Journal of Water Process Engineering 27 (2019) 24–31

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Journal of Water Process Engineering

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

Simultaneous removal of arsenate and nitrate from aqueous solutions using T

micellar-enhanced ultrafiltration process
Pegah Bahmania, Afshin Malekia, , Reza Rezaeea, Mehrdad Khamforoushb, Kaan Yetilmezsoyc, ,
⁎ ⁎

Saeed Dehestani Athara, Fardin Gharibia

a
Environmental Health Research Center, Research Institute for Health Development, Kurdistan University of Medical Sciences, Sanandaj, Iran
b
Faculty of Engineering, University of Kurdistan, Sanandaj, Iran
c
Department of Environmental Engineering, Faculty of Civil Engineering, Yildiz Technical University, Davutpasa Campus, 34220, Esenler, Istanbul, Turkey

ARTICLE INFO ABSTRACT

Keywords: Arsenate (As(V)) and nitrate (NO3– removal from aqueous solutions was investigated via micellar-enhanced
Arsenate ultrafiltration (MEUF) using a prepared polyacrylonitrile (PAN) membrane and cetylpyridinium chloride (CPC)
Nitrate as the cationic surfactant. The PAN ultrafiltration (UF) membrane was produced using the phase inversion
Micellar-enhanced ultrafiltration method and used in a dead-end cell system. The morphology and physiochemical properties of the prepared
Ultrafiltration
membrane were characterized using SEM, EDX, XRD, FTIR, and AFM. Parameters, including surfactant con-
Membrane
centration, solution pH, and transmembrane pressure (TMP) were examined to determine their effects on the
permeate flux and removal efficiency of As(V) and NO3–, besides CPC rejection. Increasing CPC concentration
from 0.1 to 5 mM, removal of As(V) and NO3– increased from 49.3% to 96.9% and from 0.3% to 90.5%, and the
permeate flux reduced from 36.6 to 10.2 L/m2/h and from 54.2 to 33.3 L/m2/h, respectively. In addition, si-
multaneous removal of As(V) and NO3– via MEUF was studied, which showed that removal of NO3– was majorly
prevented by As(V) because of competitive binding of CPC micelles between NO3– and As(V); however, As(V)
removal was only slightly inhibited by NO3–. It was shown that the prepared PAN membrane could remove more
than 90% of As(V) and NO3– under optimal conditions (CPC concentration = 5 mM, pH = 7–8, and
TMP = 1 bar), using the MEUF process.

1. Introduction converted to As(V) by oxidation under aerobic conditions [12]. Thus,

Ground water contamination by inorganic compounds is considered
a major environmental issue. This type of contamination causes great
concerns, as groundwater pollutants are highly toxic and non-
biodegradable, causing major harm to human health [1–3]. Arsenic
(As) and nitrate (NO3–) are commonly found in ground water sources all
over the world, especially in some rural regions of western Kurdistan
province, Iran.
The United States Environmental Protection Agency (US EPA) has
classified arsenic as a group A carcinogen [4]. Therefore, it poses ser-
ious threats to human health, such as arsenicosis and different types of
cancer [5–7]. Arsenic exists in the environment in two oxidation states
of arsenate (As(V)) and arsenite (As(III)). As(III) is 60 times more toxic
than As(V) [8–10]. It is noted that As(III) has a higher toxicity and is
more difficult to eliminate than As(V) [11], but As(III) is easily
As(V) is generally the dominant aqueous inorganic arsenic species
under oxidizing conditions, and is typically found in shallow ground-
water and surface waters. For this reason, studies on the treatment of
the waters typically focused on As(V) [13–15].
Nitrate-contaminated drinking water may cause several health
problems, such as blue-baby syndrome (methemoglobinemia) and
mental retardation in infants [16–19], stomach, bladder, and colorectal
cancers, and formation of carcinogenic nitrosamines in adults [20,21].
To protect human health, the World Health Organization (WHO) and
Institute of Standards and Industrial Research of Iran (ISIRI) have set
the maximum contaminant level (MCL) of 11.3 mg/L for NO3–-N
(50 mg/L NO3–) and 0.01 mg/L for As(V) in drinking water [22–24].
The current methods used to remove these pollutants from aqueous
solutions include chemical precipitation [25], adsorption [26,27], ion
exchange [28,29], Nano zero valent iron [30] and membrane

Corresponding authors.
⁎

E-mail addresses: pegah.bahmani@muk.ac.ir (P. Bahmani), malaki@muk.ac.ir (A. Maleki), rezaee.r@muk.ac.ir (R. Rezaee),
m.khamforoush@uok.ac.ir (M. Khamforoush,>, yetilmez@yildiz.edu.tr (K. Yetilmezsoy), saeed.dehestani@muk.ac.ir (S. Dehestani Athar),
fardin.gharibi@muk.ac.ir (F. Gharibi).

https://doi.org/10.1016/j.jwpe.2018.11.010
Received 18 July 2018; Received in revised form 8 November 2018; Accepted 15 November 2018
Available online 24 November 2018
2214-7144/ © 2018 Elsevier Ltd. All rights reserved.
P. Bahmani et al.
separation [31,32]. The limitations of these methods include energy
consumption and production of toxic by-products that must be treated
appropriately [33]. Recently, the membrane separation process has
been extensively utilized for the treatment of ground water containing
toxic contaminants [34]. Ultrafiltration (UF) or microfiltration (MF) is
usually used for separation of pollutants with a high molecular weight
[35,36]. To remove these pollutants, nanofiltration (NF) or reverse
osmosis (RO) can be applied considering the ion size in aqueous solu-
tions [36]. However, these processes have a restricted flux and require
high operating pressure, making them quite costly [1,37].
In the past decade, micellar-enhanced ultrafiltration (MEUF) has
been an effective method to separate inorganic pollutants from the
aqueous phase [38–40]. In the MEUF process, surfactants are added to
solutions with concentrations exceeding the critical micelle con-
centration (CMC). The surfactant molecules accumulate to form sphe-
rical micelles, which are larger than the membrane pore [41,42]. The
micelles can be bind to inorganic ions by electrostatic interaction
[38,39]. Therefore, inorganic pollutants can be removed by applying
the UF technique [37,43]. This method has advantages, such as high
removal efficiency, low energy requirement, and simple operation
[36,38,43].
Iqbal et al. [44] evaluated As(V) removal using various cationic
surfactants and attributed the highest removal efficiency (96%) to ce-
tylpyridinium chloride (CPC) surfactant. Beak et al. [45] applied CPC
surfactant for NO3– and phosphate (PO43−) removal. They reported
NO3– and PO43− removal efficiencies of 86% and 91%, respectively
when the molar ratio of CPC to pollutants exceeded three. Various
studies on the MEUF process have separated organic and inorganic
pollutants, heavy metals, and nutrients in single-pollutant systems
[46,47] and few studies have reported contaminant elimination in
multipollutant systems [48–50]. Competition owing to the difference in
the binding power of contaminants may inhibit the binding of pollu-
tants with lower binding potential in multipollutant systems [37,41].
Several authors studied the removal of As(V) or NO3– using the
MEUF process; however, to our knowledge, there are no reports on si-
multaneous removal of As(V) and NO3–. Although arsenic is usually a
natural source and nitrate is an anthropogenic source, both of the As(V)
and NO3– are commonly found in some rural regions of western
Kurdistan province, Iran. For this reason, the simultaneous removal of
As(V) and NO3– within the framework of this study. Moreover, the UF
membrane was prepared by casting solutions which consisted of PAN
polymer and dimethylformamide (DMF) solvent. The morphology and
physiochemical properties of the prepared membrane were character-
ized using SEM, EDX, XRD, FTIR, and AFM. The effects of parameters,
including transmembrane pressure (TMP), surfactant concentration,
and solution pH, on the removal efficiency and permeate flux of NO3–
and As(V) were examined. The rejection of surfactant, which may be
concern as a secondary pollutant, was also monitored. In addition,
feasibility of simultaneously removal of As(V) and NO3– by MEUF was
studied.
2. Material and methods
2.1. Materials
The cationic surfactant, cetylpyridinium chloride (CPC, C21H38ClN),
was purchased from Aldrich, USA. The chemical structure and some
physicochemical properties of the surfactant (CPC) are presented in
Table 1 [51,52]. The sodium arsenate hyptahydrate (Na2HAsO4.7H2O,
99 wt%) and nitrate standard solution (NO3–, purity ≥99%) were
purchased from Merck, Germany. Polyacrylonitrile (PAN, average mo-
lecular weight cut-off, 100,000 g/mol) was supplied by Polyacryle
Company, Iran. In addition, N-N-dimethylformamide (DMF, 99 wt%),
sodium hydroxide (NaOH, 98 wt%), and hydrochloric acid (HCl, 98 wt
%) were provided by Merck, Germany. It should be noted that the re-
agents were of an analytical grade. For all experiments, double distilled
25
Journal of Water Process Engineering 27 (2019) 24–31
deionized (DDI) water was used.
2.2. Preparation of membrane
Polymer membrane was prepared by phase inversion method. The
polymer solution was prepared by dissolving a 16% (w/v) PAN polymer
in DMF solvent. The polymer solution was placed on a magnetic stirrer
at 55–60 °C for 5 h to produce a completely homogenous solution. Then,
the solution was kept for 24 h at room temperature to eliminate air
bubbles. Subsequently, the polymer solution was cast on a glass plate
with a casting knife with a thickness of 150 μm. For the phase inversion
process, the casting solution was exposed to the atmosphere for 60 s and
then immersed in a water bath to for 24 h to remove residual solvent
[41].
2.3. