fe-Mn binary
T: 25 ◦ C PSO Langmu 95.23 mg/g FMBO ↑ Ads Weak mech
oxide (FMBO)
washing with DW→ AD: 0.025
crushing→ sieving→ g/L
Cd Pennisetum sp.
20 Aq Soln ultra sonification→ Rotation: [140]
(II) Straw Fe: Mn: BC mass
drying in water bath→ 200 rpm
ratio of 1:4:25
Pyrolysis Time: 200
min
pH: 5
T: 25 ◦ C In presence of Cu,
SSB as a cheap &
Cd n sesame straw Pyrolysis→ sieving→ AD: 0.1 g Pb & Cr, Cd shows
21 Aq Sol Langmuir 86 mg/g abundant carbon [41]
(II) biochar (SSB) washing with DW least removal
pH: 7 source.
ability.
T: 25 ◦ C Low stability
washing with DW→
AD: 0.1 g
drying→ Pyrolysis→
Cd wood shaving Combustion Rotation: WSC has a good ash WSC contributed
22 Aq Soln sieving→ adding PSO Langmuir 68.9 mg/g [141]
(II) biochar (WS) (WSC) 200 rpm content 28.9 % of original
Activated Charcoal &
Time: 120 Ads capacity of WS
combustion
min
CLC have a good ash
T: 25 ◦ C Low stability
washing with DW→ content
drying→ Pyrolysis→ AD: 0.1 g
Cd chicken litter Combustion
23 Aq Soln sieving→ adding Rotation: PSO Langmuir 60.9 mg/g [141]
(II) biochar (CL) (CLC) Higher acid Ca & Mg conc. ↓
Activated Charcoal & 200 rpm
neutralization capacity. after combustion.
combustion Time: 240
min
S. Gupta et al.

Capacity
T: 25 ◦ C Cd(OH)+ & Cd2+ ↓

AD: 1 g/L Ads capacity
heavy metal NaOH -Activated Rotation:
Cd Woody Pyrolysis→ washing A-BC550 help in Cd
24 contaminated @550 C (A- 120 rpm PSO Redlich-Peterson 216.2 mg/g [53]
(II) Sawdust (WSD) with DW→ drying Ads
waste water BC550) Time: 10 Ads ↓ as pH ↓
min
pH: 7
Grafting modification
T: 25 ◦ C PSO Langmuir >90 % Larger pore size
grinding→ Pyrolysis→ ↑ metal binding sites
precooling→ Rotation:
Higher SA
Cd acrylonitrile adding→ 180 rpm
25 Aq Soln Corn Cob (BC) acrylonitrile [142]
(II) stirring→ vacuum Higher chemical Ads highly pH
Time: 4 h 85.65 mg/g
filtration→ rinsing reactivity dependent
with DW→ drying MBC350 is acid
pH: 6.8
resistance.
MBC highly
165.77 mg/ Increase external &
T: 25 ◦ C PSO Langmuir dependent on
g internal SA
pyrolysis temp.
AD: 0.5 g/
Cd Ball-milled bone L
26 Aq Soln Cow bone Ball Milling Process [45]
(II) biochar (MBC) Rotation:
Lower hydrophobicity Low Ads capacity
160 rpm
& higher polarity at low pH.
Time: 200
min
8
pH: 5
Magnetically Separating BC
T: 25 ◦ C recyclable, cost- from the solution
slow pyrolysis→
effective & eco friendly after Ads
stirring→ sonication→
AD: 0.4 g/
Cd Corn Straw Ferric Nitrate drying in water bath→ Higher pore opening
27 Aq Soln L PSO Langmuir 48.3 mg/g [143]
(II) (BC) (MBC) calcination→ Cd penetrate the
Rotation:
sieving→ rinsing with Higher SA pores & ↓ active
1000 rpm
DW site
Time: 6 h Ion mobility ↑ with
pH: 6 temp
Pyrolysis→ T: 25 ◦ C
Homogenisation→ AD: 0.25
sieving→ ultrasound g/L No reduction Ads
Cd Nanoscale zero Synergistic effects ↑
28 Aq Soln Corn Stalk (BC) → stirring soln→ Rotation: PSO Redlich–Peterson 33.81 mg/g in Cd(II) [124]
(II) valent iron (nZVI) Ads capacity
washing with DW & 200 rpm immobilization.
C2H5OH→ vacuum Time: 2h
freeze-drying pH: 6
Ads capacity ↓ in
T: 25 ◦ C PSO Freundlich 65.4 mg/g High thermal stability. mixed soln of Cd &
Ni.
crushing→ sieving→
Cd AD: 0.02 g Graphite crystal
29 Aq Soln Rice Straw (RB) pyrolysis→ cooling to [56]
(II) Rotation: structure & Ads capacity
room temp
200 rpm graphitization degree of decreased with
the RB ↑ at the higher demineralization.
Time: 4 h
pyrolysis temp.
ultrasonic T: 22 ◦ C Redlich– 28.1 mg/g Larger SA.
irradiation→ AD: 2 g/L
Cd MnOx & oxygen have
30 Aq Soln Hickory Wood KmnO4 pyrolysis→ rinsing Rotation: [144]
(II) Peterson strong bonding affinity
with DW→ oven 50 rpm
to heavy metal ions.
drying pH: 6

