i An update to this article is included at the end

Environmental Nanotechnology, Monitoring & Management 15 (2021) 100440

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Environmental Nanotechnology, Monitoring & Management

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

Synthesis of oxidized Dioscorea dumentorum starch nanoparticles for the

adsorption of lead(II) and cadmium(II) ions from wastewater
Kehinde N. Awokoya *, Vincent O. Oninla *, Dolapo J. Bello
Department of Chemistry, Obafemi Awolowo University, Ile-Ife, Nigeria

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

Keywords: The search for efficient adsorbents for the treatment of wastewater has led to the exploration of derivatized
Oxidized starch starches. Here, Dioscorea dumentorum starch was isolated, oxidized and acid-hydrolyzed in a dual-modification
Dioscorea dumentorum approach. The native starch (NTS) and the resulting oxidized starch nanoparticles (Oxy-SNPs) were character­
Nanoparticles
ized by FTIR, SEM, XRD and TGA, and then applied in removing Pb2+ and Cd2+ ions from simulated wastewater.
Simulated wastewater
Heavy metals
Investigation of the functional properties of the starches as well as their characterization confirmed the success of
the modification and the suitability of the Oxy-SNPs as adsorbent for metal-ions removal. Adsorption of Pb2+ and
Cd2+ ions increased with augmentation of initial metal-ions concentration. Metal removal peaked and flattened
after 90 min. Freundlich isotherm gave a superior fitting of experimental data above the Langmuir and Dubinin-
Radushkevich (D-R) isotherms, indicating energetically heterogeneous Oxy-SNPs surface. Kinetic data followed
the pseudo-second-order model with R2 values of 0.9934 and 0.9989 for Pb2+ and Cd2+ ions, respectively,
signifying that the valency forces caused sharing or exchange of electrons during the interactions. Thermody­
namic parameter showed that the processes were feasible, exothermic and occurred with decrease disorderliness.
Energy values calculated from D-R model (35.36 kJ/mol for Pb2+; 28.87 kJ/mol for Cd2+), the good fitting of
Elovich model and the magnitude of ΔHº being <29 kJ/mol all suggest chemical adsorption.

1. Introduction
The use of starch-based adsorbents in the removal of toxic materials
from wastewater has gained more popularity in the recent years (Guo
et al., 2006). Starch is a natural polysaccharide that possesses remark­
able properties: it is abundant in nature, non-toxic, biodegradable,
renewable and cheap (Bashir et al., 2020; Parvathy and Jyothi, 2014),
properties which make it industrially attractive. However, starch, in its
native form, is highly hydrophobic, poorly soluble, susceptible to
retrogradation and possesses low tensile strength (Lewicka et al., 2015;
Bashir et al., 2020). These unfavorable properties limit its industrial
applications (Biduski et al., 2017). In order to improve the qualities of
starch to suit specific industrial applications, it is often modified by
various methods which include physical, chemical, enzymatic and ge­
netic approaches (Zia-ud-Din et al., 2017; Haq et al., 2019). Even though
native starch has been found to be unsuitable as adsorbent due to its
non-chelating and poor adsorption ability (Parvathy and Jyothi, 2014;
Haroon et al., 2016), a number of studies have revealed that modified
starches have been able to overcome these limitations and have been
utilized in the removal of toxic materials from wastewaters (Xiang et al.,
2016; Kweon et al., 2001; Alvarado et al., 2020; Hu and Du, 2019). In
chemical modification, specific functional properties are inserted into
the starch backbone. Methods used in achieving this include
cross-linking, acetylation, esterification, grafting, oxidation, acid hy­
drolysis and dual-modification (Haroon et al., 2016; Liu et al., 2014).
Oxidation approach ensures the introduction of carbonyl and carboxyl
functional groups at carbon 2, 3 and 6 regions of starch granules (Wang
and Wang, 2003; Hung et al., 2016). Therefore, oxidizing starch gran­
ules prior to acid hydrolysis, in a dual-modification approach, will
ensure the production of nanoparticles with improved functional
properties.
This report details the use of oxidized starch nanoparticles (SNPs) in
the removal of lead (Pb2+) and cadmium (Cd2+) ions from simulated
wastewater. Heavy metals pollution of water body constitutes a great
menace to the environment. Unfortunately, this problem is on the rise,
no thanks to increase in global population and industrialization (Zhao
et al., 2018). These toxic materials find their ways into the environment
via effluents from metal processing and related manufacturing

* Corresponding authors.
E-mail addresses: knawokoya@gmail.com (K.N. Awokoya), vinzoninla@daad-alumni.de (V.O. Oninla).

https://doi.org/10.1016/j.enmm.2021.100440
Received 27 October 2020; Received in revised form 4 January 2021; Accepted 9 February 2021
Available online 11 February 2021
2215-1532/© 2021 Elsevier B.V. All rights reserved.
K.N. Awokoya et al.
industries, refineries, mining operations, and other anthropogenic ac­
tivities (Chakraborty et al., 2020; Burakov et al., 2018). Due to their
persistence in nature, they readily accumulate in vital organs of the body
such as liver, kidney and brain when ingested, causing severe damages
(Kaushal and Singh, 2017). Metal ions such as Pb2+ and Cd2+ have been
implicated in diseases such as brain hemorrhage, cancer, renal failure,
bone and lung damage and sterility; in a number of birth defects and
impairment of the lung and cardiovascular system (Jaishankar et al.,
2014). The debilitating effects of their uptake has thus prompted the
need for their removal or reduction to, at lease, permissible levels in
water bodies. Methods employed in treating wastewaters include
membrane separation, chemical precipitation, reverse osmosis, ion ex­
change, coagulation and adsorption (Burakov et al., 2018; Chakraborty
et al., 2020; Adigun et al., 2020). Adsorption method has gained
popularity due to its efficiency and simple operational design. Unlike
other methods, it is cheap and does not lead to generation of sludge or
other secondary pollutants (Oninla et al., 2018). Activated carbon, clays,
zeolites, bio- and agro-based material, and carbon nanotubes (Burakov
et al., 2018; Kaushal and Singh, 2017) have been widely used as
adsorbent with encouraging results. Derivatized starches have also been
reported to possess metal chelating properties (Haroon et al., 2016).
Nanoscale starch are biocompatible and possesses high
surface-to-volume ratio, high bonding strength and dense structure,
properties that give it an edge over micron-sized starch granules (Liu
et al., 2018; Sharma et al., 2019), especially in its application as
adsorbent. Abidin et al. (2018) have reported the use of oxidized starch
nanoparticles in the removal of urea, while Liu et al. (2018) reported the
effectiveness of oxidized maize starch nanoparticles in the removal of
Pb2+ and Cu2+. According to their report, tremendous improvement in
heavy metal uptake was observed in oxidized SNPs over normal SNPs.
This research was, therefore, aimed at isolating native starch from
Bitter yam (Dioscorea dumentorum), followed by oxidation and prepa­
ration of nanoparticles of its granules for improved adsorption property.
Bitter yam and other Dioscorea spp. are edible root crops predominantly
found in the tropical region (Riley et al., 2004). Determination of the
physicochemical properties as well as qualitative characterization of
both native and modified starches were performed. The SNPs was sub­
sequently utilized in the removal of Pb2+ and Cd2+ ions from simulated
wastewater. The kinetics, isothermal and thermodynamics of the
adsorption process was investigated to fully understand the nature and
mechanism of the removal of the toxic metals.
2. Materials and methods
2.1. Materials
Bitter yam (Dioscorea dumentorum) was procured at a local market in
Oke Imesi, Ekiti State, Nigeria. All other reagents and chemicals: hy­
drochloric acid, nitric acid, sulphuric acid, sodium hypochlorite
(NaOCl), sodium hydroxide (NaOH) pellets, cadmium chloride hydrate
(98 %), hydroxylamine, CdCl2.1/2H2O and Pb(NO3)2 were purchased
from Sigma-Aldrich, Steinheim, Germany, and used as obtained. All
chemicals used were of analytical grade.
2.2. Starch isolation
Isolation of native starch (NTS) of bitter yam (Dioscorea dumentorum)
was performed according to the reported method of Liu et al. (2003),
with slight modification. The bitter yams were manually peeled, thor­
oughly washed with clean water and grated. With the addition of
distilled water, the grated sample was sieved. The shaft was further
ground and the sieving process was repeated. The resulting suspension
was allowed to settle and the supernatant was decanted. The sediment
was washed with distilled water, allowed to settle and again decanted.
The washing step was repeated, at least, twice. The starch obtained was
air dried for 48 h at room temperature, followed by constant oven drying
2
Environmental Nanotechnology, Monitoring & Management 15 (2021) 100440
at 40 ◦ C till roughly 9 % moisture content was attained (Biduski et al.,
2017). The dried starch was ground with mortar and pestle, sieved
(Awokoya et al., 2011) and then stored for further use.
2.3. Preparation of oxidized starch
Oxidation of the NTS was performed according to the method (with
slight modification) of Wang and Wang (2003). Starch paste was pre­
pared by dispersing 50 g starch in 250 mL distilled water. The pH was
adjusted to 9.0 with 2 M NaOH. 10 g NaOCl was added to the slurry and
constantly stirred for a period of 30 min at room temperature, while
maintaining a pH range of 9–9.5. The pH was controlled with 0.5 M of
either HCl or NaOH. The reaction was allowed to proceed for 10 min
after the addition of NaOCl. The pH was adjusted to 7 with 1 M H2SO4,
filtered, washed four times with distilled water and then air dried at
room temperatures for 48 h.
2.4. Synthesis of oxidized starch nanoparticles
Oxidized starch nanoparticles (Oxy-SNPs) were synthesized by acid
hydrolysis method as described by Kim et al. (2012). Briefly, 15 g of the
oxidized native starch (Oxy-NTS) was dispersed in 100 mL aqueous so­
