Journal of Environmental Management 317 (2022) 115385

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Journal of Environmental Management

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

Impacts of pyrolysis temperatures on physicochemical and structural

properties of green waste derived biochars for adsorption of potentially
toxic elements
Nisar Muhammad a, b, c, Liya Ge c, Wei Ping Chan c, Afsar Khan d, Mohammad Nafees b, *,
Grzegorz Lisak c, e, **
a
Department of Environmental Science, Gomal University, Dera Ismail Khan 29050, Pakistan
b
Department of Environmental Sciences, University of Peshawar, Peshawar, 25120, Pakistan
c
Residues and Resource Reclamation Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, 1 Cleantech Loop, Singapore,
637141, Singapore
d
Department of Chemistry, University of Baltistan, Skardu, 16250, Pakistan
e
School of Civil and Environmental Engineering, Nanyang Technological University, Singapore, 637141, Singapore

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

Keywords: This study comparatively investigated the influence of changes in pyrolysis temperature on the physicochemical,
Pyrolysis temperature structural, and adsorptive properties of biochars derived from a green waste (Cynodon dactylon L.). For this
Biochars purpose, the biophysically dried green wastes were pyrolyzed at 400 ◦ C, 600 ◦ C, and 800 ◦ C under the same
Potentially toxic elements
pyrolysis conditions. The results revealed that the physicochemical and structural properties were varied,
Adsorptive performance
Green waste
depending upon the pyrolysis temperatures. With the increase of pyrolysis temperature, the surface functional
groups were escaped, the structure became more porous (pore volume of 0.089 ± 0.001), the metal oxides were
remained consistent, and the biochars turned into more alkaline nature (pH of 11.9 ± 0.2). Furthermore, as
referring to the adsorptive performance for potentially toxic elements, with experimental adsorption capacity of
up to 33.7 mg g− 1 and removal rate up to 96% for a multi-metals containing solution, the biochars pyrolyzed at
high temperature (800 ◦ C) was significantly (p < 0.05) higher than those pyrolyzed at low temperature (400 ◦ C).
According to the physicochemical and structural properties, and the adsorptive performances of the biochars, the
optimal pyrolysis temperature was herein recommended to be 800 ◦ C.

1. Introduction
Biochar (BC) is a carbon (C) enriched solid product generated from
the pyrolysis of different biomass (Muhammad et al., 2021) at a rela­
tively low temperature (Lehmann and Joseph, 2009). It is different from
other biomass pyrolysis products, in which the main usage is to store C in
the soil for a long time, rather than to create raw materials for processing
industries or fuels (Cross et al., 2010). In the Amazon basin, BC has been
used as a soil amendment for more than 2000 years (Kim et al., 2007). It
has a wide range of environmental applications, which are not limited to
the fixation of carbon dioxide, the remediation of degraded soils, the
adsorption of contaminants, and the improvement of crop yield and
productivity (Abujabhah et al., 2016; Partey et al., 2016; Venegas et al.,
2016). As the environmental applications of BCs largely depend on their
physicochemical and structural characteristics, these properties should
be carefully investigated and evaluated prior to the applications (Angin
and Şensöz, 2014). BCs can be produced by the pyrolysis of different raw
materials (mainly including woods and the biomass of crops), high-yield
green wastes, agricultural by-products (such as straws of cereal and
peanut), as well as other organic wastes (such as sewage sludges and
food wastes) (Méndez et al., 2013; Yang et al., 2017). Generally, woody
feedstocks are preferentially used for BC productions, because they have
high carbon contents, and contain a large amount of cellulose, hemi­
cellulose and lignin, as well as a small amount of other organic and

* Corresponding author.
** Corresponding author. Residues and Resource Reclamation Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, 1
Cleantech Loop, Singapore, 637141, Singapore.
E-mail addresses: nafees@uop.edu.pk (M. Nafees), g.lisak@ntu.edu.sg (G. Lisak).

https://doi.org/10.1016/j.jenvman.2022.115385
Received 26 October 2021; Received in revised form 20 May 2022; Accepted 20 May 2022
Available online 28 May 2022
0301-4797/© 2022 Elsevier Ltd. All rights reserved.
N. Muhammad et al.
inorganic compounds (Suliman et al., 2016). Nevertheless, previous
studies had also recommended feedstocks with higher contents of cel­
lulose, hemicellulose and lignin compounds, which resulted compara­
tively higher yield and efficacy upon the applications (Xu and Chen,
2013; Zhao et al., 2017).
The physicochemical and structural properties of BCs depend on
both types of feedstocks and pyrolysis conditions (Bouraoui et al., 2015;
Zhang et al., 2015). Among different operating parameters, the pyrolysis
temperature plays a crucial role, because it affects the yield, properties,
and nature of BCs (Yuan et al., 2013). The pyrolysis temperature has
significant effects on the surface functional groups, pore size, pore vol­
ume, surface area, yield, elemental composition, thermal stability, and
surface charge of BCs (Guizani et al., 2017b; Shaaban et al., 2014). The
high pyrolysis temperature is positively correlated with carbon
(elemental carbon, fixed carbon and dissolved organic carbon), ash and
mineral contents, as well as the surface area, pore size, pore volume, and
cation exchange capacity (CEC) of BCs, but negatively correlated with
hydrogen, nitrogen, sulfur and oxygen contents, as well as yield, mois­
ture and volatile substances of BCs (Liang et al., 2016; Muhammad et al.,
2020; Tag et al., 2016). In brief, BCs pyrolyzed at high temperatures are
highly aromatic and difficult to decompose, which are potentially suit­
able for removing and treating contaminants (Muhammad et al., 2020).
Previous studies also demonstrated that the application of high tem­
perature (700–900 ◦ C) during pyrolysis might produce biochar with
superior performance in heavy metals adsorption (Chatterjee et al.,
2020; Li et al., 2019; Tan et al., 2014). In contrast, BCs pyrolyzed at low
temperatures have relatively less carbonized and condensed structures
of carbon, which are suitable for improving soil fertility (Zambon et al.,
2016). Recent studies also point toward the need to systematically assess
the source and availability of feedstock, optimization of the biochar
production process, development of low-cost adsorbent, demonstration
at the field, possible regeneration of adsorbent, the complexity of the
interaction of adsorption conditions, and the applicability of such
technology at rural areas and developing countries (Baltrėnaitė-Gedienė
et al., 2020; El-Naggar et al., 2021; Hu et al., 2021).
Bermuda grass (Cynodon dactylon L.) is a perennial grass that grows
naturally. As one of the most common grasses throughout the world,
Bermuda grass is a salt-tolerant, drought-resistant, potentially invasive
and facultative halophyte species, which even grows in wastelands,
barren lands and other native species dominated grasslands (Kovács
et al., 2002). It has an overgrowth property and can cover an area up to
25 m2 within 1.5 years (Horowitz, 1996). Compared with other grasses,
it has the highest concentrations of total elemental contents for C, cal­
cium (Ca), potassium (K), magnesium (Mg), sodium (Na), and phos­
phorous (P), which makes it a more competitive species (Kovács et al.,
2002). Due to the overgrowth characteristics, Bermuda grasses are cut
routinely and discarded as green wastes commonly burned in the open
environment, which becomes an important source of carbon dioxide in
the atmosphere. Therefore, the use of green waste (Cynodon dactylon L.)
for BC production is a reliable environmental-friendly solution to this
problem, which can be used to remove and immobilize contaminants in
the contaminated soil and water.
To the best of our knowledge, no previous study had been performed
to compare the BCs produced from the green waste, Bermuda grass
(Cynodon dactylon L.) at different pyrolysis temperatures and use them
to remove PTEs from wastewater or contaminated groundwater. This
study aims to comprehensively and scientifically establish the properties
of biochar generated from Bermuda grass with close relation to the
characteristics of the feedstock itself. Pyrolysis at a wider temperature
range is attempted to explore the different potential applications of the
resulted biochar. Systematic measurement and reporting of the physi­
cochemical and structural properties will help to promote the actual
usage of the BC on site in the future. Comparative assessment with other
types of biochar will allow the potential users to reach informed de­
cisions based on the local setting and needs. For instance, the use of BC
from Bermuda grass as a low-cost adsorbent for contaminated
2
Journal of Environmental Management 317 (2022) 115385
groundwater treatment before performing the irrigation on the farmland
or alternatively, for soil conditioning using this locally self-grown waste
grass derived biochar, produced from high or low pyrolysis temperature,
respectively. This study is also part of a larger research effort to explore
the use of indigenous materials for contaminated river (or groundwater)
treatment, wastewater treatment, bioremediation and soil amendment,
especially for the rural areas. Given the importance mentioned above,
the green waste was subjected to a wide pyrolysis temperature range
from 400 to 800 ◦ C. The produced BCs were comprehensively investi­
gated and compared for (i) physicochemical properties, (ii) structural
analyses, and (iii) potentially adsorptive performances of the toxic ele­
ments, with pyrolysis temperature as a critical influencer in the BC py­
rolysis process. Furthermore, a wide concentration range of PTEs
(25–250 mg L− 1) with multiple metals (7 elements) and at different
concentrations (6 points) were tested to comprehensively explore the
application potentials of this less studied green material.
2. Methods and materials
2.1. Preparation of biochar
Cynodon dactylon L. was pyrolyzed in a fixed-bed reactor (horizontal)
with a length of 100 cm and an inner diameter of 5.5 cm at different
temperatures (400 ◦ C, 600 ◦ C, and 800 ◦ C). A heating rate of 10 ◦ C min− 1
was applied to reach desired temperatures, then held to perform slowly
pyrolyzed with 100 L min− 1 N2 with a residence time of 20 min, and
finally cooled down to 50 ◦ C under continuous nitrogen gas flow. The
solid products (BCs) were collected, ground and sieved through 40 mesh
(0.45 mm). The BCs obtained under the pyrolysis temperatures of
400 ◦ C, 600 ◦ C, and 800 ◦ C were subsequently denoted as 400BC,
600BC, and 800BC, respectively.
2.2. Physicochemical analysis of biochar
The pH value of BCs was determined by mixing 1:5 (w/v) of the BCs
and deionized (DI) water, and shaking on a mechanical shaker for 1 h
(Enders and Lehmann, 2017) with a pH meter (Seven2Go™). The water
holding capacity (WHC) (Eq. (1)) was determined through the gravi­
metric method (Nguyen and Lehmann, 2009). The CEC was calculated as
the sum of all cations in meq/100 g dry BC as measured through a flame
atomic absorption spectrophotometer (FAAS, PerkinElmer 700) (Gaskin
et al., 2008). For dissolved organic carbon (DOC), 1.0 g of BCs was
mixed with 20 mL of CaCl2 solution (0.01 M) and shaken overnight. The
homogenized mixture was centrifuged at 10,000 rpm for 10 min, and the
supernatant was filtered for measurement (Cabrera et al., 2011) through
the TOC-V CSH analyzer (Shimadzu). The dried BC samples were ground
for elemental analysis, in which C%, H%, N% and S% were determined
through the CHNS analyzer (PerkinElmer 2400 Series II CHNS/O). The
O% was further calculated by Eq. (2) (Aslam et al., 2017). The contents
of PTEs (As (III), Cd, Co, Cr (III), Ni, Pb and Zn) and other main elements
(Ca, Mg, Na, K and P) for the BC samples were determined through the
application of microwave-assisted digestion (MAD) with method 3052
for siliceous and organically based matrices (ASTM, 1996) and mea­
surement through an inductively coupled plasma-atomic emission
spectrometer (ICP-AES, PerkinElmer, Optima 8300).
ms − md − mw
WHC% = × 100 (1)
md
O% = 100% − (C% + H% + N% + S% + Ash%) (2)
where, ms is the mass of filter paper saturated with DI water and sand-BC
mixture, md is mass of dried filter paper and sand-BC mixture, and mw is
the mass of wet filter paper used in Eq. (1).
N. Muhammad et al.
2.3. Structural analysis of biochar
Approximately 10 mg of each BC was dispersed into DI water (20 mL)
for 30 min with ultrasound, and then taken onto a carbon-coated copper
grid. After drying, the micromorphology was observed by a scanning
electronic microscope (SEM, Hitachi). The pore volume, pore size and
surface area were measured by a surface area analyzer (NOVA2200e,
Quantachrome) through nitrogen adsorption/desorption at 77.4 K, ac­
cording to Barrett-Joyner-Halenda (BJH) and Brunauer-Emmett-Teller
(BET) methods, respectively. Before analysis, the BCs samples were
degassed under vacuum conditions at 180 ◦ C for 24 h (Tan et al., 2014).
Energy dispersive X-ray (EDX) was used to detect elemental mapping
and chemical composition of particles, which was determined by a super
ultra-thin window X-ray analyzer (Silicon drift detector, Quantax,
Bruker) under 20 kV voltage at the highest possible resolution for
maximum percentage measurement of the elements (Purakayastha
et al., 2015). The mineralogical composition of BCs was determined by
X-ray diffraction (XRD) analysis. A Bruker 2D phaser system (D5005,
Bruker Germany) equipped with a Lynxeye detector was used for
obtaining the XRD diffractogram from 5 to 50◦ 2θ at a scan rate of 40s
per 0.05◦ 2θ step size. The diffractograms of BCs were identified by
comparing the 2θ values to ICDD-PDF software Diffrac Eva. The iden­
tification of the minerals was also achieved by comparing to the stan­
dards files of joint committee on powder diffraction (Kim et al., 2013;
Srinivasan et al., 2015). For fourier transformed infra-red spectroscopy
(FTIR), the BC samples were prepared by mixing 1.0 mg of each BC with
200 mg of KBr (FTIR reagent) and making pellets (7 × 13 mm) with
hydraulic press at a pressure of 10 tons/cm2 for 2 min. The pellets were
then scanned the infra-red absorbance in the range of 400–4000 cm− 1
using GX spectrometer (PerkinElmer, USA) (Tan et al., 2014). The BC
samples were analyzed by a Renishaw inVia Raman microscope (514 nm
laser diode) using 4 cm− 1 spectral resolution with 10% laser power and
15 min acquisition time. The Raman spectra were fitted in the range of
400–3500 cm− 1 by WiRE Raman software (version 3.6) (Mohanty et al.,
2013). The X-ray photoelectron spectroscopy (XPS) analysis of the BCs
was conducted through achromatic X-ray radiation (1253.6 eV) with an
axis-165 (Kratos analytical Inc.). The curves of C1s and O1s were fitted
by CasaXPS software (version 2.3.19, Casa Software Ltd.). For C1s and
O1s, the binding energy of 284.5 eV and 531.0 eV were used as the
reference charges, respectively (Suliman et al., 2016). The thermogra­
vimetric analysis (TGA) and derivative thermogravimetric (DTG) ana­
lyses were achieved by measuring from 25 to 1000 ◦ C at a heating rate of
10 ◦ C min− 1 and continuous flow of nitrogen gas (20 mL min− 1) using
TGA/DTG 1 STAR® system (Mettler-Toledo, Switzerland) (Tan et al.,
2014).
2.4. Adsorption performance of BCs for potentially toxic elements (PTEs)
Stock solutions of As(III), Cd(II), Co(II), Cr(III), Ni(II), Pb(II) and Zn
(II) (1000 mg L− 1 each) were prepared from their parental salts in DI
water. From the stock solutions, 250, 200, 150, 100, 50 and 25 mg L− 1
solutions were prepared through further dilutions. Each BC (100 mg)
was put into a glass bottle and added 10 mL of the diluted solutions of
each PTE to do multi-element mixed adsorption. The BC and diluted
solution were intensively mixed overnight by vortex and continuously
stirred for 4 h at 25 ± 2 ◦ C. The suspensions were then passed through
filters (0.45 μm) and analyzed for concentrations of PTEs through the
ICP-AES (ASTM, 1996). The ICP-AES was re-calibrated for standardi­
zation (R2 > 0.99) after analysis of each 10 samples. All the adsorption
experiments were performed in triplicates, and blanks were measured
for comparative analysis. The adsorption efficiency of BCs was deter­
mined as:
Ci − Cf
Ads% = × 100%
Ci
Journal of Environmental Management 317 (2022) 115385
where Ads% is the adsorption efficiency of the BCs, Ci is the initial
concentrations of PTEs in the diluted solutions and Cf is the final con­
centrations of PTEs in the filtered solutions.
To examine the statistical significance of two different sets of data, a
two-sample t-test was performed for the calculation of p-value by
GraphPad Software, and a significance level of 0.05 was set in the cur­
rent study.
3. Results and discussion
3.1. Physicochemical properties of biochars
The properties of prepared BCs (mean ± SD) are shown in Table 1.
The BCs were all alkaline and with increasing pH values for BCs
generated at the higher temperatures. Among the generated BCs, 800BC
was of the highest pH value at 11.88. This could be resulted from the
transformation of minerals and metal oxides into alkaline media during
the pyrolysis (Tan et al., 2014). The correlation of higher pH value to the
increased of pyrolysis temperature was observed in a previous study on
sewage sludge (Méndez et al., 2013), which is caused by the release of
alkali metal salts from the biomass materials (Chen et al., 2011) and the
reduction of acidic functional groups on the surface during the loss of
oxygen (Filippis et al., 2013). Generally, the alkaline pH of BCs
contributed to the immobilization of PTEs, which is attributed to the
conversion of PTE into sediments with low solubility (Kistler et al.,
1987). Furthermore, the alkaline pH of BCs contributed to avoiding their
own PTEs from being leached into the soil, and thus guaranteed the
safety of soil.
SEM images (Fig. 2) illustrated and supported that the surface area,
pore volume and pore size increased considerably with the rising in
pyrolysis temperature. Other research groups had reported similar
findings, such as BCs derived from sewage sludge (Méndez et al., 2013;
Tan et al., 2014) or derived using different biomass materials such as
peanut, canola, corn and soybean (Yuan et al., 2011). The CEC of BCs
produced from Cynodon dactylon L. correlated well with the rising in
pyrolysis temperature (p < 0.05). This is different from the previous
studies where the CEC could either increase or decrease with the py­
rolysis temperature depending on the feedstock and the temperature
range applied (Méndez et al., 2013; Tan et al., 2014; Tomczyk et al.,
2020). Nevertheless, the CEC values (from 51.2 to 94.8 cmol kg− 1) of
BCs are generally comparable to the other biomass waste materials
(from 4.6 to 122.0 cmol kg− 1). The concentrations of DOC were 19.58,
22.28 and 25.94 mg kg− 1 after pyrolysis at temperatures of 400 ◦ C,
600 ◦ C and 800 ◦ C, respectively, which increased with the rising of
pyrolysis temperature, comparable to other biomass waste materials
(Cheng et al., 2016). The concentrations of C (from 56.6 to 72.8% with
the increase in temperature) and P (from 2030 to 2920 mg kg− 1) in the
BC pyrolyzed at 800 ◦ C were relatively higher than those at lower
temperatures, which is consistent with the findings for BCs derived from
branches on C, from 62.2 to 80.0% and for P, from 0.21 to 0.34%,
respectively (Zhao et al., 2017).
With the increase in pyrolysis temperature, the surface functional
groups containing N, H, O and S were reduced with the release of vol­
atiles. This is the reason why the concentrations of these elements were
rapidly dropped as temperatures increased, while the C was remained
and converted into the fixed carbon (FC). Therefore, microstructures
developed greatly, the atomic ratios (O/C and H/C) decreased and the
amorphous carbon increased, similar to the findings for BCs derived
from different sewage sludges (Tan et al., 2014). The decrease of O/C
and H/C ratios also indicated that, during the pyrolysis of BCs, dehy­
drative polycondensation and dehydrogenative polymerization led to
the massive loss of oxygen and aliphatic hydrogen (Filippis et al., 2013).
The low O/C molar ratio of BC showed that less polar groups with higher
(3) hydrophilicity were available (Chun et al., 2004). Although the H/C
molar ratio of the BCs as the degree of carbonization is always lower
than 0.5, it was shown that high aromaticity and carbonization could
3
N. Muhammad et al. Journal of Environmental Management 317 (2022) 115385

Table 1
Physicochemical properties of biochars pyrolyzed at 400 ◦ C, 600 ◦ C and 800 ◦ C.
Parameter 400BC 600BC 800BC Parameter 400BC 600BC 800BC

pH 9.1 ± 0.2 10.3 ± 0.2 11.9 ± 0.2 Ash (%) 13.2 ± 0.13 17.8 ± 0.18 22.5 ± 0.26
WHC (%) 42.8 ± 0.7 48.7 ± 0.8 56.3 ± 0.9 VM (%) 28.7 ± 0.1 20.9 ± 0.1 13.7 ± 0.1
Surface area (m2 g− 1) 17.3 ± 0.3 36.5 ± 0.6 48.8 ± 0.8 FC (%) 53.0 ± 0.1 61.3 ± 0.1 67.8 ± 0.1
Pore volume (cm3 g− 1) 0.041 ± 0.001 0.052 ± 0.001 0.089 ± 0.001 P (mg kg− 1) 2030 ± 46 2440 ± 53 2920 ± 68
Pore diameter (nm) 3.735 ± 0.05 3.759 ± 0.06 3.778 ± 0.08 Ca (mg kg− 1) 5640 ± 120 8640 ± 190 11680 ± 221
CEC (cmol kg− 1) 51.2 ± 1.7 71.4 ± 1.8 94.8 ± 1.8 Mg (mg kg− 1) 2430 ± 53 3630 ± 72 4420 ± 88
DOC (mg kg− 1) 19.6 ± 0.3 22.3 ± 0.4 25.9 ± 0.4 Na (mg kg− 1) 228 ± 5.7 363 ± 8.5 472 ± 11.6
C (%) 56.6 ± 0.9 65.3 ± 1.1 72.8 ± 1.2 K (mg kg− 1) 8130 ± 190 10270 ± 220 13820 ± 260
H (%) 3.56 ± 0.06 2.78 ± 0.05 1.98 ± 0.03 As (mg kg− 1) 0.02 ± 0.001 0.03 ± 0.001 0.03 ± 0.001
N (%) 1.88 ± 0.03 1.62 ± 0.03 1.22 ± 0.02 Cd (mg kg− 1) 0.03 ± 0.001 0.04 ± 0.002 0.04 ± 0.002
S (%) 1.93 ± 0.03 1.67 ± 0.03 1.19 ± 0.02 Co (mg kg− 1) 0.02 ± 0.001 0.02 ± 0.001 0.03 ± 0.002
O (%) 14.1 ± 0.23 10.6 ± 0.17 7.23 ± 0.12 Cr (mg kg− 1) 0.05 ± 0.004 0.07 ± 0.005 0.08 ± 0.005
O/C 0.25 ± 0.004 0.16 ± 0.003 0.10 ± 0.002 Ni (mg kg− 1) 0.04 ± 0.001 0.05 ± 0.001 0.06 ± 0.001
H/C 0.06 ± 0.001 0.04 ± 0.001 0.03 ± 0.001 Pb (mg kg− 1) 0.08 ± 0.01 0.13 ± 0.03 0.18 ± 0.04
Yield (%) 38.3 ± 1.06 34.3 ± 1.00 32.6 ± 0.93 Zn (mg kg− 1) 4.27 ± 0.70 6.16 ± 0.96 7.94 ± 1.30
Moisture (%) 1.36 ± 0.06 1.33 ± 0.04 1.29 ± 0.03

