Desalination 535 (2022) 115807

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Desalination
journal homepage: www.elsevier.com/locate/desal

Upcycling cellulose acetate from discarded cigarette butts: Conversion of

contaminated microfibers into loose-nanofiltration membranes for
selective separation
Ashesh Mahto a, 1, 2, Mahaveer Annappa Halakarni a, 2, Ashok Maraddi a, Glenita D’Souza a,
Anita A. Samage a, Utpal G. Thummar b, Dibyendu Mondal a, *, S.K. Nataraj a, c, *
a
Centre for Nano and Material Sciences, Jain University, Jain Global Campus, Bengaluru 562112, Karnataka, India
b
Membrane Separation and Science Technology, CSIR-Central Salt and Marine Chemicals Research Institute, Waghawadi Road, Bhavnagar 364002, Gujarat, India
c ́
IMDEA Water Institute, Avenida Punto Com, 2. Parque Cientıfco Tecnologico de la Universidad de Alcala, Alcal á de Henares, 28805 Madrid, Spain

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

• Recovery and reuse of polymer from

waste and discarded cigarette filter.
• Converting polluted microfibers into
anisotropic flat-sheet membranes.
• Use of highly efficient membrane for
selective separation of organic dyes and
inorganic salts
• Membrane further used for treating real
industry wastewater treatment.
• Membrane showed high selective sepa­
ration for salt, TOC, COD and BOD
rejections.

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

Keywords: This work reports the recovery and subsequent conversion of cellulose acetate (CA) polymer from waste cigarette
Cigarettes butts filters into semi-permeable membranes. The recycling process comprised of step-wise solvent washing to remove
Value-addition the organics and other adhering impurities from the smoked filter, followed by dissolution, filtration and rep­
CA asymmetric membrane
recipitation. The recovered polymer was thoroughly characterized and compared with the commercial and
Dye-salt separation industrial effluent
treatment
unsmoked cigarette filter derived CA to determine the purity and changes in polymer’s physicochemical prop­
erties after subjection to smoke and heat. Membranes were fabricated using all three types of CA by immersion
precipitation technique, systematically characterized (ATR-FTIR, SEM, contact angle, zeta potential) and tested
for dye/salt separation. Optimized membranes showed high rejection for various dyes with <15% rejection for
monovalent and divalent salts. Furthermore, long term testing (150 h) using real industry effluent revealed
steady performance with excellent flux recovery and persistent organics rejection.

* Corresponding authors.
E-mail addresses: dmtapu@gmail.com, m.dibyendu@jainuniversity.ac.in (D. Mondal), sk.nataraj@jainuniveristy.ac.in, sknata@gmail.com (S.K. Nataraj).
1
Current affiliation: International Centre for Clean Water, 2nd Floor, B-Block, IIT Madras Research Park, Kanagam Road, Tharamani, Chennai, 600,113, Tamil
Nadu, India.
2
These authors contributed equally.

