Chemosphere 281 (2021) 130676

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Mechanistic interaction of ciprofloxacin on zeolite modified seaweed

(Sargassum crassifolium) derived biochar: Kinetics, isotherm
and thermodynamics
Thilakshani Atugoda a, Chaminda Gunawardane b, Mahtab Ahmad c, Meththika Vithanage a, *
a
Ecosphere Resilience Research Center, Faculty of Applied Sciences, University of Sri Jayewardenepura, Nugegoda, Sri Lanka
b
National Institute of Post Harvest Management, Jayanthi Mawatha, Anuradhapura, Sri Lanka
c
Department of Environmental Sciences, Faculty of Biological Sciences, Quaid-i-Azam University, Islamabad, 45320, Pakistan

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

Handling Editor: Derek Muir Modification of biochar for efficient removal of antibiotics from water could be a valuable approach in the
environmental applications. In this study, a brown seaweed (Sargassum crassifolium) was pyrolyzed at 500 ◦ C and
Keywords: the obtained biochar (SWBC) was modified with zeolite through the slurry method maintaining the ratio at 1:5
Composite (zeolite: biochar) (SWBC-Z). Batch adsorption experiments were conducted to evaluate the adsorption tendency
Antibiotics
of SWBC and SWBC-Z for the removal of ciprofloxacin (CPX) from water via pH edge, kinetics, isotherm and
Surface chemistry
thermodynamic experiments. The highest adsorption was in the pH range of 6.5–8, supported by the electrostatic
Clay minerals
Sorption attractions and hydrogen bonding with zwitterionic CPX. Experimental kinetics data was well-fitted to the
pseudo-second-order and Elovich models (R2 of 0.992 and 0.976, respectively), while the Langmuir and
Freundlich isotherm models best described the isotherm data (R2 of 0.954 and 0.976, respectively). The
maximum adsorption capacity of 93.65 mg g− 1 was recorded for the SWBC-Z. The models predicted chemi­
sorption and physisorption interactions on the heterogenous biochar surface. Well-defined peaks of silanol
groups in the FTIR spectrum of SWBC-Z and its electron microscopy confirmed the incorporation of zeolite
minerals. Post adsorption FTIR analysis elucidated the changes in the surface functional groups of the SWBC-Z.
Thermodynamic data revealed spontaneous and exothermic reaction between CPX and both the biochars. It was
concluded that modification of pristine biochar with zeolite imparted greater surface area and additional active
sites, which subsequently enhanced the overall CPX adsorption by the SWBC-Z.

1. Introduction (Li et al., 2019). Removal efficacy and ability of biochar are purely
dependent on its physical and chemical properties controlled by the
Biomass has been employed as an essential component in sustainable feedstock source and the pyrolysis conditions (Weber and Quicker,
development such as carbon sequestration, renewable energy resource 2018b).
and production of bio-based chemicals and materials. Recently, biomass The exploitation of land-based biomass as feedstock for energy
is transferred to energy by employing thermochemical techniques such generation has diverted the focus towards other alternative sources such
as hydrothermal carbonization and pyrolysis, which under limited ox­ as seaweeds. Over 1000 species of seaweeds marine algae around the
ygen produce a solid byproduct known as biochar (a carbonaceous globe grow in fresh and marine aquatic environments. Seaweed serves as
material). Carbonaceous materials are proven to have high porosity, an attractive renewable bioresource due to its high production rates,
large surface area, rich carbon content and high cation exchange ca­ easy cultivation and economic viability (Ahmed et al., 2019a; Sudhakar
pacity, making them the most studied adsorbents as an alternative to the et al., 2018). Marine biomass is expected to be utilized as a low-cost
traditionally used activated carbon (Xiang et al., 2019). In this context, adsorbent to manage various environmental contaminants, such as
biochar has been recently explored for its potential of remediating both heavy metals and dyes, in wastewater (Ok et al., 2020). However, sea­
the inorganic and organic contaminants present in soil and wastewater weeds as bio sorbents for organic contaminant removal such as

* Corresponding author.
E-mail address: [email protected] (M. Vithanage).

https://doi.org/10.1016/j.chemosphere.2021.130676
Received 2 November 2020; Received in revised form 14 April 2021; Accepted 21 April 2021
Available online 4 May 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
T. Atugoda et al. Chemosphere 281 (2021) 130676