lution of 3.16 M sulphuric acid. The dispersion was stirred for 7 days at
40 ◦ C. The suspension was centrifuged with Hitachi Eba 8 centrifuge
(Tuttlingen, Germany) at 6000 rpm for 15 min. The sediment was
washed by successive centrifugation in distilled water until neutral pH
was reached. The starch hydroxylate sediment was then freeze dried,
and the solid weight of the starch hydroxylate was measured.
2.5. Physicochemical properties of the oxidized starch
2.5.1. Carboxy and carbonyl contents determination
Carboxyl content of the starch was determined using the method
described by Parovuori et al. (1995), with slight modifications. A care­
fully weighed 5 g of the oxidized starch sample was made into a slurry in
25 mL of 0.1 M HCl with rigorous shaking for 40 min. The slurry was
filtered, and the residue was washed with distilled water until it was free
of chloride using silver nitrate test. The chloride free sample was
dispersed in 300 mL distilled water and titrated with 0.1 M NaOH to a
phenolphthalein end point. To quantify acidity due to other sources,
mainly fatty acids complexed with amylose, a blank titre was deter­
mined. Five grams of native starch were titrated to provide for a blank
value. Percentage carboxy content was determined according to Eq. (1):
(A − B) x (C) x 0.045
Percentage Carboxy = x 100 (1)
D
Where A, B, C and D connotes the sample titre, blank titre, alkali
molarity and sample weight respectively (Lawal et al., 2005).
The hydroxylamine method described by Parovuori et al. (1995) was
used for the determination of the carbonyl content, with slight modifi­
cations. A 2 g starch sample was dispersed in 100 mL distilled water and
the suspension was gelatinized by heating in a boiling water bath and
then cooled. The pH was adjusted to 3.5, and 15 mL hydroxylamine
reagent was added (the hydroxylamine reagent was prepared by dis­
solving 15 g of reagent grade hydroxylamine hydrochloride in water and
adding 100 ml of 0.5 M NaOH. The solution was made up to 300 mL with
distilled water). The sample was covered with aluminum foil and placed
in a water bath at 40 ◦ C. After 4 h, the excess hydroxylamine was
determined by rapid titration of the reaction mixture at pH 3.5 with
0.1 M HCl. The determination of the blank was similarly performed, but
only with the hydroxylamine reagent. The carbonyl content was calcu­
lated according to Eq. (2).
(A − B) x (C) x 0.028
Percentage Carbonyl = x 100 (2)
D
K.N. Awokoya et al.
Where A, B, C and D are as earlier defined.
2.5.2. Effects of temperature on swelling power and solubility
Investigation of the effects of temperature on swelling power (SP)
and solubility of NTS and Oxy-NTS were carried out as reported by
Lawal et al. (2005). A 0.1 g starch sample was digested, transferred into
a clear test tube and weighed (W1). Distilled water (10 mL) was added to
the test tube and the mixture was mixed thoroughly with a Whirlmix
mixer for 30 s. The resultant slurries were heated at varied temperature
(30–70 ◦ C) for 30 min in a thermostatic water bath, cooled at room
temperature, and then centrifuged at 6000 rpm for 15 min. The residue
obtained from the above experiment (after centrifugation) with the
water it retained and the test tube was weighed (W2). The swelling
power (SP) of the starch was calculated using Eq. (3):
Swelling power =
W2 − W1
(3)
Weight of starch
Aliquots (5 ml) of the supernatant obtained after centrifugation were
dried to a constant weight at 110 ◦ C. The residue obtained after drying
the supernatant represented the amount of starch solubilized in water.
Solubility was calculated as grams per 100 g of starch on dry weight
basis.
2.5.3. Effect of pH on swelling power and solubility
Different 1 % w/v slurries of NTS and Oxy-NTS were prepared with
distilled water and pH was adjusted to various values (pH 2–12) with
0.1 M HCl and 0.1 M NaOH. The slurries were allowed to stand for 1 h at
30 ◦ C, and then centrifuged at 6000 rpm for 15 min. The supernatant
(5 ml) was dried to constant weight at 110 ◦ C to determine percentage
solubility of the starch as stated earlier.
2.6. Characterization of the starches
The NTS and Oxy-SNPs were characterized by Fourier Transform
Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and
X-Ray diffraction (XRD). The FTIR spectra of NTS and Oxy-SNPs were
determined using Perkin – Elmer Spectrum 100 FT-IR spectrometer
Walthman (MA, USA) with an auto image system in the frequency range
4000 – 400 cm− 1; surface morphology was determined using SEM
(VEGA3 TESCAN); X-ray Diffraction were recorded using an X-ray
diffractometer (Bruker D2, Phaser DOC-M88-EXX, 155 VA-07, 2010,
Karlsruhe, Germany) using Cu tube with 1.5418(Å) radiation. Data were
recorded at a scan rate of 4O/min over a 2Ɵ range of 10O–90O.
2.7. Adsorption study
Stock solution of metal ions (Pb2+ or Cd2+) was prepared by dis­
solving accurately weighed amount of metal salt (CdCl2.1/2H2O or Pb
(NO3)2 in 1000 mL standard flask and made up to the mark with
deionized water. Required working concentrations (25–500 mg/L) were
prepared by serial dilution from the stocks. Isothermal study was per­
formed by varying initial metal-ions concentrations in the working so­
lution; kinetic study was investigated by changing contact time; while
thermodynamics study was performed by varying the process temper­
ature in batch adsorption studies. Effect of initial metal-ions concen­
tration was explored by contacting 50 mg of Oxy-SNPs with diverse
concentrations of Pb2+ or Cd2+ ions (ranging from 25 to 500 mg/L) in a
thermostatic water bath with speed controllable shaker (GFL, Burgwedel
Germany) set at 30 ◦ C. The experiment was performed without altering
the solution pH and allowed to run for 60 min. Time dependent studies
(on metal uptake by NTS and Oxy-SNPs) were investigated at room
temperature and solution pH. Agitation period was varied from 5 to
240 min; adsorbent dose and metal-ions concentrations were main­
tained at 50 mg and 50 mg/L, respectively. Experiment to check the
effect of temperature was performed at three different temperatures:
3
Environmental Nanotechnology, Monitoring & Management 15 (2021) 100440
303 K, 313 K and 323 K, with 50 mg adsorbent dose and 50 mg/L metal-
ions concentration. Agitation time was set at optimum earlier deter­
mined. After 60 min, metal-ions loaded adsorbent was recovered by
centrifugation at 6000 rpm for 10 min and the clear supernatants were
analyzed for residual metal ion concentration by Atomic Absorption
Spectroscopy (AAS).
3. Results and discussion
3.1. Carbonyl and carboxyl content in native and oxidized starch
The degree of oxidation in the Dioscorea dumentorum starch was
evaluated by determining the carbonyl and carboxyl contents of the
oxidized starch. After modification using NaOCl, the % carbonyl and
carboxyl contents were found to be 0.11 % and 0.67 %, respectively.
This clearly reveals the success of the oxidation process. Substantial
increase in carbonyl content as well as emergence of carboxyl group
have earlier been reported after oxidation of sorghum and potato
starches (Biduski et al., 2017; Fonseca et al., 2014). It should, however,
be noted that the levels of these functional groups depend on a number
of factors which include the botanical source of the starch, type of
oxidizing agent used and the modification condition (Pudjihastuti et al.,
2018). To further confirm the result obtained, FTIR analysis was carried
out on NTS and Oxy-NTS. As shown in Fig. 1, The FTIR spectra of both
starches showed broad absorption peak spanning from 3700 cm− 1 to
3200 cm− 1 and another sharp peak at 2931 cm− 1, characteristics of
hydrogen boded –OH and CH2 stretching vibration, respectively (Abi­
din et al., 2018; Wojeicchowski et al., 2018). The absorption peaks at
1639 cm− 1 in the spectrum of NTS and 1643 cm− 1 in the spectrum of
Oxy-NTS are typical of starch, attributed to –OH bending of H2O (Wu
et al., 2019). Aside slight decrease in intensity, no significant change was
observed in the absorption region of 1200–1000 cm− 1. Nevertheless, the
slight change observed could indicate the cleavage of C–O–C bond in
the glucose unit due to starch degradation (Liu et al., 2014). One major
disparity between the spectra of NTS and Oxy-NTS was the emergence of
a shoulder absorption band at 1724 cm–1, which represents the vibra­
tional band of C– – O (Kweon et al., 2001; Reis et al., 2008). This ab­
sorption band must have emerged as a result of the introduction of
carbonyl and carboxyl functional groups to the backbone of the starch
granules.
3.2. Swelling power and solubility of the starches
The swelling power (SP) which signifies the hydration capacity of the
starch under a defined condition as well as the solubility of both the
native and oxidized starch were investigated. Within 30–70 ◦ C temper­
ature range, the swelling powers and solubilities of both NTS and Oxy-
NTS increased with temperature (Fig. 2a). This phenomenon could
possibly be due to increased mobility of starch molecules, caused by
thermodynamic instability at elevated temperature, which facilitates
easy percolation of water (Lawal et al., 2005). In comparison with native
starch, oxidation in the presence of NaOCl resulted in decreased swelling
power. Depolymerization of the amylose as well as amylopectin chains
occurs during oxidation process, although amylose region is more prone
to depolymerization due to amylose linear structure and accessibility
(Fonseca et al., 2014). The reduction in swelling power of the starch
after modification, therefore, could be as a result of disintegration or
fragmentation of the internal structure of the starch granules as a result
of oxidation with NaOCl, which weakens the ability of the starch in
holding or absorbing water (Wang and Wang, 2003; Sánchez-Rivera
et al., 2014). Fonseca et al. (2014) and Lawal et al. (2005) also reported
a decrease in the swelling powers of potato and hybrid maize starches,
respectively. Conversely, modification enhanced the solubility of the
starch (Fig. 2b). This may, as well, be attributed to depolymerization
which enhanced the leaching of the amorphous region of the starch upon
oxidation (Biduski et al., 2017). Liu et al. (2014) also reported an
K.N. Awokoya et al. Environmental Nanotechnology, Monitoring & Management 15 (2021) 100440

