Chemosphere 349 (2024) 140837

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Polyacrylonitrile and polyethersulfone based co-axial electrospun

nanofibers for fluoride removal from contaminated stream
Manu Sharma a, K. Karthik b, P. Keerthi b, Somak Chatterjee a, *
a
Department of Chemical Engineering, BITS-Pilani, Pilani, Rajasthan 333031, India
b
Department of Chemistry, Anna University, Chennai, Tamil Nadu 600025, India

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Polymeric coaxial electrospun nano­

fibers were prepared under optimum Graphical abstract showing the use of PAN-PES based coaxial electrospun nanofibers for fluoride
conditions. filtration from groundwater
• Best shaped fibers contained 6 wt% PAN
and 10 wt% of PES.
• Maximum fluoride uptake was reported
as 110 mg/g at 298 K.
• Pure water flux was 39 L/m2h at 344.7
kPa and 30 l/h.
• Dynamic filtration showed 6 h break­
through time at standard operating
condition.

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

Handling Editor: Sandeep K. Lakhera Coaxial electrospun polyacrylonitrile (PAN) and polyethersulfone (PES) based nanofibers were prepared and was
used for filtration of fluoride from drinking water for the first time. Well defined fiber geometry was obtained at
Keywords: 1 ml/h of core polymer, i.e., PES flow rate, 1.4 ml/h of shell polymer, i.e., PAN flow rate, voltage of 22 kV, while
Coaxial-electrospinning the distance between the needle tip and the collector was 15–17 cm. Increase in bead like structure in fiber
Core-shell nanofibers
strands was observed with higher PAN concentration, while it decreased for lower PES concentration, thereby
Polyacrylonitrile
giving an optimum composition (6 wt% PAN and 10 wt% PES) for uniform fiber morphology. This nanofiber,
Polyethersulfone
Fluoride removal abbreviated as N2 acted as an ultrafiltration membrane having permeability in the lower range, i.e., 0.5 × 10− 11
Adsorption m/s Pa and its fluoride removal efficacy was 46%. Fibers were also hydrophilic with considerable porous nature.
Uptake of fluoride by this N2 nanofibers were evident from binding energy of 685.2 eV during XPS analysis. It is
probable that nitrile and sulfone groups present in the core and shell of the nanofibers played an active in
fluoride uptake, which was estimated as 110 mg/g at 298 K. Isoelectric point was in alkaline range which

* Corresponding author.
E-mail address: somak.chatterjee@pilani.bits-pilani.ac.in (S. Chatterjee).