S. Gupta et al.

Capacity
High moisture
banana peels chopping→ oven 103.22 mg/ Biochar productivity
T: 22 ◦ C content in
(BB) drying g was high
Cd biomass.
31 Aq Soln PSO Langmuir [50]
(II) AD: 0.5 g BB
cauliflower → slow pyrolysis→ Metal sorption capacity Chemisorption is
Time: 24 h 70.83 m g/g
leaves (CB) crushing→ sieving of BB > CB the dominant force
pH: 8 CB
Co & Fe Loaded Chopping→ crushi T: 25 ◦ C
Smaller ionic
Cd Pine Bark ng → washing with Time: 2h
32 Aq Soln PSO Langmuir 99 % Well Crystallized radius of Cd(II) [44]
(II) Waste CoFe2O4 water→ air drying→
pH: 5 reduced the Ads.
calcination
cystamine chopping→ oven T: 25 ◦ C High PV
Cd n dihydrochloride drying→ slow AD: 0.1 g Works only at
33 Aq Sol Rice husk PSO Langmuir 81.02 mg/g [145]
(II) as a modification pyrolysis→ crushing→ Time: 3h Greater SA high pH
ligand sieving pH: 8
iminodiacetic cutting & washing
acid magnetic with tap water→ 197.96 mg/
T: 25 ◦ C PSO Langmuir High SA & PV.
biochar (Fe3O4 as soaking in NaOH→ g Removal
Cd n NP) washing with Milli-Q efficiency ↓ with ↑
34 Aq Sol Palm fiber [146]
(II) water→ drying→ After 5 mass ratio of BC &
AD: 1 g/L
pyrolysis → sieving→ cycles Strong magnetic Fe3O4 NPs,
BC:Fe3O4::2:1
washing with NaOH→ Time: 12 h properties
82.18 %
oven drying pH: 8
Crushing→ T: 25 ◦ C
pyrolysis→ sieving→ AD: 0.03g
9
washing by HF & HCl Rotation:
Cd Chicken nanoscale zero Lower Ads
35 Aq Soln & DW→ adding 150 rpm PSO Freundlich 60.69 mg/g Spontaneous Ads [147]
(II) Manure valent iron capacity
NaBH4 → washing Time: 2.5h
with DW→ drying in
pH: 6
vacuum
Nano zero-valent Crushing→
T: 25 ◦ C Freundlich nZVI
Fe nZVI pyrolysis→ sieving→
Nano α hydroxy washing by HF & HCl AD: 0.67
Cd 22.37 mg/g Fe (III) on surface
36 Aq Soln Corn straw iron oxide & DW→ adding g/L [148]
(II) enhanced complexation
NaBH4 → washing Rotation:
nHIO26.43
nHIO with DW→ drying in 150 rpm
mg/g
vacuum pH: 6
T: 25 ◦ C
AD: 0.5 g
slow pyrolysis→ ultra
Cd ferromanganese Rotation:
37 Aq Soln Corn straw sonification→ drying PSO Langmuir 101 mg/g Ads ↑ as pH ↑ [62]
(II) binary oxide 1000 rpm
in water bath
Time: 2h
pH: 6
T: 27 ◦ C Langmuir-Fre Low-cost production
(EDTA) AD: 0.01 g
Liquid phase As pH ↑
Cr intercalated Mg/ Rotation:
38 Aq Soln Bamboo coprecipitation PSO 38 mg/g competition for [74]
(VI) Al layered double 180 rpm undlich Eco-friendly
method Ads sites ↑
hydroxides Time: 24 h
pH: >8
Ads efficiency high at
T: 30 ◦ C 55 mg/g
lower pH
Cr phoenix tree Fe3O4 Solvothermal
39 Aq Soln AD: 2 g/L PSO Freundlich [90]
(VI) leaves nanoparticles method After 7
Rotation: High stability
cycles84 %
200 rpm
Table
Sr No.3 (continuedMetal
) Source Biochar Modifications Synthesis Process Kinetics Isotherm %Removal- Merits Demerits Ref.
Capacity
S. Gupta et al.
Time: >24
h
pH: 2
FeS NP (FeS) air drying→ T: 20 ◦ C PSO Redlich- 130.5 mg/g FeS ↑ Ads capacity
Carboxymethyl crushing→ purging AD: 0.72
cellulose (CMC) with purifi g/L
Increasing BC
Cr Wheat Straw Rotation:
40 Aq Soln Mass ratio ed N2→ mass decreased [54]
(VI) (BC) 40 rpm Peterson Low cost production
Ads capacity
FeS :CMC :BC deposition→ stirring→ Time: 24 h
freeze drying→
1:1:1 pH: 5.5
washing with DW
crushing→ oven T: 25 ◦ C 58.82 mg/g
drying → Pyrolysis → AD: 2 g/L After 5cycles
electroplating
washing with tap Rotation: Colloid stabilization Removal
wastewater, 82.2 %
Cr nanoscale zero water & DW→ 250 rpm Positive surface charge efficiency
41 tannery Wetland reed PSO Langmuir [149]
(VI) valent iron (nZVI) sonication→ cooling increases Cr(VI) decreased with
wastewater
to room temp→ removal capacity NO−3 .
&ground water pH: 4
vacuum filtering→
vacuum oven drying
crushing→ oven HCO¡3 inhibited Cr
T: 20 ◦ C SO2¡
4 & humic acid
drying → Pyrolysis → removal.
washing with tap AD: 0.2 g/
Cr Acidic nanoscale zero water & DW→ L
42 Herb residue PSO 99.98 mg/g [101]
(VI) wastewater valent iron (nZVI) sonication→ cooling Time: 60 promoted Cr(VI) Highly pH
to room temp→ min removal dependent
vacuum filtering→ pH: 2
10
vacuum oven drying
nanoscale zero crushing→ oven
T: 25 ◦ C Low cost production
valent iron (nZVI) drying → Pyrolysis
→ washing with tap AD: 1.25
water & DW→ g/L
sonication→ cooling Rotation:
Cr
43 Aq Soln Wheat straw to room temp→ 160 rpm PSO Langmuir 112.5 mg/g Lower SA [100]
(VI) carboxymethyl
vacuum filtering→ Time: 24 h Effective adsorbent
cellulose (CMC)
vacuum oven drying→
CMC stabilization→
pH: 5.6
N2 purging→ freeze
drying
air drying→ sieving→ T: 25 ◦ C SiO2 enhance Ads
pyrolysis→ treating AD: 0.2 g/
with HCl→ L
centrifugation→ Rotation:
silicon-rich
Cr washing with DW→ 150 rpm
44 Aq Soln Rice straw biochar- 111.9 mg/g Good for groundwater [150]
(VI) oven drying→ N2 Time: 24 h
supported nZVI treatment
purging→ solids pH: 3.5
washing with
C2H5OH→ vacuum
drying
HCl-BC play a role in
Nanoscale zero Pyrolysis→ soaking
T: 25 ◦ C 17.8 mg/g alleviating the
valent Fe BC in
passivation of nZVI Excessive biochar
Cr
45 Aq Soln Corn stalk HCl soln→ washing AD: 1 g/L block active sites [99]
(VI)
with DW→ drying→ Rotation: of nZVI
nZVI with HCl Good performance
stirring→ 200 rpm
centrifugation→ Time: 2h

S. Gupta et al.

Capacity
washing with pH: 5

C2H5OH→ vacuum
drying
Carboxyl groups &
Nanoscale zero crushing→ oven
T: 25 ◦ C silicon minerals served
valent Fe drying →
as dual support sites
Pyrolysis → washing Rotation:
Cost-effective
Cr Contaminated with tap water & 150 rpm
46 Rice straw 40 mg/g [98]
(VI) groundwater DW→ sonication→ Time: 1h
nZVI cooling to room
temp→ vacuum Readily accessible
pH: 4
filtering→ vacuum
oven drying
Pyrolysis→ soaking T: 25 ◦ C Non-toxic
BC in PEG soln→ AD: 0.05 g
polyethylene washing with DW→
Treatment
Cr glycol (PEG)- drying→ stirring→ 125.22 mg/
47 Aq Soln Coconut shell PSO Sips required for [151]
(VI) stabilized nano centrifugation→ g Eco-friendly
pH: 5.6 diposal
zero-valent iron washing with
C2H5OH→ vacuum
drying
silicon-rich Ads was also enhanced
air drying→ sieving→ T: 25 ◦ C
biochar (RS) by
pyrolysis→ treating Rotation:
the dispersion
11
with HCl→ 150 rpm
centrifugation→
washing with DW→
Cr
48 Aq Soln Rice straw oven drying→ N2 Langmuir 117.1 mg/g [152]
(VI) supported nZVI&
purging→ solids
Pd Good for groundwater
washing with pH: 3.5
treatment
C2H5OH→ vacuum
drying→ Pd added→
ultrasound→ vacuum
drying
T: 25 ◦ C Rapid kinetics Lower desorption
Pyrolysis→ leaching
AD: 0.01 g
with NaOH→
Cu KOH Rotation:
49 Aq Soln Rice Husk impregnation with PSO Langmuir 265 mg/g [153]
(II) impregnation 180 rpm High SA rates
KOH→ washing with
Time: 1h
DW→ drying
pH: 5− 6
T: 25 ◦ C Higher ash content.
washing→ drying→ NaCl exerted a (-)
Cu AD: 1 g/L Higher SA & PV
50 Aq Soln Bamboo Steam Activation sieving→ pyrolysis→ Langmuir 94.66 % influence on the [154]
(II) Removal efficiency of
treating with steam pH: 2− 5 Ads of Cu2+
Cu2+ in river water
T: 25 ◦ C 91–100 % desorption Creates nuisance
AD: 0.5 g smell if not
Cu n calcined magnetic Co-precipitation Langmuir &
51 Aq Sol Banana Peel Time: 2h PSO 75.9 mg/g disposed properly [9]
(II) derivative (CMD) Method Redlich-Peterson Excellent recyclability.
& produce
pH: 6
greenhouse gas
Cu Ball-milled bone 287.58 mg/ Increase external &
52 Aq Soln Cow bone Ball Milling Process T: 25 ◦ C PSO Langmuir [45]
(II) biochar (MBC) g internal SA
S. Gupta et al.