resist the further decomposition of BCs (Yuan et al., 2013). As the py­
rolysis temperature increased, the concentrations of major elements
were increased. Compared with 400 ◦ C, the concentrations at 800 ◦ C
were increased 51.8% for calcium, 45.0% for magnesium, 51.7% for
sodium and 41.1% for potassium. These observations were comparable
with the BCs derived from apple trees (Zhao et al., 2017).
Moreover, the yield, moisture content and VM content of BCs
decreased, while the ash content increased with the rising in pyrolysis
temperature. The devolatilization of volatiles at high pyrolysis temper­
ature increased the FC contents in BCs (Yang and Sheng, 2012), whereas
FC was considered a measurement to assess the recalcitrance and sta­
bility of BCs (Mašek et al.; Zhao et al., 2013). In addition, BCs with low
VM contents were found to be suitable for agronomic applications, due
to their role in nitrification and microbial activity (Deenik et al., 2009).
A number of studies had reported similar findings for BCs derived from
sewage sludge and crops, respectively (Méndez et al., 2013; Yuan et al.,
2013). The PTE concentrations of BCs were also investigated to identify
the risk of leaching into the soil, but these concentrations are within a
safe range (He et al., 2010; Tan et al., 2014).

Fig. 1. Nitrogen adsorption-desorption isotherms and pore size distribution

3.2. Structural analysis of biochar curves (inside) of biochars.

3.2.1. Micromorphology and surface characteristics

Ca from 2.97% to 3.45%, while a decrease in the intensity of O from
As shown in the SEM images (Fig. 2-up), the pore volume and pore
22.91% to 11.99% and S from 2.44% to 1.47%, with the increase of
size were increased with the rising of pyrolysis temperature (from
pyrolysis temperature. These findings were further supported by the
400 ◦ C to 800 ◦ C), which supported the physicochemical results of pore
results from CHNS and ICP-AES (Table 1). Similar findings for C, O and S
volume and pore diameter (Table 1). Based on physicochemical results,
intensities were found in the BCs prepared from green (leaf) waste with
the pore volume was significantly increased with the rising of pyrolysis
the increase in pyrolysis temperature (Sahota et al., 2018).
temperature (p < 0.05), which was comparable to previous studies (Tan
et al., 2014; Yuan et al., 2011). With the increase in pyrolysis temper­
3.2.3. XRD analysis
ature, the N2 adsorption of the BCs also significantly (p < 0.05) increased
The XRD patterns showed the intensities of the diffracted beams
(Fig. 1). According to the IUPAC classification, the N2
(Bragg’s law) or crystalline phases on the surface of BCs. All the spectra
adsorption-desorption isotherms corresponded to the type IV isotherm
(except 40◦ ) of the BCs intensities (Fig. 3) are sharp with a compara­
(Pavan and Andrew, 2019; Sing et al., 1985). These observations indi­
tively broad peak at 40◦ , indicating crystalline structure and carbon-rich
cated that (i) mesoporous structure (2–50 nm) was found on the BCs, (ii)
phase in the BCs (Srinivasan et al., 2015). Moreover, all the BCs showed
narrow necks and wide bodies (ink bottle pores) were observed, and (iii)
no peak in 15–20 region of 2θ, which confirmed the complete decom­
in the mesopores, capillary condensation occurred (Tan et al., 2014).
position of celluloses (Regmi et al., 2012). The identified peaks belong to
The distribution of pores was at the peak position of 3.82 nm, as shown
sylvite (KCl) or apatite (Ca5(PO4)3 (Cl,F,OH), sulphate (SO2− 4 ), whe­
by the pore size curves. In addition, the pore structures were observed as
wellite (CaC2O4.H2O), calcite (CaCO3), pericalse (MgO) and quartz
uniform and channelized. The formation of mesopores was consistent
(SiO2) at the 2θ region of 28.00, 32.01, 37.02, 40.00, 43.04 and 48.02,
with the BCs derived from sewage sludge (Rio et al., 2005).
respectively (Fig. 3). These peaks (compounds) were found in the BCs
prepared from timothy grasses (Mohanty et al., 2013).
3.2.2. EDX analysis
The EDX spectra could provide quantitative and qualitative analysis
3.2.4. FTIR analysis
of the pyrolyzed BCs (Purakayastha et al., 2015). The EDX spectra
The FTIR spectra (Fig. 4) showed a number of functional groups on
(Fig. 2-down) of the BCs showed an increase in the intensity of C from
the surface of the BCs, which played an essential role in the
62.77% to 74.14%, N from 1.25% to 2.19%, K from 4.63% to 5.21% and

4
N. Muhammad et al.
Fig. 2. SEM images (up) and EDX spectra (down) of 400BC, 600BC and 800BC.
Fig. 3. XRD spectra of 400BC, 600BC and 800BC.
immobilization of PTEs by forming complexes (Ahmad et al., 2014; Lee
et al., 2010). The peaks in the 400-1500 cm− 1 (fingerprint region) exist
at 466.73, 619.09, 783.03, 1105.11, 1193.12 and 1434.91, while the
peaks from 2500 to 4000 cm− 1 exist at 2558.71, 2852.46, 2919.96,
2962.39 and 3425.27 cm− 1 showed the availability of single bond
compounds, while the peaks from 1500 to 2000 cm− 1 (1647.06 and
1872.71 cm− 1) indicated the presence of C– – O double bond stretching
(carbonyl group) (Darban et al., 2016; Mohanty et al., 2013; Zhao and
Nartey). The peaks in various regions were attributed to different
components in the feedstock, such as 400-800 cm− 1 attributed to aro­
matic hydrogen, the C–H bond from lignin compound, 1100-1200 cm− 1
attributed to C–O stretching from cellulose and C–C stretching from
alkenes function, 1300–1500 attributed to O–H, C–H, and C–O stretch
from cellulose, hemicellulose, and alcohol groups, respectively. Peaks at
