Inorganic Chemistry Communications 144 (2022) 109895

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Inorganic Chemistry Communications

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Short communication

Low cost iron modified syzygium cumini l. Wood biochar for adsorptive
removal of ciprofloxacin and doxycycline antibiotics from aqueous solution
Anushree Srivastava a, Hemen Dave b, Bablu Prasad c, Deepak M. Maurya d, Madhu Kumari e,
Mika Sillanpää f, Kumar Suranjit Prasad a, *
a
Centre of Environmental Science, Institute of Interdisciplinary Studies, University of Allahabad, Prayagraj, Uttar Pradesh, India
b
National Forensic Sciences University (NFSU), Gandhinagar, Gujarat, India
c
Department of Environmental Studies, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara, India
d
Department of Geology, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara, India
e
Department of Botany, B.R.A. Bihar University, Muzaffarpur, Bihar, India
f
Department of Biological and Chemical Engineering, Environmental Engineering, Universitetsbyen 36, 8000 Aarhus C, Denmark

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

Keywords: Antibiotic traces in household and industrial effluents have a harmful influence on the ecosystem as well as on
Antibiotics human health. Antibiotic resistance in microorganisms arises because of inadequate antibiotic removal by
Biochar conventional treatment processes. This study investigatesthe sorption of ciprofloxacin (CF) and doxycycline (DC)
Wastewater treatment
antibiotics, from an aqueousenvironment by modified wood biochar of commonly found tree species Syzygium
Ciprofloxacin
cumini L. The elemental, porosity and functional group involvement have been studied using Scanning Electron
Doxycycline
Adsorption Microscopy (SEM), Energy Dispersive X-ray (EDX), Fourier Transform Infrared (FTIR) and Brunauer-Emmett-
Teller (BET) analysis. The BET surface area was found to be 16.93 m2 g− 1, pore volume and pore sizes were
0.018 cm3 g− 1 and 42.30 Å, respectively. The maximum percent of removal of antibiotics was found to be
96.23% and 96.90% for doxycycline and ciprofloxacin, respectively. The equilibrium data weretested for fit
using Langmuir and Freundlich models. Inboth cases, the Langmuir model suited the data wellwitha maximum
adsorption capacity of 4.32 and 4.25 mg g− 1 for doxycycline and ciprofloxacin, respectively. The data indicated
the spontaneous and exothermic behavior of adsorption.Regeneration of the spent adsorbent up to ten cycles of
continuous sorption followed by desorption showeda small decrease in sorption up to 3.55% for DC and 2.85%
for CF. The biochar could be usedas an adsorbent for treating pharmaceutical effluents as well as municipal
sewage wastewater.

1. Introduction pharmaceutical effluents. Thus, exposure to these active residues of

antibiotics exerts pressure on the microbial ecosystem and increases the
It has long been known that antibiotics are used to treat illnesses survival rate for resistant strains by rendering existing antibiotics inef­
caused by bacteria, and they are also widely employed in animal fective in the treatment of a wide variety of rapidly evolving contagious
farming [1]. According to recent studies, the occurrence of different diseases [4]. Thedevelopment of a powerful and durable adsorbent is an
classes of antibiotics in the water system is reported in various parts of effective method for removing polluting antibiotics from wastewater.
the world including Indian subcontinents [2]. The rapid rise in antibiotic The adsorption method is simpler,cost-effective, and easy to use with a
use in recent years has resulted in the development of antibiotic resis­ negligible generation of any other secondary pollutants [5]. Recently,
tance genes, posing a potential risk to human and aquatic ecosystem several adsorbents such as CuO nanoparticles [6], Microporous Erionite-
security [3]. Approximately 40–90% of the administered dose is activated carbon composite [7], iron nanoparticles with magnesium
excreted as un-metabolized active residues, which then reached to the hydroxide shell [8], Fe3O4–MoO3-AC nanocomposite [9], and reduced
ecosystem through the untreated discharge of domestic and graphene oxide [10] are developed that shows high potential for