Capacity
MBC highly
dependent on
pyrolysis temp.
AD: 0.5 g/ Lower hydrophobicity Low Ads capacity
L & higher polarity at low pH.
Rotation: 160
rpm
Time: 200 min
pH: 5
T: 25 ◦ C Low-cost
AD: 1 g/L
Undaria
Cu Hydroxyapatite Hydrothermal Rotation: Highly
53 Aq Soln pinnatifida PSO Langmuir 99.01 mg/g [155]
(II) nanoparticles Thermal Synthesis 250 rpm Eco-Friendly endothermic
roots
Time: 12 h
pH: 5.8
T: 25 ◦ C Langmuir 95.24 mg/g Eco-friendly
AD: 0.05 g
slow pyrolysis→
Cu Enteromorpha Rotation:
54 Aq Soln washing with DW→ Algal biomass as cheap [156]
(II) prolifera 150 rpm
dried source
Time: 12 h
pH: 5.8
ultrasonic T: 22 ◦ C Redlich– Larger SA.
Cu MnOx & oxygen have
55 Aq Soln Hickory Wood KmnO4 pyrolysis→ rinsing Rotation: EM 34.2 mg/g [144]
(II) Peterson strong bonding affinity
12
drying pH: 6
High moisture
banana peels chopping→ oven Biochar productivity
T: 22 ◦ C 75.59 mg/g content in
(BB) drying was high
Cu Langmuir & biomass.
56 Aq Soln EM [50]
(II) AD: 0.5 g Redlich-Peterson BB
cauliflower → slow pyrolysis→ Metal sorption capacity Chemisorption is
Time: 24 h 56.25 mg/g
leaves (CB) crushing→ sieving of BB > CB the dominant force
pH: 8 CB
pH dependency of
heating→ cooling→ T: 20 ◦ C
sorption,
Cu precipitates washing High magnetization
57 Aq Soln Coconut Shell Fe loaded Rotation: Freundlich 89 mg/g [157]
(II) with DW & ethanol→ property
110 rpm Competitive Ads
oven drying
pH: 5
T: 30 ◦ C Low cost adsorbent
oven drying→
AD: 1 g/L Eco-friendly
Cu n Methyl- crushing→ sieving→
58 Aq Sol Grapefruit peel Rotation: PSO Freundlich 80.6 mg/g [158]
(II) esterification Pyrolysis→
150 rpm Higher Ads capacity
esterification
pH: 6
Steam as best
T: 30 ◦ C
activation gas
slow pyrolysis→ steam AD: 4 g/L
Cu Highly
59 Aq Soln Rice Husk Steam Activation → washing with DW→ Rotation: PSO Langmuir 25.25 mg/g [159]
(II) endothermic
dried 90 rpm Low cost
Time: 24 h
pH: 5
Low desorption
slow pyrolysis→ T: 25 ◦ C Langmuir 160 mg/g High SA
Cu n rate,.
60 Aq Sol Corn Straw MnOx loaded BC sieving→ ultrasonic→ [160]
(II) Excessive loaded
oven drying AD: 0.1 g MnOx enhanced Ads
MnOx form
S. Gupta et al.

Capacity
Rotation: agglomerates of
150 rpm bulk particles
Time: 200
min
pH: 6
T: 25 ◦ C
slow pyrolysis→ ultra AD: 0.5 g
Cu ferromanganese
61 Aq Soln Corn straw sonification→ drying Rotation: PSO Langmuir 64.9 mg/g Ads ↑ as pH ↑ [62]
(II) binary oxide
in water bath 1000 rpm
pH: 6
Cleaning→ drying→ T: 45 ◦ C
Cu impregnating with AD: 0.05 g Low Ads at low
62 Aq Soln Jackfruit Peel 99.86 % Excellent Ads capacity [161]
(II) H3PO4→ pyrolysis→ Time: 24 h metal conc
washing with DW pH: 7
T: 20 ◦ C 74.07 mg/g
washing by DW→ AD: 3.2 g/
MnAl-layered Desorption
Cu oil-tea camellia oven drying→ L Kinetics ↑ as pH Ads capacity ↓ as
63 Aq Soln double PSO Langmuir [162]
(II) shell crushing→ sieving→ Rotation: change from 3 to 5 Al3+ ↑
hydroxides
Pyrolysis 120 rpm 96 %
pH: 6.2
washing by DW→ T: 25 ◦ C High Ads efficiency
Hg oven drying→ AD: 0.02 g Highly pH
64 Aq Soln Corn Straw Na2S as modifier PSO Freundlich 5.11 mg/g Good in competitive [163]
(II) crushing→ sieving→ Time: 2h dependent
Ads
Pyrolysis pH: 6
13
T: 20 ◦ C No secondary pollution
Cleaning→ drying→
AD: 0.01
Hg n impregnating with
65 Aq Sol Pine needle Sulphur modified g/L PSO Freundlich 48.2 mg/g Low leaching rate [55]
(II) Sulphur→ pyrolysis→ Higher SA & PV
Time: 8 h
washing with DW
pH: 7
Higher thermal
T: 28 ◦ C 81 %
stability
AD: 0.5 g
Oil Palm Alumina
66 Ni (II) Aq Soln Sol-gel method Rotation: Ads ↓ as PS ↑ [8]
Bagasse (OPB) nanoparticle 13.8− 16
200 rpm Higher SA
mg/g
Time: 2h
pH: 6
T: 28 ◦ C High C content Effect of pH
Orange Peel Al2O3
67 Ni (II) Aq Soln Sol-gel method AD: 0.5 g 87.85 % Less contribution of PS [138]
(OP) nanoparticle
pH: 4− 6 on removal
T: 25 ◦ C 86 % Carboxyl, hydroxyl & Effect of pH.
amide groups ↑ Ads
Corn Cob Al2O3 AD: 5 g/L
68 Ni (II) Aq Soln Sol-gel method process. [139]
Residue (CCD) nanoparticle PS 1mm Small effect of PS.
Lignocellulosic nature
pH: 4− 6
of CCD
Ads capacity ↓ in
T: 25 ◦ C High thermal stability. mixed soln of Cd &
Ni.
AD: 0.02 g Graphite crystal
69 Ni (II) Aq Soln Rice Straw (RB) pyrolysis→ cooling to PSO Freundlich 54.6 mg/g [56]
Rotation: structure & Ads capacity
room temp
200 rpm graphitization degree of decreased with
the RB ↑ at the higher demineralization.
Time: 4 h
pyrolysis temp.
n T: 25 ◦ C 57.77 mg/g
70 Ni (II) Aq Sol Organic hay Succinylation FO Langmuir High Ads Kinetics [93]
AD: 5 g/L

S. Gupta et al.

Capacity
Time: 1h Hþ was a
After 3
competing ion in
pH: 5.8 cycles4 %
low pH
T: 25 ◦ C 99.95 mg/g High efficiency
AD: 0.1 g Desorption
Pb Rotation:
71 Aq Soln Corn stalk pyrolysis→ cooling to PSO Langmuir [164]
(II) 150 rpm Low cost
room temp 50.35 %
Time: 5h
pH: 4.5
HA increases Ads
T: 25 ◦ C 99.82 mg/g
Corn Stalk & ultrasonication→ capacity
Increase in iron%
Pb Waste Iron Artificial Humic pyrolysis→ washing Rotation:
72 Aq Soln SO Langmuir After 5 cycle High dispersibility Decrease Pb [165]
(II) (.04− .06 mol/ Acid as Activator with HCl & C2H5OH & 150 rpm
Magnetic Recovery (96 removal%
L) DW→ oven drying Time: 2h
79.18 % %)
pH: 5
RH700 (26.7 RH300 suitable for
T: 25 ◦ C Yield of BC ↓ from
mg/g) > water treatment.
oven drying→ 46.5 %–31.6 % as
Pb Water RH500 (21.7
73 Rice Husk crushing→ pyrolysis→ PSO Freundlich production temp ↑ [95]
(II) Treatment pH: mg/g) >
sieving Larger SA for RH700 from 300 to 700
7.1− 9.8 RH300 (14.1 ◦
C.
mg/g)
T: 25 ◦ C
oven drying→
Pb n AD: 2 g/L
74 Aq Sol Corn Stalk crushing→ pyrolysis→ PSO Langmuir 49.7 mg/g Cost effective Low Ads capacity [166]
(II) Time: 2.5h
sieving
14
pH: 4− 6
Modifier increased the
T: 25 ◦ C 145 mg/g At pH 2 Ads ↓
Titration→ SA,
evaporation→ AD: 0.05 Uncharged groups Destruction of
After
Pb Piggery Sludge Thiourea as washing with DW→ g/L adsorb surface groups.
75 Waste Water SO Langmuir [167]
(II) Biochar (PSB) modifier vacuum drying→ Rotation:
5cycle
calcination→ heating 150 rpm Desorption not
Pb by coordination.
in water-bath Time: 12 h easy with Ca+.
5%
pH: 5
Rapid & high Ads
T: 25 ◦ C
capacities
oven drying→ Formation of
Pb AD: 1 g/L
76 Aq Soln Sugar cane crushing→ pyrolysis→ PSO Langmuir 86.96 mg/g morphological [168]
(II) Rotation:
sieving High SA structure
120 rpm
pH: 5
T: 25 ◦ C Pb has greater affinity
Pb sesame straw Pyrolysis→ sieving→
77 Aq Soln AD: 0.1 g 102 mg/g for functional group [41]
(II) biochar (SSB) washing with DW
pH: 7 that ↑ Ads
MBC highly
Increase external &
T: 25 ◦ C dependent on
internal SA
pyrolysis temp.
AD: 0.5 g/
Pb Ball-milled bone L 558.88 mg/
78 Aq Soln Cow bone Ball Milling Process PSO Langmuir [45]
(II) biochar (MBC) Rotation: g
Lower hydrophobicity Low Ads capacity
160 rpm
& higher polarity at low pH.
Time: 90
min
pH: 5
S. Gupta et al.