1500-2000 cm− 1 indicated the presence of C– – O stretching from the
aromatic structure of hemicellulose and 2500–4000 attributed to
alcohol compound or hydrogen bonded OH stretching from lignocellu­
lose compounds (Regmi et al., 2012; Suryanto et al., 2014). Further­
more, the surface functional groups were decreased with the increase of
5
Journal of Environmental Management 317 (2022) 115385
Fig. 4. FTIR spectra of 400BC, 600BC and 800BC.
pyrolysis temperature from 400 ◦ C to 800 ◦ C, which could justify the
results of CHNS for N, H and O (functional groups elements) and O/C
and H/C ratios as shown in Table 1. The decreasing of functional groups
with the increase of pyrolysis temperature is comparable to findings
described in a previous study (Tan et al., 2014), where dehydrogenation
and reduction of carboxyl groups were observed.
3.2.5. Raman analysis
The crystalline and amorphous properties (structure evolution) of
BCs were analyzed by Raman spectroscopy, due to its sensitivity to both
the structures (Mohanty et al., 2013). The spectra from 500 to 3000
cm− 1 indicated various types of bands during the curve fitting (Fig. 5).
The spectra of the BCs with three peaks at 1344.99 cm− 1, 1579.36 cm− 1
and 2699.16 cm− 1 were commonly referred to “D”, “G” and “2D” bands.
The “D” band at 1344.99 cm− 1 was indicated as the disordered (defect)
region of carbon for methyl groups (C–C vibration), the “G” band at
1579.36 cm− 1 was the graphitic region for the in-pane vibrations of
N. Muhammad et al.
Fig. 5. Raman spectra of 400BC, 600BC and 800BC.
sp2-bonded graphitic carbon structure of aromatic carbon (C– – C) and
the “2D” band at and 2699.16 cm− 1 was actually the second order of the
“D” band (one half of the 2D band), which also represented the methyl
groups (C–C vibration) (Smith et al., 2016; Tuinstra and Koenig, 1970).
The band area of “G” peaks was less than “D” peaks in all the BCs, which
showed semicircle breathing of aromatic rings with the loss of O-con­
taining functional groups in BCs (Mohanty et al., 2013). Furthermore,
the “D”, “G” and “2D” peaks in the Raman spectra of all the BCs reflected
the impacts of pyrolysis temperature. For instance, the intensities at
1344.99 cm− 1, 1579.36 cm− 1 and 2699.16 cm− 1 peaks increased in the
order of 800BC > 600BC > 400BC with 400 ◦ C, 600 ◦ C and 800 ◦ C
(Fig. 5), which could justify the CHNS results of C contents (Table 1).
Moreover, the “2D” peak was lower than “D” peak in all the BCs, due to
the transition of non-crystalline graphite to sp2-amorphous carbon
structure (Jerng et al., 2011). Similar findings with the increase of py­
rolysis temperature had been reported by Guizani et al. (2017a) for BCs
derived from beech wood.
3.2.6. XPS analysis
The XPS surface quantitative spectroscopic results of the BCs were
Fig. 6. TGA (A) and DTG (B) curves of 400BC, 600BC and 800BC.
6
Journal of Environmental Management 317 (2022) 115385
presented in Table S1 (Supplementary Material). The C1s peaks were
measured at 284.90 (eV) and 288.00 (eV), while the O1s peak was at
533.00 (eV). The C1s peak of the BCs was deconvoluted into main peaks
and attributed to aliphatic carbon as C–C (alkanes) and C– – C (alkenes) at
284.90 (eV), and aromatic carbon as C– – C (graphene) at 288.00 (eV). At
the same time, the O1s peak was convoluted into a single peak at 533.00
(eV), which was attributed to C– – O (O-containing functional groups)
(Moulder et al., 1992; Srinivasan et al., 2015). It could be observed from
the spectra of C1s that all the BCs were rich in C and the intensities
remained high, while the intensity of O1s decreased lower, which could
be attributed to the increase in carbonization pyrolysis temperature
from 400 ◦ C to 800 ◦ C. These results were consistent with the previous
findings (Srinivasan et al., 2015). Furthermore, the XPS results could be
positively correlated to the EDX (Fig. 2-down), Raman (Fig. 5) and CHNS
(Table 1) results of all the BCs. All these findings showed that C was a
dominant element and O was in decreasing order with the increase in
pyrolysis temperature from 400 ◦ C to 800 ◦ C.
3.2.7. Thermal stability
The TGA and DTG curves of the BCs (Fig. 6) showed that distinctive
weight loss started from 300 ◦ C and reached a maximum at 900 ◦ C. The
TGA curves (Fig. 6-A) were in the thermal stability order of 400BC <
600BC < 800BC from 200 to 900 ◦ C, which confirmed that 800BC was
comparatively more stable than 600BC and 400BC. The DTG curves
(Fig. 6-B) indicated the loss of weight rate from 100 to 1000 ◦ C within a
time interval of 10–100 min. The maximum weight loss was recorded at
450 ◦ C, 750 ◦ C and 950 ◦ C for 400BC, 600BC and 800BC, respectively.
The absolute maximum weight loss of the BCs was in the order of 400BC
> 600BC > 800BC, indicating the more availability of functional groups
on the surface of 400BC than 600BC and 800BC, which supported the
results of FTIR spectra as shown in Fig. 5. Similar findings of TGA and
DTG with the increase of pyrolysis temperature for BCs derived from
sewage sludge (Tan et al., 2014).
3.3. Adsorptive performance of biochar on PTEs
The adsorptive performances of all BCs were at significant (p < 0.05)
levels for all the PTEs with different concentration levels (i.e., 25, 50,
100, 150, 200 and 250 mg L− 1) as shown in Fig. 7 and the sorption
isotherms of biochar (Fig. S1 and S2) can be found in the Supplementary
Material. Among the BCs, the highest removal rate (up to 96%) was
offered by the 800BC, followed by 600BC and 400BC. As shown in Fig. 7
N. Muhammad et al. Journal of Environmental Management 317 (2022) 115385

