Environmental Pollution 317 (2023) 120723

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Adsorption and immobilization performance of pine-cone pristine and

engineered biochars for antimony in aqueous solution and military
shooting range soil: An integrated novel approach
Basit Ahmed Khan a, c, Mahtab Ahmad a, *, Sajid Iqbal b, Fath Ullah a, Nanthi Bolan c,
Zakaria M. Solaiman c, Munib Ahmed Shafique d, Kadambot H.M. Siddique c
a
Department of Environmental Sciences, Faculty of Biological Sciences, Quaid-i-Azam University, Islamabad, 45320, Pakistan
b
Analytical Chemistry Group, Chemistry Division, Pakistan Institute of Nuclear Science and Technology (PINSTECH), P.O. Nilore, Islamabad, Pakistan
c
UWA School of Agriculture and Environment, and the UWA Institute of Agriculture, The University of Western Australia, Perth, WA, 6009, Australia
d
Central Analytical Facility Division, Pakistan Institute of Nuclear Science and Technology (PINSTECH), P.O. Nilore, Islamabad, Pakistan

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

Keywords: Antimony (Sb–V), a carcinogenic metalloid, is becoming prevalent in water and soil due to anthropogenic ac­
Remediation tivities. Biochar could be an effective remedy for Sb(V)-contaminated water and soil. In this study, we used
Sorption pristine and engineered pinecone-derived biochar as an innovative approach for treating Sb(V)-contaminated
Water treatment
water and shooting range soil. Biochar was produced from pine–cone waste (pristine biochar) and enriched
Army firing range
Stabilization
with Fe and Al salts via saturation (engineered biochar). Adsorption tests in water revealed that iron-modified
Biochar modification biochar showed higher adsorption capacity (8.68 mg g− 1) than that of the pristine biochar (2.49 mg g− 1) and
aluminum-modified biochar (3.40 mg g− 1). Isotherm and kinetic modeling of the adsorption data suggested that
the adsorption process varied from monolayer to multilayer, with chemisorption as the dominant interaction
mechanism between Sb(V) and the biochars. The post-adsorption study of iron-modified biochar by Fourier
Transform Infrared (FTIR) and X-ray diffraction (XRD) further supported the chemical bonding and outer-sphere
complexation of Sb(V) with Fe, N–H, O–H, C–O and C– –C components. The pristine and iron-modified biochars
also successfully immobilized Sb(V) in a shooting range soil, more so in the latter. Subsequent sequential ex­
tractions and post-analysis by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and
elemental dot mapping revealed that Sb in the treated soil transformed to a more stable form. It was concluded
that iron-modified biochar could act as an efficient material for the adsorption and immobilization of Sb(V) in
water and soil, respectively.

1. Introduction Bolivia (Bolan et al., 2022).

An increasing number of industrially introduced anionic pollutants
that pose severe environmental and public health threats have con­
cerned people worldwide (Lito et al., 2012; Xu et al., 2013). Frequent
anionic species including arsenate and arsenite, chromate and chromite,
and antimonate and antimonite, are some of the most harmful pollutants
in most water bodies and wastewater (Xu et al., 2013). Antimony (Sb), a
metalloid with a 1.9 million ton worldwide reserve, is one of the most
frequently used metals (Bolan et al., 2022). More than 80% of Sb-related
materials, including toys, clothing for fire-fighters, vehicle seat covers,
paint, batteries, and metal alloys, are produced in China, Russia, and
Leaching from mine wastes, weathering of sulfide ores, and man-
made activities (smelting, industry effluents, metallurgy processes,
and military shooting discharges) cause contamination of soil and
aquatic ecosystems with Sb (Diquattro et al., 2020). Moreover, Sb is
generated primarily from pharmaceuticals (Zhuang et al., 2018), in­
dustrial and dumps from mining waste (Dupont et al., 2016), wastewater
sewage sludge (Campos et al., 2019), automobile emissions (Fort et al.,
2016), seepage from plastic waste (Chu et al., 2021; Hu et al., 2020),
leachate directly draining from construction sites that dump solid waste
or electronic waste (Intrakamhaeng et al., 2020), industrial spills, wood
preservation, and metal processing (Herath et al., 2017).

* Corresponding author.
E-mail address: mahmad@qau.edu.pk (M. Ahmad).