Capacity
FO Yield% of BC ↓ as
T: 25 ◦ C 99.9 % Yield % of BCS > CCS
(BCS) temp ↑
AD: 0.21 g
Loss of volatile
(BCS) &
500 mg/g matter ↑ at higher
0.07 g
Spent waste temp.
Pb Bentonite (BCS) drying→ sieving→ (CCS)
79 Aq Soln from cigarette Langmuir Ads capacity ↑ as CaO [10]
(II) and Calcite (CCS) mixing→ pyrolysis Rotation: SO After 3
factory (BC) caused more alkalinity
200 rpm (CCS) cycles Higher
in CCS
Time: 10h volatilization of
pH: 10.19 OC blocked pores
Upto 50 %
(BCS) & & ↓ SA.
9.25 (CCS)
ultrasonic T: 22 ◦ C RO Redlich–Pet 153.1 mg/g Larger SA.
Pb MnOx &oxygen have
80 Aq Soln Hickory Wood KmnO4 pyrolysis→ rinsing Rotation: [169]
(II) erson strong bonding affinity
drying pH: 6
High moisture
banana peels 241.94 mg/ Biochar productivity
T: 22 ◦ C content in
(BB) chopping→ oven g was high
biomass.
Pb drying→ slow Freundlich &
81 Aq Soln AD: 0.5 g PSO BB [50]
(II) pyrolysis→ crushing→ Redlich-Peterson
cauliflower 100.69 mg/ Metal sorption capacity Chemisorption is
sieving Time: 24 h
leaves (CB) g of BB > CB the dominant force
pH: 8 CB
15
T: 25 ◦ C Good desorption
AD: 0.025
slow pyrolysis→
g
Pb β- sieving→ sonication→
82 Aq Soln Rice straw Time: 24 h PSO Langmuir 61.5 mg/g [170]
(II) mercaptoethanol heating→ vacuum LargeSA
Rotation:
drying
180 rpm
pH: 5
Wheat straw SA & PVs larger in WS-
Ball – milled (BM) Ball Milling Proce T: 25 ◦ C 46.33 mg/g PS of WS-BC was
(WS-CK) CK.
AD: 0.2 g/ smaller than WS-
WS-CK
L CK
Pb Rotation: 119.55 mg/
83 Aq Soln Langmuir [83]
(II) Wheat Straw 200 rpm g Carbonization & BM
ss Aromaticity ↑ &
BC (WS-BC) WS-BC enhance ion exchange
polarity ↓ with
134.68 mg/
pH: 5 carbonization.
g
WS-BC + BM
slow pyrolysis→ T: 25 ◦ C Well crystallized,
sieving→ sonication→ AD: 0.02 g
Pb heating→ vacuum Time: 200 367.65 mg/
84 Aq Soln Rice Hull ZnS nano crystal PFO Langmuir Superparamagnetic [49]
(II) drying→ calcination→ min g
properties,
surface covered by
pH: 6
hydroxyl groups
High capacity
T: 25 ◦ C
MgFe-Layered adsorbent
Pb oil-tea camellia Hydrothermal 476.25 mg/ Pb2þ Ads ↓ as Na+
85 Aq Soln double PSO Langmuir Goodmagnetic [89]
(II) shell synthesis method AD: 0.02 g g conc. ↑
hydroxides properties
pH: 6.3 Cyclic utilization
Capacity
S. Gupta et al.
Maghemite & slow pyrolysis→ T: 30 ◦ C