Fig. 7. Adsorption performance of 400BC, 600BC and 800BC from 25 mg L− 1 solution (a), 50 mg L− 1
solution (b), 100 mg L− 1
solution (c), 150 mg L− 1
solution (d),
200 mg L− 1 solution (e), and 250 mg L− 1 solution (f) of As, Cd, Co, Cr, Ni, Pb and Zn.

(f), a fair adsorption was recorded in the case of 250 mg L− 1 solution for higher adsorption performance of BCs could be achieved. The findings of
all the BCs. The overall results revealed that the increase in pyrolysis this study revealed that the green waste (Cynodon dactylon L.) pyrolyzed
temperature was positively correlated with the adsorption of PTEs. BCs (especially for 800BC) demonstrated competitive adsorption per­
Similarly, the lower concentration of PTE(s) in the target solution, the formance (for PTEs) as compared to other studies reported as shown in

7
N. Muhammad et al. Journal of Environmental Management 317 (2022) 115385

Table 2
Comparison of the adsorption performance of biochar.
Feedstock Temperature Initial concentration of PTE (mg L− 1) Adsorption capacity (mg g− 1) Removal rate (%) Reference
(◦ C)

Perilla leaf 300–700 ◦ C As at 0.05–7.0 mg L− 1. Up to 3.8 mg g− 1

Up to 90% Niazi et al.,
(2018)
− 1 − 1
Potato peel 450 ◦ C As, Cd, Cu, Pb at 5 mg L , respectively. Up to 2.1 mg g for single metal and Up to 41% for single metal Hussain et al.,
up to 5.4 mg g− 1 for multi-metals and up to 27% for multi- (2017)
metals
1 1
Sewage 500–900 ◦ C Cd at 0–200 mg L− Up to 24.0 mg g− Up to 100% Tan et al.,
sludge (2014)
− 1 − 1
Dairy 350 C◦
Cd, Cu, Pb, Zn at 1–5 mM (or 64–1036 mg L , for each Up to 165.8 mg g for single metal Up to 100% for single metal Xu et al.,
manure metal as calculated based on the respective molecular and up to 158.0 mg g− 1 for multi- and up to 79% for multi- (2013)
weights). metals. metals
Rice husk Up to 29.0 mg g− 1 for single metal Up to 18% for single metal
and up to 18.6 mg g− 1 for multi- and up to 11% for multi-
metals. metals
Bermuda 400–800 ◦ C As, Cd, Co, Cr, Ni, Pb and Zn at 25–250 mg L− 1, for Up to 33.7 mg g− 1 for multi-metals. Up to 96% for multi-metals. Current study
grass each metal, respectively.

