Separation and Purification Technology 297 (2022) 121534

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Separation and Purification Technology

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

Ammonium enrichment and recovery from synthetic and real industrial

wastewater by amine-modified thin film composite forward
osmosis membranes
Ralph Rolly Gonzales a, Yuji Sasaki a, b, Titik Istirokhatun a, b, c, Jing Li a, b, Hideto Matsuyama a, b, *
a
Research Center on Membrane and Film Technology, Kobe University, Hyogo, Japan
b
Department of Chemical Science and Engineering, Kobe University, Hyogo, Japan
c
Department of Environmental Engineering, Faculty of Engineering, Diponegoro University, Jl. Prof. Soedarto-Tembalang, Semarang, Indonesia

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

Keywords: In this study, we aimed to recover and enrich NH+ 4 from real wastewater using forward osmosis (FO). Positively-
Forward osmosis charged thin film composite (TFC) membranes were developed via chemical grafting with positively-charged
Thin film composite membrane polyethyleneimine (PEI). The TFC membrane surface was first activated using 1-ethyl-3-(3-dimethylamino­
Amine grafting
propyl) carboimide (EDC) and n-hydroxysuccinimide (NHS) to convert the carboxyl groups of polyamide into
Quaternization
Ammonium enrichment
amine-reactive NHS esters. PEI grafting significantly increased the NH+ 4 retention in the feed solution. To further
improve the NH+ 4 rejection, quaternization of the amine functional groups of PEI was conducted with iodo­
methane. Quaternization was found to further increase NH+ 4 rejection, up to over 98.5%, while maintaining
similar water permeability with the PEI-grafted TFC membrane. Fouling control of the pristine and amine-
modified TFC membranes were also demonstrated, and the quaternary amine-modified TFC membrane exhibi­
ted superior fouling resistance against organic and biological foulants. The amine-modified TFC membranes were
evaluated for applicability for dewatering and NH+ 4 enrichment of real industrial wastewater. NH4 enrichment
+

using the PEI-grafted membranes was observed following wastewater dewatering, indicating the high NH+ 4
retention ability of the TFC membranes modified via amine grafting and quaternization. Wastewater dewatering
of 90.3 and 92.4% were achieved using TFC-PEI-10 and TFC-qPEI, respectively.

1. Introduction
Nitrogen (N2) fixation is the conversion of atmospheric N2 into
ammonia (NH3) and other nitrogenous compounds in soil. When dis­
solved in water, NH3 turns into its cationic form, ammonium (NH+ 4 ) [1].
NH+ 4 pollution of freshwater sources is currently a huge issue due to the
availability of high NH+ 4 concentrations in domestic and industrial
wastewater, as well as waste disposal leachate and agricultural and
livestock runoff [2]. While NH+ 4 is an agriculturally-important resource,
high NH+ 4 concentrations in our water bodies lead to pollution, eutro­
phication, and adverse effects to human health [3]. While NH+ 4 does not
pose grave threats in terms of toxicity, it is readily converted to more
toxic un-ionized ammonia NH3 upon changes in pH and temperature
[4]. This molecule is able to diffuse across the cells of aquatic organisms
and disrupt body functions.
In order to avoid the negative effects of NH+ 4 eutrophication, several
methods have been performed to remove and recover NH+ 4 from
wastewater prior to discharge in natural waters. The conventional NH+ 4
removal methods are biological processes, ion exchange, adsorption, air
stripping, chemical precipitation, chlorination, oxidation, radiation,
struvite precipitation, and membrane separation [3]. These technologies
have their own advantages and disadvantages, in terms of NH+ 4 selec­
tivity, removal efficiency, sensitivity to temperature, pH, and presence
of other pollutants, cost, and ease of operation [5]. The most widely-
performed membrane separation process for NH+ 4 removal is reverse
osmosis (RO). This technique is known to have high removal efficiency
and simplicity of operation and design requirements, as well as rela­
tively lower energy requirement over biological and chemical methods;
however, RO operation is often limited by the fouling propensity of the
membranes, which effectively increases cost [6]. This results in the
limitation of the application of a larger-scale operation of RO for NH+4
removal [7].

* Corresponding author at: Research Center on Membrane and Film Technology, Kobe University, Hyogo, Japan.
E-mail address: matuyama@kobe-u.ac.jp (H. Matsuyama).

