Journal of Hazardous Materials 405 (2021) 124249

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Journal of Hazardous Materials

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

Fabrication of sand-based novel adsorbents embedded with biochar or

binding agents via calcite precipitation for sulfathiazole scavenging
Abdullah Almajed a, 1, Munir Ahmad b, 1, Adel R.A. Usman b, c, Mohammad I. Al-Wabel b, d, *
a
Department of Civil Engineering, King Saud University (KSU), Riyadh 11421, Kingdom of Saudi Arabia
b
Soil Sciences Department, College of Food & Agricultural Sciences, King Saud University, P.O. Box 2460, Riyadh 11451, Kingdom of Saudi Arabia
c
Department of Soils and Water, Faculty of Agriculture, Assiut University, Assiut 71526, Egypt
d
Department of Science and Environmental Studies, The Education University of Hong Kong, Hong Kong

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

Keywords: Fabrication of efficient and low-cost adsorbents through enzyme induced carbonate precipitation (EICP) of sand
Adsorption embedded with binding agents for sulfathiazole (STZ) removal is reported for the first time. Sand enriched with
Wastewater biochar (300 ◦ C, 500 ◦ C, and 700 ◦ C), xanthan gum, guar gum, bentonite, or sodium alginate (1% w/w ratios) was
Kinetic models
cemented via EICP technique. Enrichment with binding agents decreased the unconfined compressive strength,
Antibiotics, π–π EDA interactions
improved the porosity, and induced functional groups. Biochar enrichment reduced the pH, and increased the
calcite contents and electrical conductivity. Fixed-bed column adsorption trials revealed that biochars enrich­
ment resulted in the highest STZ removal (64.7–87.9%) from water at initial STZ concentration of 50 mg L− 1,
than the adsorbents enriched with other binding agents. Yoon–Nelson and Thomas kinetic models were fitted
well to the adsorption data (R2 = 0.91–0.98). The adsorbents embedded with 700 ◦ C biochar (BC7) exhibited the
highest Yoon–Nelson rate constants (0.087 L min− 1), 50% breakthrough time (58.056 min), and Thomas model-
predicted maximum adsorption capacity (4.925 mg g− 1). Overall, BC7 removed 168% higher STZ from water
than pristine cemented sand. Post-adsorption XRD and FTIR analyses suggested the binding of STZ onto the
adsorbents. π–π electron-donor-acceptor interactions, aided-by electrostatic interactions and H-bonding were the
main STZ adsorption mechanisms.

1. Introduction extensively reported antibiotics in water resources i.e., drinking water,

The intensive use of a wide range of natural, synthetic and semi-
synthetic chemicals has resulted in scarcity of clean drinking water
worldwide. The abundance of pharmaceutical compounds and their
metabolite in various water resources have been reported globally (Zhu
et al., 2019; Batista Nogueira, 2012; Gao et al., 2019). The global annual
antibiotics consumption of 100,000–200,000 tons is posing a serious
threat to the health of human beings and the ecosystem. The occurrence
of human and veterinary antibiotics in various environmental com­
partments is increasing drastically owing to their extensive use for
therapeutic purposes, antibacterial treatments, and growth supple­
ments, consequently resulting in death of about 500,000 people each
year globally (Al-Wabel et al., 2020; Liu et al., 2012). For instance,
sulfathiazole (STZ); a member of sulfonamide family, is among the
wastewater treatments effluents, as well as surface and ground water
(Zhao et al., 2016a,b; Liu et al., 2012). The elevated levels of STZ in
different water resources around the world is a serious threat for the
ecosystem. The carcinogenic potential and development of antibiotic
resistant bacteria due to the antibiotics pollution are major concerns for
the health of human beings (Yin et al., 2018; Salami and Queiroz, 2011).
Therefore, the removal of STZ from water resources is of significant
importance to ensure a sustainable ecosystem.
Most of the conventional wastewater treatment technologies have
been found ineffective in removing STZ from wastewater, consequently
the levels of STZ are increasing in the environment. Further, the toxic
effects and recalcitrance nature of STZ result in limited efficacy of the
biological wastewater treatments (Ingerslev and Halling-Sørensen,
2000). Likewise, chemical treatments require higher operation costs and

* Corresponding author at: Soil Sciences Department, College of Food & Agricultural Sciences, King Saud University, P.O. Box 2460, Riyadh 11451, Kingdom of
Saudi Arabia.
E-mail address: malwabel@ksu.edu.sa (M.I. Al-Wabel).
1
These authors share co-first authorship and contributed equally to this work.