Table 2, such as up to 90% removal of As with biochar pyrolyzed at
700 ◦ C and 80% with biochar pyrolyzed at 300 ◦ C using Perilla leaf as
feedstock (Niazi et al., 2018), more than 99% Pb, and up to 51% Cd, Zn
49% and Cu 62% removal with dairy manured BCs (Xu et al., 2013),
removal of up to 40% Pb, 42% As, 20% Cu and 5% Cd with potato peels
derived BC (Hussain et al., 2017), and removal of up to 55%, 53% and
25% As by BCs derived from organic solid waste, sewage sludge and rice
husk, respectively (Agrafioti et al., 2014).
There are multiple possible reasons for the observations on the su­
perior adsorption performance of the 800BC. These may include: (i) the
presence of main elements in the biochars and their cation exchange
capacity (Tan et al., 2014; Xu et al., 2013), (ii) comparatively alkaline
pH of the biochars (Tan et al., 2014), (iii) higher surface area of the
biochars, and (iv) larger pore size and pore volume of biochars (Agrafioti
et al., 2014). The adsorptive performance of BCs was positively corre­
lated with the presence of main elements (Ca, Mg, Na and K) and their
CEC value. Therefore, the maximum release of these elements (cations)
that occurred from BCs can provide more space for PTEs adsorption (Tan
et al., 2014; Xu et al., 2013) and contribute to the increase of ion ex­
change. Similarly, for the pH values, the higher the temperature applied
during pyrolysis, the higher the pH of BCs generated, and therefore the
higher PTEs adsorptive capacity could be achieved (Tan et al., 2014).
The 800BC has comparatively higher alkalinity (pH of 11.9 ± 0.2) than
the 600BC (pH of 10.3 ± 0.2) and 400BC (pH = 9.1 ± 0.2), which could
be the possible reason to show relatively better adsorptive performance.
Moreover, the higher surface area and pore volume of BCs also allowed
the 800BC to absorb more PTEs through site binding and pore trapping
mechanisms, respectively (Agrafioti et al., 2014), as shown in Table 1.
4. Conclusion
In this study, Bermuda grass (Cynodon dactylon L.) was applied as a
potentially overgrown grass waste to be converted into an useful biochar
material. It can be used in water/wastewater treatment and purification
to remove PTEs (especially high temperature pyrolyzed BC, such as
800BC) for water reuse, or soil conditioning for restoration of degraded
(applicable for the low temperature pyrolyzed BC, such as 400BC). The
impacts of pyrolysis temperatures on the properties of BCs were also
systematically investigated. Three types of BCs were pyrolyzed from the
green waste in a horizontal reactor through slow pyrolysis processes at
400 ◦ C, 600 ◦ C and 800 ◦ C, with a heating rate of 10 ◦ C min− 1 and 20
min residence time. The results showed that improvements in the
physicochemical, structural and PTEs adsorptive properties of the BCs
were observed, with the increase of the pyrolysis temperature from
400 ◦ C to 800 ◦ C. The possible reasons include: (i) the surface functional
groups were lost, which increased the pore size, pore volume and surface
area; (ii) The concentrations of DOC, CEC and main elements (Ca, Mg,
Na and K) were significantly increased; and (iii) The O/C and H/C ratios
were reduced. All these characteristics made the BCs optimum, which is
why the 800 ◦ C pyrolyzed BC showed comparatively better performance
in terms of PTEs adsorption than the 600 ◦ C and 400 ◦ C pyrolyzed BCs.
Credit author statement
Nisar Muhammad: Conceptualization; Investigation; Methodology;
Data curation; Formal analysis; Validation; Visualization; Writing –
original draft; Writing – review & editing; Liya Ge: Investigation;
Methodology; Data curation; Formal analysis; Writing – review & edit­
ing; Wei Ping Chan: Investigation; Methodology; Visualization; Writing
– review & editing; Afsar Khan: Conceptualization; Methodology; Vali­
dation; Writing – review & editing; Mohammad Nafees: Conceptuali­
zation; Funding acquisition; Project administration; Resources;
Supervision; Validation; Writing – review & editing; Grzegorz Lisak:
Conceptualization; Funding acquisition; Project administration; Re­
sources; Supervision; Validation; Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This research was financially supported by the Higher Education
Commission Pakistan under the International Research Support Initia­
tive Program (Grant No: 1-8/HEC/HRD/2018/8939, PIN: IRSIP 41
BMS83). We acknowledge the collaborative contributions from
Department of Environmental Sciences, University of Peshawar Pakistan
and Nanyang Technological University of Singapore for carrying out this
study.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jenvman.2022.115385.
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