Fig. 1. FTIR spectra of (a) NTS (b) Oxy-NTS (c) Oxy-SNPs (d) Pb2+-Oxy-SNPs and (e) Cd2+-Oxy-SNPs.

Fig. 2. Effect of temperature (a), (b) and pH (c), (d) on swelling power and solubility of native and oxidized starch.

4
K.N. Awokoya et al.
increase in solubility of maize starch upon oxidation, which they
attributed to increase in mobility as a result of degradation of starch
molecules, as well as introduction of hydrophilic carboxyl group. This
submission is in agreement with the report of Wang and Wang (2003),
who attributed enhanced solubility of corn starch upon oxidation to
better hydration due to introduced functional groups. The pH effect on
swelling power and solubility of the starches are shown in Fig. 2c, d.
Result showed that, at all pHs, native starch had better swelling power
and reduced solubility, when compared with modified starch. Oxidation
of starch first results in the leaching of the amorphous region of starch,
followed by the crystalline region. This leaching process might have
influenced the phenomenon observed. As pH was increased from the
acidic medium to alkaline medium, swelling power as well as solubility
of both NTS and Oxy-NTS increased. The higher value of swelling power
and solubility observed at the alkaline range might be due to the partial
gelatinization of starch (Lawal et al., 2005).
Fig. 3. Characterization results: (a) and (b) SEM micrographs of NTS and Oxy-SNPs, respectively; (c) X-ray Diffractograms; (d) TG analysis.
5
Environmental Nanotechnology, Monitoring & Management 15 (2021) 100440
3.3. Characterization of NTS and Oxy-SNPs
3.3.1. Fourier transform infrared (FTIR) spectroscopy
The synthesized Dioscorea dumentorum starch was characterized by
Fourier Transform Infrared Spectroscopy (FTIR) with the objectives of
identifying the functional groups present at the adsorbent’s surface and
identifying those responsible for the binding of Pb2+and Cd2+ ions.
Fig. 1c–e shows the spectra of unloaded and metal ions loaded Oxy-
SNPs, where Oxy-SNPs, Pb2+-Oxy-SNPs and Cd2+-Oxy-SNPs represent
unloaded Oxy-SNPs, lead-loaded Oxy-SNPs and cadmium-loaded Oxy-
SNPs, respectively. The spectrum of Oxy-SNPs (c) shows absorption
bands at 3417 cm− 1, which is less broad, compared to the spectra of
native starch (a) and oxidized starch (b). This band within the range of
3500–3200 cm− 1 has been attributed to –OH group stretching of starch,
resulting from intra-molecular and inter-molecular hydrogen bonding
(Liu et al., 2016; Ahmad et al., 2020). The vibration peak at 2926 cm− 1 is
characteristic of C–H group of starch (Pereira et al., 2013). The strong
band at 1706 cm− 1 emanated from the stretching vibration of C– – O (Reis
et al., 2008), apparently from the oxidation of native starch, while the
K.N. Awokoya et al.
peak at 1622 cm− 1 indicates bending vibration of tightly bound –OH of
water molecules in the nanoparticles (Liu et al., 2016; Ahmad et al.,
2020). Several other apparent absorbances were observed, among which
are the peaks at 1172 cm− 1 and 1028 cm− 1, characteristics of asym­
metric C–O–C and C–O vibration (Pereira et al., 2013; Wu et al.,
2019). Upon adsorption of Pb2+ and Cd2+ ions, different spectra were
obtained. The –OH stretching vibration band became more intense and
shifted to 3419 cm− 1 in the spectra of Oxy-SNPs loaded with both metal
ions. This possibly suggests metal-ions/hydroxyl interaction. This
assertion was buttressed by the shift of –OH bending vibration at
1622 cm− 1 to 1620 cm− 1 and 1616 cm− 1 in the spectra of
Pb2+-Oxy-SNPs and Cd2+-Oxy-SNPs, respectively. The position of the
C–H absorption peak remain unchanged, although more intense after
metal loading. The intensity of the C–– O absorption band at 1705 cm− 1
increased sharply, also indicating the probability of C– – O acting as a
binding site for both Pb2+ and Cd2+ ions. Visible vibrational band shifts
and decrease in intensities were noticed in the absorption peaks in the
region of 1300–1000 cm− 1, and up to the fingerprint region after metal
uptake, confirming interactions of the metal ions with the surface
functional groups of Oxy-SNPs.
3.3.2. SEM characterization of surface morphology
The structural morphologies of native starch and oxidized starch
nanoparticles (Oxy-SNPs) were studied by scanning electron microscopy
(SEM) in order to investigate possible morphological changes as a result
of oxidation and subsequent synthesis of nanoparticles. The SEM images
of both NTS and Oxy-SNPs are shown in Fig. 3(a, b). The granules of
native starch were asymmetric and irregular in shape, but largely
polygonal, smooth edged (Ahmad et al., 2020) and clustered. Moreover,
part of the granules seems wrapped in a jelly-like folding. The
morphology of the NTS granules were somewhat similar to those re­
ported by Valcárcel-Yamani et al. (2013) for olluco starch granules and
Riley et al. (2006) for different varieties of Dioscorea alata cultivars. SEM
micrograph of Oxy-SNPs indicated that the surface became rough with
fragmentation of the jelly-like folding, making the clustered granules
appearing loose in a way that suggests structural disruption. The change
in the surface morphology may be attributed to the impact of
dual-modification, which include partial depolymerization as a result of
oxidation in the presence of NaOCl, that led to rupture of the α-1,4
linkages (Wojeicchowski et al., 2018). Increased roughness suggests
improved surface area (Garg and Jana, 2011) for ligand binding at the
surface of the starch.
3.3.3. X-ray diffraction (XRD)
The X-Ray diffraction pattern of NTS of Dioscorea dumentorum, Oxy-
SNPs, Cd2+–Oxy-SNPs and Pb2+–Oxy-SNPs are shown in Fig. 3c. the
diffractogram of NTS gave strong and prominent diffraction peaks, in
form of three humps, at around Bragg angle 2θ of 15◦ , 17◦ , and 23◦ , with
the strongest diffraction peak around 17◦ occurring as a doublet at 17.2◦
And 17.9◦ . This is similar to the report of Chisenga et al. (2019) and
El-sheikh (2017) on cassava and Native maize starches, respectively.
Analysis of the X-ray diffraction patterns showed that native Dioscorea
dumentorum starch exhibited type A crystallinity (Chisenga et al., 2019).
This is in agreement with the report of Riley et al. (2004) for similar
Dioscorea spp. cultivated in Jamaica; and differs from type B crystallinity
reported for most other Dioscorea spp. (Riley et al., 2004, 2006). Type A
with staggered monoclinic crystallite pattern has been reported to be
highly rich in amylopectin, while amylose content dominates type B
with open hydrated hexagonal crystallite pattern. Type C is a composite
of A and B and, like type A, it is composed of high amylopectin and low
amylose (Riley et al., 2004; Bashir et al., 2020).
Upon oxidation and subsequent acid hydrolysis, new diffractogram
revealed the disappearance of the three humps found in the XRD pat­
terns of NTS, signifying the melting of the crystalline structure to form
amorphous structure (El-sheikh, 2017). As a result of acid-catalyzed
hydrolysis, the amorphous region of starches is first destroyed. This is
6
Environmental Nanotechnology, Monitoring & Management 15 (2021) 100440
followed by the destruction of both the amorphous and crystalline re­
gions (Wu et al., 2019), hence the amorphous structure observed for
Oxy-SNPs. The sharp peaks observed in the diffraction pattern of
Pb2+–Oxy-SNPs are obviously due to the adsorption of Pb2+ ions. The
XRD diffractogram of Cd2+–Oxy-SNPs also showed few peaks, although
less intense in comparison to those of Pb2+–Oxy-SNPs. The presence of
the metal ions possibly acted as crystallite materials.
3.3.4. Thermogravimetric analysis
Thermogravimetric analysis (TGA) was performed in order to probe
the alteration in thermal properties as a result of the oxidation and
subsequent synthesis of the nanoparticles variant of the native starch. As
shown in Fig. 3d, the TG results of both NTS and Oxy-SNPs reveal weight
losses in two stages. In NTS, the first stage occurred at around
34 ◦ C–120 ◦ C, with a weight loss of about 9 %; while a similar stage
occurred at around 37 ◦ C–98 ◦ C, corresponding to about 5 % weight loss
in Oxy-SNPs result. The first stage has been attributed to dehydration
(Okoli et al., 2018; Garg and Jana, 2011). Starch is hydrophilic and thus
can absorb up to 14 wt % moisture under standard conditions (Thiebaud
et al., 1997). The lower weight loss recorded for Oxy-SNPs is an indi­
cation of lower amount of moisture in its structure when compared with
natural starch (Pereira et al., 2013). After the initial water loss, NTS
became stable up till a temperature of 230 ◦ C. The second stage of
weight loss was observed from 230 ◦ C to 370 ◦ C for the NTS sample,
corresponding to a further 74 % weight loss. This stage has been ascribed
to thermal degradation. The thermogravimetric analysis of Oxy-SNPs
showed marked increase in thermal stability of the starch. This must
have been as a result of oxidation (Lewicka et al., 2015) and subsequent
synthesis of the oxidized starch nanoparticles. Thermal degradation of
Oxy-SNPs occurred at temperatures of 320 ◦ C–430 ◦ C, corresponding to
72 % weight loss. Water is often formed by inter/intra-molecular
condensation of hydroxyl of starch, and it constitutes the major
decomposition product at temperatures below 300 ◦ C (Thiebaud et al.,
1997; Garg and Jana, 2011). However, the process of starch oxidation in
the presence of NaOCl, is known to result in primary hydroxyl groups
being oxidized to aldehyde or carboxyl groups (Lewicka et al., 2015).
This consequently leads to fewer hydroxyl groups in the modified starch
molecules when compared with native starch. The interactions of the
carboxyl, carbonyl and hydroxyl groups then lead to improved hydrogen
bonding in the modified starch (Biduski et al., 2017), thus requiring
elevated temperature for its bond disruption.
3.4. Application of OSNPs as Adsorbent
The synthesized Oxy-SNPs of Dioscorea dumentorum starch was
investigated for its potential use as an adsorbent in the removal of toxic
pollutants from wastewater. The conceivable application in the field of
adsorption was probed by utilizing the Oxy-SNPS in sequestering Pb2+
and Cd2+ ions from simulated polluted water. This study involved the
variation of the initial metal ions concentration, contact time as well as
temperature. Obtained data were fitted into various isothermal, kinetic
and thermodynamic equations in order to possibly understand the
mechanism and nature of the processes involved in the sorption of the
two metals.
3.4.1. Effect of concentration enhancement
The effects of variation of initial concentration of Pb2+ and Cd2+ ions
removal efficiency of the synthesized Oxy-SNPs of Dioscorea dumentorum
starch are depicted in Fig. 4a. The amount of metal ions adsorbed from
the simulated wastewater progressively increased with augmentation of
metal ions concentration from 25 to 300 mg/L. Within this concentra­
tion range, the amount of Pb2+ ions adsorbed onto Oxy-SNPs improved
from around 13.7–110.9 mg/g, while Cd2+ ions removal became
enhanced from around 11.8–118.8 mg/g. Beyond concentration of
300 mg/L, metal uptake slowed until near plateau profiles were ob­
tained between 400 and 500 mg/L metal ions concentration, signifying
K.N. Awokoya et al. Environmental Nanotechnology, Monitoring & Management 15 (2021) 100440

Fig. 4. Effects of initial metal-ion concentration (a) and contact time (b) on the adsorption of Pb2+ and Cd2+ onto Oxy-SNPs.

adsorption/desorption equilibrium. Every adsorbent possesses a fixed

Table 1
number of binding sites at its surface (Azouaou et al., 2010). At lower
Calculated values for isothermal and kinetic parameters for the adsorption of
concentrations, the ratio of active sites to metal ions is large, prompting
Pb2+ and Cd2+ onto Oxy-SNPs.
the uptake of near 100 % or substantial amount of metal ions in the
simulated wastewater (Naiya et al., 2009). As metal ions concentration Parameter Cd2+ Pb2+

increases, the ratio narrows until the population of the metal ions out­ Kinetic Model
numbers that of the available binding sites. Close to the point of equal Pseudo-first-order R2 0.8634 0.9466
k1 (L/min) 0.023 0.0267
population of binding sites and metal ions, uptake of metal ions slows.
qe(exp) (mg/g) 15.47 21.737
This was observed around 300 mg/L in the present study. Beyond the qe(calc) 7.596 8.6115
point of equal population, a reverse of order is usually the case: the ratio
of metal ions to active sites becomes increasingly larger with concen­ Pseudo-second-order R2 0.9989 0.9934
tration enhancement. Adsorption/desorption equilibrium possibly sets k2 (g/mg min) 0.0035 0.0019
qe(exp) (mg/g) 19.05 28.60
in around the point of equal population. In the present study, this
qe(calc) 23.33 28.30
probably occurred between 400–500 mg/L metal ions concentration.
Uptake of Pb2+ ions onto Oxy-SNPs was higher than that of Cd2+ ions at Elovich R2 0.9587 0.9446
the adsorbate concentration of 25 mg/L to <250 mg/L. Kweon et al. α 4.1445 3.6354
(2001) also reported higher uptake of Pb2+ ions compared to that of β 0.3013 0.1814
Cd2+ by succinylated corn starch. However, equilibrium Cd2+ ions up­
Weber-Morris R2 0.7827 0.8282
take was less than that of Cd2+ ions. This is possibly due to the ionic size
kα (mg/g min½) 0.865 1.489
of Cd2+, which is smaller than that of Pb2+. Due to their smaller size, C 6.507 6.804
Cd2+ ions probably move faster and as a result become energetically
more favorable to overcoming electrostatic repulsions hindering easy Isothermal model
access to the few available sites on the already overcrowded surface at Langmuir R2 0.9434 0.9411
higher concentration. kL (L/mg) 0.024 0.080
qmax (mg/g) 96.15 88.49

3.4.2. Isothermal studies of the adsorption processes Freundlich R2 0.9560 0.9874

Obtained data from concentration dependent studies were fitted into kF (L/mg) 1.204 2.254
three different isotherms to better understand the equilibrium charac­ 1/n 0.702 0.491
teristics and nature of the processes involved in the removal of Pb2+ and
Cd2+ ions by the starch-based adsorbent. Models investigated include D-R R2 0.9449 0.8105
qm (mg/g) 151.68 182.22
the Langmuir (Langmuir, 1918), Freundlich (Freundlich, 1906) and E (kJ/mol) 28.87 35.36
Dubinin-Radushkevich (D-R) (Dubinin et al., 1947) isotherms. The
linearized equations of the Langmuir, Freundlich and D-R models
applied are given as q1 = q 1KLC + q 1 , lnqe = ln kf + n1 ln Ce and that suitably described the sorption of each of Pb2+ and Cd2+ ions was
determined by the determination coefficient, R2. Table 1 shows all the
e max e max

ln qe = ln qm − βε2 , respectively. The letter, ε of the D-R isotherm

( ) isothermal parameters calculated for the sorption processes. Experi­
symbolizes Polanyi potential, which is defined as RTln 1 + C1e (J/mol), mental data appeared to fit the Freundlich model best, with R2 values of
0.9874 and 0.9560 for the removal of Pb2+ and Cd2+ ions, respectively.
while β (mol2/kJ2) represents the D-R constant. Langmuir constant is
This indicates that the sorption of the two metal ions is multilayer,
represented by KL (L/mg), while, qm or qmax (mg/g), depending on the
occurring on an energetically heterogeneous surface. The removal of Cu
model, indicates maximum metal uptake. Letter n and Kf (mg/g)
(II) ions from aqueous solution onto crosslinked amino and di­
represent the dimensionless heterogeneity factor, which is an indicator
thiocarbamates starches was also reported to fit the Freundlich isotherm
of the effectiveness of an adsorption process (Xiang et al., 2016) and
(Li et al., 2004). The values of the reciprocal of the Freundlich hetero­
Freundlich constants, respectively; gas constant, R is valued as
geneity factor for the sorption of the two metal ions were obtained as
8.314 J/mol K, while temperature is given as T (K). Linear plots of the
0.4909 and 0.7018 for Pb2+ and Cd2+ ions, respectively. Usually, 1/n
three models were made, from which their slopes and intercepts were
value <0 and <1 signifies favorable adsorption (Hu and Du, 2019). The
interpreted to obtain the values of necessary parameters. The best model
obtained values being between 0 and 1 indicate the favorability of the

7
K.N. Awokoya et al.
adsorption of the two metal ions onto the Oxy-SNPs. The value of Kf
obtained are 2.254 L/mg and 2.204 L/mg for Pb2+ and Cd2+ ions,
respectively. These values, falling within the range of 1–20, show that
the adsorption can be considered promising (Batool et al., 2018). R2
values of 0.9411 and 0.9434 were obtained for the sorption of Pb2+ and
Cd2+ ions, respectively, when modeled with Langmuir equation, while
0.9449 was obtained for Cd(II) adsorption, when modeled with D-R
equation. The values, being equally close to unity, indicate that an
adsorption process cannot be exclusively described by a single model
(Oninla et al., 2018). The Langmuir maximum monolayer Pb2+ and Cd2+
ions removal was recorded as 88.49 mg/g and 96.25 mg/g, respectively.
These values are relatively high, and comparable with the performances
of other starch-based adsorbents (Bashir et al., 2020; Liu et al., 2017).
Dubinin-Radushkevich isotherm model has been relevant in the pre­
diction of the nature of an adsorption (Batool et al., 2018). The energy, E
value is often used to determine whether a process is physical or
chemical in nature, and it is expressed as E = √1̅̅̅̅ (kJ/mol). Any E value
2β
<8 kJ/mol indicates physisorption, 8 kJ/mol < E < 16 kJ/mol implies
the involvement of ion exchange, while E value <16 kJ/mol implicates
chemisorption (Kamal et al., 2010). In the present study, E values of
35.36 kJ/mol and 28.87 kJ/mol were calculated for the sorption of Pb2+
and Cd2+ ions, respectively. The high energy values suggest the
involvement of chemisorption in the adherence of Pb2+ and Cd2+ ions
onto the surface of Oxy-SNPs of Dioscorea dumentorum.
3.4.3. Effect of contact time
In order to estimate the optimum duration of the adsorption of Pb2+
and Cd2+ ions onto the synthesized Oxy-SNPs, effect of contact time was
studied. At room temperature (≈ 28 ◦ C), 50 mg/L metal ions concen­
tration and 50 mg adsorbent dose, adsorption of the ions of the two
metals increased linearly and approached equilibrium after 60 min for
Pb2+ ions, and 30 min for Cd2+ ions. After 90 min interactions with the
surface of the Oxy-SNPs, sorption appeared steady – no significant
sorption increase was noticed. The adsorbent seemed to have more af­
finity for Pb2+ ions when the agitation time approached 60 min. No
categorical explanation has been found for this. Nevertheless, it may not
be unconnected with the geometries and electric densities of the Oxy-
SNPs and the metals involved (Kweon et al., 2001). After 60 min,
about 22.19 mg/g and 19.17 mg/g of Pb2+ and Cd2+ ions, respectively,
were observed to have been removed from the simulated wastewater.
The time dependent profiles of the adsorption of the two metals are as
shown in Fig. 4b. Prior to adsorption, an adsorbent surface is usually rich
in unoccupied binding sites, and the binding of substrates to these sites is
dependent on the operational conditions and the specific surface area of
the adsorbent (Hu and Du, 2019). At the initiation of the sorption pro­
cess, interaction of adsorbates with the adsorbent’s surface commences,
leading to gradual occupation of the binding sites by the materials to be
removed. This initial stage has been severally reported to be very fast
(Naiya et al., 2009; Oninla et al., 2018; Kamal et al., 2010; Guo et al.,
2006). The sites occupation, however, slows after the initial rapid stage
due to depletion of active sites and repulsive forces (Liu et al., 2016). A
steady-state is eventually reached, after which further contact time
extension bears no significant effect (Batool et al., 2018), which possibly
is the case as regards the present study. The charged metal ions in the
solution most probably binds with the –OH and –C– – O of carbonyl and
carboxyl group on the Carbon 6 of the glucose units on the surface of the
Oxy-SNPs. Although native starch has been reported to possess no
adsorption quality (Parvathy and Jyothi, 2014; Haroon et al., 2016), the
present result showed a measure of metal uptake. This could be attrib­
uted to slight electrostatic properties and, probably physical entrapment
of the metal ions in the aqueous medium (Kweon et al., 2001).
3.4.4. Adsorption kinetic modelling
The kinetics of the adsorption of Pb2+ and Cd2+ ions onto the syn­
thesized Oxy-SNPs was studied by modelling the adsorption data with
8
Environmental Nanotechnology, Monitoring & Management 15 (2021) 100440
the pseudo-first-order (Lagergren, 1898), pseudo-second order (Ho and
McKay, 1999), Elovich (Cheung et al., 2000) and Weber-Morris (Weber
and Morris, 1963) equations. The study of adsorption kinetics gives
insight into optimal experimental conditions, mechanism, as well as rate
determining steps (Batool et al., 2018). Linearized equation of the
models are as follows: ln (qe − qt ) = lnqe − k1 t (Pseudo-first order),
t t
q = q −
1
(Pseudo-second order), qt = 1β ln[αβ] + 1β lnt (Elovich) and
t e k q 2
2 e
qt = kα t½ + C (Webber-Morris). The amount of metal adsorbed at a
particular time is represented as qt (mg/g); k1 (min− 1), k2 (g/mg min)
and kα (mg/g min½) symbolize the first-order, second-order and
Weber-Morris intra-particle diffusion rate constants, respectively. The
desorption constant is depicted by β, intercept by C, while α (mg/g.min)
indicates initial adsorption rate. The required kinetic parameters were
determined and calculated from the slopes and intercepts of linear plots
(Fig. 5) of the equations of the various models. Among all the models,
the pseudo-second-order best described the kinetics of the adsorption of
the two metals. This was determined by comparing the determination
coefficients, R2 of the models. As shown in Table 4, Pb2+ adsorption gave
R2 value of 0.9934, while that of Cd2+ gave R2 value of 0.9989. Both
values are closest to unity. Moreover, the theoretical qe, qe(calc) and
experimental qe, qe(exp) from the pseudo-second-order equation are
closer than those obtained from pseudo-first-order. It has been estab­
lished that the closer the R2 value of a model is to unity, the better the
model is in describing an adsorption process (Oninla et al., 2018). The
fact that the sorption data best fitted the pseudo-second order indicate
that electrons were shared or exchanged as a result of valency forces
during the interaction of Pb2+ and Cd2+ ions at the surface of the
Oxy-SNPs. It also gives information about the mechanism of the pro­
cesses: chemisorption is the rate-limiting step (Adigun et al., 2020).
Elovich models is often used in predicting the surface nature and type of
adsorption. Modelling with Elovich, the R2 values obtained for the
sorption of the two metal ions are 0.9446 and 0.9587 for Pb2+ and Cd2+
ions, respectively. The closeness of these values to unity indicates that
Elovich model also gave good representations of the adsorption pro­
cesses, thus signifying that the adsorption of the two metals most
possibly took place at a surface that was heterogeneous (Cheung et al.,
2000). It also suggests the type of the adsorption as being chemisorption
(Low, 1960).
Weber-Morris model gives information about the adsorption diffu­
sion mechanism. The intercept, C values obtained are 6.8 and 6.5 mg/g
for Pb2+ and Cd2+, respectively. The deviation of these values from zero
signifies that the point of interception was not at the origin, thus
meaning that intra-particle diffusion was not the only rate-determining
step (Hu and Du, 2019). Fig. 5d shows two stages, indicating the
involvement of more than one rate-limiting step. Knowing the other
rate-limiting step(s) involved is, thus important. The magnitude of the
intercepts implicated metal ions diffusion from the bulk liquid phase to
the interaction boundary at the adsorbent’s surface (Adigun et al.,
2020), thus suggesting that both intra-particle diffusion and external
film diffusion steps were rate-determining.
3.4.5. Adsorption thermodynamics
In order to predict the feasibility of the removal of Pb2+ and Cd2+
ions by the synthesized Oxy-SNPs, estimate the type and magnitude of
heat involved and predict the direction of spontaneous change, the
thermodynamics of the removal processes was investigated. Conven­
tional equations such as ΔGo = − RT lnKc and ΔGo = ΔHo − TΔSo
o
ΔHo
were employed, from which the van’t Hoff equation, ln Kc = ΔS R − RT ,
was formulated. Plotting lnKc versus 1/T, allows the estimation of ΔH◦
(standard enthalpy change) and ΔS◦ (standard entropy change) from the
values of slope and intercept, respectively. ΔGº signifies standard Gibb’s
free energy change, while Kc represents equilibrium constant which is
valued as Kc = CCae , where Ca denotes the concentration of metal ions on
the adsorbent at equilibrium. The calculated values of the thermody­
namic parameters are presented in Table 2. The obtained negative ΔGº
K.N. Awokoya et al. Environmental Nanotechnology, Monitoring & Management 15 (2021) 100440

Fig. 5. Kinetic plots of the adsorption of Pb2+ and Cd2+ onto OSNPs; (a) pseudo-first-order (b) pseudo-second-order (c) Elovich, and (d) Weber-Morris models.

et al., 2020).
Table 2
Calculated values for thermodynamic parameters for the adsorption of Pb2+ and
3.5. Conclusion
Cd2+ onto OSNPs.
Metal ion Parameter Oxidized starch nanoparticles have been synthesized from tubers of
ΔH◦ ΔS◦ ΔG◦ an edible root crop, Dioscorea dumentorum. The percentage carbonyl and
(kJ/mol) (J/K mol) (kJ/mol) carboxyl content, coupled with the FTIR spectra obtained after modifi­
303 K 313 K 323 K cation showed the success of the oxidation process. The oxidized starch
Cd(II) − 313.784 − 0.9411 − 28.631 − 19.200 − 9.809
(Oxy-NTS) was more soluble than its native counterpart (NTS). How­
Pb(II) − 413.712 − 1.1763 − 57.291 − 45.528 − 33.765 ever, modification resulted into reduction in swelling power of the
starch. The solubility and swelling power of both starches increased with
rise in temperature and solution pH. XRD characterization of the
values for the adsorption of the two metal ions is an indication of the starches revealed the disappearance of crystal structure and formation of
feasibility and spontaneity of their removal by the synthesized Oxy- amorphous one, while SEM analysis revealed looser granules, suggesting
SNPs. The negative values of ΔGº was observed to decrease with rise structural disintegration which made the surface more porous upon
in temperature. This shows that affinity of the synthesized Oxy-SNPs for modification. Oxy-SNPs showed greater thermal stability compared to
Pb2+ and Cd2+ ions decreased with temperature rise. The decrease in NTS. Upon adsorption application, Oxy-SNPs presented itself as an
metal uptake with temperature rise may also be due to a possible high efficient adsorbent for Pb2+ and Cd2+ removal from wastewater. Its
escape tendency of metal-ions from the adsorbent’s surface to the bulk metal removal ability was enhanced with increase in initial metal-ions
liquid phase (Azouaou et al., 2010). The enthalpy changes for the in­ concentration and contact time, until adsorption/desorption equilib­
teractions were negative, connoting exothermic process. The heat rium was attained. Isothermal data followed the Freundlich isotherm
evolved during the interactions were calculated to be – 413.7 kJ/mol while kinetic data fitted the pseudo-second-order model better than all
and – 313.7 kJ/mol for Pb2+ and Cd2+ ions. These values, being other models tested. The adsorption processes were thermodynamically
<29 kJ/mol, portray the process of the removal of the two metals as feasible and exothermic in nature. Evidences from the isothermal, ki­
chemisorption (Oninla et al., 2018), thereby, complementing the find­ netics and thermodynamics of the adsorption processes portrayed the
ings from the Dubinin-Radushkevich isotherm and Elovich kinetic adsorption of Pb2+ and Cd2+ as chemical adsorption.
model. Negative values were recorded for the entropy change. This, thus
indicates that the removal process progressed with decrease in
randomness or disorderliness at the adsorbent’s surface (Chakraborty

9
K.N. Awokoya et al.
Authors’ contributions
Kehinde N. Awokoya: conceptualization, supervision, data valida­
tion and analyses, manuscript’s editing; Vincent O. Oninla: conceptu­
alization, data validation and analyses, manuscript’s preparation;
Dolapo J. Bello: experimental and data analyses. All authors approved
the final manuscript before submission.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
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.
Acknowledgements
The authors will like to appreciate the research group, Polymer
Science and Biophysical Chemistry (PSBC) research laboratory of the
Department of Chemistry, Obafemi Awolowo University, Ile-Ife, Nigeria,
for granting access to their research facilities. We also recognize Mr. M.
A. Ramoni, the dutiful departmental chief technologist and all in­
dividuals who supported the work at one stage or the other.
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 Update
Environmental Nanotechnology, Monitoring & Management
Volume 16, Issue , December 2021, Page

DOI: https://doi.org/10.1016/j.enmm.2021.100489
 Environmental Nanotechnology, Monitoring & Management 16 (2021) 100489

Contents lists available at ScienceDirect

Environmental Nanotechnology, Monitoring & Management

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

Corrigendum

Corrigendum to “Synthesis of oxidized Dioscorea dumentorum starch

nanoparticles for the adsorption of lead(II) and cadmium(II) ions from
wastewater” [Environ. Nanotechnol. Monit. Manage. 15 (May)
(2021) 100440]
Kehinde N. Awokoya *, Vincent O. Oninla *, Dolapo J. Bello
Department of Chemistry, Obafemi Awolowo University, Ile-Ife, Nigeria

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

Keywords The search for efficient adsorbents for the treatment of wastewater has led to the exploration of derivatized
Oxidized starch starches. Here, Dioscorea dumentorum starch was isolated, oxidized and acid-hydrolyzed in a dual-modification
Dioscorea dumentorum approach. The native starch (NTS) and the resulting oxidized starch nanoparticles (Oxy-SNPs) were character­
Nanoparticles
ized by FTIR, SEM, XRD and TGA, and then applied in removing Pb2+ and Cd2+ ions from simulated wastewater.
Simulated wastewater
Investigation of the functional properties of the starches as well as their characterization confirmed the success of
Heavy metals
the modification and the suitability of the Oxy-SNPs as adsorbent for metal-ions removal. Adsorption of Pb2+ and
Cd2+ ions increased with augmentation of initial metal-ions concentration. Metal removal peaked and flattened
after 90 min. Freundlich isotherm gave a superior fitting of experimental data above the Langmuir and Dubinin-
Radushkevich (D–R) isotherms, indicating energetically heterogeneous Oxy-SNPs surface. Kinetic data followed
the pseudo-second-order model with R2 values of 0.9934 and 0.9989 for Pb2+ and Cd2+ ions, respectively,
signifying that the valency forces caused sharing or exchange of electrons during the interactions. Thermody­
namic parameter showed that the processes were feasible, exothermic and occurred with increased orderliness.
Energy values calculated from D–R model (5.00 kJ/mol for Pb2+; 3.536 kJ/mol for Cd2+), the good fitting of
Elovich model and the magnitude of ΔHº being <29 kJ/mol combinedly suggest physicochemical adsorption.