https://doi.org/10.1016/j.jhazmat.2020.124249
Received 17 May 2020; Received in revised form 24 August 2020; Accepted 8 October 2020
Available online 25 October 2020
0304-3894/© 2020 Elsevier B.V. All rights reserved.
A. Almajed et al.
Table 1
Layout for the synthesis and curing of the cemented sand based adsorbents for
characterization and fixed-bed adsorption trials to remove sulfathiazole from
aqueous solutions. EICP: enzyme induced carbonate precipitation, and DI:
deionized water.
Purpose of synthesis Weight of Amount of Curing Washed
sand + agent EICP (days) with DI
(g) Solution water (mL)
(mL)
Adsorbents trials 67.5 15 7.0 ~ 45
Chemical and 360 80 7.0 ~ 240
mechanical
characterization
energy (El-Ghenymy et al., 2014). Similarly, flocculation, sedimenta­
tion, and active sludge treatment have been reported as inefficient for
the complete removal of pharmaceutical compounds (Ahmad et al.,
2019a). Even, most of the advance wastewater treatment techniques,
such as oxidation, catalytic degradation, ozonation, and stream strip­
ping are expensive despite of their higher efficiency (Ahmad et al.,
2019a). Among all the wastewater treatment technologies, adsorption/
filtration is relatively simple, cost-effective and efficient technique;
however, selection of adsorbent/filter is of critical importance. Hence,
there is a devastating need to develop cost-effective and efficient tech­
nologies to remove STZ from wastewater streams before their intro­
duction into water resources.
Utilization of readily available and cheap materials to develop a
simple and efficient STZ removal technology may ensure sustainable
ecosystem health. Sand may serve for this purpose due to its abundance
in the earth crust, easy availability, and inexpensiveness. Although, sand
based powdered materials have already been used for water decon­
tamination purposes; however, the efficiency of such materials is sub­
stantially low (Sheng et al., 2018). For instance, the sand-based filters
may clog as well as pathogens can develop (Leupin and Hug, 2005).
Furthermore, one of the major factor responsible for reduced efficiency
of sand-based filters is the higher infiltration rate and loose texture.
Thus, improving the cementation, compactness, and other physical
characteristics of the sand filters may result in enhanced adsorption
properties. For instance, the efficiency of sand-based filters has been
improved by some researcher through inducing foreign substances such
as iron oxide, ferrihydrite, graphite oxide and manganese oxide (Gong
et al., 2015; Guha et al., 2001; Thirunavukkarasu et al., 2001).
In the last decade, researchers have attempted to develop new
technologies to cement the granular sand to improve the chemical and
mechanical properties of the sand. Among these technologies, calcite
precipitation within the pores via inter-particle binding and pore-filling
has attracted a huge attention of the researchers in recent times (Dejong
et al., 2006, 2010; van Paassen et al., 2010; Dilrukshi and Kawasaki,
2016; Whiffin et al., 2007; Hamdan et al., 2017; Neupane et al. 2015a,b;
Yasuhara et al. 2012; Almajed et al., 2018; Almajed, 2019). For instance,
in enzyme induced carbonate precipitation (EICP) technique, the calcite
precipitation can be produced when urea hydrolysis is catalyzed by
urease enzyme, consequently producing carbonate ions, which precipi­
tate as calcite (Almajed et al., 2018). All these studies confirmed that
calcite fills the voids, which leads to a significant improvement in terms
of binding the sand particles. Therefore, using these cemented sand as
filters may avoid the movement of free sand particles with water efflu­
ents. Further, incorporation of binding agents and/or adsorbent mate­
rials into the sand during the cementation process may improve the
contaminant removal efficiency of these filters.
Thus, it was hypothesized that incorporation of biochar (a black,
solid, and stable carbonaceous material obtained by the pyrolysis of
organic wastes), or other binding agents such as xanthan gums, guar
gum, bentonite and sodium alginate can improve the adsorption ca­
pacity of cemented sand based adsorbents. Addition of any of these
binding agent could enhance the surface and structural properties of the
2
Journal of Hazardous Materials 405 (2021) 124249
2000
Unconfined compressive strength (kPa)
f a
b
1500
1000
c
500
d
e
f
0
f
SC BT XG GG BC3 BC5 BC7 SA
Fig. 1. Unconfined compressive strength analyzes of cemented sand (SC)
enriched with bentonite (BT), xanthan gum (XG), guar gum (GG), biochar
produced at 300 ◦ C, 500 ◦ C and 700 ◦ C (BC3, BC5 and BC7, respectively), and
sodium alginate (SA).
cemented based adsorbents. Biochar has been recognized as a potential
adsorbent for the removal of potent inorganic and organic pollutants
from soil and water owing to its unique surface and structural charac­
teristics. The higher porosity, various functional groups, and larger
surface area enhance the bonding capability of biochar with various
pollutants (Ahmad et al., 2019b). Sodium bentonite is a natural clay,
commercial availability, used to fill the porous soil as a low-cost method
of treatment, and is environment-friendly due to no chemical additive.
Guar and xanthan gums are microbial polysaccharide extracted from
plants and bacteria. Both guar and xanthan gums serve as thickener
products and stabilizers in food industry. Sodium alginate has been
recognized as a natural polysaccharide obtained from alginic acid which
is widely found in brown marine algae and bacteria.
To the best of our knowledge, sand based adsorbents cemented with
enzyme induced carbonate precipitation and enriched with aforemen­
tioned binding agents has not yet been used for STZ adsorption. Hence,
we reported the fabrication of simple, low-cost, and efficient sand based
adsorbents via enzyme induced carbonate precipitation and augmented
with binding agents for STZ removal for the first time in this study. The
synthesized adsorbents were characterized for their chemical, mechan­
ical, and microscale properties and their efficiencies towards STZ
removal from aqueous media were investigated via fixed-bed column
adsorption trials. The STZ removal mechanisms were identified through
post-adsorption XRD and FTIR analyses, as well as simulation with ki­
netics models.
2. Materials and methods
2.1. Materials
2.1.1. EICP solution preparation
Reagent grade urea (CO(NH2)2⋅2H2O) and calcium chloride dihy­
drate (CaCl2⋅2H2O) were purchased from Sigma–Aldrich Inc. with a
purity of greater than 99%. The low activity jack bean-extracted urease,
without a specific average activity, was purchased from Fisher Scientific
Co. (Springfield, NJ). Non-fat powdered milk (Regilait UCA, Sr. Martin,
Belle-Roche, France) was purchased from a local store in Saudi Arabia.
The contents of protein and lactose in non-fat milk were 34.7% and
50.5% (w/w ratio), respectively, whereas, the contents of Na, Ca, and
Mg were 0.42%, 1.23%, and 0.10% (w/w ratio), respectively. The
electrical conductivity (EC) and pH of non-fat milk were 4.12 dS m− 1
and 6.72, respectively, while the moisture contents were < 4.0%.
A solution of 0.67 M urea and a solution of 1.0 M calcium chloride
dihydrate were prepared in deionized water and poured in a beaker with
A. Almajed et al.
Table 2
Some chemical properties and particle size distribution of cemented sand (SC) enriched with bentonite (BT), xanthan gum (XG), guar gum (GG), biochar produced at
300 ◦ C, 500 ◦ C and 700 ◦ C (BC3, BC5 and BC7, respectively), and sodium alginate (SA).