pharmaceuticals have rarely been reported in wastewater. nitrogen containing wastewater (Abedi and Mojiri, 2019; Guo et al.,
Fluoroquinolones (FQ) are listed in third place as the most commonly 2020).
prescribed antibiotics accounting for 17% of the global market (Hamad, Hence, zeolite-modified Sargassum sp. derived biochar was evaluated
2010). Discharge of untreated hospital and municipal wastewater, for its CPX adsorption efficiency with relevance to its unmodified
humans and animal excreta (applied as urban waste sludge or animal counterpart. The physical characterization of both modified and pristine
manure as fertilizer) are pathways that introduce FQ antibiotics into biochar was carried out through proximate and ultimate analyses, FTIR
environment (Parente et al., 2019). Misuse of the drug and partial spectroscopy, BET surface area and SEM imaging. Batch adsorption
metabolism in the body has led to the ubiquitous presence of antibiotics experiments in terms of pH edge, kinetics, and isotherm experiments
in the soil and water, especially from hospitals, industry, domestic and were done to evaluate the thermodynamic feasibility and mechanism of
livestock wastewater discharges (Yi et al., 2017). Ciprofloxacin (CPX) the adsorbent interaction with CPX.
has been frequently detected in wastewater effluent, which has become
an essential emerging contaminant very recently. Antibiotic concen­ 2. Materials and methods
trations are found in minute levels typically <1 μg L− 1 but have been
recorded to have reached up to 31,000 μg L− 1 in the pharmaceutical 2.1. Material and chemicals
industrial effluents (Larsson et al., 2007). Conventional treatment sys­
tems utilized in wastewater treatment plants (WWTP) in most devel­ Ciprofloxacin hydrochloride monohydrate was obtained from
oping countries cannot eliminate antibiotics to safer limits; thus, HIMEDIA Laboratories, India. For pH adjustments, 0.1 M HNO3 and 0.1
residues are being continuously discharged into the surface waters. Most M NaOH were used. All chemicals, including zeolite, were of analytical
pharmaceuticals are difficult to remove by using conventional waste­ grade, obtained from Sigma-Aldrich.
water treatment methodologies due to the hydrophilic nature and
relatively long half-life in the environment, enabling them to persist and 2.2. Algal biochar preparation
accumulate in harmful levels (Dong et al., 2013). Thus, alternative
strategies such as biological processes, sand filtration, adsorption, Seaweed (Sargassum crassifolium) biomass was collected from the
advanced oxidation process, catalytic techniques, nano/membrane southern coast, Koggala, Sri Lanka and was washed thoroughly with
filtration and sedimentation have been employed, although their overall distilled water to remove salt impurities and dried in air for 2 days. Dried
performance is frequently challenged (Hu et al., 2019; Xu et al., 2017). biomass was crushed and pyrolyzed in a muffle furnace (Nabertherm,
For instance, although some techniques like advanced oxidation process Germany) at a temperature of 500 ◦ C for 2 h with a 7 ◦ C min− 1 rate of
and membrane filtration have shown excellent removal efficiencies, the increasing temperature. Unlike woody biochar sea weed biochar does
economic viability is very low due to high cost and potential toxic sec­ not have high lignocellulose biomass and high temperature could cause
ondary pollutants can emerge (Dalrymple et al., 2007). In comparison, ash formation. Therefore, an intermediate temperature (500 ◦ C) was
adsorption techniques are simple, cheap, produce less toxic byproducts selected to avoid ash formation as well as to secure the physicochemical
and environmentally friendly (Afzal et al., 2018). properties of the biochar at its best performance. The resulted seaweed
This study aims to evaluate the adsorption performance of seaweed biochar (SWBC) was crushed using a mortar and pestle until fine par­
biochar derived from Sargassum crassifolium to remove CPX antibiotics ticles were obtained.
from aqueous media. Sargassum sp. is classified as a brown macroalga
with a fiber-like structure and the matrix is embedded with various 2.3. Biochar modification
polysaccharides and relatively large amounts of essential elements (N, S,
P, Ca, Mg, Na, Fe). The heterocyclic carbon skeleton of seaweeds gives a For biochar modification, the impregnation method was adopted.
unique characteristic to its derived biochar matrix (Kumar et al., 2020). Specifically, zeolite (0.5 g) was mixed with 100 ml of deionized water
However, seaweed-derived biochar is reported to exhibit relatively low and allowed to stir for 3 h. To the zeolite suspension, SWBC (2.5 g) was
surface area, unlike woody biochar, which contains high lignocellulosic added and kept stirring overnight. Prepared slurry was centrifuged and
matter (Parsa et al., 2019). Studies have been recently emerging on dried in air to obtain the zeolite modified biochar (SWBC-Z).
enhancing the surface area of algal biochar through compositing with
clay minerals. Clay minerals comprise of high specific surface area, high 2.4. Biochar characterization
cation exchange capacity, and porous structure and these properties of
clay minerals can be implanted into the seaweed biochar matrix (Sewu Surface morphology of the pristine (SWBC) and modified (SWBC-Z)
et al., 2019). Zeolite is a well-known, low-cost silicate clay mineral with biochars were analyzed by the Field Emission Scanning Electron Mi­
an open 3D framework structure united of silicon-oxide tetrahedral croscopy (FE-SEM) at 15 kv. The samples were dried, grounded and
[SiO4] and aluminum-oxide tetrahedral [AlO4]. The structure contains placed on a sample stub and sputter-coating with gold. The Fourier
various channels, cages, and cavities allowing ions and molecules to Transform Infrared-Attenuated Total Reflectance (FTIR-ATR) spectros­
mobile in and out of the structure. The large pores are interconnected in copy (Thermo scientific NICOLET iS10 FTIR Spectrometer, USA) was
multiple ways forming channels that are selective upon the size of the performed in the range of 550–4000 cm− 1 with 64 repetitive scans and a
molecules, which are therefore known as “molecular sieves” (Zendelska resolution of 4 cm− 1. Characterization was carried out for both SWBC
et al., 2018). Although wide metal-organic frameworks (MOF) are poor and SWBC-Z samples before and after CPX adsorption. The CPX adsor­
in stability, zeolites are considered stable under ambient environmental bed SWBC-Z was obtained from the residue in the isotherm study at the
conditions (Heard et al., 2020). Over the past years, studies have re­ highest initial CPX concentration. The suspension was filtered and the
ported the prominence of using MOF along with biochar, where zeolite solid was dried before analysis. Proximate analysis (including moisture,
was found to be one of the widely used MOF’s to improve the physico­ volatile matter, resident matter and ash) was carried out in the furnace.
chemical properties of biochar (i.e. surface area, ion exchange capacity, Ultimate analysis was carried out with a PerkinElmer 2400 Series II
functionality, etc.) (Weber and Quicker, 2018a). In combination, bio­ CHNS Analyzer for C, H, O, N determination for well-powdered samples
char and zeolite can perform synergistically to overcome their draw­ after vacuum drying. The specific surface area, pore volume and pore
backs in isolation (Mosa et al., 2020). Biochar-zeolite composites have size of both adsorbents was determined using the Brunauer-Emmett-
been promising as soil amendments to immobilize and stabilize inor­ Teller (BET) method using N2 gas sorption analyzer (NOVA-1200,
ganic and organic contaminants in soil and also by improving soil Quantachrome Corp., Boynton Beach, FL, USA). The Powder X-ray
fertility and health (Shahbaz et al., 2019; Zheng et al., 2020). Further­ diffraction (PXRD) analysis was done through Rigaku, Ultima IV (Japan)
more, biochar-zeolite composites are well effective in treating high diffractometer using Cu Kα line at 1.54 A◦ as the radiation source at 40