* Corresponding author.
E-mail addresses: [email protected] (A. Srivastava), [email protected] (H. Dave), [email protected] (B. Prasad), dmmaurya@
yahoo.com (D.M. Maurya), [email protected] (M. Kumari), [email protected] (M. Sillanpää), [email protected] (K.S. Prasad).

https://doi.org/10.1016/j.inoche.2022.109895
Received 14 April 2022; Received in revised form 2 August 2022; Accepted 17 August 2022
Available online 22 August 2022
1387-7003/© 2022 Elsevier B.V. All rights reserved.
A. Srivastava et al. Inorganic Chemistry Communications 144 (2022) 109895

Fig. 1. SEM images of ISCBC biochar(a) showing surface topography. EDAX study (b) shows the presence of different elements.

antibiotic removal but high cost and complicated process limited their 2.2. Adsorption, analysis of DC and CF, pHZPC, and desorption
application.Bio-Char is the ideal material for pollutant removal from
water as they have some advantageous physical and chemical surface Inthe batch adsorption experiment,modified biochar ISCBC was
morphology, including a large surface area and high porosity [11]. It is a examined for simultaneous removal of both antibiotics from an aqueous
cost-effective and eco-friendly adsorbent as it can be made by pyrolyzing solution. In a conical flask, a specific mass of adsorbent wasmixed with
various waste biomass sources such as garden waste, agricultural waste, 100 ml of a known concentration solution and agitated at 200 rpm. The
kitchen waste, and other bio-degradable waste [12]. Various studies residual concentration of antibiotics in the supernatant was determined
have already shown that metallic modification of biochar can improve using high-performance liquid chromatography (HPLC) instrument
pollutant removal capacity [13]. Chang et al. modified the surface of (Metrohm AG) with Metrosep C18 AQ column.The percentage removal
corn cob with sodium alginate and phosphoric acid to make biochar, and of antibiotics was investigated as a function of initial antibiotic con­
the results revealed that the adsorption capacity of the modified biochar centration (10–50 mg L− 1), biomass dosage (0.25–2 g/L), pH (4.5–9),
was increased [14]. Diclofenac, Ibuprofen and Naproxen removal have and contact time (15–60 min). A desorption procedure was carried
been studied on a hydrochar obtained from leaves of Saccharum rav­ outusing 0.1 NaCl containing 5%, 10% 15%, and 20% acetonitrile.
annaeand Saccharum oficinarum [15]. Atugoda et al have reported bio­ Striping solution 50 ml was added to exhaust adsorbent and agitated for
char prepared from seaweed thatwas further modified by zeolite using 30 min. The point of zero charges (ZPC) was estimated by following the
the slurry method. The modified adsorbent showed promising results procedure by Banerjee [21] and Bakatullah et al. [22]. Furthermore, the
against the removal of ciprofloxacin where electrostatic and hydrogen thermodynamic parameters were determined by conducting an
bonding interaction takes place between the surface of the adsorbent adsorption experiment at temperatures (28, 32, 36, 42, and 50 ◦ C) using
and the zwitterionic form of ciprofloxacin [16]. Orthophosphoric acid- 1 g of adsorbent in 100 ml of antibiotic (10 mg L− 1) solution. The pH of
modified activated banana stalk (BSAC) has been used for the sportive the antibiotic solution was adjusted by the use of 0.1 N HCl and 0.1 N
removal of ciprofloxacin [17]. Zinc modified activated biochar obtained NaOH. The removal efficiency and removal capacity (qe in mg− 1) for
fromAzolla filiculoides fern (ACAF) has been used for the removal of antibiotic adsorption were determined from the following equation:
ampicillin from an aqueous solution [18]. Similarly, Fan et al. investi­
Ci− Ce
gated the adsorption of various types of antibiotics by modifying sewage %Sorption = × 100 (1)
Ci
sludge with iron, manganese, and aluminum [19].This study reports a
sorptivebehavior of iron modified biochar (ISCBC) under various ( )
mg Ci − Ce
experimental conditions for the removal of two antibiotics e.g. doxy­ qe = ×V (2)
g M
cycline and ciprofloxacin in batch mode.
The desorption was calculated using the equation below:
2. Material and methods Cd
PercentageDesorption(%) = × 100 (3)
Ca
All of the reagents used in this study were analytical grade, and the
antibiotics doxycycline hyclate (DC) and ciprofloxacin (CF), 98% HPLC Cais adsorbed ions while Cd is amount of desorbed ions.
grade, were purchased from Merck in India.
2.3. Biochar characterization
2.1. Biochar preparation
Prepared biochar’s characterization was performed by using SEM
Biochar was produced from the dried stem of Syzgium cumin L. by a (Philips, Netherlands) with system EDAX XL-30, operating at 15–25 KV,
process described in Srivastava et al. 2021 [20]. Briefly,the dried to examine the surface morphology.A surface area analyzer (ASAP 2020,
biomass (50 g) was initially soaked in a 200 ml solution of 100 mM FeCl3 Micromeritics, USA) was used to obtain various physical attributes of
for 24 h. The biomass was further dipped into 200 ml of reducing so­ prepared adsorbents. Involvements of functional groups of ISCBC during
lution ((NaOH 5 g L− 1 and NaBH4 5 g L− 1) for 1 h. After draining the sorption were determined using anFTIR (Fourier transform infrared)
solution, the wood biomass was dried. The biomass obtained in this way spectrometer (Nicolet 6700, Thermo Scientific, MA, USA).
was pyrolyzed using a muffle furnace at 600 ◦ C for one hour followed by
grinding fine powder.

2
A. Srivastava et al. Inorganic Chemistry Communications 144 (2022) 109895

group was also found to be overlapped with increase or decrease in its

absorbance after formation and modification of biochar. Furthermore,
the –OH stretching vibrations at around 3400 cm− 1 are subsequently
changed after biochar modification that might be attributable to the
complexation, hydrogen bonding, protonation and the overlap of amino
group peak [25]. Upon comparing the three spectra modification of
biomass during pyrolysis was evident as stretching, bending of different
functional groups and ionic vibration occurred at various wave numbers
[20].
Additionally, Fig. 3 shows the Brunauer-Emmett-Teller (BET) plots
used to evaluate the surface area of the iron-loaded biochar.The
adsorption of nitrogen gas on the biochar at 120 ◦ C was used to calculate
the BET constant, C by following equation:
( )
1 C− 1 P 1
[( Po )] = + (4)
Q P− 1 Qm C Po Qm C

Where Saturation pressure is represented by Po, while equilibrium

pressure is represented by P. Q represents the amount of gas adsorbed on
the adsorbate, Qm represents monolayer adsorbed, and C represents the
Fig. 2. A comparative FT-IR spectra of raw wood (a) biochar (b) and ISCBC
BET constant. Fig. 3a shows a BET plot of adsorbed volume against
biochar (c).
relative pressure. According to IUPAC nomenclature, the isotherms were
of type IV (Sharma and Jha, 2017). The porous character of the biochar,
3. Result and discussion
which is typical of mesoporous materials, was demonstrated by the type
IV type curve.The value of the BET constant was found to be 82.65. The
3.1. Characterization by SEM, EDX,FT-IR and BET
total surface areawas obtainedfrom the equation:

The surface morphology of ISCBC was observed using SEM. Fig. 1(a) Qm
Stotal = Ns (5)
revealed a heterogeneous surface with irregular projections of the ma­ V
terial. The elemental profile obtained by EDAX is shown in Fig. 1(b),
where N is the Avogadro number and V is the volume of the adsorbed
which revealed the presence of iron, carbon, oxygen, sodium, and cal­
gas. The surface area was found to be 16.93 m2 g− . The cumulativepore
cium as an integral part of prepared biochar.
volume and pore size wereobtained from Fig. 3b. The values were found
The FTIR analysis was performed for the raw biomass, biochar, and
to be 0.018 cm3 g− 1 and 0.018 cm3g− 1, respectively.
iron-loaded biochar. The result of the data is shown in Fig. 2. A peak
around 1100 cm− 1 and 3400 cm-1is assigned to C–C and O–H bonds,
respectively [23]. The vibration peak of O–H was considerably changed 3.2. Effect of experimental conditions
when biochar was prepared from the raw biomass while a transition in
the peak was observed in iron-loaded biochar. Similarly, Peaks observed At varied concentrations of adsorbate ranging from 10 to 50 mg L− 1
around 1000 cm− 1 increased after iron functionalization of biomass, at adsorbent dosage, 2 g/L, pH 7.0 for 60 min at RT (Fig. 4a).The
indicatingthe bending vibration of the C– – O bond. The distinct IR findings revealed that the elimination efficiency of both antibiotics was
spectral bands in the fingerprint region around 600 cm− 1 can are high at lower concentrations96.40% and 95.80% for CF and DC,
attributedto the ionic vibration due to the incorporation of Fe in the respectively. A little change in antibiotic adsorption with 96.53% and
char.Meanwhile, some spectral bands in the region between 0 and 1000 95.82% of efficiency for CF and DC respectively was observed when the
cm − 1 in biochar showed overlapping with those of iron modified bio­ adsorbent dosage is greater than 2 g L− 1 (Fig. 4b). The maximum
char while the characteristic peaks were not detected or were over­ adsorption efficiency was found for 60 min of contact time with adsor­
lapped with spectra of raw biomass. The specific band of Fe–O around bent doses 1g L− 1 and sorbate 20 mg L− 1 for 60 min (Fig. 4c). Initially,
600 cm− 1 was overlapped with the bands of C–H [24]. The C– –O the rate of reaction was found to be quick which might be due to less
competition for vacant sites on the surface of the ISBC adsorbent [26].

Fig. 3. BET surface area isotherm plot (a) and pore volume distribution of ISCBC (b).

3
A. Srivastava et al. Inorganic Chemistry Communications 144 (2022) 109895

Fig. 4. Effect of sorbate concentration,(a) adsorbent dosage,(b) contact time (c) onremoval efficiency of ISCBC biochar.

Fig. 5. Effect of pH,(a) and Pzpcof ISCBC biochar (b).

Both antibiotics exhibited low removal efficiencies at pH 4.5 This allows it to have numerous acid dissociation constant values (pKa).
(Fig. 5a). Furthermore, the removal efficiency was reduced at alkaline Cationic form of DC (DC+) occurs when the pH is acidic (pH < 3) while
pH, possibly due to a large concentration of OH ion bound to an active zwitterion form (DC◦ ) exists between the range of pH 3.0 to 8.0 and as
site on biochar. ZPC value of ISCBC was calculated as 7.50 (Fig. 5b). anionic form (DC- and DC2-) when the pH ranges above 7 [6]. Similarly,
Since DC contains several ionizable functional groups including alcohol, CF also exists in a zwitterion form at a neutral pH range, cationic at
phenol, and amino, it can exist as an anion, cation, or zwitterions [27]. acidic pH (<6), and as an anionic at alkaline pH (>8) [28].In an acidic

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A. Srivastava et al. Inorganic Chemistry Communications 144 (2022) 109895

Fig. 6. Langmuir (a) and Freundlich (b) isotherm models for the adsorption of antibiotics on ISCBC.

environment, the cationic species of antibiotics experience repulsive The Freundlich constant (Kf) reflects the relative adsorption capacity
forces by positively charged biochar surfaces. In the same way, the of iron-loaded biochar, and 1/n is an empirical value that denotes the
surface of the biochar at an alkaline pH becomes filled by OH ions, intensity of adsorption [31]. In general, the adsorption capacity of the
reducing drug adsorption. As a result, neutral pH may be advantageous adsorbent rises as the Kf value increases. Itwas further demonstrated that
for antibiotic adsorption [29]. n ranged between 1 and 10, suggesting effective adsorption (Fig. 6b).
The standard error of estimate that confirms the best fitting is used to
3.3. Isothermal modeling examine the applicability of isotherm models for experimental data
analysis from Eq. (9).
The Langmuir and Freundlich models are the most commonly used. √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
√∑
According to the Langmuir model, adsorption takes place on a surface. √n
√ ⌊(qe )theo − (qe )exp⌋
2

Homogenous surface with regions of equivalent permeability and effi­ SEE =

√i=1
(9)
ciency, resulting in the generation of an adsorbate monolayer on the n’ − p’
material’s surface that saturates the pores and inhibits the migration of
molecules [30]. where qe(theo) and qe(exp) are the estimated and observed data respec­
The following formula can be used to definea non-linear expression tively. n’ is the number of experimental measurements, and p’ is the
of the Langmuir isotherm. number of parameters, therefore (n’-p’) is the degrees of freedom.The
goodness of fit between experimental data and isotherm model is
Ce
q e = q m KL (6) considered where accuracy increases as the value approaches zero
1 + KL Ce
[32,33].
qm is the adsorbent’s monolayer sorption capacity (mg g− 1) and KL is According to the best fitting of the data and higher correlation co­
the adsorption energy (L mg− 1). In both cases, a high correlation coef­ efficient R2, Langmuir’s assumption of adsorption of DC and CF onto
ficient indicates strong agreement between experimental and projected biochar is applied well. The n values obtained in the present study are
data using the Langmuir equation. The maximum adsorption capacity better or equivalent to other reported adsorbents.The lowest standard
fordoxycycline (4.32 mg g− 1) was found to be slightly greater than error of estimate for the adsorption of DC and CF further supported
ciprofloxacin (4.25 mg g− 1) (Fig. 6a).The isotherm shape can be cate­ Langmuir isotherm as a best fittedmodel.The comparative value of
gorized by (RL), which can be estimated by the following equation. different parameters of the two isotherms is presented in Table 1. the
1 lowest standard error was reported Biochar from water hyacinth was
RL = (7) studied for the removal of ciprofloxacin where maximum adsorption
1 + KL Ci
was found to be 2.71 mg g− 1 [34] while modified montmorillonite was
The estimated RL values for DC and CF are 0.053 and 0.044, reported with 1.15 mg g− 1 for the adsorption of CF [35]. Similarly,
respectively, which are less than one and larger than zero, indicating chitosan carbonbeads doped with iron oxide showed comparatively
favorable adsorption.The Freundlich model suggests that adsorption is lower adsorption capacity (4.18 mg g− 1) for the removal of doxycycline
hardly ideal and reversible and that it takes place via the development of from an aqueous solution [36].
a multilayer of analyte onto a non-uniform heterogeneous surface. The
non-linear expression of isotherm is given as follows

qe = Kf Ce1/n (8)

Table 1
Comparative values of the parameters calculated for doxycycline and ciprofloxacin removal by equilibrium models.
Langmuir Isotherm Freundlich Isotherm

Contaminant Qm (mg/g) R2value KL (L/mg) SEE Kf (L/mg) R2 Value 1/n Value SEE

CF 4.25 0.937 0.80 0.166 1.64 1.47 0.25 1.33

DC 4.32 0.972 0.97 0.03 0.898 0.912 0.28 0.09

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A. Srivastava et al. Inorganic Chemistry Communications 144 (2022) 109895

Fig. 7. Adsorption kinetic models for antibiotics uptake (3a) pseudo-first-order model for DC and CF (3b) pseudo-second-order model for DC and CF.

Table 2
Kinetic parameter obtained for adsorption of doxycycline and ciprofloxacin onto ISCBC biochar.
Pseudo First Order Pseudo Second Order
− 1 2
Contaminant K1 (min ) R value qe (mg/g) SEE K2 (g mg-1min− 1) R2 Value qe (mg/g) SEE

CF 0.045 0.879 1.877 0.08 0.027 0.951 2.10 0.007

DC 0.047 0.945 1.866 0.017 0.030 0.9926 2.15 0.012

3.4. Adsorption kinetics

The adsorption kineticsfor both the (DC and CF) antibiotics were­
investigatedfrom two models. A non-linear expression namely pseudo-
first-order and pseudo-second-orderis shown in Eqs. (7) and (8)
respectively [37].
( )
qt = qe 1 − e− kt (10)

k2 q2e t
qt = (11)
1 + k2 qe t
The slope and intercept of the plot have been used to deduce kinetic
parameters, shown in Fig. 7a,b, and Table 2.With better correlation
coefficient (R2) and lowest SEE, the adsorption of antibiotic adsorption
on modified biochar is likely to be kinetically governed by pseudo-
second-order reaction, similarly,the rate constant (K2) suggested that
doxycycline adsorbs at a faster rate than ciprofloxacin[3839]. Moreover,
the fitted model also supports a chemisorption mechanism where
possibly electrostatic interaction is involved. Fig. 8. Plot of ln KD Vs. 1/T for the estimation of thermodynamic parameters
for adsorption of DC and CF. Experimental conditions were. 2 g L− 1 adsorbent,
100 mg L− 1 of TC concentration in 50 ml solution, pH 7 buffered with phos­
3.5. Thermodynamic analysis phate buffer.

The effect of temperature and thermodynamic parameters were

Table 3
evaluated to further understand the adsorptive behavior of antibiotics
Thermodynamic parameters at various temperatures for the adsorption of
on the surface of iron-loadedbiochar. Antibiotic absorption was antibiotics.
observed to increase slightly with increasing temperature, showing that
Temperature (in CF DC
adsorption of both antibiotics on the adsorbent surface was preferred at
Kelvin)
higher temperatures. The change in standard free energy, enthalpy, and =ΔG (KJ/mol) ΔG (KJ/mol)
◦ ◦

entropy of adsorption wascalculated using the formulae below. 301 − 0.089 ΔH ¼53.63 J/
◦
− 0.058 ΔH ¼45.57 J/
◦

305 − 0.605 mol − 0.286 mol

ΔG◦ = − RTlnKD (12) 309 − 1.933 ΔS ¼ 178.6 J/
◦
− 1.491 ΔS ¼151.3 J/
◦

313 2.815 mol 1.910 mol

The temperature is T, while the universal gas constant is R (8.314 J
− −
323 − 3.884 − 3.342
mol− 1 K− 1). KD (qe/Ce) represents the distribution coefficient for the
adsorption process [40].
According to the van’t Hoff equation:

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A. Srivastava et al. Inorganic Chemistry Communications 144 (2022) 109895

Fig. 9. A proposed mechanism of adsorption of DC and CF (a) and desorption by various concentration of acetonitrile, i.e. 5–20% in 0.1.N NaCl solution.