https://doi.org/10.1016/j.envpol.2022.120723
Received 30 August 2022; Received in revised form 20 November 2022; Accepted 21 November 2022
Available online 24 November 2022
0269-7491/© 2022 Elsevier Ltd. All rights reserved.
B.A. Khan et al.
The species of Sb that is most common in the environment is Sb(V).
The Sb(V) species mostly exists in Sb(OH)-6 state under aerobic condi­
tions across a wide range of pH, and it is more mobile under the alkaline
and neutral conditions. Sb(V) is also present in natural waters as oxy­
anions and Sb(OH)-6, and it is apparently very stable under wide range of
pH (Zhu et al., 2021). Ashley et al. (2003) pointed out that stibnite
(Sb2S3) would undergo a series of chemical reactions such as oxidation
and leaching under the joint action of oxygen, water, and microorgan­
isms that eventually generates soluble SbO−3 in the wastewater.
Both forms of Sb(III) or Sb(V)-derived complexes are very dangerous
oncogenic contaminants; if exposed, animals and humans may experi­
ence adverse health effects via dermal and oral uptake, and inhalation
(Bagherifam et al., 2019; Wu et al., 2011). Sb(V) can enter the human
body through skin contact and tainted food, disrupting the viability,
synthesis, and release of metallothionein proteins. Humans who
consume too much Sb(V) are at risk of respiratory problems, rashes,
diarrhea, and nausea (Hua et al., 2021).
The oxides of aluminum (Al), manganese (Mn), and iron (Fe) can
naturally adsorb Sb discharged into soils; however, the soluble antim­
onate is found mainly under alkaline and oxidized states as Sb(V) (Ji
et al., 2017). The soil’s metalloid mobilization is influenced by several
factors, such as precipitation of minerals, ion exchange, adsorption/­
desorption, complexation, pH, electrical conductivity, leaching, phy­
tostabilization, and biotransformation (El-Naggar et al., 2018;
Palansooriya et al., 2020). The average Sb concentration in soil is 1 mg
kg− 1 (Johnson et al., 2005). However, increased Sb levels in soil samples
have been reported (up to 4400 mg kg− 1), and pore space water samples
(up to 1700 mg L− 1) from an abandoned mine (Cidu et al., 2014). The
shooting range soils are often examined to be contaminated with Sb
because it makes up 2–8% of the weight of bullets (He et al., 2019). For
instance, in Switzerland, the Sb concentration in top layer firing range
soil ranged from 35 to 17,500 mg kg− 1 (Johnson et al., 2005). A military
shooting range field in Canada had an Sb concentration of 570 mg kg− 1
(Laporte-Saumure et al., 2011), while a shooting range in Norway had
830 mg kg− 1 Sb in the topsoil (Mariussen et al., 2017).
Sb-containing wastewater is often treated via adsorption, electro­
chemical, biological, and co-precipitation/coagulation processes (Cao
et al., 2019). Adsorption technique is appealing because it is efficient,
low cost, and easy to use as compared to other techniques (Khan et al.,
2022; Murad et al., 2022). Among various adsorbents, carbon-based
materials like biochar have recently gained attention due to its low
cost and easy accessibility. However, the efficiency of pristine biochar,
particularly for anionic contaminants, remains controversial, mainly
due to its negatively charged surfaces (Amin et al., 2020). Therefore,
engineering or modifying the pristine biochar is needed to improve its
adsorption efficiency for anionic contaminants such as As and Sb. In this
context, impregnating pristine biochar with iron and aluminum mineral
salts could be advantageous. The cationic Al and Fe elements can coat
the biochar surface converting it from a negatively charged to a posi­
tively charged surface, thereby enhancing the electrostatic attraction of
anionic contaminants. Furthermore, a variety of iron oxides can strongly
adsorb Sb(III) and Sb(V), significantly impacting their mobility, speci­
ation, and environmental fate (Bolan et al., 2022).
This study aims to utilize waste pine-cones to produce pristine bio­
char modified with Fe and Al salts to produce engineered biochars which
are then tested for their adsorption potential in Sb(V)-contaminated
water and immobilization efficiency in Sb-contaminated shooting
range soil. Mechanisms of Sb(V) adsorption in water and immobilization
in soil with pristine and engineered biochars are also explored.
2. Materials and methods
2.1. Production of pristine and engineered biochars
Waste pine-cones were converted thermally to biochar via slow py­
rolysis in a muffle furnace (Khan et al., 2022). The ground feedstock was
2
Environmental Pollution 317 (2023) 120723
carbonized at 600 ◦ C under the low oxygen conditions at 5 ◦ C min− 1
heating rate, to produce pristine biochar.
Engineered biochars were produced using the impregnation modi­
fication method reported by Khan et al. (2022). The pristine biochar was
then soaked in a 3 M mineral salt solution (FeCl3 or AlCl3) in a 1:10
(w/v) ratio, agitated for 6 h at room temperature. The suspension was
centrifuged at 3000 rpm, and rinsed thoroughly using deionized water to
remove excess amounts of salts, and dried at 80 ◦ C in an oven for 24 h.
The engineered or modified biochars were named Fe-biochar and
Al-biochar.
2.2. Biochar characterization
Proximate, chemical, and ultimate analysis of all biochars were un­
dertaken. The chemical analysis for biochars includes pH, EC, and point
of zero charges (pHPZC) whereas moisture, mobile/volatile matter, ash
content, and resident/fixed carbon content were measured in the
proximate analysis (Ahmad et al., 2012b; Akhtar et al., 2021). A Nikolet
iS50 FTIR spectrometer (USA) and D/Max-B X-ray diffractometer
(Japan) were utilized to identify the functional groups and determine
the crystallography of biochars. A CHNSO (carbon, hydrogen, nitrogen,
sulphur, oxygen) elemental analyzer (Flash 2000 CHNSO analyzer, USA)
was used for the ultimate analysis.
2.3. Soil collection, processing, and characterization
A military shooting range site in the Kharian, district Gujrat of
Pakistan, was selected to collect soil samples. The top 15–20 cm of the
soil was taken from several locations within a 0.5 km radius of the
shooting range. The collected samples were mixed and homogenized in a
polyethylene bag to produce a composite sample. The soil samples after
air drying were passed through 2 mm sieve to remove pebble, gravels,
and bullet fragments to ensure that only homogeneous soil particles
were obtained. The acid digestion method (Ahmad et al., 2012a) was
used to analyze the total Sb concentration in the soil samples using an
inductively coupled plasma (ICP) spectrophotometer (iCAP 6500 of
Thermo Fisher Scientific UK). The soil was characterized for basic pa­
rameters (pH, EC, texture, organic matter, and water holding capacity)
following the methods reported in Mun-Gai & Owido, (2021). The
supplementary material includes the information about soil properties
(Table S2). The shooting range soil with a pH of 8.68 and silty clay
texture contained 28 mg kg− 1 total Sb.
2.4. Adsorption experiments
The adsorption experiments were carried out to study the effects of
adsorption variables including, solution pH, adsorbent dose, initial
concentration, and total contact time. To determine pH’s impact on the
adsorption process, four different solutions of Sb(V) at 10 mg L− 1 con­
centration whose pHs were adjusted from 3 to 9, separately. All exper­
iments were conducted over 24 h and the biochar dose was 1 g L− 1. The
initial concentration effect of Sb(V) on biochars’ adsorption potential
was measured in seven concentration ranges, i.e., 0.5, 1.0, 2.0, 5.0, 10,
20, and 40 mg L− 1. For each biochar a dosage of 1 g L− 1 was taken and
pH of the solutions was set at 7 for a contact period of 24 h. In order to
determine the biochars’ adsorption capacity for contact time experi­
ment, 1 g L− 1 dose of each biochar was treated with a 10 mg L− 1 solution
of Sb(V) at pH 7. The mixtures were left in contact for 15 min to 24 h and
analyzed solutions at regular intervals. Each experiment was performed
at 120 rpm in an orbital shaker, and filtration was made by using
Whatman 42 filter paper. The concentration of Sb(V) was analyzed by
using ICP spectrophotometer.
2.5. Adsorption modeling
The Sb(V) amount adsorbed by biochars was calculated by using the
B.A. Khan et al.
equation below:
V
Adsorbed amount = (Cₒ − Cₑ) ×
W
where Co is the initial concentration, Ce represents the final Sb(V) con­
centration (mg L− 1), V is considered as volume of the solution (L), and W
represents biochar mass (g).
The four commonly used equilibrium isotherm models (Langmuir,
Freundlich, Temkin, and Dubinin-Radushkevich) were employed to
determine the adsorption process of all biochars. Similarly, four non-
linear kinetics models (pseudo-second-order, intraparticle diffusion,
Elovich, and power function) were also used to further investigate the
adsorption mechanisms. The equations of various isotherm and kinetic
models are given in Table S3 in the supplementary material.
2.6. Soil incubation experiments
Pristine and iron-modified biochars were selected to remediate the
Sb-contaminated shooting range soil. A soil incubation experiment
included three applications of each biochar (1%, 2.5%, and 5%; w/w),
with 500 g soil placed in an air-tight polyethylene container (600 mL of
capacity) and mixed well with each biochar at the specified application
rate. The soil was moistened with 47 mL, or 50% of soil’s water holding
capacity by using de-ionized water. The containers were tightly covered,
and the incubation experiment took place for 60 days in the dark at room
temperature. The containers were checked periodically for weights, with
any weight loss was compensated by adding the desired amount of water
to keep the moisture contents constant.
2.7. Soil extraction for Sb immobilization
After incubation, all the samples of soil from each treatment were air-
dried, and Sb availability was measured using a variety of single
extraction and sequential extraction techniques to analyze the soil sta­
bilization effect of the used biochars on Sb immobilization. The water-
soluble fraction of Sb was determined by extracting 2 g of incubated
soil by using 50 mL deionized water for 2 h. In order to determine the
exchangeable amounts of Sb, the soil was extracted by using 50 mL of 1
M NH4NO3 solution for 2 h. The impact of the biochar treatments on Sb
leachability was assessed using the TCLP (toxicity characteristics
leaching procedure) method. Briefly, the soil sample was extracted in a
solution of glacial acetic acid (pH 4.93) at a ratio of 1:20 (soil/extrac­
tant) after shaking at 30 rpm for 18 h. A physiological-based extraction
test (PBET) was conducted to examine the biochar efficiency for
decreasing Sb bioavailability in human bodies. Briefly, 0.35 g of soil
sample was shaken at 30 rpm with synthetic gastric solution (35 mL) for
1 h at 37 ◦ C. The gastric solution composed of 0.4 M glycine adjusted to
pH 2.2. The above mentioned single extraction tests followed the
methods described in Alaboudi et al. (2019), Ahmad et al. (2012a) and
USEPA (1992).
For the sequential extraction method, five component fractions were
measured in a series by using the method of Tessier et al. (1979): (i)
non-specifically sorbed considering the readily soluble form, (ii) spe­
cifically sorbed form, (iii) interconnected with amorphous and imper­
fectly crystalline ferrous and aluminum hydrous oxides, (iv) linked with
the well-crystallized Fe- and the Al-hydrous oxides, and (v) residual soil
fraction.
2.8. SEM, EDX, and elemental dot mapping of soil
Scanning electron microscope (SEM) and the elemental dot mapping
were also performed by using SEM apparatus (FESEM, MAIA-3,
TESEAN, USA) equipped with the energy dispersive X-ray (EDX) spec­
troscopy systems to examine morphological and elemental changes in
the soil. X-ray dot maps were then used to highlight the distribution of
3
Environmental Pollution 317 (2023) 120723
elements such as O, N, Si, S, Pb, Sb, and Fe on the soil particles.
3. Results and discussion
3.1. Characteristics of prepared biochars
The properties of pristine and engineered biochars are shown in
Table S1. The engineered biochars (Fe- and Al-biochars) had compara­
tively higher mobile/volatile matter than that of the pristine biochar due
to the volatile organic matter’s strong affinity with FeCl3 and AlCl3
(Beesley and Marmiroli, 2011). The engineered biochars had acidic pH
values, i.e. 2.33 and 4.35 for Fe- and Al-biochar, respectively due to the
FeCl3 and AlCl3 impregnation (Shetty & Prakash, 2020). The ultimate
elemental analysis revealed that the Fe-biochar and pristine biochar had
higher amounts of total C (81.60% and 80.65%, respectively) than the
Al-biochar (59.03%). The low C content of Al-biochar may be due to
enrichment with AlCl3, resulting in reduction of the inorganic C content
after the engineering of pristine biochar (Hafeez et al., 2022). The
engineered biochars had higher H concentrations than the pristine
biochar, indicating the supremacy of the H-containing components due
to their acidic (<7) pH values. Similarly, the engineered biochars had
slightly higher total N contents than pristine biochar, possibly because of
their relative drop in the mass intensity after impregnation. The
Al-biochar had significantly higher O content than the other biochars,
indicating the prevalence of O-containing functional groups on its
surface.
3.2. SEM, EDX, FTIR and XRD descriptions
The SEM images revealed the morphological features of the biochars
(Fig. S1). All biochars had distinctive porous and tubular structures. The
presence of Fe (5.72%) and Al (7.30%) was detected in the EDX spectra
of the Fe-biochar and Al-biochar, respectively. The few other common
elements (C, O, and Cl) were also observed. Considering pristine bio­
char, primary elements (C, O, N, K, and S) were also present.
The FTIR spectra for the surface functioning of pristine biochar, Fe-
biochar, and Al-biochar are shown in Fig. 1a. All biochars had O–H
stretching developed in broad band at 3372 cm− 1 due to the vibration
effect of alcohols, carboxylic acid, and phenols in the cellulose and
lignin. Moreover, the bending vibration of O–H in pristine biochar was
attributed to the peak at 1036 cm− 1 (Hongtao et al., 2018; Jia et al.,
2020; Rahman et al., 2021b); the same peak shifted in the Fe-biochar
and Al-biochar to 996 and 1026 cm− 1, respectively, due to the
impregnation (Fan et al., 2018). For pristine biochar, the peak at 863
cm− 1 was associated with the P–O–C aliphatic group; however, this peak
shifted in the Al- and Fe-biochars to 790 cm− 1 and 873 cm− 1, respec­
tively (Amin et al., 2020), possibly due to the significant oscillation in
inorganic Fe and Al salts. Only the Fe- and Al-biochars had distinct peaks
at 584 and 515 cm− 1, reflecting Al–O and Fe–O complexes due to the
impregnation with salts (Karimipour et al., 2019; Din et al., 2021; Le
Bozec et al., 2002).
The surface minerology and crystallinity of biochars were also
examined using XRD spectroscopy (Fig. 1b). All biochars were amor­
phous in nature due their organic feedstock. The spectra of all biochars
peaked at two theta degrees of 22.6, denoting existence of crystalline
cellulose (Zhu et al., 2016; Poletto et al., 2014). The peak at 26◦ in all
biochars indicated an inorganic component mainly comprising quartz.
Furthermore, the peak at two theta degrees of 40 denoted the presence
of Al2O3 (Du et al., 2009) in the XRD pattern of the Al-biochar. In the
Fe-biochar, magnetite (Fe3O4) peaks were visible at two theta degrees of
35.6, 43.8, and 57.6 (Fan et al., 2018).
3.3. Adsorption of antimony onto biochars and isotherm modeling
The pH significantly affected biochar effectiveness in absorbing Sb
(V) and the adsorption process. The solution pH was set to 3, 5, 7, or 9
B.A. Khan et al. Environmental Pollution 317 (2023) 120723