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T. Atugoda et al. Chemosphere 281 (2021) 130676

kV and 40 mA. The 2θ angle was set at 3◦ to 80◦ with a scanning rate of Table 1
2◦ min− 1. Isotherm and kinetic equations and parameters.
Models Parameters Equations
2.5. Analytical techniques Kinetic models
Pseudo first Qt = sorption capacity (mg g− 1) Qt = Qe(1 − (2)
The filtered samples were analyzed for CPX using a Thermo Scientific order time t e− k1t )
10S UV–Vis spectrophotometer at the wavelength 276 nm with quartz Pseudo second Qe = equilibrium concentration (mg Q2e k2 t (3)
Qt =
cell of 1 cm path length. Ultrapure water was used as the blank solution order g− 1) 1 + Q2e k2 t
during the analysis. Control experiments were carried out simulta­ k2 = rate constant (g mg− 1 min− 1)
Elovich a = adsorption rate constant (mg 1 (4)
neously, giving the same conditions except for biochar. All the experi­ Qt = ln(ab) +
g− 1 min− 1) b
ments were performed in triplicates to minimize errors. b = Elovich constant (g mg− 1) 1
ln t
b
Isotherm models
2.6. Batch adsorption experiments Freundlich Kf = Freundlich adsorption Qe = Kf Cne (5)
coefficient (L g− 1)
2.6.1. Effect of pH Langmuir n = Freundlich isotherm exponent Qmax bL Ce (6)
Qe =
Qmax = maximum adsorption 1 + bL Ce
A suspension of SWBC and SWBC-Z was prepared at a dosage of 0.5 g capacity (mg g− 1)
L− 1 in separate flasks. In each flask initial CPX concentration was Temkin bL = Langmuir coefficient (L mg− 1) RT (7)
Qe = ln(AT Ce)
maintained at 10 mg L− 1. The pH of the mixture was adjusted in the Ce = equilibrium concentration (mg b
range of 3–9 using 0.1 M HCl or NaOH and at each pH samples were L− 1 )
R = gas constant (J mol− 1kg− 1)
withdrawn into separate vials. All the samples were kept to reach
Redlich Peterson T = absolute temperature (K) K r Ce (8)
equilibrium for 12 h at a speed of 150 rpm in a horizontal shaker at room AT=Temkin equilibrium binding
Qe =
1 + aCbe
temperature (25 ◦ C). After recording the final pH, all the samples were constant
filtered and the collected filtrate was analyzed for CPX. b = heat of adsorption (J mol− 1)

2.6.2. Kinetics experiment

temperature (K), R is the universal gas constant (8.314 × 10− 3 kJ K− 1
Sorption kinetics were performed with an initial CPX concentration
mol− 1) and K is the Langmuir constant or thermodynamic equilibrium
of 10 mg L− 1 and a biochar dosage of 0.5 g L− 1. The pH was maintained
constant (Gokulan et al., 2019). Other parameters were calculated using
between 6 and 8, derived from the pH edge experiment. Samples were
the following equation:
withdrawn at time intervals of 10, 20, 30, 45 min, 1, 1.5, 2, 4, 6, 8, 20
and 24 h and filtered. The filtrate was analyzed for CPX by the UV–Vis ΔG = ΔH − TΔS (10)
spectrophotometer.
where ΔH is the change in enthalpy (kJ mol− 1) and ΔS is the entropy (kJ
2.6.3. Isotherm and thermodynamics experiment mol− 1 K− 1).The values for ΔH and ΔS were obtained from the slope and
Sorption isotherm experiment was carried out with varying CPX the intercept, respectively from the graph plotted ln K vs. 1/T.
concentrations ranging from 2.5 to 150 mg L− 1, maintaining the pH 6–8 ΔS ΔH
at room temperature (298 K) at the same adsorbent dosage. After 12 h of lnK = − (11)
R RT
equilibrium time sample filtrate was collected to analyze for CPX. In
order to derive thermodynamic parameters, the isotherm experiments 3. Results and discussion
were repeated at temperatures 308 and 318 K.
Kinetic and isotherm data were modeled and the parameters were 3.1. Biochar characteristics
determined using Origin 8.0 statistical computer software.
3.1.1. Surface chemistry
2.7. Data modeling The FT-IR transmittance spectra of the pristine algal biochar and the
modified biochar are presented in Fig. 1. In the SWBC spectrum, the
2.7.1. Equilibrium sorption capacity broad band at 3445 cm− 1 represents the –OH stretching vibration of the
The amount of CPX sorbed onto adsorbents was calculated by the hydroxyl groups from alcohol, phenols, organic acids, and N–H
mass balance equation as below: stretching vibration of amides. The aliphatic C–H stretching of methyl
and methylene groups are shown at 2922 and 2851 cm− 1 (Bird et al.,
(Cο − Ce )
Qe = (1) 2012). The peak at 1634 cm− 1 corresponds to the C– – O asymmetric
m
stretching of –COOH or –CONH and N–H primary amine stretching vi­
where Qe (mg g− 1) is the equilibrium sorption capacity, Co and Ce (mg bration (Chen et al., 2018). The bending vibration of the aromatic C––C
L− 1) are initial and equilibrium aqueous phase CPX concentrations, bond and the C– O symmetric stretching are attributed to the trans­
–
respectively, and m (g L− 1) is the dosage concentration of biochar. mittance peak at 1456 cm− 1 (Zhang et al., 2020). The C–O bond vi­
bration is assigned to 1115 cm− 1 peak representing alcohols, esters,
2.7.2. Sorption kinetic and isotherm models ethers, and phenols (Ahmed et al., 2019a; Parsa et al., 2019). The C–H
Experimental kinetics and isotherm data were analyzed using non- vibrations of the poly-substituted aromatic ring are shown at 880 cm− 1
linear curve fitting models represented in Table 1. (Kumar et al., 2020). Low-intensity peaks between 650 and 1000 cm− 1
arise due to the =C–H out of plane bending of alkenes for aromatic
2.7.3. Thermodynamic calculations deformations (Han et al., 2020b; Mohamed et al., 2017) and the small
Thermodynamic parameters were calculated by conducting adsorp­ peak at 665 cm− 1 exhibits the C–Br stretch and the presence of thio­
tion isotherms at different temperatures. The standard free energy was phenic sulfur (Ahmed et al., 2019a; Zhao et al., 2018).
calculated by the following equation, using the equilibrium constants. A broad band at 3445 cm− 1 shows the free adsorbed water by zeolite
while the discrete band indicates the –OH deformation vibration modes
ΔG = − RT lnK (9) of the water molecule at 1644 cm− 1 (Abidin et al., 2017). The charac­
teristic bands of the aluminosilicate tetrahedral lattice (SiO4 or AlO4),
where, ΔG is the free energy change (kJ mol− 1), T is the absolute

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T. Atugoda et al. Chemosphere 281 (2021) 130676

Fig. 2. PXRD pattern of (a) SWBC and (b) SWBC-Z.

modernite mineral peaks in the 2θ range of 5–35 in the XRD pattern of

SWBC-Z (Kustovska, 2018; Mustain et al., 2014). Peaks at 9.95 and
22.21 show the characteristics peaks for clinoptilolite, the abundant
mineral in zeolite (Mansouri et al., 2013). Furthermore, the 2θ = 26.7
Fig. 1. FTIR spectra of zeolite, pristine biochar (SWBC), modified biochar represents the presence of quartz in zeolite as an impurity (Rahmayani
(SWBC-Z), ciprofloxacin (CPX) treated SWBC-Z and CPX. et al., 2020).

the zeolite structural unit, lies between 1200 and 600 cm− 1. Asymmetric 3.1.2. Surface morphology
vibrations of the Al–O(Si) and Si–O(Al) bonds in the lattice appeared at The surface morphology of the SWBC and the SWBC-Z is illustrated
the 976 cm− 1 together with the Si–OH bending vibration between 1050 in Fig. 3. After pyrolysis, the surface of the SWBC seems to be rough and
and 1200 cm− 1 (Sanaeepur et al., 2014; Zide et al., 2018). Other sig­ irregular due to the breakdown of biomaterial in the seaweed. Irregular
nificant bands at 750, 668 and 560 cm− 1 are ascribed to symmetric folds and ridges on the biochar provide an extended surface to interact
stretching of Si–O–Al, a six-membered ring of the alumino and with adsorbate molecules (De Bhowmick et al., 2018). Granular-like
silico-oxygen tetrahedral and Si–O–Si symmetric stretching, respectively particles in the fresh biomass are destructed during pyrolysis and
(Abidin et al., 2017; Mansouri et al., 2013). The incorporation of min­ become deposited as irregular particles on the surface (Song et al.,
erals taken place within the SWBC matrix is well defined by the com­ 2019). It is well noted that biochar derived from algal biomass does not
bination peaks arising at 1102 and 988 for the internal vibrations of the form a porous structure on the surface, unlike biochars derived from
Al, Si tetrahedral structure in the spectrum of SWBC-Z. Minor peaks in woody biomass, where the pores are well defined and unique (Ahmed
the region of 800-500 cm− 1 further confirm the presence of zeolite. et al., 2019b; Yakub et al., 2015). Biochar derived from apple tree wood
Several regions in the FTIR spectrum of CPX adsorbed SWBC-Z showed in Kim et al. (2020) exhibited by typical fiber cells, vessels and large
peak shifting, broadening and intensity lowering concerning the CPX pore spaces. In the case of seaweed-derived biochar, the original
free SWBC-Z (Ahmed et al., 2019a). The –OH band has shifted to 3423 biomass structure is subjected to vast transformation upon temperature,
cm− 1 and broadened due to the hydrogen bonding between CPX mole­ whereas in woody biochar, the feedstock structure is fully retained (Yu
cules and the SWBC-Z. The C– – O symmetric peak at 1425 cm− 1 et al., 2017b). Micropores can be barely seen on the surface due to low
decreased significantly compared to the pristine SWBC in the SWBC-Z, carbonization and low lignin and cellulose components in the algal
along with a shift towards a lower wavenumber. Peak shifting of the biomass.
C–O bond was shown from 1104 to 1102 cm− 1 with a broadening on the In contrast, Sargassum japonica and Sargassum fusiform by Poo et al.
surface of CPX adsorbed SWBC, indicating the occurrence of n- π in­ (2018) had honeycomb like structures which was not visible with the
teractions. The Al–O(Si), Si–O(Al) and Si–OH bands shifted to 1104 and particular seaweed in this study. It is confirmed that pore widening and
1000 cm− 1 with low intensities, displaying molecular interactions be­ formation could increase as the pyrolyzing temperature increases (Han
tween the SWBC-Z and CPX. et al., 2020a). In the SWBC-Z, the crystalline phases of the zeolite can be
Sharps peaks were observed in the XRD pattern for SWBC, indicating seen randomly deposited on the biochar surface. The high resolution
the crystalline mineral components in seaweed-derived biochar SEM image of the SWBC-Z indicates somewhat well-defined octahedral
compared to lignocellulose biochar (Fig. 2). This is further confirmed by crystalline characteristics. The mineral structures are scattered on the
the absence of peaks in the 2θ = 16 and 22◦ range, assigned for aromatic biochar surface and embedded in the ridges on the surface and the pore
carbon from residual cellulose (Kim et al., 2011; Liu et al., 2012). The channels. This might have resulted in pore hindering exhibited by the
presence of inorganic salt is depicted by the precipitated mineral phases reduced pore volume in the BET results.
such as calcite, halide, and sylvite on the biochar matrix (Keerthanan
et al., 2021). The single intense peak at 28.4◦ for KCl represents the 3.1.3. Surface area
typical characteristics of seaweed-derived biochar, followed by repeti­ Surface area and porosity are the principal physical characteristics of
tive peaks at 40.5, 50.1, 58.6 and 66.33◦ (Yu et al., 2017a). biochar influencing the sorption of contaminants. Table 2 summarized
The high amount of potassium present in seaweed contributes to BET surface area, pore volume and mean pore size of the pristine SWBC
greater ash yield, which is further confirmed by the proximate analysis and the modified SWBC-Z. The pristine biochar had a low specific sur­
(Milledge et al., 2015). Peaks at 27.4, 30.5, 31.6, 45.4 and 56.5◦ face area (13.372 m2 g− 1), which is characteristic of seaweed-derived
correspond to NaCl mineral presence (Kyriakou et al., 2019). The in­ biochar. In previous studies, seaweed biochar has been reported to
fluence of zeolite in the composite is well-represented clinoptilolite and have low BET surface area than that derived from lignocellulose

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T. Atugoda et al. Chemosphere 281 (2021) 130676

Fig. 3. SEM images of (a and b) SWBC at magnification × 3.00 k and × 10.00 k, respectively, (c and d) SWBC-Z at magnification × 1.50 k and × 5.00 k, respectively.

SWBC are shown in Table 3. High alkalinity (pH 10.41) was shown by
Table 2
SWBC due to the formation of metal and alkali metal hydroxides during
BET surface area, pore volume, mean pore size and pH pzc of pristine SWBC and
pyrolysis. The volatile matter (32.38%) was relatively higher than
modified SWBC-Z.
resident matter (10.00%), indicating its susceptibility to biodegradation
Sample BET (m2/ Pore volume Mean pore size Zero point charge and less stability, which could be attributed to soft biomass of algae with
g) (cm3/g) (nm) (pHpzc)
low lignin contents. However, the volatile matter in SWBC is lesser than
SWBC 13.372 4.116 9.150 1.2 other woody biochars because of the low lignin content in seaweeds,
SWBC- 124.359 2.104 4.994 1.0
yielding low carbon mass (Parsa et al., 2019). The total ash content
Z
(54.99%) was significantly higher than the rest of the components due to
the accumulation of inorganic salts in biochar.
biomass. For example, Parsa et al. (2019) discovered that the surface In contrast to lignocellulose biomass, seaweeds are typically
area of biochar derived from seaweed was 320 times less than pine enriched with macro-minerals such as Na, Mg, Ca, K, S, and P, which
sawdust-derived biochar. The breakdown of lignocellulose cellular consequently involved in greater ash content in the Sargassum sp. bio­
structures and dehydration of the biomass during carbonization pro­ char utilized in this study (Choi et al., 2017). Produced ash can catalyze
moted porous structures in the material extending its surface. Since the volatilization and destruction of the cellulose and hemicellulose
seaweed contains mainly cellulose and trehalose and a low amount of structure of the seaweed during char formation (Fakayode et al., 2020).
lignin, the formation of micropores during pyrolysis is reduced (Choi The biochar yield was 38.1%, which is regarded to be higher than the
et al., 2017). As the pyrolysis temperature increases, volatilization and woody biochar production.
thermal breakdown of compounds intensifies, giving rise to a range of Unlike woody biochars, seaweeds derived biochar contained low
pores extending from nano, micro to macro sizes (Li et al., 2017). carbon content (35.28%) due to the lack of lignocellulosic compounds in
Moreover, the ash content correlates negatively with the biochar surface the seaweed biomass. The pyrolysis temperature promotes dehydration
area due to the deposition of molten ash in the pores (Ronsse et al., and deoxygenation during the pyrolysis, drastically reducing hydrogen
2013). All these factors favor pore hindering in the SWBC, thereby and oxygen-containing groups (Ahmad et al., 2013; Weber and Quicker,
drastically reducing the pore volume, pore size and surface area. How­ 2018a). However, nitrogen (1.66%) is higher in the seaweed biochar
ever, the incorporation of zeolite in the SWBC-Z increased its surface
area by 9 folds with respect to the pristine SWBC. In contrast, the
average pore volume and the mean pore size have been reduced by 50% Table 3
in the SWBC-Z. This might attribute to the pore blockage caused by the Proximate analysis, yield and ultimate analysis of seaweed biochar.
filling of zeolite mineral particles in the mesopores (2–50 nm) of the Proximate analysis Ultimate analysis
SWBC (Ahmad et al., 2019a, 2019b). Thus, zeolite imparted high surface pH 10.41 C (%) 35.28
area in the SWBC-Z due to the higher specific surface area and high Moisture (%) 2.62 H (%) 1.96
porosity associated with it (Sun et al., 2017). Volatile matter (%) 32.38 N (%) 1.66
Resident matter (%) 10.00 O (%) 6.39
Ash (%) 54.99 Molar H/C 0.06
3.1.4. Proximate and ultimate properties Yield (%) 38.10 Molar N/C 0.06
The proximate and elemental analyses depict the physicochemical Molar O/C 0.18
properties of the biochar. Results of proximate and ultimate analysis of Molar (N + O)/C 0.24

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T. Atugoda et al. Chemosphere 281 (2021) 130676