EDTA stirring→ washing Rotation: Fe3O4 &‫ץ‬-Fe2O3
Pb 146.84 mg/
86 Wastewater Fallen leaf functionalized with DW & C2H5OH → 150 rpm PSO Langmuir enables magnetic NP reduce the SA [169]
(II) g
layered double drying→ filtration→ Time: 30 properties
hydroxides ppt washing min
T: 25 ◦ C
AD: 0.25
air drying→
Pb g/L Advantageous in
87 Aq Soln Daily manure pyrolysis→ washing L-L model 140.9 mg/g [171]
(II) Rotation: removing metals & OC
with DW
60 rpm
Time: 0.5h
T: 25 ◦ C
air drying→
Pb H3PO4 as AD: 0.3g Favours acidic
88 Aq Soln Peanut Shell pyrolysis→ washing Langmuir 35.5 mg/g High PV [172]
(II) activator Time: 24 h conditions
with DW
pH: 2.5
T: 25 ◦ C
AD: 4 g/L
Pb Hydrothermal Rotation: Highly
89 Aq Soln pinewood PSO Langmuir 4.25 mg/g High SA [104]
(II) Synthesis Method 180 rpm endothermic
Time: 5h
pH: 5
T: 25 ◦ C High SA
Pyrolysis→ drying→ AD: 0.1 g
sieving→ adding Rotation: Low Ads capacity
Zn
90 Aq Soln Rice Husk Activated Carbon NaOH→ washing with 850 rpm 14.47 mg/g in presence of [173]
(II) Cheap biochar
16
DW→ heating→ Time: 30 Silica
cooling min
pH: 5
Nanoscale zero crushing→ oven
T: 25 ◦ C 109.7 mg/g Highly efficient
valent Fe drying →
Pyrolysis → washing Desorption
with tap water & AD: 0.01 g after 5 High PV
Zn
91 Aq Soln Corn Stalks DW→ sonication→ PSO Langmuir cycles [57]
(II)
nZVI cooling to room Rotation:
temp→ vacuum 150 rpm Higher regeneration
>50 %
filtering→ vacuum Time: 4 h capacity
oven drying pH: 7
Chopping→ ultrasonic T: 25 ◦ C
treatment→ Rotation:
At high Temp
Zn Sodium- pyrolysis→ vacuum 150 rpm Larger ion exchange
92 Aq Soln Corn Straw PSO Freundlich 8.163 mg/g adsorbent behaves [174]
(II) montmorillonite filtration→ sieving→ Time: 2h capacity
abnormally
washing with DW→
pH: 6.28
dried
T: 25 ◦ C Creates nuisance
AD: 0.5 g smell if not
Zn calcined magnetic Co-precipitation Langmuir &
93 Aq Soln Banana Peel Time: 2h PSO 72.8 mg/g Excellent recyclability. disposed properly [9]
(II) derivative (CMD) Method Redlich-Peterson
& produce
pH: 6
greenhouse gas
T: 20 ◦ C
pyrolysis→ washing
AD: 0.1 g Lower Ads in
Zn Alkali with DW→ adding Higher SA
94 Aq Soln Hickory Rotation: Langmuir 1.83 mg/g presence of Pb & [175]
(II) modification NaOH soln→ washing High Ads capacity
4000 rpm Cu
with DW→ dried
pH: 5
its removal efficiency. The existence of iron on the surface of biochar size, higher ash and lignin contents. Therefore, this slow pyrolysis could
based sorbents increased the number of species of oxygen-containing be a low cost and robust option for small-scale production of biochar. In
functional groups and enhanced complexation. Fig. 3 displays the contrast to slow pyrolysis, fast pyrolysis employs shorter residence times
overall adsorption power of various ions using modified biochar. (<2 s), higher temperatures of 500− 1000 ◦ C and rapid heating rates of
In addition to the properties of adsorption, the regenerative prop >2 ◦ C /s. The drawback of this method is the lower yield of biochar (12
erties of the adsorbent are also important. For an adsorbent to possess %) as well as high yield of bio-oil (75 %) and non-condensable gases (13
any sort of an industrial application, it is imperative that it displays good %). It was also found that fast pyrolysis at lower temperatures resulted in
cyclic stability. For example, a study by Lata 2015 [58] shows that partly pyrolyzed biochar fractions vis a vis slow pyrolysis with longer
desorption rates are high with a low concentration of acid, but a low pH residence times. The third method of gasification to produce biochar
destroys the biochar based sorbents, which, in turn, reduces the biomass. leads to the conversion of biomass to gases like CO2, CO, H2 and small
However, adsorption and desorption are opposite phenomena, which amounts of CH4 by placing the biomass source in controlled oxygen
means that the greater the adsorption capacity, the more the affinity environment at high temperatures of 700− 800 ◦ C. Biochar produced is
between the metal ions and the adsorbent, which implies that the 10 % through this method with remaining being gases and tar.
desorption process will be more unfavorable. Desorption is equally In the recent past, modified biosorbents are being widely for
important, however, since it contributes to regeneration and recovery of improved metal removal efficiency even at low concentrations, easy
the adsorbent and adsorbate molecules respectively, reducing secondary recovery and reuse due to several limitations of pristine biochar and
pollution and the cost of the process. The major challenge in the other biosorbents. Metal induced sorbents or magnetic biosorbents/
deployment of biosorbents in the field of metal removal is the recovery biochar are being developed by incorporating metal nanoparticles viz.,
of liquid solvents which were used to regenerate the sorbents and re iron, nickel, chromium, titanium, zirconium, zinc, copper and alloys
searchers are hence focussing on the development of safe and green [66] in the form of salts, oxides etc which were found to have improved
options in the downstream processing [11]. surface area, pore size, thermal stability, crystalline nature, surface
Several biochar based sorbents studies have been conducted to functionality leading to higher adsorption capacity and easy recovery
improve its adsorption properties, and many have been successful. [67]. The properties of magnetic biosorbents were found to be depen
Magnetization, impregnation of nanoparticles, preparation of compos dent on the nature of biomass itself, metal nano particles, modification
ites with other adsorbents, and other modifications have been made by methods, besides process parameters like pyrolysis temperature and
researchers in the last few years to make biochar based sorbents suitable duration, particle size [59,60]. Extent of magnetisation of biochar was
for industrial applications. This paper compiles the results of the found to be proportional to pyrolysis temperatures i.e. 4.28 emu/g at
recently prepared biochar-based adsorbents, where adsorbent adsorp 400 ◦ C and 36.8 emu/g at 650 ◦ C. Ultrafine nanoparticles like metal
tion capacity and process conditions have been discussed. This paper oxides synthesized through various methods like sol gel, aqueous sol gel,
also highlights the merits and demerits of each adsorbent produced, ball milling, hydrothermal, precipitation methods could be used as
making it easier to compare adsorbents. Synthesis techniques have been successful modifiers to enhance the structural and thermal stability of
discussed to give the reader a better understanding of the requirements the adsorbents [68]. Different types of modifications viz.,
for the preparation of specific adsorbents. pre-treatment/single step, post treatment modification/double step,
microwave assisted modification, hydrothermal modification etc. are
2. Synthesis of biochar based adsorbents employed in the synthesis of magnetic biosorbents. In the pre-treatment
method, metal nanoparticles are incorporated into biomass before py
Development of appropriate synthesis protocols is very critical in rolysis leading to a larger surface area, porosity and superparamagnetic
achieving the desired attributes in the adsorbent materials thereby behaviour. In the second method of post treatment, biosorbents and
leading to improved performance in terms of metal removal efficiency. nanoparticles are prepared separately before mixing. However, this is
These synthesis protocols also control the overall process economics and less efficient and more expensive than the pre-treatment method. Mi
impact on environment. Several methods have been used for the syn crowave assisted synthesis of magnetic biosorbents is being used in the
thesis and modification of biochar based adsorbents. The most common recent past as it is very rapid taking only 5− 10 min but with highly
methods are shown in the Table 2 below. The properties of biosorbents improved adsorption capacity, surface area, pore volume [48] but with
are found to be dependent on the nature of biomass, synthesis protocols some difficulty in customization. This method is replacing conventional
employed along with modifications used besides the critical process and pyrolysis in the synthesis of magnetic biochar. Though used less, hy
design parameters of the synthesis protocol viz., temperature, pH, py drothermal method is also reported where biomass feedstock is mixed
rolysis time, material size etc [59–62]. Several factors like cost of with water at 100− 350 ◦ C to reduce greenhouse gas emissions as they
preparation, ease of synthesis, specific area, pore size, mechanical are held by water. In very recent times, engineering biochar and mag
strength, adsorption capacity, etc. are considered to assess the efficacy of netic biosorbents are being explored as an innovative approach where
these methods. Biochar among various biosorbents has been found to be plant tissues with bioaccumulation of metals or nanoparticles can be
the most economical, environmentally benign and effective biosorbent directly employed as biosorbents without any complex modification.
in heavy metal removal from waste water [63,64]. Its attributes like This is still in experimental phase and needs to be explored further [69,
carbon richness, large surface area, high porosity and great affinity for 70], as they are found to exhibit improved physico-chemical attributes
heavy metals [65]. Pristine biochar can be prepared by slow pyrolysis, and adsorption capacity. Magnetic biochar can also be produced using
fast pyrolysis, gasification and combustion methods. A variety of co-precipitation method, where a solute precipitates out from a solution
biomass wastes were reported to be used in the synthesis of biochar viz., through a carrier, which forces the solute to bind it together instead of
paper mill waste, peanut hulls, pine chips, poultry litters, forest plant being dissolved. This occurs through mechanisms of inclusion, occlusion
biomass, cotton seed hulls, manures, tyres, animal bones agro-industrial or surface adsorption. Calcination is also employed along with above
biomass, municipal solid waste etc. The nature of biomass material and mentioned methods to synthesize magnetic adsorbents. In this process, a