( ◦) ( ◦)
ΔS ΔH DC and CF antibiotics is presented in Fig. 9a. The result of desorption of
lnKD = − (13)
T RT CF and DC using different concentrations of acetonitrile in 0.1N NaCl is
presented in Fig. 9b.Results showed that binary mixture of the eluent
The slope and intercept of the plot of lnKDversus 1/T were used to
was able to strip DC (95.62 %) and CF (97.38%). The continued
determine the ΔH◦ and ΔS◦ that are displayed in Fig. 8. Table 3 lists the
desorption up to ten cycles, there were a decrease in 3.55% of DC and
thermodynamic parameters that were calculated.The magnitude of
2.85% in CF adsorption. Sodium and chloride ions could compete with a
change in Gibbs free energy (ΔG◦ ) for both antibiotics examined (DC and
cationic and anionic form of antibiotic while the organic phase of
CF) was found to be negative at all temperatures, suggesting the spon­
acetonitrile was responsible for breakage of binding due to hydrophobic
taneous and feasible nature of the reaction [41]. The enthalpy of
interaction and π bonding.
adsorption (ΔH◦ ) was calculated using slope and was found to be 45.57 J
mol− 1 for DC and 53.63 J mol− 1 for CF.Similarly, the positive magnitude
5. Conclusions
of enthalpy indicates the endothermic nature of sorption for tempera­
tures ranging from 28 to 50 ◦ C, whereas the entropy of the reaction was
The prepared iron-loaded biochar, ISCBC wasstudied for the removal
determined by the intercept of the graph, which yielded a positive value
of two antibiotics, namely doxycycline, and ciprofloxacin from an
for both the antibiotics and suggested an increase in randomness at the
aqueous solution of defined concentration. The adsorption follows the
solid–liquid interface.
Langmuir isotherm where monolayer adsorption capacity for DC and CF
was found to be at optimum condition. The kinetic model, on the other
4. Mechanism of adsorption and desorption
hand, might be well represented by the pseudo-second-order model.The
high loading capacity of ISCBC i.e.qmis greater than previously reported
The Pseudo-second-order kinetic and thermodynamic analysis pro­
antibiotics. Similarly, thermodynamic parameters revealed the sponta­
vide the best correlation favoring the chemisorption nature of adsorp­
neous, feasible, and exothermic nature of adsorption where entropy
tion, which might be due to the involvement of hydroxyl ions present on
increases at the reaction surface.Characterization by SEM, EDX, and
the surface of the adsorbent. The method through which antibiotics
FTIR has shown the physico-chemical properties of the adsorbents. The
molecules adsorb onto various proposed adsorbents has long been dis­
main mechanism of adsorption was electrostatic and π-π interaction
cussed. In the present study, the adsorptive behavior of antibiotics
between the adsorbent and aromatic rings of the adsorbate.Desorption
greatly depends on the pH that applied its effect through changing the
of studies suggested that adsorbent can be regenerated by washing with
adsorbent surface charge and affecting its structure. Similarly, antibi­
0.1 M NaCl in 20% acetonitrile. Since, reports of adsorption of emerging
otics are organic compounds having zwitterionic behavior at neutral pH.
contaminants e.g., antibiotics like DC and CF in aqueous solution are
The dominant species of CF were cations (CF+) and zwitterions (CF±)
scanty, thus iron-modified biochar ISCBC can be seen as an ideal agent
with a solution pH between 3 and 9 [42]. Likewise, doxycycline exists in
for removal of antibiotics and similar molecules from pharmaceutical as
dominant amphoteric species around neutral pH while positively and
well as municipal effluents.
negatively charged species at acidic and alkaline pH respectively [43].
The adsorption of CF molecules onto the surface of the adsorbent could
Declaration of Competing Interest
be explained through H bonding, anion-exchange, and iron- π bonding.
The –NH groups from the CF molecules and hydroxyl groups from ISCBC
The authors declare that they have no known competing financial
resulted in the formation of hydrogen bonds between them. In addition,
interests or personal relationships that could have appeared to influence
the presence of fluoride in the structure of ciprofloxacin could assist the
the work reported in this paper.
ion-exchange mechanism with hydroxyl ions present on the surface of
the adsorbent at neutral pH. Another possible mechanism is electrostatic
Data availability
interaction where positively charged cat-ions interact with a negatively
charged electron cloud of π- systems[44]. Similarly, adsorption of DC
Data will be made available on request.
occurred via acomplexation where an aromatic ring of DC interacts with
the metal ion at the surface of ISCBC while electrostatic attraction favors
adsorption by cation–anion interaction between adsorbate and adsor­ Acknowledgment
bent[45]. A diagrammatic overview of possible ways for adsorption of
KSP would like toexpress a deep sense of gratitude to the different

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A. Srivastava et al. Inorganic Chemistry Communications 144 (2022) 109895

scientific staff of the center of environmental science, University of for residual ampicillin in pharmaceutical wastewater, Biomass Convers.
Biorefinery 2021 (1) (2021) 1–13, https://doi.org/10.1007/S13399-021-01962-4.
Allahabad, India, for facilitating this research work.
[19] X. Fan, Z. Qian, J. Liu, N. Geng, J. Hou, D. Li, Investigation on the adsorption of
Funding. antibiotics from water by metal loaded sewage sludge biochar, Water Sci. Technol.
The authors declare that no funds, grants, or other supports were 83 (2020) 739–750, https://doi.org/10.2166/wst.2020.578.
received during the preparation of this manuscript. [20] A. Srivastava, H. Dave, S.K. Azad, M. Kumari, S. Karwal, P. Karma, P. Tiwari, K.
S. Prasad, Iron Modification of biochar developed from tectona grandis linn. F. for
adsorptive removal of tetracycline from aqueous solution, Anal. Chem. Lett. 11 (3)
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