https://doi.org/10.1016/j.desal.2022.115807
Received 27 January 2022; Received in revised form 20 April 2022; Accepted 20 April 2022
Available online 10 May 2022
0011-9164/© 2022 Elsevier B.V. All rights reserved.
A. Mahto et al.
1. Introduction
Extensive industrialization, agricultural boom and human activities
produce huge quantities of solid, liquid and gaseous wastes. A portion of
which is ultimately released untreated into the environment. [1].
Similarly, smoked cigarettes filters, also mentioned to as cigarette butts
(CBs) commonly discarded around the globe which lack any kind of
centralized collection and disposal system. Even more problematic is the
presence of recalcitrant cellulose acetate (CA) microfibers as the major
constituent of these butts [2], along with other toxic chemicals like
polycyclic aromatic hydrocarbons (PAH), heavy metals and other
mutagenic and carcinogenic components [3,4]. >6 trillion cigarettes
were smoked over the course of 2012 and this number is expected to
cross 9 trillion by 2025 [5,6]. Even in developed countries, roughly 75%
of CBs are discarded on the ground [7,8]. This culminates into the
generation of 340–680 million kg of CBs wastes annually [6]. CBs have
many harmful effects particularly along sea-coasts and aquatic envi­
ronments [9]. Belzagui et al. showed CBs are potential source of
microplastic pollution with an estimated 0.3 M tons of microfibers
ending up in aquatic ecosystem [10,11]. Other recent reports have
focused on sea beach pollution and CBs role as a potential source of
heavy metal vector in marine environment [12,13].
Extracting value-added materials from wastes not only reduces the
overall ecological footprint but also helps in offsetting the cost of waste
mitigation. In the context of CBs, there are many reports on carboniza­
tion of CA polymer to obtain carbon-based materials for gas adsorption,
sensors, catalysis, energy storage applications [14–21] and oil-water
separation [22–25]. However, micro-fibrous nature of the base mate­
rial (CBs) can eventually start leaching out during the separation pro­
cess. To overcome this obstacle, Li et al. fabricated a stainless-steel mesh
coated nanofibrous CA membrane via electrospinning for oil/water
separation [26]. However, the extraction of raw polymer (CA) from CBs
was achieved by hot water washing which might not rid the polymer of
PAHs and heavy metal contaminants. On similar lines, only water wash
was done to recover CA from CBs by Doyan et al., and subsequently
fabricated phase inverted membranes for oil-water emulsion separation
[27]. Conversion of CA extracted from CBs into cellulose by deacetyla­
tion process has also been studied [28]. Some studies focused on func­
tionalization of CBs extracted cellulose for catalytic degradation and
adsorption of organic contaminants from aqueous medium [29–32].
CA was the first polymer employed for the fabrication of reverse
osmosis membranes by S. Leob and S. Sourirajan in the early 1960s
[33,34]. Textile and dyeing industry produce huge quantities of hy­
persaline wastewater with appreciable quantities of dissolved dyes and
organic precursors. The current treatment protocol heavily relies on
chemical-induced coagulation and pre-filtration, followed by reverse
osmosis (RO) and multi effect evaporation (MEE) to achieve zero liquid
discharge (ZLD) and recover salts for reuse [35] and photocatalysis for
degradation of organics [36,37]. In this direction, selective separation of
dyes and other organics from salts have gained widespread attention for
different industrial effluent treatment [38–40]. Currently, there are no
reports on utilizing CBs to prepare selective asymmetric membranes for
organics-inorganics separation and wastewater treatment. Main objec­
tive of the present work is to prepare a stable selective membrane via a
simple and facile technique which can withstand long-term operation
under accelerated testing conditions and treat extremely polluted real
industrial effluents. This study can pave the way towards large-scale
production of CA membranes from waste CBs and in turn incentivise
the whole process of CBs collection and recycling.
2. Materials and methods
Details regarding materials, porosity, filtration experiments, long-
term studies and CA recovery from discarded CBs used for thorough
analysis of samples have been enlisted in the ESI section (Section S1, S2,
S3, S4 and S5, respectively).
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Desalination 535 (2022) 115807
2.1. Instrumentation
The hydrophilic nature of the CBs membranes has been examined
using a water contact angle detector following sessile drop method using
the Duravisions Systems (DS) India. The membrane sample’s active
surface was dropped with 100 μL of demineralized water. To obtain the
constant contact angle value at least 6 repetitive CA measurements were
carried out for each sample. Conductivity and TDS of all the salt solu­
tions, salt-dye mixtures, simulated wastewater, feed and permeate were
measured using conductivity meter (USA, Instruments of HANNA-
5522). Functional group of all the samples was investigated using
Fourier transform IR-spectrophotometer (FTIR) and ATR-FTIR mode
adopted to identify the functional characteristic of CA membranes (UK,
GX series 59,387 Perkin Elmer spectrum). The ATR-IR measurements
were acquired at a resolution of 4 cm− 1 and ranged from 400 to 4000
cm− 1. Roughness and surface morphologies were recorded using Field
Emission Electron Microscopy (FESEM JSM-7100F) and atomic force
microscopy (AFM Model: NT-MDT, Ntegra Aura, Russia). The feed and
permeates concentration of dyes, mixture of dyes and the colour of real
industrial wastewater were measured using UV–Visible spectroscopy
(Shimadzu, Japan) in the range 200 nm–800 nm wavelength. Surface
charge of the membranes analyzed through electrokinetic analyzer Sur
PASS 3 (AntonPaar, Austria) at 22 ◦ C with 1 mM of KCl as a background
aqueous electrolyte by measuring streaming potential with pH (3− 11).
Chemical oxygen demand (COD) was measured using a COD metre to
confirm the reduction of organic pollutants in permeate of selected
wastewater (HANNA Instrument USA). Biochemical oxygen demand
(BOD) measurements were carried out by using IS 3025(P-44) 1993 (RA-
2019) protocol. For total organic carbon (TOC) analysis, combustion
catalytic oxidation method was employed (Shimadzu TOC-TCSH) [41].
Viscosity was measured using an Ostwald viscometer.
The viscosity average molar mass of all the polymer samples were
calculated using the Mark-Howink-Sakurada (MHS) eq. (1) and referring
to a previous study [42]. DMSO was used as the solvent and the ex­
periments were performed at 25 ◦ C.
[η] = KMva (1)
The technique ASTM-D-817-91 was employed analyse degree of
acetylation of cellulose acetate (Method for Testing Cellulose Acetate). A
saponification process was used to determine the DS. About 0.1 g CA was
mixed with 5.0 mL NaOH (0.25 mol.L− 1) and 5 mL ethanol and the
mixture was left for 24 h. After that, 10 mL HCl (0.25 mol L− 1) was
added to the system, which was then allowed to sit for 30 min. Using
phenolphthalein as an indicator, the combination was tested with a
standard NaOH (0.25 mol L− 1) solution. Triplicate batches were
analyzed and the average value was calculated. The proportion of the
acetyl group was calculated using Eq. (2). The degree of substitution was
calculated using Eq. (3) [43].
[(Vbi + Vbt )μb − Va ∗ μa ]43 ∗ 100
%AG = (2)
mca
162.14 ∗ AG ∗ 0.01
DS = (3)
(60.052 − 42.037 ∗ AG ∗ 0.01)
Where percent AG denotes the fraction of the acetyl group, and Va: HCl
volume injected to the system, μa: HCl concentration, 43: molar weight
of the acetyl group, mca: weight of CA sample.
2.2. Membrane fabrication
The CA membranes were prepared via a slight variation in the
technique developed by Strathmann et al. [44]. This was done to
maximise flux and organics rejection while maintaining a low salt
retention by the membranes. Different polymer: solvent ratios, evapo­
ration time, solvent exchange bath and annealing bath temperatures
A. Mahto et al.
were studied to obtain the final optimized membrane (data not shown
here). In a typical process, the polymer solution was prepared by dis­
solving 20 wt% of CA (commercial/PCF/SCF) in acetone (40 wt%) and
formamide (40 wt%) solvent mixture. Small portions of CA were added
to a warm solvent mixture (40–45 ◦ C) under continuous stirring (300
rpm) over a period of several hours. This was followed by continuous
stirring for 12 h to obtain a homogeneous solution. The solution was
then centrifuged at 3000 rpm for 20 min and decanted to remove sus­
pended particles. Degassing was done wherein the polymer solution was
kept for 24 h for removing air bubbles. The polymer solution was then
tape casted either directly on a clean glass plate or a polyester fabric as
the support layer. The casting was done using a semi-automated flat-
sheet casting machine (Tech Inc. Pvt. Ltd.) operating with a knife gap to
achieve a membrane thickness of 100 μm. The as casted CA film was left
in open air (dust-free) for 2 min for partial solvent evaporation, followed
by immersion in cold water (4 ◦ C) for complete solvent exchange and
membrane formation (1 h). Thereafter, the CA membranes were
annealed at 60 ◦ C in water bath for 3 min. The final membranes were
stored in DI water (6–8 ◦ C) before further testing.
3. Results and discussion
Fig. 1 depicts a schematic representation of the overall process, from
collection of waste CBs to its conversion into flat-sheet membranes. All
the reported studies on value-addition of CBs had focused only on the
smoked filters (SCFs) and no comparison was made with unsmoked/
pristine filters (PCFs). This important point was also highlighted by
Marinello et al. in a recent review article on recycling of CBs [6]. Thus,
herein, a comparative study was carried out with pristine CBs and
commercially available CA polymers. The PCFs were also washed using
a similar protocol that was used for SCFs to maintain uniformity in the
process parameters before the preparation of membranes using recov­
ered CA polymers. The commercial CA was used as received without any
purification.
Fig. 2 provides a detailed comparison between the CA polymers (a-c)
and membranes (d-f) derived from PCF, SCF, and with commercially
available CA polymer (Eastman). It is quite evident from the FTIR
spectra different CA samples (Fig. 2a) that similar chemical functionality
exists for all. The three major peaks characterstic due to acetyl group’s
Fig. 1. Schematic depiction of the process for CA recovery from smoked cigarette filters and its subsequent conversion in flat-sheet semi-permeable membranes.
3
Desalination 535 (2022) 115807
vibrations at ~1750 cm− 1, ~1370 cm− 1 and 1240 cm− 1 corresponds to
the C–– O stretching, C–H bending in -CH3 group and ester’s C–O
assymetric stretching, respectively. The C-O-C linkage of the anhy­
droglucose units in the CA polymeric backbone is responsible for the
sharp peak at ~1050 cm− 1 while the broad band above 3400 cm− 1 is
owed to -OH stretching. The C–H stretching vibrations in -CH3/CH2
groups is responsible for the medium intensity peaks between 2850 and
3000 cm− 1 and its bending vibrations leads to a sharp peak around 900
cm− 1 [45].
The powder XRD pattern of the CBs derived CA polymer differed
slightly from that observed for commercial CA (Fig. 2b). The wide halo
around 2θ = 20◦ is a common feature of all organic polymers and results
due to the amorphous nature. Moreover, at lower 2θ values, 3 distinct
peaks at ~8◦ , 10◦ and 13◦ can be observed for the commercial CA
sample while these peaks are not distinctly visible for the PCF and SCF
derived CA. These peaks have been attributed to the crystalline CA
diffractions and depends on the aggregation of the parallel polymer
chain segments. The observed difference might be due to the difference
in acetyl content or the degree of substitution. A low degree of substi­
tution leads to better packing of the polymer chains and the microfi­
brillar structure is maintained due to hydrogen bonding interactions
between the hydroxyl groups. This is reflected in well-defined and
narrower peaks in the crystalline region of the CA. An increase in the
degree of acetyl content leads to an enhanced interfibrillar distance due
to disordered packing and loss in crystallinity [46]. The results suggests
that commercially available CA has a lower acetyl content than that of
PCF and SCF derived CA. The percentage of acetyl group (AG) in com­
mercial 30 kDa CA was 40.93 which translated to a degree of substitu­
tion (DS) of 1.54. Similar values were obtained for the 50 kDa CA sample
as well (41.26% AG, 1.56 DS). However, for PCF and SCF derived CA
samples, the AG values were 47.52% (1.92 DS) and 53.92% (2.33 DS),
respectively. These values confirms the previous hypotheis based on the
data obtained from the powder XRD spectra.
Further, to assess the molar mass of the polymers recovered from the
CBs, viscosity measurments were carried out using an Ostwald viscom­
eter. DMSO was choosen as the solvent system and two commercial CA
polymers (Eastman) of number average molecular weight (Mn) 30 kDa
and 50 kDa were taken as reference. As can be observed in Fig. 2c, the
reduced viscosity (specific viscosity/concentration (g/100 mL)) vs
A. Mahto et al.
Fig. 2. (a) FTIR spectra overlap of CA samples, (b) Powder XRD pattern of CA samples, (c) Reduced viscosity (100 \mathrel{\raise1pt *\raise0pt} mL/g) vs.
concentration (g/100 mL) profiles for CA samples, (d) ATR-IR spectra overlap of CA membrane samples, (e) Contact angle measurements for CA membranes (average
of 10 droplet measurements), (f) Stream Zeta potential variation of CA membranes at different pH. (It is to be noted here that only for the viscosity vs. concentration
study (c), two different commercial grade polymers with mol wt. 30 k Da and 50 k Da were used. In the rest of the experiments, only 50 k Da commercial CA was used
as reference).
concentration profiles were plotted to obtain the intrinsic viscosity
values [η] from the intercept of the liner fitted lines. Using the MHS
equation, the viscosity average molar mass (Mv) values of ~30,250 Da
and ~60,440 Da were obtained for the commercial CA polymers
(average of 5 experiments). Using similar protocol, the PCF and SCF
derived CA polymers were found to be of ~88,460 Da and ~74,960 Da,
respectively.
Flat-sheet membranes were prepared using different CA polymers
(PCF, SCF and 50 kDa commercial). 50 kDa commercial polymer was
chosen as its Mv was closer to that of PCF and SCF derived CA polymers.
ATR-IR analytical tool was used to assess the surface functionality of the
membranes (Fig. 2d). As expected, the spectra were almost identical and
the magnified overlap (inset of Fig. 2d, 550 cm− 1 to 1850 cm− 1) shows
no major changes. The major acetyl group vibrations at ~1750 cm− 1,
~1370 cm− 1, 1240 cm− 1 and the peak arrising due to CA polymer
backbone at ~1050 cm− 1 can be clearly observed in the magnified re­
gion. Another important aspect of the membrane surface is its hydro­
philicity and roughness, which directly influences the separation and
filtration performance. Sessile drop contact angle measurements using
water droplets were performed to assess these parameters and the results
are depicted in Fig. 2e The data points towards a better interaction of the
water droplets with the membranes obtained from the PCF and SCF
derived CA polymer, which results in a lower contact angle values
(around 50◦ ). On the other hand, the commerical CA derived membrane
surface has a water contact angle of 65◦ . This might also result due the
difference in the surface roughness of the membranes derived from
different polymers. Lower water contact angles might result in better
membrane performance in controlling fouling and easy cleaning
through intermittent water washes [47,48].
The charge on the surface of membrane was measured via streaming
potential measurement. Fig. 2f shows the variation in the zeta potential
values with pH. It can be observed that in the entire pH range under
study, the zeta potential of the all the CA membranes are negative and
follows the same trend. In nanofiltration membranes, the surface zeta
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Desalination 535 (2022) 115807
plays an vital role and influences the rejetion of charged moieties like
dyes, salts etc. [49]. Membranes with the polar groups -OH (hydroxyl
group) and -COOH (carboxyl group) generally respond to the solution
atmosphere in which they are present. Depending on the pH of the so­
lution -COOH and -OH can be protonated or deprotonated, therefor
altering the charge at the surface of the membrane. Also, another reason
for the change in the surface charge in wide range of pH due to
adsorption of the anions (OH- or Cl-) on the membrane surface [50]. To
know the charge of the prepared membranes the zeta potential was
carried out in the pH range of 3 to 11. As shown in the Fig. 4f, the
membrane surface charge shown positive in acidic pH. This positivity
due to presence the greater number of protons, which are adsorbing on
the membrane which results leads to positive zeta potential. Further
increasing the solution pH, the zeta potential was becoming more
electronegative. This changes due to the dissociation of acetyl groups in
basic condition as well as adsorption of anions on the membrane surface.
Many studies have proven that various non-ionogenic polymer surfaces
acquire a negative zeta potential in aqueous electrolytes [51,52].
Depending on the extent of substitution of the cellulose acetate polymer,
the adsoprtion of different anions might vary to some extent.
Fig. 3 depicts the SEM morphology of surface and cross-sectional
view of all the CA membranes. Fig. 3a3 shows the low magnification
cross-section image of the commercial CA derived membrane, which on
closer inspection (a4) displays a dense sublayer. The top surface of the
membrane (a1, a2,) that acts as the selective active layer comprises of
what seems like compactly interconnected inhomogeneous beads. On
the other hand, the top layer of the PCF and SCF derived CA membranes
(b1, b2 & c1, c2, respectively), from a morphological aspect, seem like
densely packed polymer brushes. This might be one of the contributing
factors towards the lower contact angle values of PCF and SCF CA
membranes (Fig. 2e).
A cursory glance over the cross-section image of PCF and SCF CA
membranes (b4 and c4, respectively) is enough to observe the compar­
atively porous structure than that of commercial CA membrane (a4).
A. Mahto et al. Desalination 535 (2022) 115807