Fig. 1. (a) FTIR and (b) XRD spectra of pristine biochar, Fe-biochar, Al-biochar, sand post-adsorbed PFe-biochar.

for adsorption studies. The Sb(V) adsorption for engineered biochars
changed considerably with changing solution pH (Fig. 2a). The Fe-
biochar had a higher Sb adsorption capacity at pH 7 (2.26 mg g− 1)
than the Al-biochar (1.66 mg g− 1) and the pristine biochar (0.39 mg
g− 1). The Qe of the engineered biochars increased slightly at pH 5 and 7,
most likely due to competitive binding sites between Sb(OH)6 and H+
(Rahman et al., 2021a). The pHPZC is a significant marker for the surface
charge at various solution pHs. For solution pH ranging from 3 to 9
(pHPZC 7.58), the pristine biochar had a positive charge, which may have
contributed to the electrostatic attraction of Sb(V) ions to the biochar
surface. The Fe- and Al-biochars had positively charged surfaces at pH 3
and negatively charged at pH > 5, with pHPZC values of 4.98 and 4.89,
respectively. The adsorbent surface had more negative charges at pH >
5, making them unsuitable for binding Sb(V). The OH− content in the
solution increased as pH increased and had a stronger affinity for
sorption than Sb(OH)–6, however, competition between OH− and Sb−
ions in the aqueous solution decreased the capacity for Sb(V) adsorption
(Jia et al., 2020; Khan et al., 2022) (see Fig. 3).

Fig. 2. Effect of (a) pH, (b) dose, (c) initial concentration, and (d) contact time on Sb adsorption onto pristine biochar, Fe-biochar, and Al-biochar. Experiments were
performed at an initial concentration of 10 mg L− 1 (except for Fig. (c)), a dosage of 1 g L− 1 (except for Fig. (b)), pH of 7 (except for Fig. (a)), and a contact time of 24 h
(except for Fig. (d)) for a volume of 40 mL.