pyrolysis conditions were found to play a critical role on the properties carbon material is heated in the absence of fusion in a pressurized
of biochar. Greater biochar yield is obtained with higher lignin content autoclave to remove water, drive off gases and other volatile constitu
in the biomass while higher cellulose or hemicellulose content led to ents leading to thermal decomposition [71]. Magnetic biochar synthe
simpler thermal or chemical modifications to induce functional groups. sized using this method with FeCl3.6H2O resulted in larger surface area,
In slow pyrolysis, longer residence times, high pressures, low tempera diverse morphology from macro-mesoporous structure, high crystal
tures of 300 ◦ C–700 ◦ C, low heating rates of 0.01− 2 ◦ C /s are used. This linity besides simple recovery and reusability [72]. In the recent past, a
led to the production of larger quantities of biochar with greater particle scavenger of Mg-Al layered double hydroxide (Mg/Al-LDH) with
17
ethylenediamine tetra-acetic acid (EDTA) intercalated between the blockage for heavy metal adsorption. Experiments by Shang et al., 2017
layers has been found extremely successful in the removal of heavy [101] showed better results at low pH due to presence of humic acid,
metals like Cu, Cd and Cr (VI) from waste water very rapidly in a few which promotes Chromium removal. Similar experiments by L. Lin et al.,
minutes an optimum pH [73,74]. Biochar without appropriate modifi 2017 [102] showed better adsorption of Arsenic at low pH, as it helps in
cation and functionalization was not very competent in the metal Manganese oxidation. In addition, the interaction of oxygen-containing
removal and hence there is a strong need to develop these novel and functional groups in the FMBC promoted the formation of As(III) to As
effective techniques to enhance the utility of biochar (Fig. 4). (V). At a high pH, heavy metal ions form a precipitate with coexisting
Table 2 describe synthesis methods used, depending on the re ions or in the form of their hydroxides. Therefore, generally, the best
quirements, by examining their advantages and disadvantages. performance of an adsorbent is observed in neutral or slightly acidic
conditions.
3. Overall comparison of various biochar based adsorbents Another significant parameter on which biosorption depends is
biosorbent dosage. An initial increase in the percentage of metallic ions
Biochar is a novel and a well sought after adsorbent as it could be adsorbed is observed with an increase in biosorbent doses, which may be
prepared from a wide variety of cheap and abundant feedstocks viz., due to an increase in the adsorbent surface region, raising the number of
agricultural and industrial waste, clays, bones, etc. [94]. The choice of adsorption sites available for adsorption. At biosorbent doses higher
adsorbent to be used for a specific application depends on various fac than the optimal dosage value, a decrease in the percentage of metal ion
tors, such as its cost, its selectivity for different metals, its adsorption biosorbed can be due to the concentration gradient between adsorbate
efficiency, reusability and regeneration, the adsorption and desorption and biosorbent. Increasing biomass concentration may cause a decrease
rates, its ease of synthesis and mechanical strength. in the number of metallic ions adsorbed per gram of biomass. In a few
The nature of biochar was found to be strongly influenced by studies, removal reaches a maximum and then decreases due to the
biomass and pyrolysis conditions used besides the physicochemical saturation of the sorbent [103].
modifications that led to its activation and performance enhancement. Most biosorption processes are endothermic in nature. Hence, on
Additionally, biomass pyrolysis should be performed under controlled increasing the temperature, there is an increase in the removal per
conditions to capture chemical compounds that can be used as pre centage due to an increase in surface activity, which, in turn, increases
cursors for the preparation of other essential compounds. For instance, the number of reactive sites. However, the temperature should be
adsorption studies by Shi 2019 [95] demonstrated that sorption maintained within a certain range; if the temperature is increased to a
increasing pyrolysis temperatures lead to increased capacities of rice very high value, biomolecules will start to degrade, resulting in a
husk biochar for Pb. decrease in removal percentage [104]. Moreover, high temperatures
Biochar is a porous material whose ability for sorption is greatly support metal ions binding with the biosorbent. Applying Le Chatelier’s
affected by its surface area. As a result, increasing its surface area by principle, for exothermic reactions, an increase in temperature decreases
adding nanoparticles increases its potential for metal sorption. For adsorption and vice versa [81].
example, Yan 2015 [49] synthesized magnetic biochar / ZnS composites Agitation speed is one of the critical design parameters in influencing
by depositing ZnS nanocrystals onto magnetic biochar based sorbents. the adsorption efficacy and mechanism. With the increase in agitation
The biochar based sorbents showed a maximum sorption capacity of Pb speed, turbulence increases leading to a decrease in boundary layer
up to 368 mg/g, 10 times that of the unmodified biochar. To modulate thickness around the sorbent particles and improved blending. Reported
the properties of biochar based sorbents for heavy metal removal, a studies have shown that the boundary layer and intra-particle diffusion
range of biochar modification methods have been adopted. Popular were the controlling steps in the adsorption mechanism and the optimal
approaches are chemical alteration and physical alteration. Chemical speeds employed were 120 rpm–200 rpm [105].
alteration is the most common form of alteration used. This primarily
involves acid alteration, alkalinity alteration, oxidizing agent modifi 3.2. Kinetics studies
cation, metal salts or oxidizing agent modification, and carbonaceous
material modification. Physical alteration primarily includes the purg Kinetics is used to study the rates of a chemical reaction. Examina
ing of steam and gas [96]. Metal nanoparticles, in particular iron tion of chemical kinetics incorporates cautious checking of the trial
[97–100], are the most cost-effective and advantageous modification conditions, which affect the speed of a chemical reaction and thus, help
materials due to their ferromagnetic properties for the preparation of accomplish equilibrium in the time allotted. Such examinations yield
magnetic biosorbents. Magnetic biosorbents boost surface areas, func data about the conceivable mechanism of adsorption and the different
tional groups, and active sites and, consequently, improve removal progress states while in transit to the arrangement of the final adsorbate
performance. While nanoparticles have high adsorption capacities, they - adsorbent complex and help create fitting numerical models to depict
are typically not used directly in practical applications due to their the interactions. When the reaction rates also, the dependent elements
expensive regeneration. As a result, the regeneration of the adsorbent is are explicitly known, the equivalent can be used to create adsorbent
an extremely difficult process. Therefore, to solve this problem and materials for the modern application, what’s more, will help understand
simplify the process of regeneration, nanoparticles with magnetic the complex dynamics of the adsorption process [106,107].
properties have been synthesized [51]. Upon completion of the Investigation of the kinetic model for biosorption study is essential to
adsorption process, an external magnetic field is applied to separate the comprehend the reaction pathway, mechanism of biosorption, and dy
magnetic chitosan particles from the solution. This has made it quite namics of the biosorption procedure. It helps in deciding physiochemical
easy to extract the adsorbent from the solution. interaction, mass transport, and rate-determining steps in the bio
sorption process. Different kinetic models like first order, pseudo 1st
3.1. Metal removal by biochar based sorbents order, second order, pseudo 2nd order, and Elovich models have been
tested to explain the adsorption phenomena. The first order model was
Other than adsorbent properties, there are other several factors, like proposed by Lagergren. According to Lagergren’s theory, the metal
pH, temperature, adsorbent dosage & agitation speed, on which the sorption process is first order in nature as the process depends only on a
process of biosorption depends. Various studies have shown that pH specific number of metal ions present at an interval in solution. It has
plays a very important role in determining the adsorption capacity. It been found that the pseudo 2nd order model was the most effective and
governs the dissociation of functional groups and the charge on active commonly employed as depicted in Fig. 5 in which the amount of
sites. At low pH, excess hydronium ions compete with the heavy metal adsorbate on the sorbent surface played a critical role. This shows that
ions to access the adsorption sites of the biosorbent, resulting in chemisorption was more predominant than physisorption. It was also
18
reported that pseudo 1 st order was followed during the initial stages of modification protocols as they are strongly correlated. Heavy metal
adsorption and the fast adsorption processes especially in liquid stage removal by biochar based sorbents follow different mechanisms like
frameworks [102–104,106,108]. physical adsorption, electrostatic interaction, complexation, ion ex
where q1 and qe are metal sorbed at time t and equilibrium respec change, precipitation. Metal removal is found to occur through indi
tively in mmol/g; k1 is the first order rate constant (h− 1), k2 is the vidual or combination of mechanisms stated above. Biochar based
second order apparent rate constants (kg mmol− 1 h− 1, α (mmol kg− 1 adsorbents have high surface area with diverse pore network ranging
h− 1) & β (kg mmol− 1) are initial Elovich sorption & desorption constant from micro, meso and macropores [176]. Pore volumes with high af