https://doi.org/10.1016/j.seppur.2022.121534
Received 11 May 2022; Received in revised form 10 June 2022; Accepted 15 June 2022
Available online 17 June 2022
1383-5866/© 2022 Elsevier B.V. All rights reserved.
R.R. Gonzales et al.
In recent, technologies are shifting from NH+ 4 removal toward NH4
+
recovery as a valuable resource from wastewater and this NH+ 4 recovery
is currently an important study of interest, as wastewater management is
primarily related to the development of a circular economy wherein
resources from wastewater are sustainably recovered and recycled for
other purpose [8]. However, due to the variation of NH+ 4 concentrations
in wastewater and technological limitations, NH+ 4 recovery is currently a
great challenge. This has led to the NH+ 4 recovery application using
forward osmosis (FO), which aims to improve the limitations of RO for
NH+ 4 removal. During FO operation, the water transport from the feed
solution (FS) with lower solute concentration toward the more solute-
concentrated draw solution (DS) across a permselective membrane is
mainly governed by the osmotic gradient between the two streams. FO
has previously been tested for feasibility for a number of applications,
such as seawater desalination [9], osmotic power generation [10],
concentration of food and beverage [11], wastewater treatment
[12–14], and resource recovery [15]. Unlike RO, FO is known to have
lower fouling propensity and energy requirements, while exhibiting
higher recovery ratio [16]. When seawater is used as DS, the FO process
energy consumption is quite low due to spontaneous water permeation
occurs without no additional applied pressure [17].
Previous research has shown that while FO is able to separate organic
substances and phosphorus during the enrichment of low-strength
municipal wastewater; however, the NH+ 4 rejection of conventional FO
membranes proves to be a bottleneck in this field of study [18]. This was
found to be primarily due to the ability of the NH+ 4 ion, whose size is
similar to that of water molecules, to diffuse through the FO membrane,
as well [19]. This knowledge has started the interest in modification of
the FO membranes to enhance NH+ 4 rejection capacity.
Among the chemical modification strategies to enhance the mem­
brane NH+ 4 selectivity is the introduction of positive charged surface on
the FO membrane surface, which could electrostatically repel cations,
such as NH+ 4 [20]. FO operation usually utilizes a thin film composite
(TFC) membrane, composed of a highly porous polymeric support and a
dense, ultrathin selective layer (typically, polyamide). The selective
polyamide layer typically has negative charge, due to the presence of the
carboxyl groups, thus it is unable to reject positively-charged species
because the positively-charged species can go through the membrane
due to electrostatic interactions and dissolution-diffusion mechanisms
[13]. By the membrane surface modification, introduction of positively-
charged species on the polyamide layer surface may be possible for use
in enrichment and recovery of NH+ 4 from wastewater.
Polyethylenimine (PEI), a polymer containing repeated units of
positively-charged amine functional groups, was chosen as the mem­
brane modification agent to prepare TFC FO membranes with positively-
charged surface. PEI has been widely used as a modification agent in
previous studies due to its ability to endow positive charges on mem­
brane surfaces [21,22]. It can be used as the amine reactant for poly­
amide formation via interfacial polymerization [23] or grafting on a
membrane surface [19,24]. Another effective method in introduction of
positive charges on membrane surface is quaternization. Quaternization
is the introduction of four alkyl groups around the N atom of a tertiary
amino group with an appropriate alkylating agent [25]. It is a known
effective method to introduce positive charges on membrane surfaces for
better separation performance [26,27].
In this study, TFC FO membranes are grafted with tertiary and
quaternary amine groups using PEI. It is hypothesized that the intro­
duction of the positively-charged tertiary and quaternary amine groups
on the TFC membrane surface could enhance the rejection of positively-
charged ions, such as NH+ 4 . The polyamide selective layer was first
reacted with activating agents, in this case, 1-ethyl-3-(3-dimethylamino­
propyl) carboimide (EDC) and N-hydroxysuccinimide (NHS). EDC-
mediated coupling with NHS was found to be an efficient chemical
modification method for conversion of the carboxyl groups of polyamide
into amine-reactive NHS esters, which could allow the TFC membrane
surface to react with PEI. After grafting with PEI, quaternization using
2
Separation and Purification Technology 297 (2022) 121534
iodomethane took place to form quaternary amine groups on the TFC
membrane surface. The surface morphology, chemical composition,
surface potential, osmotic performance, and ammonium rejection were
evaluated. The fouling resistance of the PEI-grafted membranes was also
observed after FO operation with model foulants and microorganisms.
Finally, NH+4 was enriched from real industrial wastewater using the
PEI-grafted membrane. This work aimed to show how simple strategies
such as ester-activated amine grafting and quaternization could be used
for practical wastewater dewatering and NH+ 4 enrichment.
2. Materials and methods
2.1. Materials
Aliphatic polyketone (MW = 2x105 g/mol, Asahi Kasei Co., Ltd.,
Japan) was chosen as the membrane substrate material, and the mem­
brane substrate preparation used the following solvents (Fujifilm Wako
Pure Chemical Corp., Japan): resorcinol, methanol (MeOH), acetone,
and hexane. Interfacial polymerization for polyamide formation was
performed using benzene-1,3,5-tricarbonyl chloride (trimesoyl chloride,
TMC), benzene-1,3-diamine (m-phenylenediamine, MPD), N,N-dieth­
ylethanamine (triethylamine, TEA), (1S)-(+)-10-camphorsulfonic acid
(CSA), and sodium dodecyl sulfate (SDS) (Wako Pure Chemical Co.,
Japan). Polyethylenimine (PEI, MW = 0.6, 1.8, 10, and 750 kDa, Sigma-
Aldrich, Japan), 1-ethyl-3-(3-dimethylaminopropyl)carboimide hydro­
chloride (EDC, Tokyo Chemical Industry Co., Ltd., Japan), N-hydrox­
ysuccinimide (NHS, Tokyo Chemical Industry Co., Ltd., Japan), 2-(N-
mopholino)ethanesulfonic acid (MES, Sigma-Aldrich, Japan), ethyl­
enediamine (Wako Pure Chemical Co., Japan), and iodomethane
(Sigma-Aldrich, Japan) were used for chemical modification. Membrane
testing was conducted with sodium chloride (NaCl, Wako Pure Chemical
Co., Japan), and ammonium chloride (NH4Cl, Wako Pure Chemical Co.,
Japan). Fouling control studies were conducted using the following:
bovine serum albumin (BSA, Wako Pure Chemical Co., Japan), humic
acid (HA, sodium salt, Sigma-Aldrich, Japan), sodium alginate (SA,
Nacalai Tesque, Inc., Japan), Escherichia coli (E. coli, NBRC 3301, Bio­
logical Resource Center, National Institute of Technology and Evalua­
tion, Japan). Tryptic soy broth (TSB, pH = 7.3 ± 0.2, soybean casein
digest medium, Oxoid, Thermo Fisher Scientific, Japan) was used to
culture E. coli. LIVE/DEAD BacLight Bacterial Visibility test kit (Life
Technologies, Thermo Fisher Scientific, Japan) and glutaraldehyde
(25% in water, Sigma-Aldrich, Japan) were used to stain and fix E. coli,
respectively, prior to characterization.
2.2. TFC membrane preparation
The aliphatic polyketone membrane substrate was prepared via
conventional non-solvent-induced phase separation (NIPS) process,
while the polyamide selective layer was prepared via interfacial poly­
merization (IP) on the membrane substrate surface, respectively, as
described in earlier studies [28,29]. A 10 wt% polyketone solution in 65
wt% aqueous resorcinol was casted onto a glass plate and coagulated in
a 35 wt% aqueous MeOH bath, and the nascent membrane substrate was
washed with acetone and hexane. IP was conducted with the reaction of
an aqueous amine monomer solution (containing 2 wt% MPD, 2.3 wt%
CSA, 1.1 wt% TEA, and 0.15 wt% SDS), and the acyl chloride solution
(0.1 wt% TMC in hexane), followed by heat-catalyzed cross-linkage at
90 ◦ C.
2.3. Amine grafting and quaternization
The polyamide layer was grafted with PEI, after the reaction with
MES buffer solutions containing 140 mM EDC and 75 mM NHS, which
promotes the conversion of the polyamide carboxyl groups into amine-
reactive ester groups, hereby activating the grafting process. The amine-
reactive NHS esters could allow the TFC membrane surface to react with
R.R. Gonzales et al.
PEI. 2 wt% PEI of different molecular weights (0.6, 1.8, 10, and 750
kDa) were grafted on the TFC membranes. These molecular weights
were chosen to show the possible influence of PEI chain length on the
grafting process. The reaction scheme is shown in Fig. 1. The PEI-grafted
membranes are denoted as TFC-PEI-0.6, − 1.8, − 10, and − 750, respec­
tively, depending on PEI molecular weights. The grafting process was
performed for three consecutive cycles. Grafting with an amine mono­
mer (ethylenediamine) was also performed (TFC-EN) to compare its
performance against PEI grafting.
The best performing PEI-grafted TFC membrane was further modi­
fied via quaternization with iodomethane, also shown in Fig. 1 [30]. A
37.5 % (v/v) iodomethane in ethanol solution was prepared and kept
below 5 ◦ C prior to quaternization. The amine-modified TFC membrane
was soaked in the iodomethane solution for 24 h in dark conditions and
below 5 ◦ C. The quaternized membrane (TFC-qPEI) was washed with
copious amounts of ethanol and DI water.
2.4. Membrane characterization
Membrane surface morphology was imaged using a field-emission
scanning electron microscope (FE-SEM, JSF-7500F, JEOL, Japan). Sur­
face chemical composition was determined using X-ray photoelectron
spectroscope (XPS, JPS-9010 MC, JEOL, Japan) with AlKα X-rays and
Fourier transform infrared-attenuated total reflectance detector (FTIR-
ATR) spectroscope (Nicolet iS5 (FTIR)/ iD5 (ATR), Thermo Fisher Sci­
entific, Japan). The membrane hydrophilicity was evaluated by water
contact angle measurements using an optical contact angle goniometer
(Drop Master 300, Kyowa Interface Science Co., Japan). The membrane
surface roughness was evaluated using 3D laser scanning microscopy
(VK-X3000, Keyence, Japan). The surface zeta potential of the TFC
membranes was evaluated using an electrokinetic analyzer for solid
surface analysis (SurPASS 3, Anton-Paar GmbH, Austria). Membrane
characterization techniques were adapted from our previous studies
[28].
2.5. Membrane intrinsic transport properties and osmotic performance
Pure water permeability (PWP, A, L m− 2h− 1 bar− 1) and solute
permeability (BNaCl, L m− 2h− 1) were determined using a cross-flow RO
system using DI water and 1000 ppm NaCl feed solutions, respectively,
Fig. 1. Membrane preparation reaction scheme: (a) EDC/NHS coupling-mediated PEI grafting and (b) quaternization.
3
Separation and Purification Technology 297 (2022) 121534
following the same parameters from our previous study [12]. A and
BNaCl values were calculated using equations reported in the same study.
Using the NaCl solute diffusion coefficient D (1.45 × 10− 9 m2 s− 1 at
25 ◦ C), the TFC membrane structure parameter (S, μm) was calculated
according to a previous study [31].
The osmotic performance of the TFC membranes (water flux and
NH+ 4 rejection) was evaluated using a laboratory-scale FO system
[12,31], with an effective membrane area of 4.5 cm2. 1 L solutions of
100–1000 ppm NH4-N (prepared from NH4Cl) and 3.5% (w/w) NaCl
were used as FS and DS, respectively. The pH of all the FS containing
NH4Cl was adjusted to 7.0. During the FO tests conducted for 2 h, the
selective layer of the TFC membrane was facing the FS. The flow rates of
both FS and DS were maintained at 300 mL min− 1, and transmembrane
pressure (TMP) was kept at minimum. The mass changes of the FS were
recorded using a top-loading balance (FX-3000i, A&D Company,
Limited, Japan) connected to a computer. Water flux (Jw) was calculated
using equations presented in previous study [12], while ammonium
rejection (RNH4) was calculated from the permeating NH+ 4 into the DS,
measured using an ammonia test kit (Hach Co., Japan). All tests were
performed in triplicate, and statistical analysis (determination of mean
and standard deviation) were performed.
2.6. Fouling
The fouling control ability of the membranes were evaluated by FO
operation similar to a previous study [28]. The comprehensive foulant
solution contained 500 ppm each of BSA, HA, and SA was prepared.
Using the comprehensive foulant solution as FS and 3.5% (w/w) NaCl as
DS, the membranes were tested for fouling resistance for 24 h operation,
followed by 3 h backwashing with DI water, and another 24 h operation.
The normalized water flux, or the ratio of the instantaneous and initial
water flux values, were used to evaluate the fouling propensity and flux
recovery.
Dynamic biofouling FO operation was also conducted similar to
previous studies [32,33]. E. coli was precultured in TSB medium at 30 ◦ C
for 12 h, and afterwards, the precultured microorganism suspension was
diluted further with TSB medium until a final optical density of 0.05 at
450 nm (106-107 CFU mL− 1), as measured by a spectrophotometer (V-
650, Jasco, Japan). FO operation with DI water as FS and 3.5% (w/w)
NaCl as DS was first performed for 1 h, and the FS was replaced with the
R.R. Gonzales et al. Separation and Purification Technology 297 (2022) 121534

E. coli suspension, and operation was resumed for 5 h. Two 6 h operation
cycles were conducted. After the FO operation, the membrane samples
were rinsed with 0.85% (w/w) NaCl solution (aq.) and stained with
SYT09 for 20 min and fixed with 2.5% glutaraldehyde solution for 3
min. The membrane samples were then imaged using FE-SEM and
confocal laser scanning microscopy (CLSM, FV1000D, Olympus Corp.,
Japan).
2.7. Long-term ammonium enrichment from model and real industrial
wastewater
Long-term FO operation was first conducted using a model waste­
water containing 200 ppm NH4-N from NH4Cl to show the long-term
NH4-N content enrichment without the influence of foulants and other
inorganic substances. After that, long-term FO operation using real in­
dustrial wastewater obtained locally in Japan was conducted. Prior to
FO operation, the wastewater was filtered through a 0.22 μm filter. The
wastewater has a pH of 8.01, total dissolved solids of 477 mg L− 1,
chemical oxygen demand of 555 mg L− 1, and NH+ 4 content of 130 mg
L− 1. The pristine and amine-modified membranes were used to dewater
the model and industrial wastewater and enrich the ammonium content.
FO operation was conducted using the wastewater as FS until approxi­
mately 10% of the initial FS volume remains or until osmotic flow ceases
to compare the membrane NH+ 4 enrichment performance.
success of grafting. Fig. 2 shows the ATR-FTIR and XPS spectra of the
TFC membranes. As shown from Fig. 2(a), all TFC membranes exhibited
the representative stretching and vibrations of polyamide, observed at
around 1620 and 1450 cm− 1, respectively corresponding to the carbonyl
C–N and –C = C– groups of polyamide. The PEI-grafted membranes
exhibited vibrations and stretching at 1650 cm− 1, which both corre­
spond to amine N–H group, and at around 1200 cm− 1, which can be
attributed to the C–N group of amines. Fig. 2(b) shows the wide-scan
XPS spectra of the TFC membranes, showing the dominant C, N, and
O peaks. Speciation of the N-containing groups are shown in the narrow
N1s scan of TFC and TFC-PEI-10 membranes in Fig. 2(c) 2(d), respec­
tively. The pristine TFC membrane only showed the presence of
carbonyl amide group, whereas TFC-PEI-10 showed both the amide and
amine groups, indicating the success of grafting. Table 1 shows the
elemental composition of the pristine and amine-modified membranes.
While both pristine TFC and TFC-EN membranes showed similar surface
elemental composition, there was a slightly higher N content for the
ethylenediamine-grafted TFC membrane, as shown by the higher N/C
Table 1
Surface elemental composition of the pristine and amine-modified TFC
membranes.
Membrane C (%) N (%) O (%) N/C ratio

TFC 72.54 11.34 16.12 0.156

3. Results and discussion TFC-EN 72.49 11.67 15.84 0.161
TFC-PEI-0.6 72.63 12.31 15.06 0.169
TFC-PEI-1.8 72.12 13.14 14.74 0.182
3.1. Influence of amine grafting TFC-PEI-10 71.23 14.95 13.82 0.210
TFC-PEI-750 70.49 15.99 13.52 0.227
The surface chemistry of the pristine and amine-modified TFC TFC-qPEI 70.56 16.07 13.37 0.227
membranes was characterized by ATR-FTIR and XPS to determine the

Fig. 2. (a) FTIR and (b) XPS wide scan spectra of the pristine and amine-modified TFC membranes; narrow N1s scan spectra of (c) pristine TFC, (d) TFC-PEI-10, and
(e) TFC-qPEI membranes.

4
R.R. Gonzales et al.
ratio for TFC-EN. PEI-grafted TFC membranes exhibited an increase in
surface N content as molecular weight of PEI increased. TFC-PEI-750
and TFC-qPEI both showed N/C ratio of 0.227 (as shown in Table 1),
which was the highest value for all membranes prepared, indicating the
successful PEI and the succeeding quaternization modification process.
The surface zeta potential measurements of the pristine and amine-
modified TFC membranes are shown in Fig. 3. The isoelectric point of
each membrane is indicated by the pH at which the zeta potential was
measured to be zero. The pristine TFC membrane exhibited an isoelec­
tric point of 3.82. After the introduction of amine functional groups on
the polyamide surface, the isoelectric points of the amine-modified TFC
membranes were observed to be higher, providing evidence that
positively-charged amine groups were introduced on the surface, mak­
ing the TFC membranes less negative than the pristine one. All amine-
modified TFC membranes were observed to have isoelectric points of
approximately pH 6.0. At pH values below the isoelectric point, the
amine functional groups grafted on the TFC membrane surface are
protonated, providing overall positive charges [19]. Furthermore, it is
also noticeable that regardless of the pH values, amine grafting on the
TFC membrane surface resulted in less negative zeta potential values
than that of the pristine TFC membrane.
Fig. 4 shows the surface morphology of the TFC membranes prepared
in this study All the membrane surface images show the characteristic
ridge-and-valley structure of TFC membranes, indicating that the
grafting method does not alter the membrane morphology. However,
the cross-section FE-SEM images revealed that the polyamide layer
thickness increased after amine grafting. Furthermore, there was also an
observed increase in thickness as the molecular weight of PEI grafted
onto the membrane surface increased. The pristine TFC membrane
exhibited an average selective layer thickness of 156 nm (Fig. 4.2(a)).
Grafting with 0.6, 1.8, 10, and 750 kDa PEI resulted to average poly­
amide layer thickness values of 206, 218, 231, and 247 nm, respectively
(Fig. 4.2(b-f)). Finally, the quaternized TFC membrane showed the
average selective layer thickness of 236 nm (Fig. 4.2(g)), attributed to
the successive PEI grafting and quaternization processes.
Fig. 5 shows the surface roughness measurements of the pristine and
modified TFC membranes. Membrane surface roughness measurements
revealed an increase in surface roughness following the modification
processes. The pristine TFC membrane showed an average surface
roughness of 1.439 μm using a 3D laser microscope, while the quater­
nized membrane sample (TFC-qPEI) showed an average surface rough­
ness of 2.23 μm. PEI-grafted TFC membranes exhibited similar surface
roughness values within the range of 1.90 to 2.10 μm. The hydrophilicity
of the membranes was also characterized using the surface water contact
angle (CA) measurements, as also shown in Fig. 5. The water CA of the
Fig. 3. Zeta potential of the pristine and amine-grafted TFC membranes as a
function of pH.
5
Separation and Purification Technology 297 (2022) 121534
pristine TFC membrane was significantly higher than those of the amine-
grafted membranes, indicating that the introduction of amine groups on
the polyamide surface could result in higher hydrophilicity. Amine
groups are known to be more polar and hydrophilic than amide groups.
The TFC-EN membrane showed a water CA of 71.4◦ , while the PEI-
grafted TFC membranes have water CA values of about 55◦ . The PEI-
grafted membranes exhibited similarly low water CA values despite
the increase in surface roughness as molecular weight of PEI grafted
onto membrane surface increased. Also, the quaternized membrane also
showed the lowest water CA value but highest surface roughness.
Endowment of the membrane surface with highly hydrophilic amine
groups resulted in the lower water CA values even if the modification
process resulted in higher surface roughness.
Table 2 shows the intrinsic transport properties of the TFC mem­
branes. The pristine TFC membrane showed the highest water perme­
ability of 1.46 L m− 2h− 1 bar− 1, and amine grafting on the membrane
surface generally resulted in a slightly lower water permeability. This
may seem contradictory with the water contact angle measurements of
the TFC membranes; however, amine grafting could possibly have
resulted in the formation of a thin amine-rich layer on top of the poly­
amide surface, hereby blocking the membrane pores and leading to
additional transmembrane transport resistance for the amine-grafted
TFC membranes [34]. This also resulted in the amine-grafted TFC
membranes generally exhibiting higher NaCl rejection values of over
96% compared with the pristine TFC membrane (94.4%). The lower
water permeability of the amine-grafted membranes could possibly be a
result of the higher structure parameter (S value). The pristine TFC
membrane has a structure parameter of 166 µm, while the TFC mem­
brane grafted with 750 kDa PEI has an S value of 209 µm. The higher
structure parameter values of the modified membranes corresponded
with the higher thickness of the selective polyamide layers (as shown in
Fig. 4.2). The lower water permeability values of the modified TFC
membranes could also be a result of the thicker selective layers, which
could increase the transport resistance of the membranes [35].
The FO performances of the TFC membranes using model NH+ 4-
containing wastewater and seawater (3.5% (w/w) NaCl) as the FS and
DS, respectively, are shown in Fig. 6. As expected from the pure water
permeability and structure parameter values from Table 2, the pristine
TFC membrane showed the highest Jw among all membranes tested.
Using 100 ppm NH+ 4 FS, the pristine TFC membrane had a water flux of
18.4 L m− 2h− 1, while the amine-grafted TFC membranes showed Jw
values of 10.8–12.3 L m− 2h− 1. PEI grafting onto the TFC membrane
surface could cause blockage of the membrane pores and likewise in­
crease TMP, effectively reducing water flux. As the FS concentration
increased to 400 and 1000 ppm NH+ 4 , water flux of all membranes was
observed to decrease, due to the decrease in the osmotic driving force
caused by the increase of the osmotic pressure of the FS. What is more
interesting to note from Fig. 6 is the effect of amine grafting, as well as
the amine polymer molecular weight, on NH+ 4 rejection. Using 100 ppm
NH+ 4 FS, the pristine TFC membrane was only able to reject an average of
53.3% NH+ 4 from the FS, and the grafting of the ethylenediamine
monomer dramatically increases the NH+ 4 rejection to 89.2%. The poor
NH+ 4 rejection of the pristine TFC membrane is due to the similar po­
larity and radii of the water molecule and NH+ 4 ion [36] and electrostatic
interaction between the negative charge of polyamide layer and
positively-charged NH+ 4 . After PEI grafting, the protonated amine groups
grafted on the TFC membrane surface are able to exhibit strong elec­
trostatic repulsion against NH+ 4 [20]. The TFC grafted with 10 kDa PEI
was found to have the highest NH+ 4 rejection of 98.5%, but all PEI-
grafted TFC membranes exhibited NH+ 4 rejection values of over 96%.
Using 400 ppm NH+ 4 FS, the NH4 rejection of the pristine TFC membrane
+
further decreased to 50.4%, while only two amine-grafted membranes
exhibited excellent NH+ 4 rejection of over 95%, TFC-PEI-10 (95.4%) and
TFC-PEI-750 (95.6%). The operation with 1000 ppm NH+ 4 FS further
decreased NH+ 4 rejection of the pristine TFC membrane, and the higher
performing membranes were found to be TFC-PEI-10 (91.3%) and TFC-
R.R. Gonzales et al. Separation and Purification Technology 297 (2022) 121534

Fig. 4. (1) Surface and (2) cross-section morphology of the (a) pristine, (b-f) amine-grafted, and (g) quaternized TFC membranes.