1)
Binding agents pH EC (dS m−
SC 8.62 ± 0.32 0.12 ± 0.01
BT 8.51 ± 0.35 0.08 ± 0.00
XG 8.29 ± 0.49 0.27 ± 0.01
GG 8.17 ± 0.23 2.99 ± 0.16
BC3 7.82 ± 0.29 4.26 ± 0.31
BC5 8.02 ± 0.27 2.71 ± 0.20
BC7 7.97 ± 0.34 2.95 ± 0.12
SA 7.81 ± 0.26 3.27 ± 0.19
1:1 ratio (v/v). After mixing thoroughly, milk (4.0 g L− 1) and urease
enzyme (3.0 g L− 1) were added into this solution and mixed to prepare
EICP solution as mentioned by Almajed et al. (2018). Scheme 1 presents
the step-wise preparation of the EICP solution. The purpose of adding
non-fat milk into EICP solution was to provide nucleation point, which
controls the precipitation rate and the morphology of calcite. Further,
the casein protein present in milk can bind the calcium ions to urea,
which results in carbonate precipitation (Farrell et al., 2002). Several
studies have investigated the advantageous effects of using milk as
nucleation points and in controlling the precipitation rate (Almajed
et al., 2019; Farrell et al., 2002).
2.1.2. Binding agent materials
Biochar, sodium bentonite, guar gum, xanthan gum, and sodium
alginate have been used as binding agents with EICP in this study. All of
the gums and bentonite clay were obtained commercially, while bio­
chars were produced from date palm tree waste. For producing the
biochar, date palm tree waste was collected from local agricultural farms
in Riyadh (Saudi Arabia), washed, and dried in air. The dried leaf waste
was separated, chopped into small pieces and pyrolyzed in an oxygen-
limited environment by using a muffle furnace. Various biochar were
produced by using a pyrolysis temperature of 300 ◦ C, 500 ◦ C, and
700 ◦ C, with a resident time of 4.0 h. The obtained biochars at 300 ◦ C,
500 ◦ C, and 700 ◦ C were washed, labeled as BC300, BC500, and BC700,
respectively, and stored in airtight containers. The characteristics of the
produced biochars can be found elsewhere (Usman et al., 2015).
2.2. Synthesis of cemented columns
Uniform and poorly graded silica sand was purchased locally (Al-
Rasheed Silica Plant) in Saudi Arabia. The sand was characterized with a
specific gravity of 2.65, surface area of 43.0 cm2 g− 1, and dry density in
the range of 1.44–1.65 g cm− 3. The characteristics of the used sand can
be seen elsewhere (Almajed et al., 2019). Two sets of the samples were
prepared; one for the mechanical (unconfined compressive strength
(UCS)), microscale, and chemical characterization, while the other for
fixed-bed adsorption trials. To fabricate the first set of the samples, the
crushed sand was mixed with 1% (w/w ratio) of either biochars, sodium
bentonite, guar gum, xanthan gum, or sodium alginate. After uniform
mixing, 360 g of sand-binding agent mixture was filled into an acrylic
cylinder (101 mm in high and 50.8 mm in diameter) with a relative
density of 55% by pluviation. Then, 80 mL (approximately one pore
volume) of a freshly prepared EICP solution was percolated from the top
of the cylinder. The purpose of using a clear acrylic cylinder was to
ensure the visibility of sand particles in order to avoid any suspended
substances, which may affect the reaction of EICP. After one week of
curing, samples were washed with 240 mL of deionized water (triplicate
amount of EICP) to minimize the contents of non-calcite precipitations
which might have been produced with EICP treatment. The cemented
columns were taken out from the acrylic cylinders, dried in oven at
45 ◦ C for 72 h. Thereafter, the adsorbents were stored at room tem­
perature (23 ± 2 ◦ C) for chemical and mechanicals characterization.
Journal of Hazardous Materials 405 (2021) 124249
CaCO3 (%) Particle size distribution (%)
Calcimeter Washing 50–2000 µm 2.0–50 µm
0.84 ± 0.01 0.80 ± 0.01 99.62 ± 3.32 0.38 ± 0.13
1.23 ± 0.12 1.30 ± 0.11 93.22 ± 2.64 6.78 ± 0.26
3.59 ± 0.16 3.20 ± 0.38 97.74 ± 4.61 2.26 ± 0.31
2.77 ± 0.19 2.91 ± 0.25 91.62 ± 3.99 8.38 ± 0.61
1.74 ± 0.06 1.71 ± 0.10 92.80 ± 5.61 7.20 ± 0.36
2. 17 ± 0.11 2.15 ± 0.18 90.52 ± 6.23 9.48 ± 1.20
1.59 ± 0.08 1.90 ± 0.08 86.43 ± 3.15 13.57 ± 2.11
4.07 ± 0.23 3.61 ± 0.59 95.50 ± 4.68 4.50 ± 0.39
Scheme 1 shows the steps for fabrication of the columns, while Table 1
represents different treatments and curing details for the preparation of
the samples.
To fabricate the second set of samples for adsorption trials, crushed
sand with the desired quantity of binding agents was filled in a plexiglass
column (115 mm length × 29 mm diameter) at a relative density of 55%
by pluviation, after making a layer of glass-wool at the bottom of the
column to avoid particles movement. The bottoms of the columns were
closed tightly to avoid any leakage. About 15 mL (approximately one
pore volume) of the freshly prepared EICP solution was gently pene­
trated from the top of the column with the help of a syringe. These
columns were left for a week for curing, and thereafter, the bottoms of
these columns were opened and columns were washed thrice with
45 mL of deionized water to minimize the contents of non-calcite pre­
cipitations. The synthesized adsorbents were dried at 45 ◦ C in oven for
72 h, and then stored at room temperature (23 ± 2 ◦ C). The prepared
adsorbents after EICP treatment were termed as SC (sand alone), BT
(bentonite + sand), XG (xanthan gum + sand), GG (guar gum + sand),
BC3 (BC300 + sand), BC5 (BC500 + sand), BC7 (BC700 + sand), and
SA (sodium alginate + sand).
2.3. Adsorbent characterization
2.3.1. Chemical and microscale analyses
The percentage of calcite contents in the synthesized adsorbents was
determined by using washing and calcimeter method (Horváth et al.,
2005). For calcimeter determination, 2.0 g of adsorbent was treated
with 0.1 N hydrochloric acid (HCl) and the volume of CO2 evolved was
recorded. The percent calcite was calculated by comparing the volume
of CO2 evolved from the sample with the volume of CO2 evolved from
pure CaCO3. To analyze the contents of calcite by washing method, a
portion from each sample was weighed in a dry condition and soaked in
4.0 M HCl solution. Thereafter, the sample was separated, washed using
adequate volume of deionized water, and dried in an oven till constant
weight. The difference in weight was accounted as the calcite contents
for each sample. The EC and pH of the fabricated materials were
measured in 1:5 (w/v ratio) suspension of material-deionized water. The
pHZPC (pH at zero-point charge) was estimated in pH range of 2.0–12
with 0.1 M NaCl (Ahmad et al., 2019b). The particle size distribution of
the samples was analyzed by using Malvern Mastersizer 2000 equipped
with Hydro 2000S. The UCS tests were performed by using a strain rate
of 1.27 mm min− 1, after leveling the top and bottom of the column. The
ratio of each sample was kept 2:1 (length: diameter) for UCS testes ac­
cording to the ASTM D2166 (ASTM, 2003). The variation in the
mineralogical phases of the synthesized adsorbent materials was
investigated with X-ray diffractometer (XRD) analyses by using MAX­
ima_X XRD-7000, Shimadzu, Japan. Briefly, the samples were grinded
and passed through a screen to obtain particle size of < 50 µm. The
powdered sample was placed onto a sample holder and XRD patterns
were obtained from –2.0 to 80 degree- theta using 30 mA Cu-Kα radi­
ation with a scanning speed of 2.0◦ /min under continuous scanning. The
composition of the functional groups in the fabricated adsorbent
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A. Almajed et al. Journal of Hazardous Materials 405 (2021) 124249