4
B.A. Khan et al.
Fig. 3. Fittings of (a) Langmuir, (b) Freundlich, (c) Temkin, and (d) Dubinin Radushkevich isotherm models to the experimental data of Sb adsorption onto pristine
biochar, Fe-biochar, and Al-biochar. Solid lines indicate the respective models fittings.
Fig. 2b represents the effect of doses on the adsorption capacity of
three biochars. It was observed that adsorption capacity for all biochars
decreased as the adsorbent dose increased. The adsorption capacity for
low dose was higher because of the availability of more active sites to
bind the Sb(V) in the solution. However, Fe-biochar showed higher
adsorption capacity than pristine biochar and Al-biochar because of
stronger affinity with Sb(V) due to the presence of Fe-functional groups
and more active sites on its surface (Zhang et al., 2019). Fig. 2c illus­
trates how the initial concentration affects the ability of various biochars
to adsorb Sb(V). Among the three biochars, the Fe-biochar had the
highest adsorption capacity (3.95 mg g− 1) at concentration of 40 mg
L− 1. Because Sb(V) ions cover active sites on the surface of biochar and
interact with adsorbed functional groups, and all biochars can adsorb
more Sb(V) as the initial concentration increases (Liu, 2015).
Increasing the contact time generally increases biochars’ Sb(V)
adsorption (Fig. 2d). However, within a relatively short period, the
number of active sites on biochar declines, thereby decreasing Sb(V)
adsorption. Sb(V) began to bind quickly to the biochars within 15 min,
resulting in 5.20 mg g− 1 adsorption for Fe-biochar, 2.52 mg g− 1 for Al-
biochar, and 2.41 mg g− 1 for pristine biochar, and all biochars had
reached equilibrium by 5 h. After 24 h the Fe-biochar has the highest
adsorption capacity (8.68 mg g− 1), followed by Al-biochar (3.40 mg g− 1)
and pristine biochar (2.49 mg g− 1). All biochars reacted immediately at
the start of the agitation process because the surface of biochars has
more active sites, which initially led to increased adsorption.
Four isotherm models (Langmuir, Freundlich, Temkin, and Dubinin-
Radushkevich (D-R)) were compared to check the fitness of Sb(V)
adsorption data for the different biochars. Table 1a shows the equilib­
rium isotherm models calculated parameters. The pristine biochar
adsorption data fitted well to the Langmuir (R2 = 0.841), Temkin
5
Environmental Pollution 317 (2023) 120723
(0.821), and D-R models (0.869); the Fe-biochar data fitted well to the
Langmuir (0.841), Freundlich (0.826), and D-R (0.819) models, while
the Al-biochar data only fitted well to the D-R isotherm model (0.869).
The Langmuir model represents monolayer adsorption on homogeneous
surfaces, while the Freundlich, Temkin and D-R models represents het­
erogeneous adsorption (Amin et al., 2021; Liu et al., 2010), indicating
the overall heterogeneity of the biochar surfaces. The Fe-biochar had a
greater KF (Freundlich predicted adsorption capacity) value (0.706 mg
g− 1) than the other two biochars (0.609 and 0.350 mg g− 1). Similarly,
the Fe-biochar had a greater QD (D-R predicted adsorption capacity)
value (3.574 mg g− 1) than the pristine biochar (2.28 mg g− 1) and
Al-biochar (2.854 mg g− 1). According to the Langmuir model, the
Fe-biochar had a higher adsorption capacity (Qmax = 4.825 mg g− 1) than
pristine (2.681 mg g− 1) and Al-biochar (4.247 mg g− 1). These results
demonstrate that Fe-biochar favors Sb(V) adsorption in water. .
3.4. Adsorption kinetics
Adsorption kinetics was used to assess the effectiveness of pristine
and engineered biochars at adsorbing Sb(V). In the first 5 h, all biochars
significantly increased their ability to adsorb Sb(V) (Fig. 2d), which was
related to adsorption by the high-affinity sites or the precipitation of
adsorbate on the adsorbent surface. Table 1b presents the constant pa­
rameters for the different kinetic models. The pseudo-second-order R2
and χ2 values for various biochars ranged from 0.755 to 1 and
0.008–0.175. Pristine biochar had a higher rate constant (k) (0.067 mg
g− 1 min− 1) than the other two biochars (0.011 and 0.037 mg g− 1
min− 1), while Fe-biochar had the highest adsorption capacity (8.534 mg
g− 1) than pristine biochar (5.211 mg g− 1) and Al-biochar (2.381 mg
g− 1), respectively. In the Elovich model, the pristine biochar, Fe-
B.A. Khan et al. Environmental Pollution 317 (2023) 120723

biochar, and Al-biochar had R2 values of 0.993, 0.971, and 0.872,

respectively, and χ2 values of 0.004, 0.185, and 0.091, respectively.

0.065
0.086
0.150
E (kJ mol− 1)
Experimental data for the intraparticle model did not fit well, while the

V
8.839
7.180
5.315
kinetic experimental data fit well to the power function model (R2 >
0.90 and χ2 > 0.01). The Fe-biochar had a higher power function

K (mg g− 1)
adsorption capacity (4.83 mg g− 1) than the pristine biochar (1.68 mg

0.943
1.68
4.83
g− 1) and Al-biochar (0.943 mg g− 1). The fitting of these models clarifies
QD (mg g− 1)
the chemical interaction between the biochars and Sb(V) that could

2.281
3.574
2.854
trigger a physicochemical sorption or adsorption process via valence

0.005
0.233
0.073
Power function
forces by sharing or electron transfer between the sorbent and sorbate

χ2
Dubinin Radushkevich

(chemisorption) (Chen et al., 2019; Wu et al., 2019). Furthermore, all

models predicted that Fe-biochar significantly outperformed the pristine
1.204
3.832
3.103

0.992
0.967
0.900
and Al-biochars in terms of Sb(V) adsorption.
χ2

R2 Interestingly, several adsorption mechanisms can be implicated in

1.520 the removal of Sb(V) from water due to the biochar’s multifunctional
4.670
1.019
0.869
0.819
0.869

properties. Monolayer-to-multilayer, surface complexation, and ion-

R2

exchange adsorption of Sb onto the biochar surface may be the domi­

nant adsorption mechanisms in this study(Fig. 4; Table 1).
kd (mg g− 1)
A (L g− 1)

The Fe-biochar showed highest adsorption capacity (8.68 mg g− 1)

1.917
3.034
1.484

0.042
0.149
0.058

towards Sb(V) removal in this study, which is greater than some other
reported engineered biochars. For example, Jia et al. (2020) used
Intra-particle diffusion

Mn-coated biochar and reported only 0.94 and 0.73 mg g− 1 of Sb(III)

B (J mol–)

0.364
3.760
0.194

and Sb(V) adsorption, respectively. Likewise, Wang et al. (2018) re­

χ2
926.0
848.8
609.9

ported 4.85 mg g− 1 Sb(V) adsorption onto magnetic biochar. However, a

greater adsorption of Sb(V) is observed in some studies using engineered
0.434
0.476
0.730

Fe-biochars. For instance, Wang et al. (2018) further modified the

R2
Parameters calculated by (a) isothermal, and (b) kinetic models for Sb adsorption onto pristine biochar, Fe-biochar, and Al-biochar.