as TFC-PEI-750. The surface morphology of the TFC-qPEI membrane

(Fig. 4.1(g)) shows a tighter and denser polyamide surface after qua­
ternization. Due to the presence of the highly positive quaternary amine
group on the membrane surface of TFC-qPEI, the membrane has
exhibited the highest zeta potential measurements in this study, as
shown in Fig. 3. The isoelectric point of the TFC-qPEI membrane was
found to be at pH 8.75.
The intrinsic transport properties of the TFC-qPEI membrane was
also determined and presented in Table 2. TFC-qPEI membrane exhibi­
ted slightly lower pure water permeability than TFC-PEI-10; however,
this membrane showed an outstanding NaCl solute rejection of 98.7%
and a specific reverse NaCl flux of 0.15 bar, owing to the denser poly­
amide structure shown from Fig. 4.1(g). The TFC-qPEI membrane also
has a structure parameter of 205 µm. The denser polyamide structure of
TFC-qPEI contributed to enhanced draw solute rejection and permse­
lectivity of the membrane. The enhanced draw solute rejection could
also result in the enhanced NH+ 4 rejection of the TFC-qPEI membrane.
Fig. 5. Surface roughness (Ra, μm) and water contact angle measurements of
Ion exchange mechanism could be used to explain the retarded diffusion
the pristine and modified TFC membranes.
of NH+ 4 from the FS to the DS. Reverse draw solute diffusion would
hamper the diffusion of FS solute [37,38], and in the case of TFC-qPEI,
Table 2 since the Na+ ion in the simulated seawater DS could not diffuse through
Intrinsic transport properties (A, B, and S values) of the pristine and amine- the membrane, NH+ 4 would, in turn, not diffuse to the DW to maintain
modified TFC membranes. electroneutrality.
Membrane A (L m− 2h¡1 RNaCl BNaCl (L BNaCl/A S
FO operation of the TFC-qPEI membrane was conducted with the
bar¡1) (%) m− 2h¡1) (bar) (µm) same conditions as with the pristine and amine-grafted TFC membranes
and the Jw and NH+ 4 rejection values are also presented in Fig. 6. The
TFC 1.46 ± 0.12 94.4 ± 0.47 ± 0.08 0.32 166
0.8 membrane exhibited slightly lower water flux values than the non-
TFC-EN 1.20 ± 0.11 96.1 ± 0.37 ± 0.15 0.31 181 quaternized TFC-PEI-10 membrane; however, TFC-qPEI exhibited
1.1 excellent retention of NH+ 4 in the FS, with an NH4 rejection of 98.7, 95.6,
+
TFC-PEI- 1.21 ± 0.19 96.5 ± 0.35 ± 0.04 0.29 188 and 93.2%, with 100, 400, and 1000 ppm NH+ 4 as FS, respectively, all
0.6 0.7
TFC-PEI- 1.17 ± 0.17 96.8 ± 0.32 ± 0.06 0.27 199
better than those of TFC-PEI-10 (98.2, 95.4, and 91.3%, respectively).
1.8 1.3 This excellent NH+ 4 rejection capability is mainly due to the increased
TFC-PEI-10 1.19 ± 0.11 96.2 ± 0.34 ± 0.10 0.28 206 overall positive charge of the TFC membrane surface due to the presence
0.5 of the quaternary amine. The overall positive charge of the TFC mem­
TFC-PEI- 1.11 ± 0.08 96.7 ± 0.32 ± 0.09 0.29 209
brane surface resulted in the electrostatic repulsion of positively-
750 0.8
TFC-qPEI 1.05 ± 0.12 98.7 ± 0.16 ± 0.09 0.15 205 charged NH+ 4 , as exhibited already in previous studies involving
1.1 cationic species separation using positively-charge-modified membrane
surfaces [19,39,40].

PEI-750 (90.5%). No significant difference was observed for the NH+

4
rejection of both TFC-PEI-10 and TFC-PEI-750, regardless of FS con­
centration. Following these osmotic performance results, TFC-PEI-10
was chosen to be further modified via amine quaternization.
3.2. Influence of amine quaternization
The membrane characterization data for the quaternized TFC
membrane initially grafted with 10 kDa PEI were also shown in Figs. 2-5.
FTIR and XPS analysis showed similar surface chemistry between TFC-
PEI-10 and TFC-qPEI. However, upon inspection of the narrow N1s
scan of the TFC-qPEI membrane using XPS (Fig. 2(e)), the presence of
the quaternary amine group was detected. Elemental composition
analysis of the TFC-qPEI surface (Table 1) revealed similar composition
3.3. Membrane fouling
Since the TFC membranes would be tested using real industrial
wastewater which contains not only NH+ 4 but also several foulants and
pollutants, it is highly important to assess the fouling propensity of the
membranes. The membrane fouling propensity was evaluated using a
comprehensive foulant solution containing three representative model
foulants (BSA, HA, and SA). Fig. 7(a) shows the water flux profiles of
three chosen TFC membranes (TFC, TFC-PEI-10, and TFC-qPEI) during
FO operation with the comprehensive foulant solution was FS. Fouling
significantly affected the performance of all TFC membranes, especially
the pristine TFC membrane, which can be attributed to the deposition
and accumulation of foulant molecules. Within four hours of FO oper­
ation, the pristine TFC membrane experienced flux decline, while the

6
R.R. Gonzales et al. Separation and Purification Technology 297 (2022) 121534

Fig. 6. Water flux and NH+

4 rejection of the TFC membranes during FO operation using three different concentrations of feed solution: (a) 100 ppm NH4 , (b) 400 ppm
+

NH+4 , and (c) 1000 ppm NH4 ; Draw solution was 3.5 % (w/w) NaCl for all tests.
+