1. Introduction
The use of starch-based adsorbents in the removal of toxic materials
from wastewater has gained more popularity in the recent years (Okoli
et al., 2014; Okoli and Ofomaja, 2018). Starch is a natural poly­
saccharide that possesses remarkable properties: it is abundant in na­
ture, non-toxic, biodegradable, renewable and cheap (Bashir et al.,
2020; Parvathy and Jyothi, 2014), properties which make it industrially
attractive. However, starch, in its native form, is highly hydrophobic,
poorly soluble, susceptible to retrogradation and possesses low tensile
strength (Lewicka et al., 2015; Bashir et al., 2020). These unfavorable
properties limit its industrial applications (Biduski et al., 2017). In order
to improve the qualities of starch to suit specific industrial applications,
it is often modified by various methods which include physical, chem­
ical, enzymatic and genetic approaches (Zia-ud-Din et al., 2017; Haq
et al., 2019). Even though native starch has been found to be unsuitable
as adsorbent due to its non-chelating and poor adsorption ability (Par­
vathy and Jyothi, 2014; Haroon et al., 2016), a number of studies have
revealed that modified starches have been able to overcome these lim­
itations and have been utilized in the removal of toxic materials from
wastewaters (Xiang et al., 2016; Kweon et al., 2001; Alvarado et al.,
2020; Hu et al., 2019). In chemical modification, specific functional
properties are inserted into the starch backbone. Methods used in
achieving this include cross-linking, acetylation, esterification, grafting,
oxidation, acid hydrolysis and dual-modification (Haroon et al., 2016;
Liu et al., 2014). Oxidation approach ensures the introduction of
carbonyl and carboxyl functional groups at carbon 2, 3 and 6 regions of
starch granules (Wang and Wang, 2003; Hung et al., 2016). Therefore,
oxidizing starch granules prior to acid hydrolysis, in a dual-modification
approach, will ensure the production of nanoparticles with improved

DOI of original article: https://doi.org/10.1016/j.enmm.2021.100440.

* Corresponding authors.
E-mail addresses: knawokoya@gmail.com (K.N. Awokoya), vinzoninla@daad-alumni.de (V.O. Oninla), dolapobello2013@gmail.com (D.J. Bello).

https://doi.org/10.1016/j.enmm.2021.100489

Available online 28 May 2021

2215-1532/© 2021 Published by Elsevier B.V.
K.N. Awokoya et al.
functional properties.
This report details the use of oxidized starch nanoparticles (SNPs) in
the removal of lead (Pb2+) and cadmium (Cd2+) ions from simulated
wastewater. Heavy metals pollution of water body constitutes a great
menace to the environment. Unfortunately, this problem is on the rise,
no thanks to increase in global population and industrialization (Zhao
et al., 2018). These toxic materials find their ways into the environment
via effluents from metal processing and related manufacturing in­
dustries, refineries, mining operations, and other anthropogenic activ­
ities (Chakraborty et al., 2020; Burakov et al., 2018). Due to their
persistence in nature, they readily accumulate in vital organs of the body
such as liver, kidney and brain when ingested, causing severe damages
(Kaushal and Singh, 2017). Cd and Pb were selected in this study
because of their toxicity and hazardous effects on human health. Both
metals have been implicated in diseases such as brain hemorrhage,
cancer, renal failure, bone and lung damage and sterility; in a number of
birth defects and impairment of the lung and cardiovascular system
(Jaishankar et al., 2014). The debilitating effects of their uptake has thus
prompted the need for their removal or reduction to permissible levels in
water bodies. Methods employed in treating wastewaters include
membrane separation, chemical precipitation, reverse osmosis, ion ex­
change, coagulation and adsorption (Burakov et al., 2018; Chakraborty
et al., 2020; Adigun et al., 2020). Adsorption method has gained
popularity due to its efficiency and simple operational design. Unlike
other methods, it is cheap and does not lead to generation of sludge or
other secondary pollutants (Oninla et al., 2018). Activated carbon, clays,
zeolites, bio- and agro-based material, and carbon nanotubes (Burakov
et al., 2018; Kaushal and Singh, 2017) have been widely used as
adsorbent with encouraging results. Derivatized starches have also been
reported to possess metal chelating properties (Haroon et al., 2016).
Nanoscale starch are biocompatible and possesses high
surface-to-volume ratio, high bonding strength and dense structure,
properties that give it an edge over micron-sized starch granules (Liu
et al., 2018; Sharma et al., 2019), especially in its application as
adsorbent. Abidin et al., 2018 have reported the use of oxidized starch
nanoparticles in the removal of urea, while Liu et al., 2018 reported the
effectiveness of oxidized maize starch nanoparticles in the removal of
Pb2+ and Cu2+. According to their report, tremendous improvement in
heavy metal uptake was observed in oxidized SNPs over normal SNPs.
This research was, therefore, aimed at isolating native starch from
Bitter yam (Dioscorea dumentorum), followed by oxidation and prepa­
ration of nanoparticles of its granules for improved adsorption property.
Bitter yam and other Dioscorea spp. are edible root crops predominantly
found in the tropical region (Riley et al., 2004). Determination of the
physicochemical properties as well as qualitative characterization of
both native and modified starches were performed. The SNPs was sub­
sequently utilized in the removal of Pb2+ and Cd2+ ions from simulated
wastewater. The kinetics, isothermal and thermodynamics of the
adsorption process was investigated to fully understand the nature and
mechanism of the removal of the toxic metals.
2. Materials and methods
2.1. Materials
Bitter yam (Dioscorea dumentorum) was procured at a local market in
Oke Imesi, Ekiti State, Nigeria. All other reagents and chemicals: hy­
drochloric acid, nitric acid, sulphuric acid, sodium hypochlorite
(NaOCl), sodium hydroxide (NaOH) pellets, cadmium chloride hydrate
(98 %), hydroxylamine, CdCl2.1/2H2O and Pb(NO3)2 were purchased
from Sigma-Aldrich, Steinheim, Germany, and used as obtained. All
chemicals used were of analytical grade.
2.2. Starch isolation
Isolation of native starch (NTS) of bitter yam (Dioscorea dumentorum)
2
Environmental Nanotechnology, Monitoring & Management 16 (2021) 100489
was performed according to the reported method of Liu et al. (2003),
with slight modification. The bitter yams were manually peeled, thor­
oughly washed with clean water and grated. With the addition of
distilled water, the grated sample was sieved. The shaft was further
ground and the sieving process was repeated. The resulting suspension
was allowed to settle and the supernatant was decanted. The sediment
was washed with distilled water, allowed to settle and again decanted.
The washing step was repeated, at least, twice. The starch obtained was
air dried for 48 h at room temperature, followed by constant oven drying
at 40 ◦ C till roughly 9% moisture content was attained (Biduski et al.,
2017). The dried starch was ground with mortar and pestle, sieved
(Awokoya et al., 2011) and then stored for further use.
2.3. Preparation of oxidized starch
Oxidation of the NTS was performed according to the method (with
slight modification) of Wang and Wang (2003). Starch paste was pre­
pared by dispersing 50 g starch in 250 mL distilled water. The pH was
adjusted to 9.0 with 2 M NaOH. 10 g NaOCl was added to the slurry and
constantly stirred for a period of 30 min at room temperature, while
maintaining a pH range of 9–9.5. The pH was controlled with 0.5 M of
either HCl or NaOH. The reaction was allowed to proceed for 10 min
after the addition of NaOCl. The pH was adjusted to 7 with 1 M H2SO4,
filtered, washed four times with distilled water and then air dried at
room temperatures for 48 h.
2.4. Synthesis of oxidized starch nanoparticles
Oxidized starch nanoparticles (Oxy-SNPs) were synthesized by acid
hydrolysis method as described by Kim et al. (2012). Briefly, 15 g of the
oxidized native starch (Oxy-NTS) was dispersed in 100 mL aqueous
solution of 3.16 M sulphuric acid. The dispersion was stirred for 7 days
at 40 ◦ C. The suspension was centrifuged with Hitachi Eba 8 centrifuge
(Tuttlingen, Germany) at 6000 rpm for 15 min. The sediment was
washed by successive centrifugation in distilled water until neutral pH
was reached. The starch hydroxylate sediment was then freeze dried,
and the solid weight of the starch hydroxylate was measured.
2.5. Physicochemical properties of the oxidized starch
2.5.1. Carboxy and carbonyl contents determination
Carboxyl content of the starch was determined using the method
described by Parovuori et al. (1995), with slight modifications. A care­
fully weighed 5 g of the oxidized starch sample was made into a slurry in
25 mL of 0.1 M HCl with rigorous shaking for 40 min. The slurry was
filtered, and the residue was washed with distilled water until it was free
of chloride using silver nitrate test. The chloride free sample was
dispersed in 300 mL distilled water and titrated with 0.1 M NaOH to a
phenolphthalein end point. To quantify acidity due to other sources,
mainly fatty acids complexed with amylose, a blank titre was deter­
mined. Five grams of native starch were titrated to provide for a blank
value. Percentage carboxy content was determined according to Eq. (1):
(A − B) x (C) x 0.045
Percentage Carboxy = x 100 (1)
D
Where A, B, C and D connotes the sample titre, blank titre, alkali
molarity and sample weight respectively (Lawal et al., 2005).
The hydroxylamine method described by Parovuori et al. (1995) was
used for the determination of the carbonyl content, with slight modifi­
cations. A 2 g starch sample was dispersed in 100 mL distilled water and
the suspension was gelatinized by heating in a boiling water bath and
then cooled. The pH was adjusted to 3.5, and 15 mL hydroxylamine
reagent was added (the hydroxylamine reagent was prepared by dis­
solving 15 g of reagent grade hydroxylamine hydrochloride in water and
adding 100 mL of 0.5 M NaOH. The solution was made up to 300 mL
K.N. Awokoya et al.
with distilled water). The sample was covered with aluminum foil and
placed in a water bath at 40 ◦ C. After 4 h, the excess hydroxylamine was
determined by rapid titration of the reaction mixture at pH 3.5 with 0.1
M HCl. The determination of the blank was similarly performed, but
only with the hydroxylamine reagent. The carbonyl content was calcu­
lated according to Eq. (2).
(A − B) x (C) x 0.028
Percentage Carbonyl = x 100 (2)
D
Where A, B, C and D are as earlier defined.
2.5.2. Effects of temperature on swelling power and solubility
Investigation of the effects of temperature on swelling power (SP)
and solubility of NTS and Oxy-NTS were carried out as reported by
Lawal et al. (2005). A 0.1 g starch sample was accurately weighed and
transferred into a clear test tube. The test tube with its content was
weighed (W1). Distilled water (10 mL) was added to the test tube and the
mixture was mixed thoroughly with a Whirlmix mixer for 30 s. The
resultant slurries were heated at varied temperature (30–70 ◦ C) for 30
min in a thermostatic water bath, cooled at room temperature, and then
centrifuged at 6000 rpm for 15 min. The residue obtained from the
above experiment (after centrifugation) with the water it retained and
the test tube was weighed (W2). The swelling power (SP) of the starch
was calculated using Eq. (3):
W2 − W1
Swelling power = (3)
Weight of starch
Aliquots (5 mL) of the supernatant obtained after centrifugation
were dried to a constant weight at 110 ◦ C. The residue obtained after
drying the supernatant represented the amount of starch solubilized in
water. Solubility was calculated as grams per 100 g of starch on dry
weight basis.
2.5.3. Effect of pH on swelling power and solubility
Different 1% w/v slurries of NTS and Oxy-NTS were prepared with
distilled water and pH was adjusted to various values (pH 2–12) with 0.1
M HCl and 0.1 M NaOH. The slurries were allowed to stand for 1 h at 30
◦
C, and then centrifuged at 6000 rpm for 15 min. The supernatant (5 mL)
was dried to constant weight at 110 ◦ C to determine percentage solu­
bility of the starch as stated earlier.
2.6. Characterization of the starches
The NTS and Oxy-SNPs were characterized by Fourier Transform
Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and
X-Ray diffraction (XRD). The FTIR spectra of NTS and Oxy-SNPs were
determined using Perkin–Elmer Spectrum 100 FT-IR spectrometer
Waltham (MA, USA) with an auto image system in the frequency range
4000–400 cm− 1; surface morphology was determined using SEM
(VEGA3 TESCAN); X-ray Diffraction were recorded using an X-ray
diffractometer (Bruker D2, Phaser DOC-M88-EXX, 155 VA-07, 2010,
Karlsruhe, Germany) using Cu tube with 1.5418(Å) radiation. Data were
recorded at a scan rate of 4◦ /min over a 2Ɵ range of 10◦ –90◦ .
2.7. Adsorption study
Stock solution of metal ions (Pb2+ or Cd2+) was prepared by dis­
solving accurately weighed amount of metal salt (CdCl2.1/2H2O or Pb
(NO3)2 in 1000 mL standard flask and made up to the mark with
deionized water. Required working concentrations (25–500 mg/L) were
prepared by serial dilution from the stocks and their volume in contact
with the adsorbent was maintained at 30 mL. The adsorption process
was performed in 100 mL plastic containers with lids. Isothermal study
was performed by varying initial metal-ions concentrations in the
working solution; kinetic study was investigated by changing contact
3
Environmental Nanotechnology, Monitoring & Management 16 (2021) 100489
time; while thermodynamics study was performed by varying the pro­
cess temperature in batch adsorption studies. Effect of initial metal-ions
concentration was explored by contacting 50 mg of Oxy-SNPs with
diverse concentrations of Pb2+ or Cd2+ ions ranging from 25 to 500 mg/
L (0.121–2.413 mmol L− 1 Pb2+ or 0.222–4.448 mmol L− 1 Cd2+) in a
thermostatic water bath with speed controllable shaker (GFL, Burgwedel
Germany) set at 30 ◦ C. The experiment was performed without altering
the solution pH and allowed to run for 60 min. Time dependent studies
(on metal uptake by NTS and Oxy-SNPs) were investigated at room
temperature and solution pH. Agitation period was varied from 5 to 240
min; adsorbent dose and metal-ions concentrations were maintained at
50 mg and 50 mg/L, respectively. Experiment to check the effect of
temperature was performed at three different temperatures: 303 K, 313
K and 323 K and optimum agitation time earlier determined. Adsorbent
dose was maintained at 50 mg, while metal-ions concentration was kept
at 50 mg/L. Upon contacting each metal ions solution with adsorbent for
a pre-determined period, metal-ions loaded adsorbent was recovered by
centrifugation at 6000 rpm for 10 min and the clear supernatants were
analyzed for residual metal ion concentration by Atomic Absorption
Spectroscopy (AAS). Amount of metal ions adsorbed was determined as
qe = (Co − mCe ) V (in mg/g or mmol/g). Co and Ce represent initial and
equilibrium concentrations of metal ions, respectively; V depicts contact
volume, while m represents mass of adsorbent.
3. Results and discussion
3.1. Carbonyl and carboxyl content in native and oxidized starch
The degree of oxidation in the Dioscorea dumentorum starch was
evaluated by determining the carbonyl and carboxyl contents of both
native and oxidized starches. The carbonyl content of NTS was 0.07 %,
while carboxyl content was 0%. After modification using NaOCl,
carbonyl and carboxyl contents were found to be 0.11 % and 0.67 %,
respectively. This clearly reveals the success of the oxidation process.
Substantial increase in carbonyl content as well as emergence of
carboxyl group have earlier been reported after oxidation of sorghum
and potato starches (Biduski et al., 2017; Fonseca et al., 2014). It should,
however, be noted that the levels of these functional groups depend on a
number of factors which include the botanical source of the starch, type
of oxidizing agent used and the modification condition (Pudjihastuti
et al., 2018). To further confirm the result obtained, FTIR analysis was
carried out on NTS and Oxy-NTS. As shown in Fig. 1, The FTIR spectra of
both starches showed broad absorption peak spanning from 3700 cm− 1
to 3200 cm− 1 and another sharp peak at 2931 cm− 1, characteristics of
hydrogen bonded − OH and CH2 stretching vibration, respectively
(Abidin et al., 2018; Wojeicchowski et al., 2018). The absorption peaks
at 1639 cm− 1 in the spectrum of NTS and 1643 cm− 1 in the spectrum of
Oxy-NTS are typical of starch, attributed to − OH bending of H2O (Wu
et al., 2019). Aside slight decrease in intensity, no significant change was
observed in the absorption region of 1200–1000 cm− 1. Nevertheless, the
slight change observed could indicate the cleavage of C–OC– bond in
the glucose unit due to starch degradation (Liu et al., 2014). One major
disparity between the spectra of NTS and Oxy-NTS was the emergence of
a shoulder absorption band at 1724 cm− 1, which represents the vibra­
tional band of C– – O (Kweon et al., 2001; Reis et al., 2008). This ab­
sorption band must have emerged as a result of the introduction of
carbonyl and carboxyl functional groups to the backbone of the starch
granules.
3.2. Swelling power and solubility of the starches
Within 30–70 ◦ C temperature range, the swelling powers and solu­
bilities of both NTS and Oxy-NTS increased with temperature (Fig. 2a).
This phenomenon could possibly be due to increased mobility of starch
molecules, caused by thermodynamic instability at elevated
K.N. Awokoya et al. Environmental Nanotechnology, Monitoring & Management 16 (2021) 100489

Fig. 1. FTIR spectra of (a) NTS (b) Oxy-NTS (c) Oxy-SNPs (d) Pb2+-Oxy-SNPs and (e) Cd2+-Oxy-SNPs.

Fig. 2. Effect of temperature on swelling power (a) and solubility (b) and effect of pH on swelling power (c) and solubility (d) of native and oxidized starch.

temperature, which facilitates easy percolation of water (Lawal et al.,
2005). In comparison with native starch, oxidation in the presence of
NaOCl resulted in decreased swelling power. Depolymerization of the
amylose as well as amylopectin chains occurs during oxidation process,
although amylose region is more prone to depolymerization due to
amylose linear structure and accessibility (Fonseca et al., 2014). The
reduction in swelling power of the starch after modification, therefore,
could be as a result of disintegration or fragmentation of the internal
structure of the starch granules as a result of oxidation with NaOCl,
which weakens the ability of the starch in holding or absorbing water

4
K.N. Awokoya et al.
(Wang and Wang, 2003; Sánchez-Rivera et al., 2014). Fonseca et al.
(2014) and Lawal et al. (2005) also reported a decrease in the swelling
powers of potato and hybrid maize starches, respectively. Conversely,
modification enhanced the solubility of the starch (Fig. 2b). This may, as
well, be attributed to depolymerization which enhanced the leaching of
the amorphous region of the starch upon oxidation (Biduski et al., 2017).
Liu et al. (2014) also reported an increase in solubility of maize starch
upon oxidation, which they attributed to increase in mobility as a result
of degradation of starch molecules, as well as introduction of hydro­
philic carboxyl group. This submission is in agreement with the report of
Wang and Wang (2003), who attributed enhanced solubility of corn
starch upon oxidation to better hydration due to introduced functional
groups. The pH effect on swelling power and solubility of the starches
are shown in Fig. 2c,d. Result showed that, at all pHs, native starch had
better swelling power and reduced solubility, when compared with
modified starch. Oxidation of starch first results in the leaching of the
amorphous region of starch, followed by the crystalline region. This
leaching process might have influenced the phenomenon observed. As
pH was increased from the acidic medium to alkaline medium, swelling
power as well as solubility of both NTS and Oxy-NTS increased. The
higher value of swelling power and solubility observed at the alkaline
range might be due to the partial gelatinization of starch (Lawal et al.,
2005).
3.3. Characterization of NTS and Oxy-SNPs
3.3.1. Fourier transform infrared (FTIR) spectroscopy
The synthesized Dioscorea dumentorum starch was characterized by
Fourier Transform Infrared Spectroscopy (FTIR) with the objectives of
identifying the functional groups present at the adsorbent’s surface and
identifying those responsible for the binding of Pb2+and Cd2+ ions.
Fig. 1c-e shows the spectra of unloaded and metal ions loaded Oxy-SNPs,
where Oxy-SNPs, Pb2+-Oxy-SNPs and Cd2+-Oxy-SNPs represent unloa­
ded Oxy-SNPs, lead-loaded Oxy-SNPs and cadmium-loaded Oxy-SNPs,
respectively. The spectrum of Oxy-SNPs (c) shows absorption bands at
3417 cm− 1, which is less broad, compared to the spectra of native starch
(a) and oxidized starch (b). This band within the range of 3500 – 3200
cm− 1 has been attributed to − OH group stretching of starch, resulting
from intra-molecular and inter-molecular hydrogen bonding (Liu et al.,
2016; Ahmad et al., 2020). The vibration peak at 2926 cm− 1 is char­
acteristic of CH– group of starch (Pereira et al., 2013). The strong band
at 1706 cm− 1 emanated from the stretching vibration of C– – O (Reis
et al., 2008), apparently from the oxidation of native starch, while the
peak at 1622 cm− 1 indicates bending vibration of tightly bound − OH of
water molecules in the nanoparticles (Liu et al., 2016; Ahmad et al.,
2020). Several other apparent absorbances were observed, among which
are the peaks at 1172 cm− 1 and 1028 cm− 1, characteristics of asym­
metric C–O–C and CO– vibration (Pereira et al., 2013; Wu et al.,
2019). Upon adsorption of Pb2+ and Cd2+ ions, different spectra were
obtained. The − OH stretching vibration band became more intense and
shifted to 3419 cm− 1 in the spectra of Oxy-SNPs loaded with both metal
ions. This possibly suggests metal-ions/hydroxyl interaction. This
assertion was buttressed by the shift of − OH bending vibration at 1622
cm− 1 to 1620 cm− 1 and 1616 cm− 1 in the spectra of Pb2+-Oxy-SNPs and
Cd2+-Oxy-SNPs, respectively. The position of the CH– absorption peak
remain unchanged, although more intense after metal loading. The in­
tensity of the C–– O absorption band at 1705 cm− 1 increased sharply,
also indicating the probability of C–
– O acting as a binding site for both
2+ 2+
Pb and Cd ions. Visible vibrational band shifts and decrease in in­
tensities were noticed in the absorption peaks in the region of
1300–1000 cm− 1, and up to the fingerprint region after metal uptake,
confirming interactions of the metal ions with the surface functional
groups of Oxy-SNPs.
3.3.2. SEM characterization of surface morphology
The structural morphologies of native starch and oxidized starch
5
Environmental Nanotechnology, Monitoring & Management 16 (2021) 100489
nanoparticles (Oxy-SNPs) were studied by scanning electron microscopy
(SEM) in order to investigate possible morphological changes as a result
of oxidation and subsequent synthesis of nanoparticles. The SEM images
of both NTS and Oxy-SNPs are shown in Fig. 3(a,b). The granules of
native starch were asymmetric and irregular in shape, but largely
polygonal, smooth edged (Ahmad et al., 2020) and clustered. Moreover,
part of the granules seems wrapped in a jelly-like folding. The
morphology of the NTS granules were somewhat similar to those re­
ported by Valcárcel-Yamani et al. (2013) for olluco starch granules and
Riley, et al. (2006) for different varieties of Dioscorea alata cultivars.
SEM micrograph of Oxy-SNPs indicated that the surface became rough
with fragmentation of the jelly-like folding, making the clustered
granules appearing loose in a way that suggests structural disruption.
The change in the surface morphology may be attributed to the impact of
dual-modification, which include partial depolymerization as a result of
oxidation in the presence of NaOCl, that led to rupturing of the α-1,4
linkages (Wojeicchowski et al., 2018). Increased roughness suggests
improved surface area (Garg and Jana, 2011) for ligand binding at the
surface of the starch. This assertion was validated by measuring the
particle sizes of both NTS and Oxy-SNPs using ImageJ software. As
shown in Fig. 3(c,d), the mean particle sizes of NTS and Oxy-SNPs were
1.91 μm and 334 nm, respectively, indicating nearly 6-fold reduction in
average particles size as a result of the dual-modification treatment.
3.3.3. X-ray diffraction (XRD)
The X-Ray diffraction pattern of NTS of Dioscorea dumentorum, Oxy-
SNPs, Cd2+–Oxy-SNPs and Pb2+–Oxy-SNPs are shown in Fig. 4a. The
diffractogram of NTS gave strong and prominent diffraction peaks, in
form of three humps, at around Bragg angle 2θ of 15◦ , 17◦ , and 23◦ , with
the strongest diffraction peak around 17◦ occurring as a doublet at 17.2◦
And 17.9◦ . This is similar to the report of Chisenga et al. (2019) and
El-sheikh (2017) on cassava and Native maize starches, respectively.
Analysis of the X-ray diffraction patterns showed that native Dioscorea
dumentorum starch exhibited type A crystallinity (Chisenga et al., 2019).
This is in agreement with the report of Riley et al. (2004) for similar
Dioscorea spp. cultivated in Jamaica; and differs from type B crystallinity
reported for most other Dioscorea spp. (Riley et al., 2004; Riley et al.,
2006). Type A with staggered monoclinic crystallite pattern has been
reported to be highly rich in amylopectin, while amylose content dom­
inates type B with open hydrated hexagonal crystallite pattern. Type C is
a composite of A and B and, like type A, it is composed of high amylo­
pectin and low amylose (Riley et al., 2004; Bashir et al., 2020).
Upon oxidation and subsequent acid hydrolysis, new diffractogram
revealed the disappearance of the three humps found in the XRD pat­
terns of NTS, signifying the melting of the crystalline structure to form
amorphous structure (El-sheikh, 2017). As a result of acid-catalyzed
hydrolysis, the amorphous region of starches is first destroyed. This is
followed by the destruction of both the amorphous and crystalline re­
gions (Wu et al., 2019), hence the amorphous structure observed for
Oxy-SNPs. The sharp peaks observed in the diffraction pattern of
Pb2+–Oxy-SNPs are obviously due to the adsorption of Pb2+ ions. The
XRD diffractogram of Cd2+–Oxy-SNPs also showed few peaks, although
less intense in comparison to those of Pb2+–Oxy-SNPs. The presence of
the metal ions possibly acted as crystallite materials.
3.3.4. Thermogravimetric analysis
Thermogravimetric analysis (TGA) was performed in order to probe
the alteration in thermal properties as a result of the oxidation and
subsequent synthesis of the nanoparticles variant of the native starch. As
shown in Fig. 4b, the TG results of both NTS and Oxy-SNPs reveal weight
losses in two stages. In NTS, the first stage occurred at around 34 ◦ C–120
◦
C, with a weight loss of about 9%; while a similar stage occurred at
around 37 ◦ C–98 ◦ C, corresponding to about 5% weight loss in Oxy-SNPs
result. The first stage has been attributed to dehydration (Okoli et al.,
2018; Garg and Jana, 2011). Starch is hydrophilic and thus can absorb
up to 14 wt % moisture under standard conditions (Thiebaud et al.,
K.N. Awokoya et al. Environmental Nanotechnology, Monitoring & Management 16 (2021) 100489

Fig. 3. SEM micrographs of NTS (a) and Oxy-SNPs (b), and particle size analyses of NTS (c) and Oxy-SNPs (d).

Fig. 4. X-ray Diffractograms (a) and Thermographs (b) of NTS and Oxy-SNPs.

6
K.N. Awokoya et al.
1997). The lower weight loss recorded for Oxy-SNPs is an indication of
lower amount of moisture in its structure when compared with natural
starch (Pereira et al., 2013). After the initial water loss, NTS became
stable up till a temperature of 230 ◦ C. The second stage of weight loss
was observed from 230 ◦ C to 370 ◦ C for the NTS sample, corresponding
to a further 74 % weight loss. This stage has been ascribed to thermal
degradation. The thermogravimetric analysis of Oxy-SNPs showed
marked increase in thermal stability of the starch. This must have been
as a result of oxidation (Lewicka et al., 2015) and subsequent synthesis
of the oxidized starch nanoparticles. Thermal degradation of Oxy-SNPs
occurred at temperatures of 320 ◦ C–430 ◦ C, corresponding to 72 %
weight loss. Water is often formed by inter/intra-molecular condensa­
tion of hydroxyl of starch, and it constitutes the major decomposition
product at temperatures below 300 ◦ C (Thiebaud et al., 1997; Garg and
Jana, 2011). However, the process of starch oxidation in the presence of
NaOCl, is known to result in primary hydroxyl groups being oxidized to
aldehyde or carboxyl groups (Lewicka et al., 2015). This consequently
leads to fewer hydroxyl groups in the modified starch molecules when
compared with native starch. The interactions of the carboxyl, carbonyl
and hydroxyl groups then lead to improved hydrogen bonding in the
modified starch (Biduski et al., 2017), thus requiring elevated temper­
ature for its bond disruption.
3.4. Application of OSNPs as adsorbent
The synthesized Oxy-SNPs of Dioscorea dumentorum starch was
investigated for its potential use as an adsorbent in the removal of toxic
pollutants from wastewater. The conceivable application in the field of
adsorption was probed by utilizing the Oxy-SNPS in sequestering Pb2+
and Cd2+ ions from simulated polluted water. This study involved the
variation of the initial metal ions concentration, contact time as well as
temperature. Obtained data were fitted into various isothermal, kinetic
and thermodynamic equations in order to possibly understand the
mechanism and nature of the processes involved in the sorption of the
two metals.
3.4.1. Effect of concentration enhancement
The effects of variation of initial concentration of Pb2+ and Cd2+ ions
removal efficiency of the synthesized Oxy-SNPs of Dioscorea dumentorum
starch are depicted in Fig. 5a. The amount of metal ions adsorbed from
the simulated wastewater progressively increased with augmentation of
metal ions concentration from 25 to 300 mg/L. Within this concentra­
tion range, the amount of Pb2+ ions adsorbed onto Oxy-SNPs improved
from around 13.7–110.9 mg/g, while Cd2+ ions removal became
enhanced from around 11.8–118.8 mg/g. Beyond concentration of 300
mg/L, metal uptake slowed until near plateau profiles were obtained
between 400 and 500 mg/L metal ions concentration, signifying
adsorption/desorption equilibrium. Every adsorbent possesses a fixed
number of binding sites at its surface (Azouaou et al., 2010). At lower
Fig. 5. Effects of initial metal-ion concentration (a) and contact time (b) on the adsorption of Pb2+ and Cd2+ onto Oxy-SNPs.
7
Environmental Nanotechnology, Monitoring & Management 16 (2021) 100489
concentrations, the ratio of active sites to metal ions is large, prompting
the uptake of near 100 % or substantial amount of metal ions (Naiya
et al., 2009). As metal ions concentration increases, the ratio narrows
until the population of the metal ions outnumbers that of the available
binding sites. From that point, competitions among the metal ions for
the available binding sites become heightened. This, coupled with
electrostatic repulsions between the already adsorbed ions and the
aspiring candidates for the neighboring available sites possibly slows
down metal ions uptake. This phenomenon probably started around 300
mg/L in the present study. Above the concentration of around 300 mg/L,
adsorption/desorption equilibrium possibly sets in. In the present study,
this probably occurred between 400–500 mg/L metal ions concentra­
tion. Uptake of Pb2+ ions onto Oxy-SNPs was higher than that of Cd2+
ions at the adsorbate concentration of 25 mg/L to < 250 mg/L. Kweon
et al. (2001) also reported higher uptake of Pb2+ ions compared to that
of Cd2+ by succinylated corn starch. However, equilibrium Cd2+ ions
uptake was less than that of Cd2+ ions. This is possibly due to the ionic
size of Cd2+, which is smaller than that of Pb2+. Due to their smaller size,
Cd2+ ions probably move faster and as a result become energetically
more favorable to overcoming electrostatic repulsions hindering easy
access to the few available sites on the already overcrowded surface at
higher concentration.
3.4.2. Isothermal studies of the adsorption processes
Obtained data from concentration dependent studies were fitted into
three different isotherms to better understand the equilibrium charac­
teristics and nature of the processes involved in the removal of Pb2+ and
Cd2+ ions by the starch-based adsorbent. Models investigated include
the Langmuir (Langmuir, 1918), Freundlich (Freundlich, 1906) and
Dubinin-Radushkevich (D–R) (Dubinin et al., 1947) isotherms. The
linearized equations of the Langmuir, Freundlich and D–R models
applied are given as q1 = q 1KLC + q 1 , lnqe = ln kf + 1n ln Ce and
e max e max
ln qe = ln qm − βε2 , respectively. The letter, ε of the D–R isotherm
( )
symbolizes Polanyi potential, which is defined as RTln 1 + C1e (J/mol),
while β (mol2/kJ2) represents the D–R constant. Langmuir constant is
represented by KL (L/mg), while, qm or qmax (mg/g), depending on the
model, indicates maximum metal uptake. Letter n and Kf (mg/g)
represent the dimensionless heterogeneity factor, which is an indicator
of the effectiveness of an adsorption process (Xiang et al., 2016) and
Freundlich constants, respectively; gas constant, R is valued as 8.314
J/mol K, while temperature is given as T (K). Linear plots of the three
models were made, from which their slopes and intercepts were inter­
preted to obtain the values of necessary parameters. The best model that
suitably described the sorption of each of Pb2+ and Cd2+ ions was
determined by the determination coefficient, R2. Table 1 shows all the
isothermal parameters calculated for the sorption processes. Experi­
mental data appeared to fit the Freundlich model best, with R2 values of
0.9874 and 0.9560 for the removal of Pb2+ and Cd2+ ions, respectively.
K.N. Awokoya et al. Environmental Nanotechnology, Monitoring & Management 16 (2021) 100489