https://doi.org/10.1016/j.chemosphere.2023.140837
Received 25 August 2023; Received in revised form 10 November 2023; Accepted 26 November 2023
Available online 7 December 2023
0045-6535/© 2023 Elsevier Ltd. All rights reserved.
M. Sharma et al.
promoted negative fluoride ion uptake on positive nanofiber surface. Lead played higher masking effect in the
uptake of fluoride in comparison to arsenic as coexisting ion. Dynamic cross flow filtration was also studied with
this nanofiber in both synthetic and real life feed solution.
1. Introduction
Water is getting polluted due to geochemical and anthropogenic
activities during the recent times. Fluoride contamination in drinking
water is one such significant pollution issues that affects worldwide
population (Bhatnagar et al., 2011). This problem is prevalent in Asian
countries, such as, India, Bangladesh, China and Pakistan, (Meenakshi
and Maheshwari, 2006; Tolkou et al., 2021). In these countries, con­
centration of fluoride in water is excessively high, leading to widespread
occurrence of related diseases. Amongst these countries, China and India
are heavily impacted. In India, especially in states, like, Assam, Rajas­
than, Telangana and West Bengal, concentration of fluoride is quite
high, ranging from 5 mg/l to 20 mg/l (Ali et al., 2019). Consequently,
various diseases, like, dental fluorosis, skeletal fluorosis, urolithiasis,
impaired thyroid function, cognitive delays, decreased birth rates and
muscle fiber degeneration result due to excessive fluoride uptake from
drinking water (Duggal and Sharma, 2022; Aggeborn and Öhman,
2021). Moreover, prolonged fluoride dust and gas exposure is associated
with other ailments, such as, bladder cancer, osteosarcoma, rare bone
cancers and respiratory issues (Eunice Jayashree et al., 2020). However,
small amounts of fluoride is beneficial as it helps to strengthen bones
and prevent dental caries (Mousazadeh et al., 2021). Thereby, it is
crucial to maintain optimum fluoride levels in water. World health or­
ganization (WHO) has set a permissible limit of 1.5 mg/l for fluoride in
drinking water (Bhatnagar et al., 2011).
Scientific community is actively engaged in developing effective
solutions to address this problem, recognizing the importance of
ensuring safe drinking water (Annouar et al., 2004; Arora et al., 2004;
Ayoob et al., 2008; Damtie et al., 2019). Joint venture of WHO and the
United Nations have provided access to clean water for many people.
Various methods that were developed to decontaminate fluoride from
groundwater, include, advanced oxidation processes, adsorption, elec­
trocoagulation, photocatalysis, ozonation and filtration (Adhikary et al.,
1989; Singh et al., 2016). Among these methods, adsorption shows
excellent potential for eliminating these persistent contaminants from
water, due to its simplicity, cost-effectiveness and reusability (Bhatnagar
et al., 2011; Mohapatra et al., 2009). However, adsorption is an equi­
librium governed process and has delayed kinetics. Additionally, spent
adsorbent removal from processed stream is extremely difficult and
costly (Qasem et al., 2021). Thereby, a novel method has to be devel­
oped, which can curb these limitations.
Electrospun nanofibers are one such class of material which can
function both as an adsorbent and a filtration agent. Nanofibers are
usually produced by electrospinning, which is mainly done by spraying
polymers over a charged surface (Nadaf et al., 2022). This method
produces highly porous fibers spanning from submicron to nanoscale
level. These nanofibers have high specific surface area and flexible
thickness to improve infiltration rate and contaminant rejection ratio.
However, electrospun nanofibers are prone to swelling because of their
hydrophilic support. As a result, their mechanical strength gets reduced
during water filtration, resulting in bursting. An alternative method, i.e.,
coaxial electrospinning, may be utilized to address this limitation
(Agrawal et al., 2021). Dual-layered fibers with a hydrophobic base, i.e.,
core and a hydrophilic top layer, i.e., shell are produced collection in a
drum when electrospinning with coaxial nozzles are performed. Higher
selectivity with reduced structural traits and internal concentration
polarization can also be exploited in these nanofibers by blending
compatible polymers. Polyacrylonitrile (PAN) can be used as the shell
material to provide mechanical strength and stability to the resulting
nanofibers. PAN is known for its high surface area, chemical resistance
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Chemosphere 349 (2024) 140837
and excellent adsorption capacity, making it an ideal choice for fluoride
removal (Chen et al., 2021). On the other hand, polyethersulfone (PES)
can be used in the core material to offer enhanced permeability, hy­
drophilicity and fouling resistance, thereby improving overall perfor­
mance and durability of the of electrospun nanofibers. Process
parameters, such as, flow rates and concentration of polymer along with
the applied voltage can be varied to optimize the nanofiber’s perfor­
mance and characteristics (Zambare et al., 2017; Haider et al., 2018).
PAN-PES based coaxial electrospun nanofibers holds diverse applica­
tions in filtration, catalysis, tissue engineering and drug delivery, since
its customized properties may be fine-tuned to meet a particular need.
There are few reports in literature about the synthesis of PAN-PES based
electrospun nanofiber and their use in water treatment. Till date,
PAN-PES based pure polymeric coaxial electrospun nanofibers have only
been used for removing methylene blue (MB) from aqueous solutions
(Pervez et al., 2022).
In the current study, a distinct PAN-PES coaxial electrospun nano­
fibers has been developed for fluoride removal from water. An optimum
ratio of PAN and PES polymers have been exploited in the coaxial
nanofibers to obtain the best fluoride removal efficiency and water
permeability. Different morphological and surface property based
characterization methods were performed to determine the structure-
property relationship of the as-prepared nanofibers. Fluoride uptake
performance of the nanofibers were carefully examined by equilibrium
studies that includes effect of temperature, coexisting ions, pH and
reusability. Dead end and cross flow ultrafiltration performance of the
prepared nanofibers were also performed by depositing the same on a
substrate in order to highlight the change in flux and fluoride removal
efficiency against transmembrane pressure drop and cross flow rates.
Finally, real life feed was obtained from a nearby affected source and it
was used for determining the actual performance of the nanofibers.
2. Experimental
2.1. Materials
Polyacrylonitrile (average molecular weight: 150 kDa) and poly­
ethersulfone (average molecular weight: 98 kDa) was purchased from
eSpin Nanotech Pvt. Ltd., India. N, N-Dimethylformamide (DMF: density
944 kg/m3) used as a solvent. Dextran standards (70 kDa molecular
weight), polyethylene glycol (PEG, 400 Da, 6 kDa, 10 kDa, 20 kDa, 35
kDa, 100 kDa and 200 kDa molecular weight) and Sodium Fluoride
(NaF, average molecular weight: 42 g/mol) was supplied by M/s, Merck
Pvt. Ltd., India. All the chemicals were of analytical grade and used
without further purification. Deionized water was used in experimental
process.
2.2. Instruments
Details of the instruments used in the current study is explained in
the supplementary section (Refer appendix A1).
2.3. Preparation of electrospun nanofibers
Coaxial electrospun nanofibers were prepared by using electro­
spinning process (See Fig. 1). Briefly, the setup comprises of two syringe
pumps equipped with blunt-tipped needles. One syringe pump is con­
nected to the inner needle, dispensing the core (i.e., PES), while the
other one is linked to the outer needle, delivering the shell (i.e., PAN).
Distance between the needles and the applied voltage were controlled
M. Sharma et al.
during preparation steps (Danny Pratama Lamura et al., 2021). In order
to prepare the solution, pre-weighed amount of polymers was dissolved
in solvent. The solution was constantly stirred and heat was applied
intermittently to ensure proper homogenization for 48 h (Chatterjee and
De, 2015). Finally, it was sonicated for another 24 h in a sonicator. Once
ready, the solution was brought back to room temperature (298 K),
before using in the syringe assembly of the electrospinning setup.
Weight percentage of polymers, i.e., PAN and PES were varied from 2 wt
% till 10 wt%. Accordingly, membranes were named based on varied
concentration of polymers (See Table 1).
For example, nanofiber sample N1 contains 2 wt% of PAN and 10 wt
% of PES. Similarly, sample N2 contains 6 wt% of PAN and 10 wt% of
PES. Variation in composition of the polymeric solution were made on
the basis of defluoridation performance of the nanofiber, which is
explained in section 3. Process parameters were optimized to produce
PAN-PES coaxial nanofibers with best morphology. For example, flow
rate was 1 ml/h for the core and 1.4 ml/h for the shell, while voltage was
kept at 22 kV and the distance between the needle tip to the collector
was 15–17 cm. Drum (on which fibers were collected) was rotating at
1500 rpm and the temperature is maintained at 298 K.
2.4. Regeneration studies
Optimum nanofibers were further subjected to regeneration studies.
The nanofibers were used for uptake experiments in the first cycle,
following which it was desorbed using 0.1 (M) sodium hydroxide for 24
h. Following this step, it was again used for fluoride uptake studies. This
process was repeated for 4 cycles.
2.5. Filtration studies
Permeability, porosity and molecular weight cut off (MWCO) of the
nanofibers were assessed using a dead-end ultrafiltration cell (Refer
Appendix B7) (Chatterjee and De, 2014).
2.6. Equilibrium studies
Uptake capacity of the prepared nanofibers was also evaluated
(Mishra et al., 2022; Chatterjee and De, 2014). Related data were fitted
using Langmuir and Freundlich isotherm (Shrestha et al., 2013). Details
about the fittings are provided in supplementary section (Refer Appen­
dix B8). Impact of pH on uptake capacity of PAN-PES nanofibers was
examined using 10 mg/l of fluoride solution, where pH was varied from
2 to 11 at 298 K. Effect of arsenic and lead on fluoride removal by the
Fig. 1. A schematic illustration of preparation of PAN-PES electrospun nanofibers.
3
Chemosphere 349 (2024) 140837
nanofiber was also studied.
2.7. Dynamic filtration studies
A cross-flow cell (make: Technoquip Separations Pvt. Ltd., India) was
employed in total recycle mode for dynamic filtration of the chosen
nanofiber (with support). Effect of operating parameters, i.e., cross-flow
rate and transmembrane pressure drop (TMP), were performed to assess
its effect on defluoridation capacity and flux of the prepared nanofiber.
Experiments were stopped, when the permissible limit (1.5 mg/l) of
fluoride concentration in the permeate was reached (Maiti et al., 2010).
Continuous filtration study was also performed for a groundwater so­
lution, which was collected from Harinagar colony, ward number 3,
behind Birla Museum (28.21⁰ N and 75.34⁰ E), Pilani, Rajasthan, India.
The concentration of different ions (both anion and cation) present in
the sample was measured by an ion-selective electrode.
3. Results and discussions
3.1. Morphology
Scanning electron microscopic images and EDS analysis of PAN-PES
nanofibers are shown in Fig. S1 (a) and Fig. 2, respectively. EDS spec­
trum of N2 nanofiber is same as compared to other nanofibers prepared.
This is due to same polymer type, being used in all preparation steps.
Composition of N2 nanofibers shows the presence of carbon (C), oxygen
(O) and sulfur (S) as the fundamental elements. The EDS data calculated
the relative atomic proportions of these elements. For example, 70 wt%
of N2 nanofibers is carbon, 24 wt% is oxygen and 5.6 wt% is sulfur.
Following equilibration with fluoride solution, a fluoride peak (sub­
stantiating to 28 wt%) has been observed (refer Fig. S1(b)).
SEM images (as per Fig. 2) exhibit a densely interwoven web
spreading throughout the nanofibers. Diameter of these synthesized
nanofibers ranges from 100 to 1000 nm. Average diameter is reported at
300 nm. It is observed that the weight percentages of polymer play an
important role in determining morphology of the nanofibers. For
example, N1 nanofibers (2 wt% PAN and 10 wt% PES) show bead like
morphology along its structure, as observed from Fig. 2(a) and (b).
However, as the concentration of PAN is increased to 6 wt% (for N2
nanofiber), bead like morphology is reduced (refer Fig. 2c and d). But, as
the composition of PAN is further increased (8 wt%), bead like
morphology starts appearing. When PAN is kept at 8 wt% and PES is
varied to 6 wt%, prepared fibers instead show less amount of beads in its
structure (See Fig. 2g and h). Same is observed is case of N5 fibers,
M. Sharma et al. Chemosphere 349 (2024) 140837

Table 1
Nomenclature of different electrospun nanofibers.
Nomenclature Composition Permeability (m/ Porosity Contact Photograph Visualization Viscosity Fluoride Fluoride Uptake
s. Pa) (%) Angle (0) (mPa. s) Rejection (%) capacity (mg/g)
× 10− 11
PAN PES PAN PES

N1 2 10 0.1 38 67 19 110 41 4.92

N2 6 10 0.5 67 64 940 110 46 5.52

N3 8 10 2 51 83 2283 110 33 3.96

N4 8 6 2 70 68 2283 9 5 0.6

N5 8 2 2 68 83 2283 3 14 1.68

Note: All measurements are subjected to 5% error.

containing 8 wt% PAN and 2 wt% PES (Refer Fig. 2i and j). Apparently,
viscosity of the polymeric solution plays an important role over here
(Chatterjee and De, 2014). For example, PAN solution used in synthesis
of N1 nanofibers has viscosity of 19 mPa s. However, it increases to
2283 mPa s, when concentration of PAN increases to 8 wt%. Thereby,
highest beads formation is observed in case of N3 nanofibers, having
highest viscosity of shell polymer solution. However, for N4 and N5
nanofibers, bead formation reduces once the viscosity of core polymer
solution reduces (see Table 1). Usually, rough surfaces result due to
sporadic bead formation along the fiber strands, which further give rise
to anisotropic surface characteristics (Pervez et al., 2022). This phe­
nomenon might affect the membrane performance, which is discussed
hereby. As observed earlier, uniform surface (devoid of any such bead
morphology) shows best membrane properties. For example, fibers,
containing lesser beads in its strands, i.e., N2, N4 and N5, show higher
porosity values, i.e., 67%, 70% and 68%, respectively. However, for N1
and N3 beads, the porosity values are less, i.e., 38% and 51%, respec­
tively. A similar trend has been observed in case of contact angle, which
is indicative of the hydrophilicity of nanofibers. For example, N2 and N4
nanofibers have a contact angle (measured by sessile drop technique) of
64◦ and 68◦ . However, N3 and N5 nanofibers have higher contact angle
of 83◦ , which shows that they are relatively hydrophobic. Fibers
showing most uniform structure, i.e., N2, delivers highest fluoride
removal efficacy of 46% and uptake capacity (5.5 mg/g), as observed
from Table 1. The uptake of fluoride on the surface of N2 nanofibers is
also evident from the SEM images. For example, when Fig. 2d and f are
compared, it was observed that the fibers after fluoride equilibration
shows rough morphology compared to its naive form. At a higher
magnification (refer Fig. 2l), it was observed that the crystal of fluoride
salts adhered to the surface of the nanofibers. Thereby, further charac­
terizations were performed with N2 nanofibers. Particle characteriza­
tions, related to thermal analysis, surface functionalities and area were
discussed in supplementary section B. Corresponding observations are
shown in Figs. S2, S3 and S4, respectively. Controlled and
fluoride-exposed nanofiber samples are imaged using SEM The
elemental composition of the nanofiber surface is investigated using EDS
analysis. The samples are typically coated with a thin layer of conduc­
tive material (e.g., gold or carbon) to enhance image quality. Examine
modifications in the surface morphology, including the emergence of
novel structures, aggregation phenomena, or alterations in the orienta­
tion of fibers. Nanofiber structure may develop layers or clusters as a
result of fluoride uptake. Presence of fluoride in N2 nanofibers after
filtration is indicated by distinctive peaks in the EDS spectrum.
Effectiveness of nanofibers employed in water purification is greatly

4
M. Sharma et al.
Fig. 2. Scanning electron micrographs of (a) & (b) N1; (c) & (d) N2; (e) & (f) N3; (g) & (h) N4; (i) & (j) N5; (k) & (l) fluoride loaded N2 nanofibers.
influenced by surface wettability, especially hydrophilicity. This makes
it a useful indication for determining if a membrane is suitable for a
certain water treatment procedure since it directly affects water
permeability, fouling resistance, pollutant removal, and overall effi­
ciency. Contact angle for each of the coaxially electrospun nanofibers
was used to assess the hydrophilicity. As shown in Table .1, the contact
angle having 83◦ indicating low hydrophilicity, whereas nanofibers
having low contact angle such as 67◦ has higher hydrophilicity. This
might be accomplished by adding a hydrophilic polymer, such PAN,
which can increase the hydrophilicity of the material as a whole by
forming hydrophilic carboxylic groups on the surface of the blended
PAN/PES membrane, which lowers the contact angle. Additionally,
prior research shown that adding PAN polymer to the PES solution tends
to reduce the membranes’ contact angle. Overall, this finding suggests
that due to PAN/PES membrane’s hydrophilicity and thus increased
compatibility with aqueous solutions, more fluoride molecules would be
adsorbed [Pervez et al., 2022].
3.2. X-ray photoelectron spectroscopy
X-ray photoelectron spectroscopy (XPS) plot shown in Fig. 3. This
figure shows essential details on the chemical states and relative abun­
dance of elements on the surface. Peak intensity (arbitrary units) has
been represented against binding energy (eV). As observed from this
figure, C 1s peak at 284.6 eV indicates presence of carbon-based com­
pounds in the nanofibers. Carbon-carbon (C–C) and carbon-hydrogen
5
Chemosphere 349 (2024) 140837
(C–H) bonds are often linked to this peak. Presence of oxygen-
containing functional groups, such as, carbonyl (C– –O) and hydroxyl
(O–H), are indicated by O 1s peak at 532 eV. These functional groups are
essential to the uptake of fluoride ions by N2 nanofibers. Notably,
presence of fluorine species in the nanofibers is confirmed by the F 1s
peak at 685.2 eV (Mishra et al., 2022). Fluorine enrichment is added to
the corresponding functional groups during the subsequent experi­
ments. These functional groups increase the nanofibers affinity for
fluoride ions, increasing its effectiveness in this application. As a result
of creating solid hydrogen bonds with fluoride ions, oxygen function­
ality may aid in its uptake, as per the existence of oxygen-containing
functional groups (Refer appendix B6). Additionally, it is also
observed that the intensity of the some of the elemental peaks gets
decreased due fluoride uptake on thee nanofibers. For example, corre­
sponding peak intensity of carbon and nitrogen gets decreases at the
same binding energy levels. However, peak for oxygen gets increased,
which is contrary to the previously observed phenomena. This might be
due to strong interaction between fluoride and oxygen atoms on the
surface of the prepared nanofibers (see Fig. 3).
3.3. Equilibrium study
The uptake capacity of the N2 nanofibers at various temperatures,
pH and coexisting ions was investigated using artificially synthesized
fluoride solution in an orbital shaker. Related experimental conditions
are mentioned in the relevant figures.
M. Sharma et al. Chemosphere 349 (2024) 140837

Fig. 2. (continued).

different feed concentrations (Refer Fig. 4). After the experiments were
over, the equilibrium concentration of the filtrate was measured for
fluoride ion concentration.
At all temperatures, it has been noted that uptake capacity increases
with equilibrium concentration. For example, uptake capacity is 80 mg/

Fig. 3. XPS analysis of PAN-PES nanofibers before and after equilibrium

with fluoride.

3.3.1. Effect of temperature

Impact of temperature (carried at 298 K, 308 K and 318 K) on the
uptake capacity of fluoride by the N2 nanofibers was analyzed using Fig. 4. Uptake capacity of fluoride using N2 nanofibers.

6
M. Sharma et al.
g at equilibrium concentration of 660 mg/l. It increases to 105 mg/g at
2000 mg/l. It can also be observed that as concentration rises above
1200 mg/L, the uptake capacity stabilizes and marginally increases. For
instance, uptake capacity remains at 105 mg/g between 1200 mg/L and
1600 mg/L. Also, it is quite evident that uptake capacity increases with
temperature. At 298 K, equilbrium uptake capacity is noted at 110 mg/g.
At 308 K and 318 K, it increases to 230 mg/g and 340 mg/g, respec­
tively. It is therefore apparent that higher temperatures lead to increased
molecular mobility and enhanced diffusion rates, thereby enhancing
fluoride uptake by the nanofibers. Two adsorption isotherms, i.e.,
Langmuir and Freundlich were used to propose the uptake phenomena.
Relevant observations are enlisted in Table S1 (see supplementary sec­
tion). At 298 K, monolayer uptake capacity for N2 nanofibers is 146 mg/
g, while it increases to 478 mg/g at 308 K and 582 mg/g at 318 K. In
terms of Freundlich isotherm, adsorption capacity initially remains 1.5
mg1− n (l/g)n at 298 K and increases to 4 mg1− n (l/g)n at 318 K. Another
parameter of this isotherm, i.e., adsorption intensity varies between 1.2
and 1.9 for all the three temperatures. This value suggest that uptake is
uniform and favorable (Wen et al., 2015). Average relative error for all
the isotherms were obtained. It was observed that for Langmuir
isotherm, this error varies between 16 and 44%, while that for
Freundlich, it varies between 23 and 51%. Hence, based on this obser­
vation, it can be concluded that uptake is guided by Langmuir isotherm,
i.e., monolayer adsorption.
3.3.2. Effect of pH
Effect of solution pH on the fluoride uptake capacity of N2 nanofibers
is presented in Fig. 5. It is observed that the uptake capacity of N2
nanofibers decreases with pH of the solution. For example, at a solution
pH 2, uptake capacity is 110 mg/g for fluoride feed concentration of 10
mg/l. However, as the pH becomes 5, uptake capacity for N2 nanofibers
becomes 56 mg/g. It is the least at pH 11 (50 mg/g). This behavior can
be attributed to the mobile charges, i.e., zeta potential on the surface of
the nanofibers. Figure provided at the inset, details the variation of zeta
potential of N2 nanofibers with solution pH. As the pH increases the zeta
potential on the surface also increases. For example, at acidic pH, i.e., pH
4, the zeta potential is − 236 mV. When solution pH becomes alkaline
(pH 10), the zeta potential is 1 mV. Therefore, the isoelectric point (pH
at zero-point charge or pHZPC) is 9.7. Solution pH, having values lesser
than this, will make the surface positive. Fluoride, being a negative ion,
will get easily attracted towards positive surface of the nanofiber (Sahoo
et al., 2022). This is reason for high uptake capacities in the pH range of
Fig. 5. Effect of pH on adsorption efficiency of fluoride ions using
N2 nanofiber.
7
Chemosphere 349 (2024) 140837
2–7 (110-52 mg/g). The driving force for the uptake of fluoride ions
decreases as the solution pH nears the isoelectric point. As the solution
pH exceeds the isoelectric point, the surface becomes negatively charged
and repels any similar charges, i.e., fluoride ions. Thereby, the uptake
capacity becomes minimum at pH 11, as explained above.
3.3.3. Effect of co-existing ions
Table S2(a) shows the effects of arsenic and lead on fluoride uptake
by N2 nanofiber. In this study, feed concentrations of 50 μg/l and 100
μg/l of both ions were considered. It can be observed from this figure
that arsenic and lead competed with fluoride ions for active sites. At a
neutral pH, fluoride is removed at 46% in synthetic feed, having no
coexisting ions. However, when concentration of arsenic and lead was
increased to 50 μg/l, fluoride rejection capacity of N2 nanofibers were
reduced. For example, fluoride removal was 11% at 50 μg/l for arsenic
and 32% for lead ions. However, when concentration of arsenic was
increased to 100 μg/l, fluoride removal efficiency of N2 nanofibers was
increased to 22%. Hence, at higher arsenic concentration, there may be
some synergistic effect or cooperative interaction for fluoride ions. But,
this is not observed in case of lead ions. For example, the fluoride
removal efficiency was decreased marginally to 29%, when concentra­
tion of lead was increased to 100 μg/l. Thereby, lead being a dipositive
heavy metal ion gets adhered to the active sites of N2 nanofibers than
fluoride. Hence, there is an antagonistic effect offered by lead on fluo­
ride ions. When two ions, i.e., arsenic and lead were combined, effi­
ciency decreases to 21% from 46%. This is for the case, when both the
ions are present in equal proportions. However, of concentration of
arsenic increases to 100 μg/l, while lead is fixed at 50 μg/l, efficiency
decreases further to 16%. This may be due opposing effect produced by
lead ions, which is masking the synergistic nature of arsenic ions (Zheng
et al., 2020). In case of an exactly opposite situation, i.e., when lead is
increased to 100 μg/l and arsenic remains at 50 μg/l, fluoride removal
efficiency almost remains same (18%). This happens due to saturation
effect provided by the two ions (Mishra et al., 2022). Impact of sodium
and chloride coexisting ions on fluoride uptake has been investigated in
Table S2(b). In this study, feed concentration of 50 mg/l and 100 mg/l
with respect to both ions were considered. As the concentration of both
sodium and chloride ions was 50 mg/l, fluoride rejection capacity of N2
nanofibers were reduced from 46% to 37%. As concentration of sodium
was increased to 100 mg/l, while keeping concentration of chloride
constant (at 50 mg/l) fluoride removal efficiency decreased slightly to
33%. However, as concentration of chloride increases to 100 mg/l
(keeping concentration of sodium fixed at 50 mg/l), efficiency decreases
further to 21%. Both the ions poses hindering effect on uptake of fluoride
by the nanofibers. However, chloride being negative shows highest
hindrance, as observed from the results, in comparison to sodium.
3.4. Dynamic filtration study
In case of dynamic cross flow filtration, the concentration of feed
remains constant. In this study, two transmembrane pressure drop