because of nitrogenous compounds such as proteins and amino acids in ±

and biochar becomes prominent due to strong electrostatic attraction
the biomatrix. with the biochar surface achieving the maximum adsorption by SWBC
The H/C, O/C and N/C ratios are essential parameters for deter­ and SWBC-Z (Song et al., 2019). The attraction with the SWBC-Z be­
mining the aromaticity and the surface functionality of the biochar. comes prominent during the particular pH range due to both positive
Increasing the pyrolysis time and temperature can decrease the car­ and negative silanol groups on the surface. In alkaline conditions (pH >
boxylic, hydroxyl, and amino groups, leading to low H/C, O/C and N/C 8.7), the biochar surface and the zeolite surface become negative,
ratios (Li et al., 2017). The H/C ratio was as low as 0.06, indicating the generating repulsive forces between the anionic CPX and as a result, the
high surface aromaticity of the produced SWBC due to the fusion of the adsorption is declined.
ring structures (Ahmad et al., 2013). The polarity index denoted by the
surface hydrophilicity is exhibited by the O/C (0.18) and the (O + N)/C 3.3. Sorption kinetics
(0.24) ratios. The removal of oxygen was promoted with ash formation,
resulting in such low polarity index (Zhang et al., 2020). Thus, the ul­ The kinetic studies shown, determines the effect of contact time on
timate and proximate analysis indicates that the SWBC was highly ar­ the adsorption of CPX on SWBC and SWBC-Z. At the initial time, the
omatic and comprised of less polar functional groups on the surface. sorption process is vigorous as the biochar surface is abundant with free
actives sites that could be taken up by CPX molecules easily. As the re­
3.2. Influence of pH on sorption of ciprofloxacin action proceeds, the unoccupied active sites reduce drastically,
restricting the solution and solid’s adsorption rate to attain the steady
The pH of a system plays an essential role in the adsorption phe­ state subsequently. Both the SWBC and SWBC-Z reached equilibrium
nomenon. It was observed that both SWBC and SWBC-Z displayed within 5 h. The adsorption data were modeled by the non-linear fitting
similar adsorption trends at pH range of. The CPX adsorption gradually of pseudo first order, pseudo-second-order and Elovich models to
increased with the rising pH, achieving consistent adsorption between elucidate the possible mechanism associated with the process. Accord­
pH 6.5 and 8 (Fig. 4). However, the SWBC-Z exhibited much greater ing to regression co-efficient (R2) and statistical parameters (SSE)
adsorption capacity (21.43 mg g− 1) than the pristine SWBC (14.12 mg pseudo-second order and Elovich models fitted best with the kinetic data
g− 1) at pH 6.5–8. The surface charge potential of the biochar surface and (Table S1) and therefore sorption processes for CPX by SWBC and SWBC-
the speciation of CPX molecule can elucidate such adsorption behavior. Z with CPX were well described using these two models. The pseudo-
In previous studies, Sargassum sp. derived biochar had pHpzc less than 3 second-order model assumes that the rate-limiting step of the adsorp­
(Song et al., 2019). The experimental pHpzc obtained for pristine biochar tion process is governed by chemisorption, which involves covalent
from Sargassum crassifolium and the composite was between pH 1–2, bonding through sharing or exchanging electrons between the adsorbent
indicating that both SWBC and SWBC-Z surfaces are negatively charged and the adsorbate. Similarly, the Elovich model assumes multilayer
above pH 2. In addition to that, the pHpzc of zeolite is 8, where it remains chemisorption and external mass transfer on a heterogeneous substrate
positive below pH 8 due to protonation of the silanol groups (≡Si–OH+ 2) surface (Lyubchik et al., 2016). Hence, both these models best describe
(de Sousa et al., 2018; Saadi et al., 2020). Hence, the surface negativity that the sorption of CPX on SWBC and SWBC-Z occurs through chemi­
is slightly reduced in SWBC-Z due to the positive charge rendered by the sorption. It is evident that the surface functional groups of the biochar
zeolite. Ciprofloxacin inherits amphoteric properties and, therefore, surface can promote interaction with ionic moieties of CPX molecules
depicts two dissociation constants i.e. pKa1 = 6.1 and pKa2 = 8.7 (Atu­ through valency forces. In SWBC-Z, adsorption of CPX is elevated as the
goda et al., 2020). At very low pH the adsorption is minimum as elec­ chemical interactions are further enhanced due to the high surface area
trostatic repulsions exist with the protonated biochar surface and the and additional functional groups imparted on the pristine biochar by
CPX+. The surface of the SWBC-Z remains more positive, reducing the zeolite (Ashiq et al., 2019).
sorption drastically than the pristine biochar. The elevation of pH
transforms cationic CPX into its zwitterionic form depicting a gradual 3.4. Sorption isotherm
increase in adsorption. During pH 6.5–8.0, the interaction between CPX
The CPX concentration acts as the driving force for adsorption, which
was evaluated through the isotherm experiment. A gradual increase of
the adsorption capacity was observed when the initial CPX concentra­
tion was increased as binding sites can readily encounter the adsorbate.
Once the active sites are saturated at a particular concentration, the
adsorption remains unaffected with concentrations higher than that.
The non-linear data was simulated using the empirical isotherm models
to elucidate the adsorption behavior and fitted well with Freundlich and
Langmuir models (Fig. 5). Adsorption data of both SWBC and SWBC-Z
fitted well to the Freundlich model with >0.98 R2 values and lowest
SSE (Table 4). According to the Freundlich model, multilayer adsorption
occurs on a heterogeneous surface comprising active sites of varying
energy (Mayakaduwa et al., 2016). This implies that the physisorption
mechanism governs the CPX binding onto the SWBC and SWBC-Z sur­
faces. The n parameter of Freundlich indicates the favorability of the
reaction, which is in the case of n < 1, is favorable and n > 1, is unfa­
vorable (Keerthanan et al., 2020). Since both adsorbents had n < 1, the
adsorption process of CPX was favorable. Initially, active sites with high
energy sites are engaged with strong bonding, followed by low energy
sites with weak bonding. As the adsorption proceeds, the decrease of
binding energy allows multilayer formation on the substrate (Tang et al.,
2007). The Langmuir model represents a monolayer coverage, which
indicates that each site can be held by one adsorbate molecule on a
Fig. 4. pH-dependent adsorption of CPX by SWBC and SWBC-Z, dosage 0.5 g homogenous substrate i.e. active sites are energetically equivalent (Chen
L− 1, initial CPX concentration 10 mg L− 1 at 25 ◦ C. et al., 2018). Unlike the Freundlich model, Langmuir gives a

6
T. Atugoda et al. Chemosphere 281 (2021) 130676

affinity for CPX than the pristine SWBC.