Fig. 2. X-ray diffraction patterns of cemented sand (SC) enriched with bentonite (BT), xanthan gum (XG), guar gum (GG), biochar produced at 300 ◦ C, 500 ◦ C and
700 ◦ C (BC3, BC5 and BC7, respectively), and sodium alginate (SA) before and after sulfathiazole (STZ) removal from aqueous solutions. (S: SiO2, C: CaCO3, K: KCl,
N: Urea-N, and CO: CaO).

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A. Almajed et al. Journal of Hazardous Materials 405 (2021) 124249

Table 3
Occurrence and shifts of X-ray diffraction peaks (2θ degree) of cemented sand (SC) enriched with bentonite (BT), xanthan gum (XG), guar gum (GG), biochar produced
at 300 ◦ C, 500 ◦ C and 700 ◦ C (BC3, BC5 and BC7, respectively), and sodium alginate (SA).
Mineral phase SC BT XG GG BC3 BC5 BC7 SA

SiO2 20.66 20.86 20.61 20.56 20.78 20.88 20.86 20.56

SiO2 24.70 24.00 24.56 24.68 27.77 24.84 24.80 24.76
SiO2 26.42 26.6 26.40 26.28 26.58 26.72 26.64 26.50
CaCO3 29.28 29.38 29.18 29.02 29.52 29.42 29.40 29.20
CaO 32.76 32.42 – 32.24 32.58 32.66 32.66 32.44
Urea-N 35.82 35.48 35.28 35.06 35.40 35.54 35.48 35.82
CaCO3 39.30 39.46 39.24 39.08 39.38 39.50 39.44 39.22
CaCO3 43.06 43.26 43.00 42.86 43.08 43.20 43.16 42.98
CaCO3 47.34 47.44 47.26 47.08 47.44 47.46 47.44 47.28
SiO2 50.48 50.54 50.08 50.32 49.98 50.14 50.14 50.10
SiO2 60.52 59.92 60.62 60.52 60.64 60.86 60.84 60.68
SiO2 – – 65.2 65.2 – – – –
KCl – – 67.98 67.90 67.12 68.16 68.08 67.98
SiO2 – – 77.50 77.50 – – – –

materials was assessed with the help of Fourier Transform Infrared standards were also analyzed as unknown samples for the quality
Spectroscopic (FTIR) analyses by using Alpha-Eco ATR-FTIR (Bruker assurance and the obtained recovery was 95.63–104.69%.
Optics Inc.). Briefly, a specific amount of crushed sample was directly The total volume of the effluents can be calculated through Eq. (1):
placed onto ATR-FTIR crystal and analyzed under transmission mode.
Veff = Q.ttotal (1)
The FTIR spectra of the samples were obtained in the scan range of
4000 –400 cm− 1.
where, ttotal stands for total flow time (min) and Q represents volumetric
flow rate (mL min− 1).
2.4. Fixed-bed column adsorption trials The breakthrough capacity at 50% (Ct/C0 = 0.5) was estimated by
using Eq. (2).
Fixed-bed adsorption batch studies were conducted by using the
t0.5 × Q × Co
fabricated cemented columns. Briefly, the fixed-bed columns were syn­ Q0.5 = (2)
m
thesized by cementing the sand with binding agents within the plex­
iglass columns (as described in Section 2.2). The bed-height of the where, Q0.5 stands for 50% breakthrough capacity (mg g− 1), Co is the
columns was kept as 65 mm for each adsorbent. A layer of glass-wool concentration of STZ (mg L− 1) in influent, t0.5 is time at 50% break­
was placed on the bottom of columns to avoid particle loss. Likewise, through, and m is the mass of the adsorbent (g).
a layer of glass-wool was spread onto the top of column followed by a The maximum adsorption capacity (qtotal) of the adsorbents can be
layer of glass-beads for uniform distribution of the influent. estimated by calculating the area above breakthrough curve, which in
Sulfathiazole, purchased from Sigma–Aldrich Inc. was used for the turn can be estimated by integrating the total STZ adsorbed (Cad) vs time
fixed-bed adsorption trials. The pKa values of STZ are 2.32–7.24, and (min) by using Eq. (3):
therefore, it can act as an anion, cation, or neutral ion depending on ∫
solution pH (Bellú et al., 2007). The solubility of STZ in water has been QCo t=ttotal
qtotal = Cad dt (3)
reported as 4.6 g L− 1 at pH 5.5 (Vree and Hekster, 1987). A stock so­ 1000 t=0
lution containing 1000 mg L− 1 of STZ was prepared in 1% methanol in The total amount of STZ (Wtotal) entered into each of the column can
deionized water (18.2 MΩ cm resistivity; Milli-Q, Germany). The stock be calculated by Eq. (4) as follows:
solution was diluted further in deionized water to prepare standard and
Co Q
working solutions. For column adsorption trials, a solution containing Wtotal = (4)
50 mg L− 1 of STZ was prepared by diluting the stock solution and its 1000
initial pH was adjusted at 4.5. The STZ solution was delivered on top of The ATZ removal (%) at saturation was calculated by using Eq. (5) as
the column using a peristaltic pump at a fixed flow rate of 5.0 mL min− 1. follows:
The effluent, after passing through the column, was collected at bottom qtotal
of the column after every 5.0 min interval in amber-colored bottles. The Removal(%) = × 100 (5)
Wtotal
collected effluent samples were stored at 4.0 ◦ C for further analyses. All
the adsorption studies were replicated thrice to test reproducibility at The linear forms of Yoon–Nelson and Thomas kinetic models (Eqs.
23 ± 2 ◦ C and continued until the complete exhaustion of the adsorbent. (6) and (7), respectively) were employed to the adsorption data to
The effluents were passed through 0.45 µm syringe filters to remove investigate the breakthrough performance and adsorption capacities of
any particles. The concentration of STZ in the effluents was determined the tested adsorbents (Yoon and Nelson, 1984; Thomas, 1944).
by using a high-performance liquid chromatography (HPLC) technique. Ct
The Prominence-i, LC-2030C (Shimadzu, Japan) HPLC, which was In = KYN t − τKYN (6)
Co − Ct
equipped with high-speed drive auto-sampler, a low-pressure gradient
solvent delivery pump, a PDA detector, a reversed-phase Raptor C18 where, KYN = Yoon–Nelson rate constant (min− 1), τ = time for 50%
column (100 mm × 21 mm, 2.7 µm particle size), and a degasser unit breakthrough (min), Ct = STZ concentration in effluent (mg L− 1), and
was used in this study. A gradient flow system was used for the STZ t = sampling time (min).
analyses by using 70% mobile phase A (comprising 99.9% of ultrapure ( )
Co KTh qo m
water and 0.1% of formic acid) and 30% of mobile phase B (comprising In − 1 = − (KTh Co ) (7)
Ct Q
99.9% of acetonitrile and 0.1% of formic acid). The injection volume of
10 μL and flow rate of 0.15 mL min− 1 were maintained throughout the
where, KTh stands for the Thomas rate constant (L min− 1 mg− 1), and qo
analyses. The calibration curve (R2 ~ 0.99) was constructed between
stands for the maximum or adsorption capacity (mg g− 1).
STZ concentrations versus absorbance by using STZ standards. The STZ

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A. Almajed et al. Journal of Hazardous Materials 405 (2021) 124249

Fig. 3. Fourier-transform infrared spectroscopy spectra of cemented sand (SC) enriched with bentonite (BT), xanthan gum (XG), guar gum (GG), biochar produced at
300 ◦ C, 500 ◦ C and 700 ◦ C (BC3, BC5 and BC7, respectively), and sodium alginate (SA) before and after sulfathiazole (STZ) removal from aqueous solutions.

3. Results and discussion
3.1. Adsorbents characterization
3.1.1. Mechanical analyses
The UCS of each adsorbent cemented with EICP and different binding
agents are illustrated in Fig. 1. The results indicated that adding binding
agent has not enhanced the strength of the treated specimens except for
BC3 and SA. In fact, most of the binding agents (except BC3 and SA)
resulted in reduced strength and required several cycles to achieve a
cemented sample (Almajed et al., 2019). The BC5 and BT specimen
showed 225 and 240 kPa of UCS, respectively, which indicates a 6.5 and
7.0-fold reduction in strength, respectively, compared to SC. Alike, the
sample treated with XG and GG exhibited 83% and 255% reduction in
strength, respectively, compared to SC. Contrarily, the UCS of BC3 and
SA increased by 6.0% and 10.5% as compared to SC, whereas, BC7
exhibited zero UCS. Therefore, the cemented sand enriched with BC700
(BC7) did not produce a strong and compacted sample, rather produced
a chunk of sand. Our results are in agreement with Arab et al. (2019),
where it was demonstrated that adding SA led in improved shear
strength of the clay and sand. Additionally, Almajed et al. (2019) stated
that one cycle treatment of sand with biochar resulted in poor UCS.
Almajed (2019) reported that four cycles were required in order to
achieve a compacted and cemented material with BC300 and BC500
enrichment. This variation in strength could be due to the binding af­
finity of each binding agent towards sand and calcite. Each of the biding
agents has a different capability of cross-linking and void filling during
the EICP treatment owing to varied physio-chemical composition such

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A. Almajed et al. Journal of Hazardous Materials 405 (2021) 124249

1.2 1.2
(a) (b)
1.0 1.0

0.8 0.8
Ct/Co

Ct/Co
0.6 0.6

0.4 0.4

SC BC3
0.2 0.2
BT BC5
XG BC7
0.0 GG 0.0 SA

0 20 40 60 80 100 120 0 20 40 60 80 100 120

Time (min) Time (min)

5 5
(c) (d)
4 4

3 3
ln[Ct/(Co-Ct)]

ln[Ct/(Co-Ct)]
2 2

1 1

0 SC 0 BC3
BT BC5
-1 XG -1 BC7
GG SA
Regression Regression
-2 -2

0 20 40 60 80 100 120 0 20 40 60 80 100 120

Time (min) Time (min)

4 4
(e) (f)
SC BC3
3 3
BT BC5
2 XG 2
BC7
GG SA
Regression
ln[(Co /Ct) - 1]

ln[(Co /Ct) - 1]

1 Regression 1

0 0

-1 -1

-2 -2

-3 -3

-4 -4

-5 -5
0 20 40 60 80 100 120 0 20 40 60 80 100 120

Time (min) Time (min)

Fig. 4. Breakthrough curves for the removal of sulfathiazole (STZ) through cemented sand (SC) enriched with bentonite (BT), xanthan gum (XG), guar gum (GG),
biochar produced at 300 ◦ C, 500 ◦ C and 700 ◦ C (BC3, BC5 and BC7, respectively), and sodium alginate (SA). (a, b: Experimental breakthrough curves, c, d:
Yoon–Nelson model predicted breakthrough curves, and e, f: Thomas model predicted breakthrough curves).

as particle size, porosity, functional groups, and hydration potential.
Further, the addition of binding agents can differently reduce the void
space, subsequently generating a different rigid structure.
3.1.2. Chemical and microscale analyzes
The pH, EC, contents of calcite, and particle size distribution of the
produced adsorbents are presented in Table 2. The contents of calcite
were increased with the addition of binding agent (BT, XG, GG, SA, BC3,
BC5, and BC7) compared to SC. This is due to the fact that the binding
agents such as BT, XG, GG, SA act as hydrogel agents, and may
encapsulate the organic cementation. This cementation did not allow
the complete washing of the non-calcite precipitation with deionized
water. Thus, organic cementation may result into an inaccurate result
for the amount of CaCO3. These results are in agreement with others that
hydrogel agents will lead to an inaccurate result in terms of CaCO3
(Almajed, 2017). However, the samples without hydrogel agent, such as
BC3, BC5, and BC7 gave a reasonable value that is in agreement with
previous work on bio-cemented specimens through calcite (Hamdan
et al., 2017; Neupane et al., 2015a,b; Yasuhara et al., 2012; Almajed
et al., 2018; Almajed, 2019). Moreover, the enrichment of sand with

7
A. Almajed et al. Journal of Hazardous Materials 405 (2021) 124249

(a)

Effluent STZ concentration (mg L-1)

50

40

30
SC
BT
XG
20
GG
BC3
BC5
10
BC7
SA
0
0 10 20 30 40 50 60 70 80 90 100 110 120

Time (min)
100
(b)

80
STZ removal (%)

60

40

20

0
SC BT XG GG BC3 BC5 BC7 SA

Fig. 5. (a) Sulfathiazole (STZ) concentration dynamics in the effluents and (b) STZ removal efficiency of cemented sand (SC) enriched with bentonite (BT), xanthan
gum (XG), guar gum (GG), biochar produced at 300 ◦ C, 500 ◦ C and 700 ◦ C (BC3, BC5 and BC7, respectively), and sodium alginate (SA).

structure of the samples. The particle size distribution suggested that

Table 4 99.62% of particles were in the range of sand fraction (50–2000 µm) in
Parameters obtained from linear regression of Yoon–Nelson and Thomas kinetic SC sample. Addition of binding agents reduced the percentage of sand
models for sulfathiazole adsorption onto cemented sand (SC) enriched with fraction, where maximum reduction (15%) was observed in BC7.
bentonite (BT), xanthan gum (XG), guar gum (GG), biochar produced at 300 ◦ C, The XRD analyses of the pristine and loaded adsorbents are shown in
500 ◦ C and 700 ◦ C (BC3, BC5 and BC7, respectively), and sodium alginate (SA).
Fig. 2. These XRD patterns shown various peak shifts and changes in
Adsorbent Yoon–Nelson model Thomas model peak intensities with addition of different amendments. The location
KYN τ R2 qo KTh R2 and shifts in XRD peaks can be seen in Table 3. Five major peaks
(L min− 1) (min) (mg g− 1) (L min− 1
mg− 1) occurring around 20.66◦ , 24.70◦ , 26.42◦ , 50.50.48◦ , and 60.52◦ in SC,
SC 0.037 24.124 0.98 0.506 0.036 0.95 and with little shifts in all other adsorbents (Table 3), were attributed to
BT 0.051 39.607 0.96 2.829 0.108 0.96 SiO2 owing to the sand as major constituent in all the adsorbents
XG 0.065 38.393 0.94 2.327 0.102 0.97 (Almajed, 2019). However, addition of two SiO2 peaks were identified at
GG 0.063 33.416 0.91 1.436 0.092 0.94
65.20◦ and 77.50◦ in XG and GG (Fig. 2b). The presence of a sharp peak
BC3 0.061 47.075 0.97 3.167 0.121 0.97
BC5 0.079 51.856 0.94 3.857 0.126 0.98
around 29.28◦ in SC, and with little variations in other adsorbents
BC7 0.087 58.054 0.95 4.925 0.142 0.98 suggested the existence of higher CaCO3 contents; however, the in­
SA 0.074 44.641 0.93 3.414 0.129 0.93 tensity of the aforementioned peaks was lower in adsorbents containing
biochars (BC3, BC5 and BC7). Additionally, peaks of CaCO3 were also
identified around 39.30◦ , 43.06◦ , and 47.34◦ in SC, and with shifts in
BC500 and BC700 resulted in higher CaCO3 contents than SC, whereas
other adsorbents. The peak around 67◦ in all the adsorbents (except SC
yielded lower UCS, which could be due to higher porosity and functional
and BT) was ascribed as KCl. A peak around 32.76◦ in SC was owing to
groups of biochar. Haque et al. (2014) reported that the contents of lime
the presence of CaO in all the adsorbents with some shifts, with excep­
do not affect the cementation process in biochar-soil system. Further, the
tion of XG. A peak of N was obvious around 35◦ in all the adsorbents,
two calcite determination methods i.e., calcimeter and washing with
which resulted due to the treatment of the adsorbents with urea solution.
HCl yielded comparable values of calcite contents in the samples. The
The composition of surface functional groups of the adsorbents
pH of the samples reduced, while the EC increased with the incorpora­
before and after STZ adsorption as investigated through FTIR spectra is
tion of biochars and other binding agents. The higher EC of BC3, GG,
shown in Fig. 3. A band around 700 cm− 1, and few tiny bands in its
BC5, BC7, and SA could be due to binding of more Ca2+ within the
vicinity were ascribed as Si–O, owing to the presence of sand. A

8
A. Almajed et al. Journal of Hazardous Materials 405 (2021) 124249

Table 5
Comparison of maximum adsorption capacities of various adsorbents for sulfathiazole sorption.
Adsorbent Conditions Maximum adsorption Mechanism Reference
(mg g¡1)

Graphite pH 1.0, Temp. 4.22 Hydrophobic interaction, π–π EDA interaction, and electrostatic Liu et al. (2016)
25 7‾C interaction
Graphite pH, Temp. 25 ◦ C 5 8.02 Hydrophobic interaction, π–π EDA interaction and electrostatic Liu et al. (2016)
interaction
Graphite pH 11, Temp. 0.932 Hydrophobic interaction, π–π EDA interaction and electrostatic Liu et al. (2016)
25 ◦ C interaction
Aligned multi-walled carbon pH 7, Temp. 25 ◦ C 62.6 H-bonds, Lewis acid-base interactions, hydrophobic interactions, Zhao et al. (2016)
nanotubes and π–π interaction
Small multi-walled carbon pH 7, Temp. 25 C◦
25.1 H-bonds, Lewis acid-base interactions, hydrophobic interactions, Zhao et al. (2016)
nanotubes and π–π interaction
Large multi-walled carbon pH 7, Temp. 25 ◦ C 33.8 H-bonds, Lewis acid-base interactions, hydrophobic interactions, Zhao et al. (2016)
nanotubes and π–π interaction
Large multi-walled carbon pH 7, Temp. 25 ◦ C 28.0 H-bonds, Lewis acid-base interactions, hydrophobic interactions, Zhao et al. (2016)
nanotubes and π–π interaction
− 3
High-silica zeolite pH 4.7, Temp. 1.58 × 10 Hydrophobic interactions Fukahori et al. (2011)
25 ◦ C
Silt loam soil pH 5.5 − 7.252 – Kim et al. (2012)
Silt loam soil pH 7.0 − 6.654 – Kim et al. (2012)
Silt loam soil pH 8.5 − 4.930 – Kim et al. (2012)