Fig. 7. Water flux profiles of TFC, TFC-PEI-10, and TFC-qPEI membranes during FO operation using 3.5 % (w/w) NaCl solution as draw solution and (a)
comprehensive foulant solution (500 ppm BSA, HA, and SA) and (b) E. coli NBRC 3301 as feed solution; (c) CLSM and (d) FE-SEM images of the TFC membranes after
dynamic biofouling FO operation.

amine-grafted TFC membranes exhibited stable FO performance within
10 h (TFC-PEI-10) and 14 h (TFC-qPEI). The flux of the pristine TFC
membrane continued to decline during the course of the first 24 h
operation, and after 24 h, the flux declined to 29.9% of the initial water
flux. TFC-PEI-10 and TFC-qPEI, on the other hand, also experienced flux
decline, with final water flux values which were 36% and 53.3% of the
respective initial water flux measurements. The observed fouling in the
amine-grafted TFC membranes could be attributed to the electrostatic
interactions between the positively-charged TFC membrane surface and
the negatively-charged BSA (isoelectric point: pH 4.5–5.0) [32]. Despite
the electrostatic interactions, the increased hydrophilicity of the amine-
grafted TFC membranes resulted in the lesser effect of fouling on the FO
performance of both TFC-PEI-10 and TFC-qPEI. The membranes were
backwashed for 3 h to evaluate the flux recovery ability. After back­
washing, the pristine TFC membrane exhibited 77.5% of its initial water
flux, while both TFC-PEI-10 (88.7%) and TFC-qPEI (96.6%) were able to
recover the water flux better. These results indicate that the amine-
grafted TFC membranes is highly hydrophilic, and the foulants which
accumulated on the surface were easily washed out. At the end of the
second 24 h FO operation, the flux of the pristine TFC membrane
declined to 15.2% of its initial, while the flux of both TFC-PEI-10 and
TFC-qPEI declined to 31.7 and 51.9%, respectively.
Dynamic biofouling FO operation with E. coli was conducted to show
the practical application and effect of amine grafting and the subsequent
quaternization on biofouling control and biofilm formation. Fig. 7(b)
shows the water flux profiles of the three chosen TFC membranes during
the biofouling FO operation. After 6 h of operation, all membranes
exhibited flux decline, but all final flux values were above 50% of the
initial water flux (58.4, 77.1, and 86.3% for TFC, TFC-PEI-10, and TFC-
qPEI, respectively). Flux recovery was observed for all TFC membranes
during the onset of the second cycle. For both cycles, the TFC-qPEI
membrane exhibited gradual flux decline (only less than 15%), indica­
tive of its superior biofouling control. The increased hydrophilicity of
the quaternary amine-modified membrane also increased the surface