0.004
0.185
0.091

magnetic biochar by doping with La that improved the Sb(V) adsorption

χ2

to 18.92 mg g− 1. Similarly, Rahman et al. (2021a) reported 98.04 mg

min− 1)

g− 1 Sb(V) adsorption using Zr–Fe-biochar. This comparison with other

Temkin

studies reveal that adsorption efficiency of Fe-biochar could be

0.821
0.763
0.688

1
R2

enhanced by doping or coating with additional transition metals.

β (mg g−

6.339

However, this will add to the cost of the adsorbent.

1.46
3.60
KF (mg g− 1)

3.5. Adsorption mechanism(s) of biochar interactions with Sb(V) in water

min− 1)
0.609
0.706
0.350

The adsorption experiments revealed that Fe-biochar is more effec­

3.48 × 1046
2.71 × 1039
1

3.1 × 105

tive than pristine biochar and Al-biochar, which might be driven by

α (mg g−

modification during FeCl3 engineering. For example, the Fe-biochar had

0.391
0.488
0.597

iron-associated and positively charged functional groups on its surface

n

(FTIR; Fig. 1a) that could be involved in increased adsorption. To sup­

0.004
0.185
0.091

port this finding, FTIR and XRD analysis of Fe-biochar after adsorption
0.005
0.262
0.082

χ2

were carried out. The peak in PFe-biochar shifted from 1026 to 1136
χ2

cm− 1 with increasing amounts of iron oxide adsorbed via the inner-
Freundlich

Elovich

0.993
0.971
0.872

sphere complex and the presence of hydroxyl groups from adsorbed

0.686
0.826
0.748

R2

antimonate. This suggests that ion exchange or electrostatic attraction

R2

mechanism play a vital role in Fe-biochar adsorbing Sb(V) (McComb

min− 1)

et al., 2007). All biochars exhibited a band at 2356 cm− 1 indicating the
KL (L g− 1)

C–– C stretching vibrations in alkyne groups and the affinity of Sb(V)

–
0.191
0.103
0.058

with alkynes. Specifically, after Sb(V) adsorption onto Fe-biochar, the

K (g mg−

C–– C peak intensity increased and its position changed (Amin et al.,
0.067
0.011
0.037

–
2021; Ayoob et al., 2008; Saka, 2012). After adsorption the N–H peak
shifted from 1577 cm− 1 to 1599 cm− 1, the O–H peak shifted from 1026
Qmax (mg g− 1)

cm− 1 to 1136 cm− 1, and the Fe–O peak shifted from 584 cm− 1 to 587
qe (mg g− 1)

cm− 1 in the PFe-biochar. These spectral alterations demonstrate in­

2.681
4.825
4.247

5.211
8.534
2.381

teractions between the Sb(V) ion and Fe–O–OH, N–H, and O–H surface
functional groups in the Fe-biochar surface. The Fe–O–Sb bands were
Pseudo-second-order

attributed to the spectroscopic peak at 587.8 cm− 1, showing that the

5.70
0.17
0.18

0.008
0.018
0.175

iron oxides on the surface of the Fe-biochar adsorbed Sb(V) (Wang et al.,
χ2

χ2

2020; Zhang et al., 2019). According to McComb et al. (2007), peak

Langmuir

intensities at around 1100 cm− 1 and 3200–3400 cm− 1 change as the

0.841
0.841
0.790

0.988
1.000
0.755

inner-sphere complex formation due to adsorption of Sb(V) onto iron

R2

R2

oxide with the help of hydroxyl groups from adsorbed antimonate.

Interesting alterations occurred in the XRD pattern of post-adsorbed
Fe-biochar

Fe-biochar
Al-biochar

Al-biochar

Fe-biochar (Fig. 1b). After the Sb(V) interaction with Fe-biochar, new
Biochar

Biochar
Table 1

peaks emerged at two thetas of 60.45◦ and 80.53◦ (in PFe-biochar). The
senarmontite mineral (Sb2O3) had a characteristic peak around 80.53◦