Fig. 3. SEM images detailing morphology of membrane top active surface and cross-sectional view. Cross-section view of membranes obtained from (a) commercial
CA polymer, (b) Pristine cigarette filter (PCF) CA and (c) Smoked cigarette filter (SCF) CA. Magnified top view of the membrane surface (a1, a2) commercial CA
polymer, (b1, b2) PCF CA and (c1, c2) SCF CA. Magnified cross-sectional view of membrane derived from (a3, a4) Commercial CA, (b3, b4) PCF CA, and (c3, c4) SCF CA.

These images (b4 and c4) make it clear that the relatively tight top layer
is sitting on top of a ultraporous sub-layer. Comparing SCF CA mem­
brane’s cross-section (c4) with that of PCF CA (b4), it can be seen that the
former comprises on highly interconnected micropores while the latter
is less porous. Albeit these differences, all these membranes fall under
the category of ‘anisotropic/asymmetric membranes’ with a relatively
tight active selective layer supported on a porous structure. The differ­
ence in morphology of these membranes will influence the permeability
as well as the separation and rejection performance. The subsequent
section sheds light on these differences by thoroughly analysing the
membrane performance using a range of feed solutions.
Fig. 4 represents the as prepared membrane’s AFM micrographs and
section analysis. The peaks in leftmost micrographs can be ascribed to
the nodules, while the pores can be envisaged as the dark depressions
[53–55]. The micrographs were processed to determine the surface
roughness characteristics. Different parameters like peak-to-peak
maximum distance, mean value of peak-to-peak distance, average
arithmetic roughness, and root mean square roughness were calculated
and the data is presented in Table S3 (ESI). As can be seen from Table S3,
surface roughness is in the order PCF > Commercial > SCF.
The AFM images in Fig. 4 (middle images) were further evaluated in
terms of the maximum and lowest heights (Z-scale) of the crest and
trough morphology. The height difference (Z) might be interpreted as
localised nodule surface roughness. The Commercial CA membrane’s
surface had the shortest height of all the nodules. The nodule heights
ranged from 20 to 80 nm, while the root square value for commercial CA
was 9.17 nm. The maximum height of all nodules peaks for PCF was
40–120 nm with a root square value of 11.7 nm, whereas the SCF
membrane had a root square value of 5.25 nm and a maximum height of
20–100 nm.
The initial performance testing was carried out for commercial CA
membranes. Fig. 5a depicts the pure water flux (PWF) and aqueous NaCl
and MgSO4 rejection profiles as a function of applied pressure (1–4 bar).
As expected, the flux linearly improved with an increase in trans-
membrane pressure difference. The maximum flux achieved was
around 20 LMH (L.m− 2.h− 1) at 4 bar pressure. The difference between
the PWF and the flux for salt solutions decreased gradually as the
pressure was increased and became almost similar at 4 bars. The
rejection of both the inorganic salts however remained almost constant
in the experimental pressure range. The rejection of NaCl salt varied
between ~5–10% while that for MgSO4 was observed to slightly higher
at low pressures, but remained around 10% only. As the rejection of salt
is low, or in other terms the salt leakage is high, the effect of concen­
tration polarization is negligible. Therefore, it is imperative that the
PWF and the aqueous salt solution flux to be in similar range. Consid­
ering huge quantities of dyes Fig. 5b shows flux and rejection of three
dye molecules with different molecular weights tested as feed. Congo
red (CR) dye removal efficiency was the highest with the membrane

5
A. Mahto et al. Desalination 535 (2022) 115807

Fig. 4. AFM micrographs (a) Commercial CA, (b) SCF and (c) PCF membranes.

Fig. 5. Commercial CA derived membrane performance under different feeds at an external applied pressure of 1–4 bars. (a) Pure Water Flux (PWF), NaCl and
MgSO4 aq. solution (2000 ppm) flux and rejection, (b) Congo Red (CR), Eriochrome Black T (EBT) and Red Brown (RBN) dyes aq. solution (25 ppm) flux and rejection
study. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

achieving ~99% rejection at all pressures. Eriochrome black T (EBT)
exhibited slight elevation in rejection with increase in pressure with
variation from 95 to 97%. At low pressures, the rejection of red brown
dye (RBN) was around 90% (at 1 bar), while it increased to ~95% at 4
bar pressure. The rate of increase in flux with pressure variation (1–4
bars) was highest for RBN feed and lowest for CR. This is in accordance
with the rejection profiles of these dyes due to Donnan repulsion in
which strong electrostatic repulsion instigated by negatively charged
surface on the membrane [56,57]. Till 3 bars, the flux for EBT followed
the trend as CR, but at an applied pressure of 4 bars, the fluxes for EBT
and RBN feed were almost the same. The UV–Vis spectra with inset
photographs of feed and permeate for all dyes are shown as Fig. S1 (see,
ESI).
Fig. 6(a-c) summarises the performance of SCF derived CA mem­
branes with respect to PWF, salts and dyes rejection and flux profiles.
While Fig. S2(a-c) ESI corresponds to the same data sets for PCF derived

6
A. Mahto et al. Desalination 535 (2022) 115807

CA membranes. Comparing Fig. S2(a & d), it can be observed that the
rate of change of flux with increase in pressure is higher for PCF CA
membranes than that for SCF CA membranes till 3 bars. At 4 bars, both
the membranes yielded similar flux performance, albeit PCF CA mem­
brane flux was slightly higher. The salt rejections for both the mem­
branes were similar to that of commercial CA membrane. The values
remained either close to or <10%. It should be noted that although there
was no variation in the rejection of salts, the fluxes were higher for PCF
and SCF derived CA membranes when compared with commercial CA
membranes (Fig. 5a). At 4 bar pressure, the difference is close to 50% (an
increase of ~10 LMH). This difference can be attributed to the dense
cross-sectional sub-layer of the commercial CA membranes which might
create additional hinderance to the permeate flow, thereby decreasing
the flux (Fig. 3a4). The subtle change in the porosity of PCF (58 ±
0.05%, 17 ± 1.1 nm) and SCF (55 ± 0.03%, 12 ± 1.5 nm) derived CA
membranes (Fig. 3b4 and c4, Table S3 ESI respectively) did not lead to
significant difference in the flux profiles of both the membranes. On the
contrary, the PCF CA membranes yielded better average flux data in the
tested pressure range than the SCF CA membranes. Moving to the dye
rejection studies, some stark differences can be observed just by a
cursory glance over the Fig. 6(b-c). In addition to the 3 dyes tested using
commercial CA membranes, two additional dyes namely crystal violet
(CV) and methylene blue (MB) were also tested using the PCF and SCF
derived CA membranes. The flux profile of MB dye solution using PCF
CA membrane stands out the most, with maximum flux reaching close to
60 LMH at 4 bar pressure (Fig. S2b), while the rest of dye feeds showing
a maximum between ~11.5–21 LMH. The corresponding rejection of
MB was bound to be low (Fig. S2c) and was observed to be between
~56–62%, while the rejection of all the other dyes were in the range of
~90–99%. For SCF CA membranes, highest flux values in the range of
~26 LMH were obtained for RBN, EBT and CR dye feeds at 4 bar
operating pressure Fig. 6b. CV dye feed yielded the lowest flux values of
about 11 LMH at the same pressure, while MB dye feed was somewhere
intermediate at ~21 LMH. In the case of SCF CA membranes also, MB
dye rejection was the lowest and was found to fluctuate between
~78–83%. RBN dye also showed <90% rejection using the same
membrane (~86–87%). While for the rest of the dye feeds (EBT, CV and
CR), high rejection rates between 95 and 99% were observed Fig. 6c.
The UV–Vis spectra with inset photographs of feed and permeate for all
dyes are shown as Fig. S3–S4 (ESI). The anomalous case of MB can be
attributed to the positive charge developed on the dye molecules in
aqueous solution in conjunction to its lowest molecular weight among
all the dyes tested. As the membrane surface is negatively charged,
attractive electrostatic interaction between the organic dye pollutant
and functionality on the membrane might lead to lower rejection rates.
Although CV is also positively charged in aqueous medium at neutral
pH, it has a higher molecular weight than MB. Moreover, the 3D
structure of MB dye in aqueous medium is a slightly bent linear geom­
etry with restricted freedom of rotation, while the CV dye has a trian­
gular geometry with the two 4-dimethylaminophenyl groups in
staggered configuration [58]. Thus, the effective molecular size of CV,
considering all 3D coordinates is much larger than that of MB. This
might lead to CV dye’s better rejection and also justify the lowest flux
values obtained for both PCF and SCF derived CA membranes. On the
other hand, CR dye, being an anionic moiety, achieved high retention
rates when filtered through the negatively charged CA membranes. After
a thorough assessment of different solute rejection pattern including
both inorganic (NaCl, MgSO4) and organic solutes (dyes) with mol. wt.

Fig. 6. SCF CA derived membrane performance (a) Pure water (PWF), NaCl and MgSO4 aq. Solution (2000 ppm) flux and rejection, (b) Methylene Blue (MB), Crystal
Violet (CV), Congo Red (CR), Eriochrome Black T (EBT) and Red Brown (RBN) dyes aq. solution (25 ppm) flux, (c) rejection plots and (d) Separation factor (βA/B)
and selective figure of merit for dye/salt separation plotted against dyes with increasing molecular weight (A and B subscripts represents dye and salt, respectively).
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

7
A. Mahto et al.
ranging from 58.44 Da to 696.6 Da in both as individual and mixture of
feed stocks, as shown in Table S4 of ESI. However, organic solute with
>400 Da has shown >90% rejection for both PCF and SCF membranes.
Accordingly, it is broadly concluded that MWCO of newly developed
membranes stand above 400 Da.
After thoroughly investigating individual solutes for their rejection
and effect on permeate flux, separation studies for binary salt/dye
mixtures were carried out. Feed solutions were prepared with all 10
combinations possible with 5 dye molecules and 2 salts and tested using
PCF and SCF derived CA membranes. Fig. S2d ESI and Fig. 6d depicts the
selective figure of merit (FOM) and separation factor (βA/B) plotted
against the dye molecules arranged according to the increasing order of
their molecular weight (x-axis). For PCF as well as SCF derived CA
membranes, the best separation factor was achieved for CR and salt
mixtures. For PCF CA membranes, the filtration behaviour of NaCl/CR
mixture showed slightly higher β value than that for MgSO4/CR, while in
the case of SCF CA membranes the separation factor was the same in
both cases. The poorest separation efficiency was achieved for MB/salt
mixture which was evident from the individual dye rejection studies as
well. The selective figure of merit (FOM) was also calculated by
normalizing the separation factor with the molecular weight ratio of
dye:salt. Taking the example of CR/salt mixtures, it can be observed that
for MgSO4 salt mixture the FOM was higher than that obtained for NaCl
mixture. This is because the molar mass of the former is more than
double the molar mass of the later. Similar trend can be observed for all
the dye/salt mixtures except for those cases where the dye rejection is
low (MB).
Because of the rising production and discharge of dye-contaminated
saline wastewater, selective molecular separation of organics from
inorganic ionic species in a mixture of pollutants is becoming increas­
ingly important. Out of the 90,000 t of commercially available dyes per
year, roughly 10–20% is released into the environment untreated
Fig. 7. SCF CA derived membrane performance (a) simulated wastewater treatment, (b) flux of real industry wastewater, (c) dye-salt rejection of real industry
wastewater and (d) rejection of TOC and COD.
8
Desalination 535 (2022) 115807
[59,60]. These dyes not only endanger the environment, but they also
harm humans as and when they enter the food chain [61,62]. Since the
presence of inorganic species (salt-ions) and water-soluble dyes mole­
cules in the dye wastewater system, three types of simulated feed mix­
tures of dye wastewater were prepared to assess selective separation
efficiencies of the SCF derived CA membranes. These feeds include,
simulated wastewater (C1), simulated brackish water (C2) and simu­
lated seawater (C3), all spiked with a mixture of dyes. Separation of dyes
from these mixtures were performed using SCF membranes at 4 bar
pressures as depicted in Fig. 7a and PCF membrane results represented
Fig. S5a ESI. CA membranes derived from PCF and SCF gave a flux of
<28 LMH with <12% rejection of inorganic salts and dye rejection was
<99%. The UV–Vis spectra with inset photographs of feed and permeate
for dyes are shown in Fig. S6–S7 ESI. An observation can be made
regarding the above discussed performance data that both the mem­
branes performed best in the presence of higher NaCl salt (C3) con­
centration. The dye rejection was highest while the salt rejection was
almost similar to that observed for C1 and C2. Textile dyeing industry
uses high amounts of salts and their wastewater generally comprises of
dye molecules, its precursors and high TDS due to dissolved salts (NaCl,
Na2SO4) [63,64]. The membranes proposed in this study can effectively
segregate organics and the concentrated salt solution. The aqueous so­
lution of this concentrated salt can potentially be reused in the dye bath
for exhaustion of dye molecules on the fabrics. An in-depth discussion on
the influence of salts on dye retention and the mechanism behind
increased rejection of dyes can be found in previous studies [65–67].
After thoroughly characterizing the PCF and SCF CA membranes for
its performance using various simulated feeds, an attempt was made to
the separation efficacy of real industrial effluents. Five different
wastewaters were tested for the segregation of organics and dissolved
salts. The initial characterization of the separation performance was
done using UV–Vis spectroscopy and conductivity measurements of
A. Mahto et al.
initial feed and permeates. As can be seen in Fig. S8 and S9 (ESI),
different wastewaters were characterized for a single intense band in the
UV region of the spectrum. Fig. 7b-d represents the performance of SCF
CA membranes and PCF CA shown Fig. S5b-d ESI using different
wastewaters as feeds. The PCF CA membrane yielded average 22.5 LMH
of flux with 19.7% of salt, and 60.7% of colour rejection for pharma,
sugar industry, molasses processing and dye effluent wastewater. The
best separation performance was achieved for the treatment of tannery
wastewater flux wherein an average flux of 23.8 ± 1 LMH was recorded
with a low salt rejection of 16.3 ± 0.6% and high colour rejection of 76.8
± 5%. The performance of SCF CA membranes for the treatment of in­
dustrial wastewater were similar to that of PCF CA membranes, but the
salt retention was, on an average, 5% lower. For example, the salt
rejection was 15.7 ± 3.1%, 18.0 ± 2% and 12.9 ± 0.2% for molasses
processing, sugar industry and tannery wastewater, respectively. The
Fig. 8. Long-term filtration studies using real industry effluent. Pharmaceutical industry wastewater treatment using (a) Commercial, (b) SCF and Tannery effluent
treatment using (c) Commercial CA, (d) SCF CA membrane and (e and f) The digital photographs showing pharmaceutical wastewater and tannery wastewater before
and after treatment using SCF and commercial CA membranes.
9
Desalination 535 (2022) 115807
total organic carbon (TOC) rejection for different wastewaters using SCF
and PCF CA membranes Fig. 7d and Fig. S5d ESI. An average rejection of
64% to 88% was achieved for different wastewaters. In general, PCF CA
membranes performed slightly better than the SCF CA. Fig. 7d repre­
sents the initial and final chemical oxygen demand (COD) of different
wastewaters before and after treatment with SCF CA membranes. The
total of oxygen required to oxidise soluble as well as particulate organic
matter (POM) in water is measured by COD. Better result was observed
for the treatment of tannery wastewater wherein the initial COD of 5.7 K
± 57 ppm reduced to 0.7 K ± 45 ppm after filtration, a rejection of
almost 88%. Comparison of different compositional parameters of in­
dustrial wastewaters before and after filtration through SCF and PCF CA
membranes are provided in Table S5 and S6 of ESI. The performance of
industrial wastewaters treatment using commercial NF20 membrane as
shown in Fig. S10 ESI. The average flux (31.3 LMH) was higher than SCF
A. Mahto et al.
but salt separation efficiency from the industry waste was less due to
higher rejection of salt and dyes.
Approximately 150 h of repeated filtration tests were performed
using commercial, SCF CA membranes with high volumes of pharma­
ceutical industry wastewater (Fig. 8a-b) and tannery industry effluent
(Fig. 8c-d) as feed. The experimental set-up used for long-term testing
comprised of 3 testing cells connected in series as shown in Fig. S12 of
ESI. It was observed that the trend of normalized flux for commercial CA
membrane for both the feeds decreased with time (Fig. 8a & c). So,
although flux recovery was found after 24 h of water washing, the flux
reduction trend is still visible, indicating plausible foulant surface de­
positions. However, for PCF membranes flux retention was significantly
stable while for the SCF membranes, flux retention was moderate
(Fig. S11a-b ESI). The salt permeation was high for all membranes and
the separation efficiency for dyes were high. Similarly, Fig. 8(e & f) and
Fig. S11(c & d) depicts the digital photographs of industrial wastewater
before and after treatment.
Using the long-term testing data, the flux decline ratio (FDR) and flux
recovery ratio (FRR) were calculated to quantify the membrane’s
fouling tolerance. The FDR values in case of the pharmaceutical
wastewater filtration experiments using PCF and SCF membranes were
average 42.8% and 52.2%, respectively, lower than that of commercial
CA membrane (81.1%) (Fig. 9a) for PCF Fig. S13a ESI. Similar trend was
observed for the tannery effluent as showed in Fig. 9c for PCF Fig. S13c.
The flux recovery ratio (FRR) values obtained after water washing was
examined to confirm the antifouling performance of the optimized
membranes. After the DI water wash, the FRR were 37.7%, 66.5%, and
68.4% for the commercial CA, PCF and SCF membranes using pure
Fig. 9. Long term performance of commercial and SCF CA membranes. Flux decline ratio (FDR) and flux recovery ratio (FRR) calculated from long-term study using
(a) Pharmaceutical wastewater, (c) Tannery effluent. Irreversible fouling ratio (Fir) and reversible fouling ratio (Fr) for (b) Pharmaceutical wastewater, (d) Tan­
nery effluent.
10
Desalination 535 (2022) 115807
water after pharmaceutical wastewater run, respectively. For tannery
effluent, FRR values were 63.8%, 88%, and 85.2% for the commercial
CA, PCF and SCF membranes, respectively. Thus, the FRR of PCF and
SCF derived CA membranes showed higher performance compared to
the standard commercial CA membrane. During the initial testing,
commercial CA membrane showed irreversible fouling ratio (Fir) of
64.1% for pharmaceutical wastewater as feed, whereas, Fir values for
PCF membrane and SCF membrane were 42.9% and 55.3%, respectively
Fig. 9b for PCF Fig. S13b. An interesting trend was observed during the
long run of pharmaceutical wastewater for commercial CA and PCF CA
derived membranes wherein the Fir values plummeted to ~20% and
20–28%, respectively. While for the SCF CA membranes, the values
remained between ~63–72%, much closer to the initial recorded value
of ~55%. This might be due to the surface roughness difference between
the membranes. The PCF CA and commercial CA membranes had similar
surface roughness parameters (Table S3, ESI) while the SCF CA mem­
brane showed comparatively less average roughness values. In the long
run, this might lead to delamination of the cake layer due to unfav­
ourable interaction with the active surface (for PCF and commercial CA
membranes), which might explain the reduction in the irreversible
fouling ratio. An important factor affecting the Fr and Fir ratios is the
wastewater composition, as exemplified from the different trend of Fir
values recoded with tannery effluent (Fig. 9d) for PCF Fig. S13d. The
initial difference in the Fir value of commercial CA membrane with PCF
and SCF CA membranes subsequently reduced during the long-run and
were in close proximity after 125 h of testing. The reversible fouling
ratio (Fr) of commercial CA membrane was 12.8% using pharmaceutical
wastewater as a feed. The Fr values for PCF membrane and SCF
A. Mahto et al.
membrane were 13.7% and 15.5% (Fig. 9b) for PCF Fig. S13b. In case of
tannery effluent, Fr values of ~37.2%, 28.1% and 22.5% were recoded
for commercial CA, PCF CA, and SCF CA membranes, respectively. Thus,
the prepared membranes are more favourable towards antifouling
property while maintaining high flux rates and cycle life. These results
are due to the hydrophilic surface of the membrane, which prevents the
accumulation and fouling of feed constituents on the selective layer of
the membrane.
Fig. 10 depicts the SEM images of the membranes at different mag­
nifications after long-term operation using pharmaceutical wastewater.
The common feature in all the cases (commercial, PCF, SCF) is the loss in
original surface morphology as compared to the original membranes.
This can be ascribed to the deposition of irreversible fouling layer, also
referred to as the cake layer, which is clearly visible in the high
magnification SEM images (Fig. 10c-commercial, 10f-SCF CA) for PCF
Fig. S14c ESI. It should be noted that only intermittent water washing
was done during the membrane testing and no cleaning agents were
applied before SEM analysis. A consequence of fouling is the change in
zeta potential or surface charge of the membranes.
Fig. S15 in ESI represents the zeta potential variation of the fouled
membranes. When associated with the surface charge of the pristine
membranes (Fig. 2f), the fouled ones exhibited lower negative values.
The difference is more pronounced in the case of PCF CA membranes,
but the same trend can be observed for the other two membrane samples
as well. Nevertheless, fouling is an indispensable phenomenon, partic­
ularly for wastewater remediation application, and can be circumvented
to some extent by using different cleaning agents to recover the mem­
brane surface and flux. On the other hand, Table 1 gives comparative
study data of recently reported NF membranes for dye desalination
application which clearly shows the advantage of present work over
other reported strategies. Moreover, these studies also lack the in-depth
analysis of membrane’s performance in treating real industry effluents.
4. Conclusion
The present work provides a detailed analysis on the prospect of
using waste CBs derived CA to prepare membranes for selective sepa­
rations. An anisotropic membrane morphology was obtained wherein
relatively tight selective top layer was supported on a porous sub-layer.
Fig. 10. Active layer/surface SEM micrographs at different magnifications after long-term testing (pharmaceutical wastewater). (a-c) Commercial CA membrane, (d-
f) SCF CA membrane.
11
Desalination 535 (2022) 115807
Owing to the negative surface charge of the as prepared membranes,
high separation factor was achieved for negatively charged dye and salt
solutions (CR-NaCl/MgSO4). Best results in terms of separation effi­
ciency were observed for the treatment of tannery and pharmaceutical
industry effluents. Good reduction in TOC values was observed for all
the wastewaters (~70–90%), while high COD rejection were observed
for tannery and pharmaceutical industry effluents. Long-term testing
results using two industrial wastewaters pointed towards better per­
formance of PCF and SCF CA derived membranes towards the treatment
of pharmaceutical wastewater, while the commercial CA derived
membranes performed better for tannery effluent filtration. The results
obtained in this study can set a benchmark for large-scale upcycling of
waste cigarette filters to obtain high-performance membranes for se­
lective separation and recovery of valuables from industrial wastewater
streams. Such kind of membranes can also reduce the burden on reverse
osmosis processes, which is currently the de facto standard technology
for final wastewater treatment.
CRediT authorship contribution statement
Ashesh Mahto: Conceptualized idea and initiated preliminary ex­
periments, Visualization, Writing - Original Draft
Mahaveer Halakarni: Carried out all the experiments, analysis and
drafted manuscript
Ashok Maraddi, Glenita D’Souza, Anita A Samage, Utpal G. Thum­
mar: Assisted in all experiments and analysis
Dibyendu Mondal: Involved in discussions, writing manuscript and
supervision.
S. K. Nataraj: Idea development, supervised complete project, ar­
ranged funding and finalized manuscript.
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.
A. Mahto et al. Desalination 535 (2022) 115807