relatively sharp band in all the adsorbents appearing around 1090 cm− 1
was owing to the presence of O-containing functional groups. These
bands could be due to Si–O stretching owing to the presence of sand
particles, and C–O stretching of aromatic ester groups of biochars (Li
et al., 2014; Fu et al., 2018; Premarathna et al., 2019). Bands around 870
and 2855 cm− 1 in all the adsorbents were ascribed as C–H stretching.
Likewise, a band around 1430 cm− 1 was identified as O–H stretching.
The band at 1620 cm− 1 was credited to C˭O, which could be owing to
the aromatic structures of the biochars as well as gums used in the ad­
sorbents synthesis (Usman et al., 2015). A small band around 2410 cm− 1
was ascribed as C–N stretching due to the N-loadings resulting from urea
enrichment.
3.2. Fixed-bed column STZ adsorption and kinetics modeling
The efficiency of the produced adsorbents for STZ adsorption in
columns under a constant flow rate and a constant adsorbent amount
was evaluated and the experimental breakthrough curves are shown in
Fig. 4a and b. It is obvious from the figure that Ct/Co increased gradually
with the passage of time and each of the adsorbent reached to the
saturation after a specific time interval. The adsorbent SC and GG
quickly reached to the saturation point, whereas the adsorbent BC7 took
the maximum time to acquire saturation point. Overall, the order of
saturation time was BC7 > BC5 > BC3 > SA > XG > BT > GG > SC.
Likewise, the dynamics of STZ concentration in the effluent followed the
similar trend with highest saturation time for BC7 (Fig. 5a). Likewise,
the STZ removal percentage as presented in Fig. 5b, followed the order
BC7 > BC5> BC3 ≥ SA > XG ≥ BT > GG > SC. The adsorbent BC7
removed the highest STZ (87.9%) from the aqueous solution in the given
time, followed by BC5, BC3 and SA (78.0%, 64.7%, and 63.0%,
respectively). These results suggested that BC7 was able to decontami­
nate the STZ-polluted water for longer period of time as compared to rest
of the tested adsorbents.
However, the accurate determination of the breakthrough curves is
very important for the successful operation of the fixed-bed columns
(Lonappan et al., 2019). Hence, the dynamics of STZ adsorption and
breakthrough behavior of the produced adsorbents was further investi­
gated through applying kinetics models onto the experimental adsorp­
tion data. The linear forms of regression were performed, and the
parameters obtained from Yoon–Nelson and Thomas models are pro­
vided in Table 4 (Amin et al., 2017). Based on correlation coefficient
(R2) values, Yoon–Nelson and Thomas models were able to describe the
dynamics of STZ adsorption onto all the tested adsorbents (R2 =
0.91–0.98 and 0.93–0.98, respectively).
The Yoon–Nelson model is considered a relatively simple model,
where the detailed properties of the adsorbate and the adsorbent ma­
terial are not needed. Moreover, it does not require the physical prop­
erties of the adsorption bed. The Yoon–Nelson rate constants (KYN) and
time required for 50% breakthrough (τ) as calculated from the plot of
time (min) vs ln[Ct/(Co − Ct)] have been provided in Table 4, and the
resultant Yoon–Nelson breakthrough curves are presented in Fig. 4c and
d. The highest KYN value was exhibited by the adsorbent BC7
(0.087 L min− 1), followed by BC5, SA, XG, GG, BC3, BT, and SC (0.079,
0.074, 0.065, 0.063, 0.061, 0.051 and 0.037 L min− 1, respectively).
Likewise, BC7 showed the highest τ value (58.056 min), followed by
BC5 and BC3 (51.856 and 47.075 min, respectively), whereas the lowest
τ value was exhibited by SC (24.124 min).
The Thomas rate constants (KTh) and maximum adsorption capacities
(qo) of the adsorbents as calculated through plotting time (min) against
ln[(Co/(Ct) − 1)] are shown in Table 4, and the resultant breakthrough
curves are presented in Fig. 4e and f. The qo followed the order of; BC7
(4.925 mg g− 1) > BC5 (3.857 mg g− 1) > SA (3.414 mg g− 1) > BC3
(3.167 mg g− 1) > BT (2.829 mg g− 1) > XG (2.327 mg g− 1) > GG
(1.436 mg g− 1) > SC (0.506 mg g− 1). A similar trend was also obtained
in terms of KTh values, where BC7 exhibited the highest value
(0.142 L min− 1 mg− 1), followed by SA (0.129 L min− 1 mg− 1), and BC5
(0.126 L min− 1 mg− 1), whereas the minimum value was shown by GG
(0.092 L min− 1 mg− 1), and SC (0.036 L min− 1 mg− 1). The Thomas
model predicted qo was in agreement with the STZ removal percentage
as shown in Fig. 5b.
Maximum adsorption capacities of various adsorbents towards STZ
sorption have been enlisted in Table 5. It can be seen that the majority of
the adsorbents have adsorption capacities similar to this study. For
instance, silica based adsorbents exhibited lower adsorption capacities
(− 7.252 to 1.58 × 10− 3 mg g− 1) as compared to this study; however,
carbon nanotubes shown relatively higher adsorption capacities
(25.1–62.6 mg g− 1) due to nano-sized structure and higher surface area
(Ahmed et al., 2017a,b; Liu et al., 2016; Zhao et al., 2016a,b; Fukahori
et al., 2011; Kim et al., 2012).
3.3. STZ adsorption mechanism
The STZ adsorption onto various adsorbents is largely influenced by
the characteristics of the particular adsorbent, such as porosity, func­
tional groups, surface area etc., as well as the sorption conditions such as
the solution pH, contact time, adsorbent dose, temperature, and adsor­
bate concentration. Among these factors, pH of the solution is of critical
importance owing to the amphoteric nature of the STZ molecule. As

9
A. Almajed et al. Journal of Hazardous Materials 405 (2021) 124249

(a)
1.0

0.8
STZ+ STZ0 STZ-

Fraction 0.6

0.4

0.2

0.0
0 1 2 3 4 5 6 7 8 9 10

pH
(b)
pHZPC
10
pH at 5 min
pH at 120 min
Solution pH
9

8
pH

SC BT XG GG BC3 BC5 BC7 SA

Fig. 6. (a) Transformation of sulfathiazole (STZ) forms with change in pH and (b) pH at zero-point charge (pHZPC) as well as pH after 5 min and 120 min of STZ
adsorption onto cemented sand (SC) enriched with bentonite (BT), xanthan gum (XG), guar gum (GG), biochar produced at 300 ◦ C, 500 ◦ C and 700 ◦ C (BC3, BC5 and
BC7, respectively), and sodium alginate (SA).

indicated in Fig. 6a, the STZ can exist either a cation (STZ+), anion
(STZ− ) or a neutral ion (STZ0) depending upon the solution pH due to
protonation-deprotonation interactions (Pei et al., 2014). Therefore, the
electrostatic interactions on the surface of adsorbate and adsorbent as
well as the ringed structure of STZ could play a major role in the removal
of STZ from the aqueous solution. For instance, it has been reported
earlier that the adsorption of STZ onto soil particles was higher under
acidic environment owing to electrostatic attraction between the posi­
tively charged STZ molecules and negatively charges soil particles
(Kahle and Stamm, 2007; ter Laak et al., 2006). Contrarily, the solution
pH in the current study was acidic, while it remained alkaline when
interacted with adsorbents (Fig. 6b). Previous studies demonstrated that
with gradual increment in pH from acidic to basic, the STZ+ molecule
can transform into STZ0 and subsequently into STZ− with further in­
crease in pH (Pei et al., 2014). Therefore, in current study, based on the
solution pH, the dominant STZ species could be STZ0 and STZ–. Thus,
Lewis acid base electronic interactions could contribute in STZ0 sorption
under slightly acidic pH, as STZ molecule is comprising of a sulfonamide
group attached with a thiazole group at N-position, as well as a lone pair
of electrons at amino-group on the aromatic ring (Fig. 7). Owing to the
lone pair of electrons on the amino-groups, STZ molecule has affinity to
interact with –OH groups of the adsorbents, suggesting the occurrence of
Lewis acid base electronic interactions for STZ removal at pH when STZ
behaves as a neutral species. However, with further increase in pH, STZ−
species developed, generating a repulsive force between STZ molecules
and the adsorbents, consequently reducing the STZ removal (Pei et al.,
2014). However, the incorporation of biochars into the samples induced
both positive and negative surface charges, which continued to adsorb
STZ− even at higher pH.
Additionally, the transportation of STZ molecules and diffusion into
the pore could also participate for the STZ removal from influent (Jing
et al., 2014). The porous structure of the adsorbents facilitated the mass
transportation of the STZ molecules into the pore via monolayer diffu­
sion (Ahmed et al., 2017b). Therefore, the higher removal of STZ onto

10
A. Almajed et al.
S
N
NH
δ+
δ-
O
S
O O
Electrostac
interacons
O
N
H
O O
H+
Hydrogen bonding
Fig. 7. Proposed mechanisms for the adsorption of sulfathiazole (STZ) onto cemented sand based absorbents enriched with either bentonite, xanthan gum, guar gum,
or biochars.
the adsorbents enriched with biochars and sodium alginate could be
attributed owing to diffusion as a result of higher surface area and
reduced pore diameter (Ahmed et al., 2017b). However, the contribu­
tion of pore-filling in adsorption is generally less effective in case of
fixed-bed continuous sorption batches, as compared to the isotherm
batches. Thus, the diffusion was not a rate limiting step for the removal
of STZ onto the synthesized adsorbents in this study.
Based on the experimental results and kinetics modeling data, it was
observed that each of the adsorbent exhibited different affinity towards
STZ. The variations in the STZ adsorption efficiency of the tested ad­
sorbents could be due to surface functional groups, surface charges,
porosity and solution pH. The adsorption of STZ onto various adsorbents
was further confirmed by post-adsorption FTIR and XRD analyses.
Various shifts and changes in peak intensities are clear from the XRD
patterns of the post-sorption analyses (Table 3 and Fig. 2). A small peak
appearing at 23◦ in all the post-adsorption columns was designated to
STZ. The intensity of the calcite peak around 29.2◦ and 47.3◦ was
decreased with the adsorption of STZ onto BC3, BC5, SC, BT, XG, and
GG. Likewise, the intensity of Si–O peaks around 20.8◦ and 50◦ was
decreased with STZ adsorption onto all of the adsorbents. Similarly, the
peak representing N around 35.8◦ was vanished after STZ adsorption.
Alike, the changes in various peak intensities in FTIR spectra were
occurred after STZ adsorption as indicated in Fig. 3. The intensity of a
band around 1620 cm− 1 owing to C-˭O groups was decreased in all the
post-adsorption columns. In contrast, the intensity of the C–O band
(1090 cm− 1) increased in all the columns after STZ adsorption. The O–H
stretching (1430 cm− 1) were vanished after the adsorption of STZ onto
BC3, BC5, BC7 and SA (Fig. 3c and d), while the C–H stretching
(2855 cm− 1) were removed after STZ adsorption onto SC, GG, BT, and
XG adsorbents (Fig. 3a and b). The involvement of C–H, C-˭O, and O–H
based functional groups in STZ adsorption onto biochar based adsor­
bents has also been reported previously. These functional groups may
serve as π-electron-donor-acceptor sites (Liu et al., 2016), whereas,
owing to the presence of a lone pair of electrons and N-heteroaromatic
rings, the STZ molecules serve as π-electron-acceptors. Additionally, the
initial solution pH of 4.5 aided the STZ molecules to become π-electron
acceptors owing to their π-electron withdrawing capability (Liu et al.,
11
Journal of Hazardous Materials 405 (2021) 124249
π-π electron donor acceptor
H interacons
N2
δ- = π-electron donor
δ+ = π-electron acceptor
δ-
H
H+
2016). Thus, electrons transferred from the –OH groups of biochar as
well as sodium alginate enriched adsorbents to the amino-group of STZ
molecule developing strong π–π electron-donor-acceptor interactions
(EDA). However, the release of –OH groups from STZ into the solution
may increase the pH of the solution gradually owing to exchange of
protons with H2O molecules (Fig. 6b). Therefore, the resultant mole­
cules generated negative charged assisted H-bonds with surface func­
tional groups of the adsorbents (Ahmed et al., 2017b; Teixidó et al.,
2011). Moreover, the –NH groups of the STZ may also interact with O–H
functional groups of the adsorbents subsequently developing H-bonds
(Fig. 7) (Ahmed et al., 2017b). Martucci et al. (2013) demonstrated the
similar findings suggesting H-bonding as the main mechanism for sul­
fonamide adsorption onto zeolite. Therefore, π–π EDA interactions were
more dominant for STZ removal than the H-bonding under acidic pH
conditions. Henceforth, based on these findings, π–π EDA interactions
were found to be the major mechanisms, which were further aided by
electrostatic interactions and H-bonding for STZ adsorption onto the
tested adsorbents. Furthermore, the BC7 exhibited the highest STZ
adsorption capacity and removal efficiency among the tested adsorbents
in this study.
4. Conclusion
Enrichment of biochars or other binding agents within the cemented
sand based adsorbents decreased the bonding strength (except BC3 and
SA), and improved the surface structure and functional groups. The
adsorption data was subjected to Yoon–Nelson and Thomas kinetics
modeling. Yoon–Nelson and Thomas kinetic models were fitted well to
the STZ adsorption data by generating R2 of 0.91–0.98 and 0.93–0.98,
respectively. The adsorbents enriched with biochar produced at higher
temperature (700 ◦ C) shown the highest Yoon–Nelson rate constants
(0.087 L min− 1) and time at 50% breakthrough (58.056 min) as
compared to the rest of the studied adsorbents. Among all the tested
adsorbents, enrichment with 700 ◦ C biochar performed outclass by
removing 87.9% of the STZ from aqueous media. Likewise, it showed the
highest maximum adsorption capacity (4.925 mg g− 1) as predicted by
Thomas kinetic model. Post-adsorption analyses of FTIR and XRD
A. Almajed et al.
Scheme 1. Schematic illustration for the preparation of enzyme induced carbonate precipitation (EICP) solution and cementation processes to fabricate sand
based adsorbents.
evidenced the binding of STZ onto the synthesized adsorbents. π–π
electron-donor-acceptor interactions were found to be the major
mechanisms controlling STZ adsorption onto the adsorbents; however,
these mechanisms were further aided by electrostatic interactions and
H-bonding. Hence, cost-effective and simple remediation technologies
to remove STZ from contaminated wastewater can be developed by
producing biochar at higher pyrolysis temperature and embedding it
into cemented sand based adsorbents.
CRediT authorship contribution statement
Abdullah A. Almajed: designing and conceptualization of the
project, synthesis of the filters, investigation, characterization of mate­
rials, and manuscript writing. Munir Ahmad: characterization of the
materials, accomplishment of fixed-bed sorption trials, formal analyzes,
statistical analyzes, and writing of the manuscript. Adel R.A. Usman:
designing and conceptualization of the project, methodology, supervi­
sion, manuscript review and editing. Mohammad I. Al-Wabel: Project
administration, supervision, manuscript review 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.
Acknowledgment
The authors extend their appreciation to the Deputyship for Research
& Innovation, “Ministry of Education” in Saudi Arabia for funding this
research work through the project number IFKSUHI-1439-043.
12
Journal of Hazardous Materials 405 (2021) 124249
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