6
B.A. Khan et al.
Fig. 4. Fittings of (a) pseudo-second-order, (b) Elovich, and (c) power function models for Sb adsorption onto pristine biochar, Fe-biochar, and Al-biochar. Solid lines
indicate the respective models fittings.
two theta degrees. Furthermore, the peak at 35.6◦ two theta degrees in
Fe-biochar shifted to 34.6◦ two theta degrees in PFe-biochar, and the
peaks at 43.8◦ and 57.6◦ two theta degrees decreased after Sb(V)
adsorption onto Fe-biochar. The mineral phase of Sb2O3 developed
when Sb(V) decreased onto the solid surface during sorption by Fe-
biochar (Rahman et al., 2021b).
Antimonates should bind to biochar primarily through an ion-
exchange mechanism because it mainly exists as an anionic species in
solution. The Sb(V) in an aqueous solution by sorption onto biochar is
generally caused by one or more of the following factors: (i) electrostatic
attraction; (ii) formation of nodules through hydrogen bonding; (iii)
surface complexation and multilayer adsorption; (iv) ligand exchange of
Sb(V) with biochar; and (v) co-precipitation. Specifically, for Fe-
biochar, the unoccupied orbitals on Fe could aid Sb(V) complexation
by forming inner Fe–O–Sb complex hydrogen bonds (Rahman et al.,
2021a). Moreover, the protonated functional groups on the engineered
biochar surface could facilitate antimonate adsorption. The following
dissociation reaction controls Sb(V) existence as an oxyanion or neutral
species in the aqueous solution (Rahman et al., 2021a):
Sb(OH)5 + H2O → Sb(OH)–6 + H+
The FTIR and XRD analyses confirmed the presence of O–H, N–H,
Fe–O–OH, Fe–O, and CO/C–O–C groups on the Fe-biochar surface,
which could enhance its capacity for complexing with Sb(V), resulting in
ligand exchange at the Sb(V) center. The peak at 587.8 cm− 1 related to
the Fe–O–Sb band in the FTIR spectra, and the peak at 80.53◦ two theta
related to senarmontite minerals in the XRD spectra confirmed that Sb
(V) adsorbed onto the Fe-biochar surface through surface complexation
and electrostatic attraction (Han et al., 2017; McComb et al., 2007;
Rahman et al., 2021a; Yin et al., 2020; Zhang et al., 2022).
7
Environmental Pollution 317 (2023) 120723
3.6. Effect of biochars on Sb immobilization in soil
Considering good results of Sb adsorption onto Fe-biochar in aqueous
medium, it was further used to remediate the Sb-contaminated shooting
range soil in comparison with pristine biochar. Fig. 5 shows that both
pristine and modified biochar application gradually decreased the
various extracted forms of Sb in shooting range soil, including water-
soluble, exchangeable, PBET, and TCLP-extracted fractions of Sb. The
water-soluble fraction was the most readily available form for plant
uptake and likely had the highest soil bioavailability. Here, both the
treatments of applied biochars significantly decreased the water-soluble
Sb level (Fig. 5a) from 0.12 mg kg− 1 (control soil) to almost zero for both
biochars at all application rates. The sorption of Sb through carbonyl
functional groups of biochars behaving as proton donors could be one
reason for Sb immobilization in soil. Likewise, the exchangeable fraction
significantly decreased with biochar addition (Fig. 5b), suggesting that
Sb bioavailability to plants decreased.
The PBET test was also used to examine the effects of biochar on
mammals’ direct consumption of Sb-contaminated soil. Fig. 5c repre­
sents the findings of the PBET test for Sb content in the polluted-soil
treated with biochars. The PBET test is usually performed in acidic
conditions, hence, the control soil without biochar had the highest PBET
Sb content (7.33 mg kg− 1). Both biochars significantly decreased Sb bio-
accessibility, further decreasing with increasing biochar application.
Increased soil Sb immobilization was evident in both biochars, reaching
reduction rates of 33.33% for pristine biochar and 37.50% for Fe-
biochar.
The TCLP test is used to reveal the metal toxicity of soil, especially for
metal leaching from soil to groundwater due to acid rain. The control
soil (without biochar) had a high level of TCLP Sb (3.20 mg kg− 1;
Fig. 5d) and thus greater susceptibility to Sb toxicity driven by leaching
B.A. Khan et al. Environmental Pollution 317 (2023) 120723

Fig. 5. (a) Water-soluble, (b) exchangeable, (c) physiologically based extraction test (PBET), and (d) toxicity characteristic leaching procedure (TCLP) extracted Sb
concentrations in shooting range soil amended with pristine biochar and Fe-biochar. ** not detected.

into groundwater. The biochars at various applications significantly

reduced Sb leaching. The amount of Sb immobilized in the soil increased
with increasing biochar application, possibly reducing groundwater
toxicity. Similar to bioavailable Sb, Fe-biochar decreased the leachable
Sb fraction to a greater extent (up to 54%) than pristine biochar (up to
52%), suggesting that Fe-biochar had a stronger binding affinity with Sb
than pristine biochar. Overall, both biochars successfully immobilized
Sb, reduced its ability to induce toxicity, and remediated the Sb-
contaminated soil. The greater immobilization effect of the Fe-biochar
as compared to the pristine biochar is due to the strong chemical
interaction between the Sb and Fe-biochar surface. The results of the Sb
removal from water were well-aligned with those for Sb remediation in
contaminated soil.
We reported good efficiencies for the pristine and Fe-biochars
compared to the limited research on Sb immobilization in soil using
engineered biochar. For example, according to some investigations,
ferrous sulfate immobilizes Sb by reducing Sb(V) to Sb(III), bonding
with iron oxide/hydroxide (Wang et al., 2019a). Similarly, other re­
searchers used Fe- and Fe–Mn-modified biochars for Sb immobilization
in soil (Almås et al., 2019; Tandy et al., 2017; Wang et al., 2019b). Fig. 6. Sequentially extracted fractions of Sb in shooting range soil amended
with pristine biochar and Fe-biochar. F1: non-specifically sorbed, F2: specif­
ically sorbed fraction, F3: interconnected with amorphous and imperfectly
3.7. Sequential extractions of Sb in soil crystalline ferrous and aluminum hydrous oxides, F4: linked with well-
crystallized Fe- and Al-hydrous oxides, and F5: residual soil fraction.
Fig. 6 shows Sb fractions in soil obtained from sequential extractions,
with the most predominant well-crystallized hydrous oxides of Fe/Al significantly changed the distribution of Sb fractions in the soil,
and residual phases, occupying 53.94% and 9.42%, respectively in the increasing the residual Sb fraction to 45.30% (pristine biochar) and
unamended control soil. The soil contained 0.75% and 1.25% of Sb 61.23% (Fe-biochar) and the well-crystallized hydrous oxides of the Fe/
associated with non-specifically and specifically sorbed fractions, Al fraction of Sb to 31.47% (pristine biochar) and 24.23% (Fe-biochar).
respectively. A minor amount of Sb was present in the amorphous and In contrast, in the Sb fractions associated with specifically sorbed and
poorly crystalline hydrous oxide of Fe/Al (0.54%). Biochar addition non-specifically sorbed decreased in the biochar-amended soils and