at time t (Fig. 6). finity towards metals can follow adsorption, negatively charges surface
of the sorbent can attract positive metals through electrostatic attrac
3.3. Thermodynamic studies tion, ligands and various modifiers can form complexes or precipitates
with metals to be removed [177–179].
Equilibrium models and adsorption isotherms demonstrate the na In physical adsorption, metal removal occurs through diffusional
ture of interactions between adsorbent and adsorbate [109]. It helps in movement of metal ions through pores without any chemical bond
understanding the biosorption mechanism and assists with determining formation. Higher carbonization temperatures favour this mechanism
the course of action of biosorption sites and biosorption of metal parti due to enhanced surface area and pore volume and the mechanism could
cles on the outside of the sorbent. It helps in improving the utilization of be better explained by film pore diffusion model. In ion exchange
biosorbent for a specific framework. The linear regression analysis has mechanism, the ionisable cations on the sorbent are exchanged with
recently been among the most prominent and feasible methods heavy metals in solution whose efficiency depends on the contaminant
commonly used to analyze experimental results from the adsorption size and surface functionality. It has been found that non-woody and
process. It has been utilized to characterize the best fitting relationship grassy biochars with high O content and acidic sites exhibit higher
that evaluates the dissemination of adsorbates and furthermore in the cation exchange capacity [180]. In electrostatic interaction, surface
check of the consistency of adsorption models and the theoretical as charged sorbent and metal ions leads to their immobilization. The pH,
sumptions of adsorption models [110]. Studies have indicated that the point of zero charge (PZC) and carbonization temperatures are found to
error structure of experimental information is normally changed during play a critical role in this mechanism [176,181]. In the mechanism of
the change of adsorption isotherms into their linearized structures complexation, the ligands and metals are found to form multi-atom
[111]. It is against this background nonlinearized regression examina complexes. This is mostly prevalent in the presence of transition
tion got undeniable, since it gives a numerical technique to determine metals, oxygen containing functional groups and employing plant
adsorption parameters in utilizing a unique form of isotherm conditions derived biochars. In the last mechanism of precipitation which is very
[112,113]. In contrast to linear regression, nonlinear regression nor common in the removal of metals and rare earth elements, immobili
mally includes the minimal error between the observational data and the zation occurs by the formation of solids either in solution or on the
expected isotherm [114]. This activity is not, at this point computa sorbent surface during the sorption process. Precipitation mechanism is
tionally troublesome in view of the accessibility of computer calcula widely observed at high pH and mineral content, in both plant and an
tions [115,116]. Few common equilibrium models reportedly used to imal derived biochars [182,183].
explain this biochar based adsorption were Langmuir, Freundlich, As discussed in the preceding sections, biochar by itself is inferior in
Langmuir-Freundlich, Redlich-Peterson, Double Langmuir model, etc. metal removal. Hence, modifications of various kinds viz., mineral
Langmuir model, uptake of metal happens on a homogeneous surface by impregnation, nanoscale metal additions, surface oxidation and surface
monolayer sorption. The model likewise delineates the connection be reduction. These modifications are found to enhance the performance of
tween metal adsorption on the sorbent surface and its equilibrium biochar in terms of metal removal capacity, thermal and structural
concentration in the effluent. This model depends on three assumptions, stability, desired morphology, easy recovery and reuse [99,133,149,
that are, adsorption can happen at a specific site present on a surface, 184–186]. It has been found that modifications and mechanisms of
adsorption can only take place in a monolayer design (just one layer of metal removal are strongly correlated. Characterization studies revealed
atoms will append to the sorbent surface) and adsorbate is emphatically that carboxyl and hydroxyl functional groups introduced through
pulled in to sorbent in a solution. Freundlich isotherm portrayed a su modification underwent complexation with heavy metals before and
perior fit at lower concentrations. It has the ability of portraying the after adsorption. Also, oxygen containing functional groups are found to
biosorption procedure on a wide variety of biosorbents. This model release H+ after ion-exchange thereby reducing solution pH [187]. The
additionally communicates the sorbent surface as heterogeneous and charge characteristics on the sorbent surface are found to affect the
adsorption as multilayer with various intermolecular interactions. strength of materials through electrostatic adsorption with PH playing a
Among these, the Langmuir model based on single-layer adsorption was vital role in achieving the desired metal removal capacity. It is found
found to be the best fit followed by the Freundlich model based on that when pH is more than pHzpc (point of zero discharge), the nega
multilayer heterogeneous process [117–122] process. Shraboni tively charged surface due to deprotonation led to strong electrostatic
Mukherjee et al., [107,123], have done thermokinetic studies on attraction towards the metals leading to enhanced removal. Conversely,
defluoridation using various biosorbents. Their studies mostly found the with pH higher than pHzpc, the positively charged surface due to pro
process to follow Langmuir and pseudo-second order models as per the tonation led to lower affinity towards the metal besides lower avail
process parameters and nature of biomass. They have also found bio ability of sites due to competition between protons and metal thereby
sorptive removal of heavy metals like Fe, Cu and As using superheated leading to lower metal removal [188,189]. Besides above said mecha
steam activated biochar (SSAB) derived from Colocasia esculenta to nisms, the modified biochar is also found to follow precipitation and
follow same thermokinetic behaviour [108]. reduction mechanisms to further enhance affinity towards metals.
Table 3 summarizes the recent methods of synthesis and alteration of Oxygen-containing functional groups were found to follow electrostatic
biosorbents, their use in the removal of heavy metals, methods of pro attraction, ion exchange and complexation mechanisms, which is,
cessing, kinetics, isotherms and their recovery for recycling. illustrated by stronger oxidizing ability of HNO3 vis a vis KMnO4. XPS
and FTIR spectra studies revealed the changes in these functional groups
4. Mechanisms of metal removal by biochar based adsorbents before and after adsorption [190,191]. The presence of metals in the
feedstock or through modification is found to enhance metal removal
Mechanisms of heavy metal removal is vital as they control the ef through the formation of precipitates like carbonates, phosphates, sili
ficacy of the process, to have deeper insight into the micro-aspects of the cates with metals [171,192]. Nanoscale modifications in the biochar
process and to develop novel sorbents through effective synthesis and based adsorbents led to metal removal through the mechanisms of
19
Fig. 7. Principles of Metal Removal Mechanisms.
electrostatic attraction and ion exchange [133,193]. Variable valence operation. To make the adsorption cycle more efficient, adsorbent
metals like Cr, Pb are found to follow reduction mechanism primarily in regeneration is essential. A good adsorbent would convey a high reuse
metal removal besides others [194,195]. and recycling capacity for industrial applications and could substan
The Fig. 7 below illustrates the interplay between modifications and tially reduce the cost of biochar sorbents as a repeated sorption-
mechanisms while Table 4 summarizes different mechanisms followed desorption process [196,197]. The adsorption regeneration process
by different biochar based adsorbent materials. As discussed, since may be repeated a few times, which indicates that the adsorption effi
modification methods have a strong bearing on mechanisms, selection of ciency can decrease slightly during the regeneration period. Adsorption
appropriate modification methods and their combinations is very much efficiency is often reduced by the number of cycles the biochar un
essential to achieve desired performance in terms of removal efficiency, dergoes [198–200].
stability, recyclability and safe disposal. It is interesting to note that if There are two concepts of regeneration: adsorbate desorption and
CO2 is used instead of N2 in pyrolysis process, it is found to give more adsorbate decomposition. Some regeneration techniques are thermal
favourable results in terms of surface modifications and hence the regeneration [198], solvent regeneration [196], [197], microwave
adsorptive performance. It was also found that using ferromanganese irradiation regeneration [197] and supercritical fluid regeneration.
dioxide during modification instead of separate ferrum and manganese Effective desorption involves the proper selection of elutants, which is
oxide led to stronger affinity towards metals, higher magnetization and highly dependent on the form of biosorbent and the mechanism of
stability. Microwave assisted heating along with other modifications is biosorption. Elutants must not harm biochar and must be cost-effective
found to have positive influence. Therefore, the future research should and environment-friendly [201] (Fig. 8).
focus on using a combination of appropriate modification protocols Low concentrations of acids or bases (0.1− 0.2 M) are recommended
during synthesis to have much desired safe and green metal removal for the desorption of contaminants from magnetic bio-sorbents. Re
from wastewater. ported studies have shown that acids & bases viz., HCl, HNO3, H2SO4,