4. Postulated sorption mechanism

Physical characteristics and adsorption models can simply elaborate

the adsorption behavior and mechanism of the adsorbents (SWBC and
SWBC-Z biochar) in this study. Graphitic nature and aromaticity can
deliver electron-rich π clouds into the biochar structure, acting as π
donors. The electron-deficient moieties of CPX (π acceptors) can interact
with biochar through π-π electron-donor-acceptor (EDA) interaction
enhancing the overall adsorption mechanism (Song et al., 2019). When
the positive charge on the CPX organocation is delocalized in the het­
erocyclic ring, interaction is explicitly known as π+− π EDA interactions.
The fluorine atom and the delocalized carboxylic groups can render
electron deficiency in the adjacent aromatic ring, thereby inducing π
acceptor properties, while the amine group renders π donating proper­
ties in the adjacent ring. At low pH the surface functional groups and
unsaturated arene groups are protonated; thus the π electron donor
interaction is at a minimum with the CPX. However, when pH increases
CPX transforms into the zwitterionic state and becomes capable of acting
as both π donor and acceptor to promote interactions with biochar
Fig. 5. Adsorption isotherms fitted to the Langmuir and Freundlich surface (Ahmed et al., 2017; Li et al., 2018b). Simultaneously hydroxyl
isotherm models.
groups in the biochar become π donors while the resonated carboxylic
groups become π acceptors. Previous studies have reported that these
Table 4
π+− π EDA interactions a have displayed a prominent role in governing
Langmuir and Freundlich non-linear isotherm parameters and coefficients of the mechanisms between veterinary antibiotics and biochar (Xiao et al.,
determination for CPX adsorption onto SWBC and SWBC-Z. 2015). Carbonyl oxygen in the biochar can involve in n- π interactions
with the aromatic ring of CPX acting as electron acceptors, which was
Model Parameters SWBC SWBC-Z
further evidenced through the FTIR peak shifting and broadening of C–O
Freundlich Kf (L mg− 1) 2.840 2.414 bond (Tran et al., 2017). Although there is a possibility of π donor-donor
n 0.462 0.646
R2 0.984 0.978
and π acceptor-acceptor interactions, their contribution is minimal for
SSE 8.686 46.598 the adsorption (Li et al., 2018a). Since the highest adsorption was ach­
Langmuir Qmax (mg g− 1) 34.403 93.654 ieved in the neutral environment and zwitterions display the greatest
b (L mg− 1) 0.023 0.010 hydrophobicity among the rest of the CPX species, the contribution of
R2 0.946 0.976
hydrophobic forces for the sorption enhancement has been significant
SSE 29.598 50.926
(Kim et al., 2020). Furthermore, the presence of polar groups such as
SSE - Sum of squared estimate of errors. carboxylic, amide, alcohols, esters, ethers, and phenol on the biochar
surface act as active sites to interact with ionic CPX electrostatically by
quantitative interpretation of the solute phase distribution between the weak Vander-Waals forces and hydrogen bonds. The nitrogen atom in
solution and the solid. The maximum adsorption (Qmax) simulated by the the aromatic ring and the heterocyclic ring of the antibiotic molecule
model for the pristine SWBC is 34.40 mg g− 1, while the SWBC-Z is 93.65 can donate the lone electron pair to the hydrogen atom of –COOH or
mg g− 1. The sorption by the SWBC-Z increased by 2.7 times than that of –OH group in the biochar matric to form Lewis acid-base interactions
the pristine SWBC, and it is evident that the amalgamation of zeolite (Ahmed et al., 2017). However, low surface area and low porosity set
improved the number of surface-active sites for CPX. Hence the restrictions on the number of active sites available on the biochar sur­
adsorption mechanism of this study exhibits a combination of chemi­ face demonstrating poor sorption capacity.
sorption and physisorption. Seaweed biochar modified with zeolite performed well for the
removal of CPX from the aqueous media. The FTIR spectrum of the CPX
3.5. Adsorption thermodynamic parameters adsorbed SWBC-Z defines the molecular interactions between the
functional groups on the biochar surface. Although no additional peaks
Thermodynamic parameters of the CPX adsorption by the biochar were observed after binding, the peak alteration was observed in the Si,
were assessed in order to investigate the reaction feasibility. All the ΔG Al crystal lattice and the biochar surface. Zeolite structure typically
values were negative, revealing the adsorption reactions between the consists of Brønsted acid sites (BAS) that comprise ≡Si–OH–Al≡ groups,
CPX and pristine SWBC (− 26.84 to − 27.44 kJ mol− 1) and SWBC-Z which can simply undergo hydrolysis, giving rise to terminal ≡Si–OH.
(− 37.37 to − 38.27 kJ mol− 1) were both spontaneous. The presence of Si–OH bonds is confirmed by the peaks arising at the
According to previous studies, 0 > ΔG > − 20 kJ mol− 1 represents 1050-1200 cm− 1 range of the FTIR spectrum (Fig. 1). The silanol group
physisorption while the − 80 > ΔG > − 400 represents chemisorption is protonated under acidic conditions (≡Si–OH+ 2 ) and deprotonated
(Han et al., 2020b). Therefore, the adsorption mechanism is directed by under alkaline conditions (≡Si–O-). As the pH reaches 6–8, the simul­
physical forces. The ΔH determines the adsorption process’s energy taneous number of ≡Si–O- groups and zwitterionic CPX increase
transfer; a negative value indicates that the reaction is exothermic and a (CPX+/-), enhancing attractive electrostatic forces and forming
positive value indicates that the reaction is endothermic. The ΔS reflects hydrogen bonds between the SWBC-Z and the polar functional groups of
the adsorbate’s affinity to the biochar’s surface, whereas the positive adjacent CPX molecules (de Sousa et al., 2018). Such interactions are
entropy indicates the solvent molecules occupied on the surface are evident through the shifting and broadening of the peaks assigned to
easily displaced by CPX molecules improving the adsorption capacity –OH, Al–O(Si), Si–O(Al) and Si–OH bonds in the mineral fraction of the
(Gokulan et al., 2019). The negative free energy and positive enthalpy SWBC-Z.
values by both adsorbents reflect that the adsorption is favorable with Sorption enhancement can be also assisted with pore diffusion into
the temperature increment, however the SWBC-Z exhibited a greater the zeolite channels accessing more active sites in the mineral