7
R.R. Gonzales et al.
hydration, which minimized the electrostatic interactions between the
membrane surface and the foulant [33]. To further understand the
biofouling operation results after 12 h, membrane characterization
using CLSM and FE-SEM was performed, and the images are shown in
Fig. 7(c)-7(d). Bacterial cells were found to adhere on the surface of the
pristine TFC membrane; however, the surface was not fully covered,
thus the flux decline was not severe. Even less bacterial attachment was
observed for TFC-PEI-10, while almost no bacterial attachment could be
seen for TFC-qPEI. The outstanding biofouling control of TFC-qPEI
might be due to its hydrophilicity, which regulates the adsorption of
E. coli, and the biocidal effect of the quaternary amine group [32]. It
could be hypothesized that the PEI-grafted TFC membranes would be
more susceptible to biofouling due to the electrostatic interactions be­
tween the generally negatively-charged E. coli and the positively-
charged membrane surface. However, as observed in this work, bacte­
rial attachment was barely observed on the membrane surface after the
dynamic biofiltration process. This is primarily due to the improved
hydrophilicity of the membranes brought about by the PEI modification
and the succeeding quaternization process. The enhanced surface hy­
drophilicity could overcome the electrostatic attractions and result in
less bacterial attachment and biofouling propensity, as observed in our
earlier work [32].
3.4. Ammonium enrichment from model and real industrial wastewater
In order to evaluate the applicability of the quaternary amine-grafted
TFC membrane for concentrating ammonium in real wastewater, TFC-
qPEI was tested and compared with the pristine TFC and TFC-PEI-10
membranes. Figs. 8 and 9 show the performance of the pristine TFC,
TFC-PEI-10, and TFC-qPEI membranes during FO operation with model
and real wastewater, respectively. As seen in Fig. 8(a) and (b), the long-
term water flux profiles of the three membranes tested (TFC, TFC-PEI-
10, and TFC-qPEI) are presented. The pristine TFC membrane, consis­
tent with its short-term performance with model wastewater (Fig. 6),
showed the highest initial water flux; however, during the course of the
long-term operation, its water flux declined to around 20% of the initial
water flux at the end of the operation. Both TFC-PEI-10 and TFC-qPEI,
on the other hand, also showed flux declines during the FO operation
with wastewater, but not as sharp as that of the pristine one (flux de­
clines of 50% and 40% for TFC-PEI-10 and TFC-qPEI, respectively).
Since the FS used in this long-term FO operation did not involve fouling
substances, as well as other inorganic species, the long-term FO opera­
tion performance could only be attributed to the changes in osmotic
pressure difference of the FS and DS, as a result of either NH+ 4 rejection
capacity of the TFC membranes or reverse salt flux from DS. The decline
in the water flux of the pristine TFC membrane was most likely due to
Na+ reverse diffusion brought about by the ion exchange with NH+ 4,
which could result in increased reverse salt flux [36,37], whereas the
amine-grafted TFC membranes, whose NH+ 4 rejection abilities are
outstanding, was able to enrich the NH+ 4 ions in the FS as the model
Fig. 8. (a) Water flux profile of the TFC, TFC-PEI-10, and TFC-qPEI membranes during FO operation with model wastewater (200 ppm NH4-N from NH4Cl) as FS and
3.5 % (w/w) NaCl as DS; (b) normalized water flux of the TFC, TFC-PEI-10, and TFC-qPEI; and (c) dewatering and enrichment performance of the membranes.
8
Separation and Purification Technology 297 (2022) 121534
wastewater was dewatered, with little to no leakage toward the DS.
Starting with an initial 200 ppm NH4-N concentration of the model
wastewater, all three TFC membranes were able to dewater over 90% of
the model wastewater (Fig. 8(c)). Model wastewater enrichment to final
NH4-N concentrations of 1350 ppm (90.3% dewatering), 1800 ppm
(91.2% dewatering), and 3000 (94.2% dewatering) for TFC, TFC-PEI-10,
and TFC-qPEI membranes, respectively.
Long-term FO operation using real industrial wastewater tells a
different story, as the presence of fouling substances and other inorganic
species in the wastewater could influence the wastewater dewatering
and enrichment performance. The presence of fouling substances could
result in the fouling cake formation atop the surface of the TFC mem­
brane and detrimentally affect the flux. As seen from Fig. 9, the pristine
TFC membrane exhibited a sharp flux decline (around 50%) within the
first 2 days of operation, and eventually osmotic transport stopped after
5 days of operation. Both TFC-PEI-10 and TFC-qPEI membranes
exhibited lower flux declines, indicating the ability of the amine-grafted
membranes to withstand fouling substances present in the wastewater,
mainly due to its increased surface hydrophilicity (Fig. 5). However, the
flux decline of the amine-grafted TFC membranes could be attributed to
their positively-charged surface, which could also attract negatively-
charged foulants in the wastewater. Fig. 9(c) compares the dewatering
and NH+ 4 enrichment performances of the membranes. Due to the
combination of the effects of fouling, poor NH+ 4 retention in the FS, and
simultaneous enrichment of other inorganic species in the wastewater
FS, the pristine TFC membrane was able to dewater only 76.6% of the
real wastewater, whose final NH4-N concentration was only 400 ppm.
Osmotic transport was halted due to the absence of osmotic driving
force, as a result of reverse salt flux and poor NH+ 4 rejection of the
pristine TFC membrane. Both amine-grafted membranes were able to
operate for a longer period compared with the pristine TFC membrane,
thus achieving 90.3 and 92.4% wastewater dewatering for TFC-PEI-10
and TFC-qPEI, respectively. Furthermore, these two membranes
retained most of the NH+ 4 in the wastewater, resulting in respective final
wastewater NH4-N concentrations of 1000 and 1200 ppm for TFC-PEI-
10 and TFC-qPEI. These results indicate that amine-grafted TFC mem­
branes could deliver outstanding NH+ 4 enrichment performance using
real wastewater.
4. Conclusions
Positively-charged amine groups of PEI were successfully grafted on
the surface of TFC membranes using sequential activation with NHS and
EDC and amine coupling. Although modification of the membrane
resulted in slightly lower water permeability, there was a significant
enhancement of NH+ 4 rejection and antifouling capability. Molecular
weight of PEI influenced separation performance by enhancing hydro­
philicity and surface positive charge. Further modification of the PEI-
grafted TFC membrane via quaternization with iodomethane was con­
ducted. The quaternary amine-grafted TFC membrane exhibited similar
R.R. Gonzales et al.
Fig. 9. (a) Water flux profile of the TFC, TFC-PEI-10, and TFC-qPEI membranes during FO operation with real industrial wastewater as FS and 3.5 % (w/w) NaCl as
DS; (b) normalized water flux of the TFC, TFC-PEI-10, and TFC-qPEI; and (c) dewatering and enrichment performance of the membranes.
water flux with the PEI-grafted membranes and an even higher NH+
rejection. Fouling control of the pristine and amine-grafted TFC mem­
branes were also demonstrated, and the quaternary amine-grafted TFC
membrane exhibited superior fouling resistance against organic and
biological foulants. The membranes prepared in this study were also
used for applicability for enrichment of NH+
4 in real industrial waste­
water. The poor NH+ 4 rejection performance (53%) of the conventional
TFC FO membrane does not make it suitable for enrichment of NH+ 4 from
wastewater, and results of this study showed that amine grafting (NH+
rejection: 98%) and quaternization (NH+ 4 rejection: 99%) on the TFC
membrane surface could allow it to successfully enrich NH+ 4 in the
wastewater during FO operation. Despite the lower water permeability,
the PEI-grafted membranes were found to enhance wastewater dew­
atering and NH+ 4 enrichment, due to the high NH4 rejection ability of the
+
modified TFC membranes. Wastewater dewatering of 90.3 and 92.4%
were achieved using TFC-PEI-10 and TFC-qPEI, respectively, corre­
sponding to respective final wastewater NH4-N concentrations of 1000
and 1200 ppm. To the best of the authors’ knowledge, this is the first
TFC FO membrane study which was applied for the dewatering and
resource enrichment of real industrial wastewater. PEI grafting and
quaternization on the TFC membrane surface proved to be facile and
effective methods to improve wastewater dewatering and NH+
enrichment.
CRediT authorship contribution statement
Ralph Rolly Gonzales: Conceptualization, Methodology, Formal
analysis, Investigation, Data curation, Writing – original draft, Writing –
review & editing, Visualization. Yuji Sasaki: Conceptualization, Meth­
odology. Titik Istirokhatun: Methodology, Formal analysis, Investiga­
tion, Data curation. Jing Li: Methodology, Formal analysis,
Investigation, Data curation. Hideto Matsuyama: Writing – review &
editing, Resources, Supervision, Project administration, Funding
acquisition.
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.
Data availability
No data was used for the research described in the article.
Acknowledgment
This work is part of a project (Project number: JPNP18016)
commissioned by the New Energy and Industrial Technology Develop­
ment Organization (NEDO), Japan.
Separation and Purification Technology 297 (2022) 121534
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