EDTA, Ca(NO3)2, NaOH, NaNO3 were attempted as reagents for in the
5. Regeneration of the sorbents regeneration. It was found that As could be desorbed from magnetic
sorbents using 0.5 M NaOH [11,202], with even better desorption levels
Biochar based sorbents regeneration is an inverse adsorption with HCl, HNO3 and H2SO4 as eluents. Metal ion desorption is preferred
Fig. 8. Regeneration protocols of biochar-based sorbents.
20
over the use of acids as solvents as acidic conditions could hamper the considered for final disposal i.e. incineration [213], regeneration and
adsorption of metal ions [203,204]. The acidic environment favours the reuse [214], landfill [215,216], fertilizer [214,217], and other safe
removal of iron and aluminium oxide /silicate adsorption surfaces, thus disposal techniques [218], [219].
favouring the discharge of adsorbed metals [205]. Adding a strong acid Biosorbents have an ample number of biomolecules such as cellulose
will create competition for heavy metal ions and H3O+ and H+ for active and lignin. Using incineration as a method of final disposal not only
sites. For example, it can be seen from the Kołodyńska 2017 [206] reduces volume and mass of spent biomass but also helps us in heavy
analysis that Cu was desorbed by 3.5 M HNO3 with an efficiency of 95 metal and thermal energy recovery energy [220]. Work is done by Ding
percent. But, higher acid concentrations can damage the biochar struc et al. (2014) [221] on hexacyanoferrate functionalized walnut shell
ture and thus reduce sorption and desorption efficiency [206]. There biosorbents for removal of caesium ions used incineration method for
fore, acidic eluents should only be used if the adsorbent has good final disposal of the spent adsorbent. In this study significant reduction
mechanical strength and stability. of mass and volume was observed but caesium ion did not volatise from
High rates of desorption can also be achieved by using chelating adsorbent. Whereas, a study on pinecone shell conducted by Martín-Lara
agents such as ethylenediaminetetraacetic acid (EDTA). Such agents et al. (2016) [222] for adsorption of Cu2+ and Pb2+ in a solution studied
have a high number of electrons donating groups, such as carboxylic and pyrolysis under nitrogen atmosphere for final disposal. It was found
amine groups, which have a high affinity to metal ions and can form biomass left after pyrolysis had a higher amount of carbon content,
stable complexes with them. Metal ions are then separated from the lower amount of oxygen, nitrogen, and sulphur content when compared
adsorbent and form complexes with these chelating agents. In the study to coal, which indicated lower corrosive and toxic gas and a new source
reported by Hu and Shipley, 2013 [207], EDTA and common ion solu of thermal energy on combustion.
tions such as NaNO3, NaCl, CaCl2, NaHCO3, MgSO4 and NaHPO4 were Another method for disposal of spent adsorbent can be treating the
used to assess the ability of nano-TiO2 to recover Pb(II), Cu(II) and Zn biomass in landfill [215], [216]. The operation of this method is also
(II). The use of common ion solutions caused in minimal desorption, simple and inexpensive similar to domestic landfill [223]. Biosorbent
whereas the use of EDTA solutions produced 92 percent desorption. containing toxic metal ion should be desorbed before using this method
Increased regeneration cycles lead to a decrease in overall adsorption in order to avoid secondary pollution. After proper desorption waste
and desorption, possibly due to the stronger chelating properties of biomass could be spread on the surface of the land or could be buried
EDTA. The reason proposed to explain this increased adsorption capa underneath and later natural decomposition could complete the final
bility was the activation of new adsorption sites by EDTA-4Na. disposal.
It was observed that the degree of protonation of the adsorbent Disposal and regeneration in many cases are interlinked processes.
surface reduced with the introduction of an alkali medium, which, in Regeneration and reuse of spent biomass are other effective methods for
turn, causes desorption. Also, heavy metal(s) from chemical adsorbents undergoing the final disposal method. Biochar has the ability to re-
viz., manganese-coated powder, iron-coated powder, nano zero valent adsorb heavy metal after regeneration. This property of biosorbent
iron, Fe(III) oxide or hydroxide nanoparticle-based agglomerate sus can be used for increasing the life span of biosorbent and in turn
pension, and magnetic wheat straw, were found to be removed using reducing the need for generation of fresh biosorbent. In a study reported
alkalis [58]. In an experiment by S. Wang et al., 2017 [131] it was seen by Jeon and Park, 2005 [224] the EDTA metal complex was effectively
that adsorption equilibrium was reached, and arsenic was successfully separated into EDTA solid and metals chloride by using HCl after the
desorbed with 0.1 M NaOH. After a 24 -h desorption, 98.2 percent regeneration process. The successful separation of EDTA metal complex
Arsenic was released from the spent adsorbents [131,208]. Upon into 2 different parts can be a permanent solution for disposal of used
completion of the desorption cycle, the adsorbent adsorption sites are biochar as it can be reused several times and efficiency of the same after
simply reactivated by making the pH of the medium neutral, with the 5− 6 cycles remain nearly the same [207]. Magnetic and centrifugal
support of an acid or alkali. sedimentation can also be possible methods for the separation of
The final disposal of the spent adsorbent should be done with care. iron/iron oxide modified biosorbent [225]. Spent biosorbent can be
Biosorption moves sorbate from the aqueous solution to the solid phase recycled to produce bricks and cement for the construction industry, but
biosorbent, which raises operational concerns regarding the final safe usage in large quantities can affect its mechanical strength. Also, heavy
handling of the filled biosorbent and sorbate. While these laboratory metals loaded on biochar based sorbents can be used for the production
studies have demonstrated the potential to regenerate biosorbents using of supercapacitors. For example, Microwave oxidation carried out with
acids, alkalis and complexing agents, the feasibility of the entire process Ni2+ loaded BC, reduces the carbon content, and increases oxygen
on an industrial scale remains doubtful. content which increases the capacitance, charge-discharge capacity, and
power density [52,226,227]. Research shows that BC has a high po
6. Safe Disposal of spent biochar based sorbents tential for replacing expensive synthetic carbon nanoparticles for future
supercapacitors [228].
Few studies regarding biochar focus on regeneration and utilization Generally, the raw material for biochar comprises algae, microbes,
of spent adsorbent without giving proper insight into the final disposal forestry, and agricultural waste. Organic substances present in these
of biosorbent. Disposal of spent biomaterials contaminated with harmful materials are useful for the poor quality of soil hence, these biomasses
organic ions also poses social and environmental problems, especially in can also be used as fertilizers [214,217]. In a study conducted to remove
developing nations where furnaces and engineered landfills are deficient Zn2+ from wastewater with the help of marine algal biomass, spent
[209–211]. The disposal of biochar containing heavy metals may take biomass was finally disposed of in the form of fertilizer to enhance soil
place after the recovery of heavy metals or immediately after the quality [214]. Similarly, a study conducted by Tay et al. (2016) [217] on
adsorption process, in both situations there maybe be secondary pollu fishbone meat waste on lead reported that waste biomass could be used
tion from used biochar and the chemicals used to prepare the biochar as organic compost or composite filler material in the downstream
[212]. Even then, biochar loaded with heavy metals have lethal effects industry.
on the environment and humans. Henceforth, used biochar should be There are other paths too apart from these conventional methods
released in nature only after the complete recovery of heavy metals from which were followed to aid safe disposal of biosorbent after use. In a
the biochar surface [58]. Oladipo et al., 2019 [9] in their experiment work by Vilar et al. (2007) [229] spent biomass was sterilized with the
used banana peels if banana peel waste is not effectively managed, it help of microwave irradiation and then was given seal treatment while
creates odor and subsequently produces greenhouse gases. Prior to the placing it into inert material. Another option for safe disposal is using
commercialization of biosorbent proper attention towards final disposal plants to Phyto remediate these contaminants later; these plants can be
should be paid. In general, there are five methods which can be used for biochar synthesis. Few researchers Ramrakhiani et al. (2017);
21
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Journal of Water Process Engineering

Latest trends in heavy metal removal from wastewater by biochar

Fig. 1. Mechanisms of heavy metal removal by biochar based sorbents [5,46].

Fig. 2. Advantages of deploying Biochar based sorbents.

Fig. 3. Comparison of metal removal performance of different sorbents [45,51–57].

Equal proportion of liquid,

elimination of heavy metals relies on the concentration of the pollutants,

Fig. 5. Common kinetic models in metal removal by biosorbents [94].

Ion Composition Parameter Adsorption

Ion Composition Parameter Adsorption

Pine bark AD: 1.2 g/

Ion Composition Parameter Adsorption

T: 25 ◦ C Cd(OH)+ & Cd2+ ↓

(continued on next page)

Ion Composition Parameter Adsorption

(continued on next page)

Ion Composition Parameter Adsorption

washing with pH: 5

Ion Composition Parameter Adsorption

Ion Composition Parameter Adsorption

(continued on next page)

Ion Composition Parameter Adsorption

Ion Composition Parameter Adsorption

Maghemite & slow pyrolysis→ T: 30 ◦ C

Fig. 7. Principles of Metal Removal Mechanisms.

Fig. 8. Regeneration protocols of biochar-based sorbents.

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