7
T. Atugoda et al. Chemosphere 281 (2021) 130676

compartment of the SWBC-Z. Micropores of zeolite are large enough Lankan coastal region, yet, it is mainly used as a raw material for in­
(0.3–1.5 nm) for CPX molecules to escape into the crystalline structure dustrial purposes as biofuel production (Thadhani et al., 2019; Widya­
(Blasioli et al., 2014). In some cases, cationic exchange interactions can ningrum, 2016). The used material, has the potential to be used as a
occur between the CPX+ and the monovalent and divalent cations pre­ feedstock for biochar, which can be further upgraded by zeolite.
sent in the crystalline zeolite structure (Sun et al., 2017). Cation bridging Developing countries have soakage pits that receive grey water
with negatively charged zeolite and COO− groups of the antibiotic was (laundry, kitchen, bath wastewater) at domestic level as an on-site
reported in a previous study (Otker and Akmehmet-Balcioglu, 2005). sanitation system (Hettiarachchi and Hettiarachaci, 2006), where
Hence, it is possible that as Ca2+ and Mg2+ are abundant in the seaweed gravel is used as a surface for the anaerobic microbes to grow, however,
matrix, anionic CPX can bind to the biochar surface through ligand there is no potential contribution for adsorption. The SWBC-Z composite
binding and such chemical bonding should be evident as new peaks produced in this study can be an excellent alternative as a porous ma­
emerging in the FTIR spectrum. More often, cationic bridging in­ terial to be used in these soakage pits to effectively treat domestic
teractions were not significant enough to impart changes in the greywater containing a wide variety of pharmaceuticals and personal
spectrum. care products. Additionally, biochar from seaweeds can be quickly
Adsorption isotherm and kinetic studies reveal that the mechanism is produced at the household level, especially in coastal regions, mixed
mainly governed by chemisorption assisted with physisorption in­ with zeolite to introduce into soakage pits which becomes a feasible and
teractions. The possible mechanisms for CPX adsorption by SWBC could cost-effective approach to remediate wastewater at the community
be π+− π EDA interactions, hydrophobic interactions, hydrogen bonding level.
and van der Waals interactions, and with zeolite modification electro­
static interactions, hydrogen bonding and cationic bridging and pore- 6. Conclusions
filling became more remarkable (Fig. 6). The surface heterogeneity of
the adsorbent supports all these interactions. The high negative value Zeolite-modified biochar developed greater adsorption affinity for
derived for Gibbs free energy further confirms the adsorption by the ciprofloxacin than the pristine biochar due to increased surface area and
SWBC-Z is spontaneous and poses a greater affinity towards CPX, which additional active sites for binding the contaminant through electrostatic
is enhanced due to the incorporation of zeolite. interactions, hydrogen bonding and cationic bridging. Adsorption
behavior was pH-dependent exhibiting maximum adsorption capacity
5. Application perspective between the pH range of 6.5–8 when ciprofloxacin was in its zwitter­
ionic form. The overall mechanism is governed by monolayer chemi­
Seaweeds are a popular food source globally, especially in Asia, and sorption at a low concentration of CPX, whereas with the increase of CPX
therefore regarded as a traditional food for centuries (Tiwari and Troy, loading, the mechanism moves towards heterogeneous multilayer
2015). The potential growth of seaweeds is very high in tropical coun­ physisorption as observed by the isotherm and kinetic data modeling.
tries due to receiving high nutrient loads (viz., nitrogen and phospho­ The ciprofloxacin reaction with both the pristine and modified biochar
rous) into the marine waters, shallow tidal zone, developed coral reefs in was spontaneous and exothermic derived by the Gibbs free energy and
the coastal region and typical warm climate (Xiao et al., 2017; Yu et al., enthalpy.
2014). Sargassum crassifolium is a brown seaweed abundant in the Sri

Fig. 6. Various mechanisms of SWBC and SWBC-Z interaction with CPX.

8
T. Atugoda et al. Chemosphere 281 (2021) 130676

Declaration of competing interest Chen, Y.D., Lin, Y.C., Ho, S.H., Zhou, Y., Ren, N.Q., 2018. Highly efficient adsorption of
dyes by biochar derived from pigments-extracted macroalgae pyrolyzed at different
temperature. Bioresour. Technol. 259 (February), 104–110. https://doi.org/
The authors declare that they have no known competing financial 10.1016/j.biortech.2018.02.094.
interests or personal relationships that could have appeared to influence Choi, J.H., Kim, S.-S., Ly, H.V., Kim, J., Woo, H.C., 2017. Effects of water-washing
the work reported in this paper. Saccharina japonica on fast pyrolysis in a bubbling fluidized-bed reactor. Biomass
Bioenergy 98, 112–123.
Dalrymple, O.K., Yeh, D.H., Trotz, M.A., 2007. Removing pharmaceuticals and
Acknowledgments endocrine-disrupting compounds from wastewater by photocatalysis. J. Chem.
Technol. Biotechnol.: Int. Res. Process Environ. Clean Technol. 82 (2), 121–134.
De Bhowmick, G., Sarmah, A.K., Sen, R., 2018. Production and characterization of a
Financial support from the Research Council for the Ecosphere value added biochar mix using seaweed, rice husk and pine sawdust: a parametric
Resilience Research Center, and the analytical support from the Instru­ study. J. Clean. Prod. 200, 641–656.
ment Center, Faculty of Applied Sciences, University of Sri de Sousa, D.N.R., Insa, S., Mozeto, A.A., Petrovic, M., Chaves, T.F., Fadini, P.S., 2018.
Equilibrium and kinetic studies of the adsorption of antibiotics from aqueous
Jayewardenepura, Sri Lanka, are acknowledged. solutions onto powdered zeolites. Chemosphere 205, 137–146. https://doi.org/
10.1016/j.chemosphere.2018.04.085.
Appendix A. Supplementary data Dong, Z., Senn, D.B., Moran, R.E., Shine, J.P., 2013. Prioritizing environmental risk of
prescription pharmaceuticals. Regul. Toxicol. Pharmacol. 65 (1), 60–67. https://doi.
org/10.1016/j.yrtph.2012.07.003.
Supplementary data to this article can be found online at https://doi. Fakayode, O.A., Aboagarib, E.A.A., Zhou, C., Ma, H., 2020. Co-pyrolysis of
org/10.1016/j.chemosphere.2021.130676. lignocellulosic and macroalgae biomasses for the production of biochar - a review.
Bioresour. Technol. 297, 122408. https://doi.org/10.1016/j.biortech.2019.122408.
Gokulan, R., Avinash, A., Prabhu, G.G., Jegan, J., 2019. Remediation of remazol dyes by
Credit author biochar derived from Caulerpa scalpelliformis—an eco-friendly approach.
J. Environ. Chem. Eng. 7 (5) https://doi.org/10.1016/j.jece.2019.103297.
Thilakshani Atugoda: Experimentation, data interpretation, data Guo, X., Cui, X., Li, H., 2020. Effects of fillers combined with biosorbents on nutrient and
heavy metal removal from biogas slurry in constructed wetlands. Sci. Total Environ.
validation, writing the first draft. Chaminda Gunawardane: Data anal­ 703, 134788.
ysis, data interpretation, data validation. Mahtab Ahmad: Data analysis, Han, X., Chen, H., Liu, Y., Pan, J., 2020a. Study on removal of gaseous hydrogen sulfide
writing-reviewing and editing. Meththika Vithanage: Conceptualiza­ based on macroalgae biochars. J. Nat. Gas Sci. Eng. 73, 103068.
Han, X., Chen, H., Liu, Y., Pan, J., 2020b. Study on Removal of Gaseous Hydrogen Sulfide
tion, supervision, funding acquisition, writing-reviewing and editing. Based on Macroalgae Biochars. Elsevier B.V.
Heard, C.J., Grajciar, L., Uhlík, F., Shamzhy, M., Opanasenko, M., Čejka, J.,
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