8
B.A. Khan et al.
those associated with the poorly crystalline hydrous oxides of Fe/Al
fraction of Sb did not significantly differ. The biochars, particularly Fe-
biochar, transformed the pre-existing Sb into the residual form, the most
stable form of any metal in soil. The success of an immobilizing agent in
soil depends on the increase in the residual fraction of contaminant.
Here, the biochar was an efficient immobilizing agent for Sb in the
shooting range soil.
Other soil parameters, such as pH and EC, were examined to assess
how biochars affect soil quality, with no significant difference in these
parameters before or after incubation, indicating that treating Sb-
contaminated soil with biochar did not adversely impact plant growth
under these soil conditions .
3.8. Mechanism of Sb immobilization by biochars in soil
The characteristics of biochar itself (e.g., presence of abundant
Fig. 7. SEM, EDX, and elemental dot maps of shooting range soil amended with Fe-biochar.
9
Environmental Pollution 317 (2023) 120723
functional groups) directly influence Sb immobilization in soil, where it
is most commonly found as oxides, hydroxides, or oxyanions. The sur­
face of Fe-biochar is abundant in oxygen-containing functional groups,
such as hydroxyl, carboxyl, amine, and phenolic , to be involved in the
conversion of Sb into a residual fraction. Sb immobilization by iron
oxide adsorbents could be due to strong iron-associated ions resulting in
direct precipitation, co-precipitation, and adsorption (Guo et al., 2009,
2014; Wu et al., 2010). In this context, non-destructive elemental dot
mapping may provide information on the association between target
contaminants and other elements in soil. Microstructural variations and
Sb prevalence in soils were identified using SEM and EDX (Fig. 7). The
EDX spectrum of Fe-biochar amended soil showed the occurrence of Si,
Pb, Fe, and Sb elements. Elemental dot maps further revealed that Sb
was associated with Fe, Si, and O in the soil, which assumed the for­
mation of some type of stable Sb compounds with Fe, O and Si elements
in the Fe-biochar amended soil. Pb was also predicted because shooting
B.A. Khan et al.
range soils generally contain substantial amount of Pb.
Most of the elemental forms in the residual state are found in sili­
cates; thus, silicates may be responsible for the elevated residual fraction
of Sb in the soil. On the other hand, Sb(V) occurs as H2SbO4 and Sb(OH)–6
and is the predominant oxidation state at pH 2.7–12 in soils (Okkenhaug
et al., 2011). Complexation, reduction, and electrostatic interactions
may be the main driving forces behind Sb immobilization in soils.
Additionally, the soil sequential extraction data revealed that the addi­
tion of Fe-biochar considerably enhanced the residual fraction of Sb in
soils, which could be due in part to the occurrence of geochemically
stable Fe(III) antimonate mineral (tripuhyite, FeSbO4) (Wang et al.,
2019a; Zhang et al., 2019). Hence, it can be speculated that Sb in the
shooting range soil transformed into the stable Fe–O–Sb(OH)5 complex
by addition of Fe-biochar. In the natural environment, tripuhyite and
schafarzikite are geochemically stable forms of Sb in soil (Leverett et al.,
2012; Teng et al., 2020).
4. Conclusions
This study investigated pinecone-derived pristine biochar and its
engineered biochars (Fe- and Al-biochars) as potential adsorbents for Sb
(V) removal from aqueous solution. The experimental adsorption data
revealed that Fe-biochar had better adsorption capacity than the other
two biochars due to the high affinity of Sb(V) to iron-associated func­
tional groups on its surface. The post-adsorption experiments with FTIR
and XRD further confirmed the association of minerals like Fe, O–H,
N–H, FeO–OH, C–O and C– – C with Sb(V) adsorption onto Fe-biochar.
–
Furthermore, isotherm and kinetics models revealed that Sb adsorp­
tion onto biochars followed the chemisorption phenomena. Similarly,
the pristine and Fe-biochars immobilized Sb in a shooting range soil
(particularly the Fe-biochar) as indicated by the decline in water-
soluble, exchangeable, PBET, and TCLP-extracted Sb levels. The pri­
mary mechanism for Sb immobilization and stabilization was attributed
to the formation of more stable forms of Sb bound to O− , Fe− and Si-
associated minerals.
Credit author statement
Basit Ahmed Khan: Conceptualisation, Experimentation, Writing –
original draft, Methodology, Investigation, Formal analysis, Data cura­
tion. Mahtab Ahmad: Conceptualisation, Supervision, Formal analysis,
Data curation, Writing – original draft, and editing. Sajid Iqbal: Formal
analysis, Data curation, Investigation, Results interpretation. Fath Ullah:
Experimentation, Investigation, Formal analysis. Nanthi Bolan: Results
interpretation, Writing, Reviewing and editing. Zakaria Solaiman: Re­
sults interpretation, Writing, Reviewing and editing. Munib Ahmed
Shafique: Formal analysis, Investigation, Results interpretation.
Kadambot H. M. Siddique: Results interpretation, Writing, Reviewing
and 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.
Data availability
No data was used for the research described in the article.
Acknowledgements
The study was supported by the International Research Support
Initiative Program of the Higher Education Commission of Pakistan (No:
1–8/HEC/HRD/2022/11965), and by the University Research Fund
(URF) of Quaid-i-Azam University.
10
Environmental Pollution 317 (2023) 120723
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.envpol.2022.120723.
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