Table 1 studied. At room temperature (≈ 28 ◦ C), 50 mg/L metal ions concen­

Calculated values for isothermal and kinetic parameters for the adsorption of tration and 50 mg adsorbent dose, adsorption of the ions of the two
Pb2+ and Cd2+ onto Oxy-SNPs. metals increased linearly and approached equilibrium after 60 min for
Parameter Cd2+ Pb2+ Pb2+ ions, and 30 min for Cd2+ ions. After 90 min interactions with the
Kinetic Model
surface of the Oxy-SNPs, sorption appeared steady – no significant
Pseudo-first-order R2 0.8634 0.9466 sorption increase was noticed. The adsorbent seemed to have more af­
k1 (L/min) 0.023 0.0267 finity for Pb2+ ions when the agitation time approached 60 min. No
qe(exp) (mg/g) 15.47 21.737 categorical explanation has been found for this. Nevertheless, it may not
qe(calc) 7.596 8.6115
be unconnected with the geometries and electric densities of the Oxy-
Pseudo-second-order R2 0.9989 0.9934
k2 (g/mg min) 0.0035 0.0019 SNPs and the metals involved (Kweon et al., 2001). After 60 min,
qe(exp) (mg/g) 19.05 28.60 about 22.19 mg/g and 19.17 mg/g of Pb2+ and Cd2+ ions, respectively,
qe(calc) 23.33 28.30 were observed to have been removed from the simulated wastewater.
Elovich R2 0.9587 0.9446 The time dependent profiles of the adsorption of the two metals are as
α 4.1445 3.6354
β 0.3013 0.1814
shown in Fig. 5b. Prior to adsorption, an adsorbent surface is usually rich
Weber-Morris R2 0.7827 0.8282 in unoccupied binding sites, and the binding of substrates to these sites is
kα (mg/g min½) 0.865 1.489 dependent on the operational conditions and the specific surface area of
C 6.507 6.804 the adsorbent (Hu and Du, 2019). At the initiation of the sorption pro­
cess, interaction of adsorbates with the adsorbent’s surface commences,
Isothermal model
leading to gradual occupation of the binding sites by the materials to be
Langmuir R2 0.9434 0.9411
kL (L/mg) 0.024 0.080 removed. This initial stage has been severally reported to be very fast
qmax (mg/g) 96.15 88.49 (Naiya et al., 2009; Oninla et al., 2018; Kamal et al., 2010; Guo et al.,
Freundlich R2 0.9560 0.9874 2006). The sites occupation, however, slows after the initial rapid stage
kF (L/mg) 1.204 2.254 due to depletion of active sites and repulsive forces (Liu et al., 2016). A
1/n 0.702 0.491
D–R R2 0.8296 0.9304
steady-state is eventually reached, after which further contact time
qm (mmol/g) 0.932 0.539 extension bears no significant effect (Batool et al., 2018), which possibly
E (kJ/mol) 3.536 5.000 is the case as regards the present study. The charged metal ions in the
solution most probably binds with the − OH and –C = O of carbonyl and
carboxyl group on the Carbon 6 of the glucose units on the surface of the
This indicates that the sorption of the two metal ions is multilayer,
Oxy-SNPs. Although native starch has been reported to possess no
occurring on an energetically heterogeneous surface. The removal of Cu
adsorption quality (Parvathy and Jyothi, 2014; Haroon et al., 2016), the
(II) ions from aqueous solution onto crosslinked amino and di­
present result showed a measure of metal uptake. This could be attrib­
thiocarbamates starches was also reported to fit the Freundlich isotherm
uted to slight electrostatic properties and, probably physical entrapment
(Li et al., 2004). The values of the reciprocal of the Freundlich hetero­
of the metal ions in the aqueous medium (Kweon et al., 2001).
geneity factor for the sorption of the two metal ions were obtained as
0.4909 and 0.7018 for Pb2+ and Cd2+ ions, respectively. Usually, 1/n
3.4.4. Adsorption kinetic modelling
value < 0 and < 1 signifies favorable adsorption (Hu and Du, 2019). The
The kinetics of the adsorption of Pb2+ and Cd2+ ions onto the syn­
obtained values being between 0 and 1 indicate the favorability of the
thesized Oxy-SNPs was studied by modelling the adsorption data with
adsorption of the two metal ions onto the Oxy-SNPs. The value of Kf
the pseudo-first-order (Lagergren, 1898), pseudo-second order (Ho and
obtained are 2.254 L/mg and 2.204 L/mg for Pb2+ and Cd2+ ions,
McKay, 1999), Elovich (Cheung et al., 2000) and Weber-Morris (Weber
respectively. These values, falling within the range of 1–20, show that
and Morris, 1963) equations. The study of adsorption kinetics gives
the adsorption can be considered promising (Batool et al., 2018). R2
insight into optimal experimental conditions, mechanism, as well as rate
values of 0.9411 and 0.9434 were obtained for the sorption of Pb2+ and
determining steps (Batool et al., 2018). Linearized equation of the
Cd2+ ions, respectively, when modeled with Langmuir equation, while
models are as follows: ln(qe − qt ) = lnqe − k1 t (Pseudo-first order),
0.9304 was obtained for the adsorption of Pb2+ ions, when modeled t t 1
q = q − (Pseudo-second order), qt = 1β ln[αβ] + 1β lnt (Elovich) and
with D–R equation. The values, being equally close to unity, indicate t e k q 2
2 e

that an adsorption process cannot be exclusively described by a single
model (Oninla et al., 2018). The Langmuir maximum monolayer Pb2+
and Cd2+ ions removal was recorded as 88.49 mg/g and 96.25 mg/g,
respectively. These values are relatively high, and comparable with the
performances of other starch-based adsorbents (Bashir et al., 2020., Liu
et al., 2017). Dubinin-Radushkevich isotherm model has been relevant
in the prediction of the nature of an adsorption (Batool et al., 2018). The
energy, E value is often used to determine whether a process is physical
or chemical in nature, and it is expressed as E = √1̅̅̅̅ (kJ/mol). Any E
2β
value < 8 kJ/mol indicates physisorption, 8 kJ/mol < E < 16 kJ/mol
implies the involvement of ion exchange, while E value < 16 kJ/mol
implicates chemisorption (Kamal et al., 2010). In the present study, E
values of 5.0 kJ/mol and 3.54 kJ/mol were calculated for the sorption of
Pb2+ and Cd2+ ions, respectively. These values being < 8, suggest
physisorption process in the adherence of Pb2+ and Cd2+ ions onto the
surface of Oxy-SNPs of Dioscorea dumentorum.
3.4.3. Effect of contact time
In order to estimate the optimum duration of the adsorption of Pb2+
and Cd2+ ions onto the synthesized Oxy-SNPs, effect of contact time was
qt = kα t½ + C (Webber-Morris). The amount of metal adsorbed at a
particular time is represented as qt (mg/g); k1 (min− 1), k2 (g/mg min)
and kα (mg/g min½) symbolize the first-order, second-order and
Weber-Morris intra-particle diffusion rate constants, respectively. The
desorption constant is depicted by β, intercept by C, while α (mg/g.min)
indicates initial adsorption rate. The required kinetic parameters were
determined and calculated from the slopes and intercepts of linear plots
(Fig. 6) of the equations of the various models. Among all the models,
the pseudo-second-order best described the kinetics of the adsorption of
the two metals. This was determined by comparing the determination
coefficients, R2 of the models. As shown in Table 1, Pb2+ adsorption gave
R2 value of 0.9934, while that of Cd2+ gave R2 value of 0.9989. Both
values are closest to unity. Moreover, the theoretical qe, qe(calc) and
experimental qe, qe(exp) from the pseudo-second-order equation are
closer than those obtained from pseudo-first-order. It has been estab­
lished that the closer the R2 value of a model is to unity, the better the
model is in describing an adsorption process (Oninla et al., 2018). The
fact that the sorption data best fitted the pseudo-second order indicates
that electrons were shared or exchanged as a result of valency forces
during the interaction of Pb2+ and Cd2+ ions at the surface of the
Oxy-SNPs. It also gives information about the mechanism of the

8
K.N. Awokoya et al. Environmental Nanotechnology, Monitoring & Management 16 (2021) 100489

Fig. 6. Kinetic plots of the adsorption of Pb2+ and Cd2+ onto OSNPs; (a) pseudo-first-order (b) pseudo-second-order (c) Elovich, and (d) Weber-Morris models.

processes: chemisorption is the rate-limiting step (Adigun et al., 2020).

Elovich model is often used in predicting the nature of adsorbents sur­ Table 2
Calculated values for thermodynamic parameters for the adsorption of Pb2+ and
face, and it has been generally applied to chemisorption kinetics. When
Cd2+ onto OSNPs.
modelled with Elovich equation, R2 values of 0.9446 and 0.9587 were
obtained for the sorption of Pb2+ and Cd2+ ions, respectively. The Metal ion Parameter

closeness of these values to unity indicates that Elovich model also gave ΔH◦ (kJ/mol) ΔS◦ (J/K mol) ΔG◦ (kJ/mol)
good representations of the adsorption processes, thus signifying that 303 K 313 K 323 K
the adsorption of the two metals most possibly took place at a surface
Cd(II) − 313.784 − 0.9411 − 28.631 − 19.200 − 9.809
that was heterogeneous. The values also suggest the involvement of Pb(II) − 413.712 − 1.1763 − 57.291 − 45.528 − 33.765
chemisorption kinetics (Cheung et al., 2000). As shown in Fig. 6d, the
plots of the Weber-Morris model failed to start from the origin. This
signifies that intra-particle diffusion was not the only rate determining metal uptake with temperature rise may also be due to a possible high
step (Hu and Du, 2019). escape tendency of metal-ions from the adsorbent’s surface to the bulk
liquid phase (Azouaou et al., 2010). The enthalpy changes for the in­
3.4.5. Adsorption thermodynamics teractions were negative, connoting exothermic process. The heat
In order to predict the feasibility of the removal of Pb2+ and Cd2+ evolved during the interactions were calculated to be − 413.7 kJ/mol
ions by the synthesized Oxy-SNPs, estimate the type and magnitude of and − 313.7 kJ/mol for Pb2+ and Cd2+ ions. These values, being <29
heat involved and predict the direction of spontaneous change, the kJ/mol, portray the process of the removal of the two metals as chem­
thermodynamics of the removal processes was investigated. Conven­ isorption (Oninla et al., 2018), thereby, complementing the findings
tional equations such as ΔGo = − RT lnKc and ΔGo = ΔHo − TΔSo from the Elovich kinetic model. Negative values were recorded for the
o
were employed, from which the van’t Hoff equation, ln Kc = ΔSR − ΔH
o
entropy change. This, thus indicates that the removal process progressed
RT ,
was formulated. Plotting lnKc versus 1/T, allows the estimation of ΔH◦ with increased orderliness at the adsorbent’s surface (Chakraborty et al.,
(standard enthalpy change) and ΔS◦ (standard entropy change) from the 2020).
values of slope and intercept, respectively. ΔGº signifies standard Gibb’s
free energy change, while Kc represents equilibrium constant which is 3.5. Conclusion
valued as Kc = CCae , where Ca denotes the concentration of metal ions on
the adsorbent at equilibrium. The calculated values of the thermody­ Oxidized starch nanoparticles have been synthesized from tubers of
namic parameters are presented in Table 2. The obtained negative ΔGº an edible root crop, Dioscorea dumentorum. The research employed
values for the adsorption of the two metal ions is an indication of the oxidation /acid hydrolysis methods in a dual modification approach,
feasibility and spontaneity of their removal by the synthesized Oxy- leading to incorporation of C–
– O functional group into the structural
SNPs. The negative values of ΔGº was observed to decrease with rise backbone of the native starch and conversion of the starch granules to
in temperature. This shows that affinity of the synthesized Oxy-SNPs for nano-scale particles. The percentage carbonyl and carboxyl content,
Pb2+ and Cd2+ ions decreased with temperature rise. The decrease in coupled with the FTIR spectra obtained after modification showed the
success of the oxidation process. The oxidized starch (Oxy-NTS) was

9
K.N. Awokoya et al.
more soluble than its native counterpart (NTS). However, modification
resulted into reduction in swelling power of the starch. The solubility
and swelling power of both starches increased with rise in temperature
and solution pH. XRD characterization of the starches revealed the
disappearance of crystal structure and formation of amorphous one,
while SEM analysis revealed looser granules, suggesting structural
disintegration which made the surface more porous upon modification.
Oxy-SNPs showed greater thermal stability compared to NTS. Upon
adsorption application, Oxy-SNPs presented itself as an efficient adsor­
bent for Pb2+ and Cd2+ removal from wastewater. Its metal removal
ability was enhanced with increase in initial metal-ions concentration
and contact time, until adsorption/desorption equilibrium was attained.
Isothermal data followed the Freundlich isotherm while kinetic data
fitted the pseudo-second-order model better than all other models
tested. The adsorption processes were thermodynamically feasible and
exothermic in nature. Evidences from the isothermal, kinetics and
thermodynamics of the adsorption processes portrayed the adsorption of
Pb2+ and Cd2+ ions as physicochemical adsorption.
The authors regret that the printed version of the above article
contained a number of errors. The correct and final version follows. The
authors would like to apologise for any inconvenience caused.
Authors’ contributions
Kehinde N. Awokoya: conceptualization, supervision, data valida­
tion and analyses, manuscript’s editing; Vincent O. Oninla: conceptu­
alization, data validation and analyses, manuscript’s preparation and
revision; Dolapo J. Bello: experimental and data analyses. All authors
approved the final manuscript before submission.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Acknowledgement
The authors will like to appreciate the Polymer Science and Bio­
physical Chemistry (PSBC) research group of the Department of Chem­
istry, Obafemi Awolowo University, Ile-Ife, Nigeria, for granting access
to their research facilities. We also recognize Mr. M.A. Ramoni, the
dutiful departmental chief technologist and all individuals who sup­
ported the work at one stage or the other.
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