(344.7 and 482.6 kPa) and two cross flow rates (30 l/h and 60 l/h) were
taken for the study. Apart from this a real life feed (concentration 2 mg/
l) was used at an operating condition of 344.7 kPa and 30 l/h. Relevant
observations (flux and concentration as a function of filtration time)
were drawn in Fig. 6. For each experiments, separate nanofibers (on
aluminium foil base substrate) were used for 6 h of filtration time.
Fluoride concentration in feed was kept at 10 mg/l for all studies done
with synthetic solution.
The rationale behind choosing 6 h of filtration time was made on the
basis of breakthrough, i.e., the time when the concentration of permeate
exceeds beyong the WHO limit (1.5 mg/l). It can be observed from this
figure that flux increases with transmembrane pressure drop and cross
flow rates. For example, at 1 h of filtration time, flux at 344. 7 kPa was
39 L/m2h, while that for 482.6 kPa, flux was almost doubled to 71 L/
m2h. In both these two cases, cross flow rate was kept constant at 30 l/h.
M. Sharma et al.
Fig. 6. Effect of operating conditions in dynamic filtration of fluoride using N2
nanofiber a) Flux b) Concentration.
Similarly, when cross flow rate was increased to 60 l/h at 344. 7 kPa,
flux was observed to be 44. 8 L/m2h for initial period of 1 h. However,
when the experiment gradually progressed with filtration time, flux was
observed to decrease for a fixed operating condition. For example, flux
for three and 6 h of filtration time was 36 L/m2h and 34 L/m2h,
respectively at an operating condition of 344.7 kPa and 30 l/h.
Concentration of fluoride in permeate increases due to saturation of
active sites with filtration time (Chatterjee et al., 2020). For example, at
1 h, concentration of fluoride in permeate was 0.5 mg/l, which increases
to 1.5 mg/l at 6 h duration. It can also be observed that concentration
increase with pressure drop and cross flow rate, due to less interation
time between nanofibers and solute (Chhaya et al., 2012). This results in
drop of breakthrough time, i.e., time when the concentration of fluoride
is permeate exceeds or becomes equal to WHO limit (1.5 mg/l). For
example, at 344.7 kPa and 30 l/h, breakthrough was 6 h, which de­
creases to 2.5 h for 482.6 kPa and 30 l/h. Similarly, lesser breakthrough
time of 2.6 h was observed for an operating condition of 344.7 kPa and
60 l/h. In case of real life feed, the breakthrough time was 5 h, which is
lesser than that of synthetic feed at the same operating condition (344.7
kPa and 30 l/h). This happens due to higher concentration of coexisting
ions in the real life feed (Chatterjee and De, 2017). Moreover, due to
presence of these coexisting ions, flux for real life feed was 35 L/m2h for
1 h filtration time, which decreases to 31 L/m2h at 6 h. Material cost per
8
Chemosphere 349 (2024) 140837
m2 of area for the best nanofiber is 5879 INR (70 USD). Considering an
overhead cost of 20%, the net cost the nanofiber is 7054 INR (84 USD)
(Refer Table S3).
3.5. Uptake mechanism and regeneration studies
The employed adsorbent underwent regeneration through treatment
with a 0.1 (M) NaOH solution, subsequently being reused for F−
adsorption. The regeneration adsorbent demonstrated an approximately
50% adsorption capacity compared to its fresh counterpart (refer to
Fig. 7). These findings imply that the spent adsorbent can be partially
restored by exposure to a potent alkaline solution, indicating the pres­
ence of robust interactions between F− ions.
This outcome not only supports the proposed mechanism but also
emphasizes the effectiveness of the regeneration process.
Uptake mechanism could be due to synergistic effect of adsorption
and electrostatic interaction. Physical adsorption might be possible due
to the weak van Der Waals forces that causes the fluoride ions to adsorb
on the surface of the nanofibers (Rathnayake et al., 2022). Electrostatic
interactions between these negatively charged fluoride ions and posi­
tively charged nitrile surface causes effective defluoridation (Khalid and
Nazir, 2022). These interactions, however depend on various parame­
ters, such as, temperature, pH and co-existing ions (Tolkou and Zou­
boulis, 2023).
4. Conclusion
Polyacrylonitrile and polyethersulfone based core-shell nanofibers
were prepared using coaxial electrospinning technique. Fibers prepared
with 6 wt% PAN and 10 wt% PES showed well structure morphology in
its fiber strands. Porosity of the lower grade ultrafiltration membrane
was 67% and contact angle of 64◦ , that indicated enhanced hydrophilic
nature. Carbon (70%), oxygen (24%) and sulfur (5.6%) constituted as
the main elements of the fiber. Three subsequent weight loss occurred in
the range of 30◦ –510 ◦ C, 520◦ –610 ◦ C and 615–800 ◦ C during thermal
analysis of the nanofibers. Nitrile, sulfone and carboxyl groups were
active in the fiber structure, which resulted in 46% fluoride removal in
batch ultrafiltration experiments. However, in equilibrium studies, the
uptake capacity was noted as 110 mg/g at 298 K, 230 mg/g at 308 K and
340 mg/g at 318 K. The mechanism is guided by assumptions of Lang­
muir isotherm. The surface area of this optimum concentration based
nanofiber is 12.3 m2/g (see Supplementary section B5) and it follows a
type- IV isotherm in nitrogen adsorption and desorption cycle. Highest
uptake was observed at acidic pH, i.e., pH 2, while isoelectric point was
observed pH 9.7. At 100 μg/l of arsenic and lead concentration in the
feed (fluoride concentration 5 mg/l), removal capacity was masked from
46% to 22% and 29%, respectively. Flux was 39 L/m2h and 35 L/m2h for
synthetic and real life feed water solution during 1 h at 344.7 kPa and
30 l/h of dynamic filtration. Breakthrough time was 6 h for synthetic
feed while it decreased to 1 h for real life feed.
CRediT authorship contribution statement
Manu Sharma: Methodology, Formal analysis, Visualization,
Investigation, Data curation, Writing - original draft, Investigation,
Writing - review & editing. K. Karthik: Formal analysis, Data curation,
Writing - review & editing. P. Keerthi: Data curation, Writing - review &
editing. Somak Chatterjee: Conceptualization, Supervision, Method­
ology, Formal analysis, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
M. Sharma et al. Chemosphere 349 (2024) 140837