Table 1
Performance comparison between recently reported NF membranes and the CA membranes reported in this study for dye desalination application.
Sl. Membrane Pure water flux Rejection of salt Rejection of organic Salt recovery rate Dye loss rate (%) Dye loss & salt Ref.
No (LMH) (%) molecule (%) (%) recovery rate of RIWW
(%)

01 TAIP (M4) 43.2 NaCl:2.2 CR:99.40 NaCl:97.6 CR:0.6 – [68]

MgSO4:12.2 RB:99.19 MgSO4:85.9 RB:0.8
Na2SO4:9.4 Na2SO4:89.6
MgCl2:6.7 MgCl2:27.1
02 Fe/GO-TA20 61.2 NaCl:9 CR:99 NaCl:90.1 CR:1 Simulated textile w w [69]
Na2SO4:19 MB:99 Na2SO4:76.5 MB:1 Dye:1
EB:99 EB:1 Salt:90.1
03 Ceramic 190 NaCl:7 MB:15 NaCl:92.4 MB:85 – [70]
membrane Na2SO4:39 EBT:98.7 Na2SO4:36 EBT:1.3
RB-KNR:97 RB-KNR:3
BG4:20 BG4:80
RB5:96 RB5:4
RHE7B:98 RHE7B:2
04 PRGO/HNTs- 8.8 NaCl:6.8 RB5:97 NaCl:92.7 RB5:3 – [71]
PSS MgSO4:4.7 MgSO4:95
Na2SO4:14.3 Na2SO4:83.3
MgCl2:4.7 MgCl2:95
05 PMIA-NF 80 NaCl:5.5 EBT:99.9 NaCl:41.8 EBT:0.1 – [72]
EBBB:98.7 EBBB:1.3
AR:98.1 AR:1.9
06 DGO-PPy@TiO2 436.9 NaCl:8.0 MB:91.2 NaCl:91.2 MB:8.8 – [73]
MgSO4:20.9 NR:98.6 MgSO4:73.4 NR:1.4
Na2SO4:23.1 TB:99.3 Na2SO4:69.9 TB:0.7
MgCl2:24.4 CR:99.4 MgCl2:67.6 CR:0.6
EBT:94.7 EBT:5.3
07 M-PSf 54.0 NaCl:10 CR:98.2 NaCl:88.8 CR:1.8 – [74]
Na2SO4:16.5 Na2SO4:80.2
M-MGO 44.4 NaCl:13.0 CR:98.4 NaCl:85.0 CR:1.6 –
Na2SO4:17.3 Na2SO4:79.0
08 TFN-AA/GO(3) 11.3 NaCl:20.2 RhB:99.2 NaCl:74.6 RhB:0.8 – [75]
Na2SO4:95 RB:99.9 Na2SO4:21.3 RB:0.1
09 TFN0.02 L 128.4 NaCl:1.1 CR:99.9 NaCl:98.8 CR:0.1 – [76]
Na2SO4:2.4 Na2SO4:97.5
10 Commercial NF3 113 NaCl:60 organic molecule: 94 NaCl:39.8 All organic – [77]
molecule: 6.1
11 Commercial 40.3 NaCl:80.5 Colour:99.9 NaCl:19.4 Colour:0.1 Real industry This
NF20 Wastewaters work
Salt Dye
P. 29.7 8.1
Iww: 31.5 4.8
S. 27.9 3.1
Iww: 26.5 8.9
M. 24.4 0.8
ww:
D.
Effl:
T.
Iww:
12 SCF 29.2 NaCl:9.4 CR/CV:91.3 NaCl:89.6 CR/CV:8.7 P. 87.7 36.5
Iww: 78 39.9
S. 81.3 39.9
Iww: 85.5 66.3
M. 85.1 12
ww:
D.
Effl:
T.
Iww:

CR: Congo red, RB: Rose Bengal, MB: Methylene blue, EB: Evans blue, EBT: Eriochrome black T, RB-KNR: Reactive brilliant blue KN-R, BG4: Basic green, RB5: Reactive
blue 5, EHE7B: Evercion red H-E7B, EBBB: Eriochrome blue black B, AR: Alizarine red, NR: Nutral red, TB: Trypan blue, RhB: Rhodamine B, CV: Cristal violate, RIWW:
Real industry wastewater, P.Iww: Pharmaceutical industrial wastewater, S.Iww: Sugar industry wastewater, M.ww: Molasses wastewater, D.Effl: Dye effluent, T.Iww:
Tannery industry wastewater.

12
A. Mahto et al.
Acknowledgements
SKN expresses gratitude for Department of Science and Technology,
Ministry of Science and Technology, Government of India for Technol­
ogy Mission Division grant (DST/TMD/HFC/2K18/124G), DST-INSPIRE
Faculty Grant (IFA12-CH-84) and DST-NANOMISSION GRANT (SR/
NM/NT-1073/2016). SKN also thank Community of Madrid Spain for
Talent Attraction Program (2017-T1/AMB5610) and financial assis­
tance. RSC Research Fund grant R21-9087288636 was gratefully
acknowledged by DM. MAH thanks the Karnataka Government for Mi­
nority Scholarship. AM would like to acknowledge Mr. Pratyush Maiti of
CSIR-CSMCRI, Bhavnagar for useful discussions.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.desal.2022.115807.
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