Fig. 7. (a) Regeneration of N2 nanofibers and (b) proposed uptake mechanism.

Data availability C0 arsenic concentration in the feed, (mg/l)

Ce equilibrium concentration of arsenic in solution, mg/l
Data will be made available on request. i number of data points
v volume of the filtrate collected for batch adsorption, l
Acknowledgements Vm maximum monolayer adsorption capacity (Langmuir
isotherm), mg/g
(1) The research work is supported by Science and Engineering K adsorption equilibrium constant (Langmuir isotherm), l/mg
Research Board (SERB), Startup Research Grant (SRG) (Ref No: SRG/ kf adsorption intensity (Freundlich isotherm), mg((n− 1)/n) l1/n /g
2021/001118), dated December 15, 2021, offered to Dr. Somak Chat­ m mass of adsorbent (membrane samples) used, g
terjee. It is also a result of collaborative efforts between Dr. Somak n adsorption intensity (Freundlich isotherm)
Chatterjee and Dr. Keerthi. qe amount of arsenic adsorbed, mg/g
(2) The authors would like to thank the organizing committee of qe,meas experimentally measured value of qe, mg/g
SRM_IST ICONN 2023 conference for shortlisting the paper for qe,calc fitted value of qe from isotherm, mg/g
presentation.
(3) The authors would like to thank Mr. Utkarsh Adhikari (First Appendix A. Supplementary data
Degree Student enrolled as a study project intern under Dr. Somak
Chatterjee) for carrying out a part of the experimental studies. Supplementary data to this article can be found online at https://doi.
(4) The authors thankfully acknowledge the characterization facil­ org/10.1016/j.chemosphere.2023.140837.
ities at the Department of Chemical Engineering and other concerned
Departments at Birla Institute of Technology and Science (BITS), Pilani. References

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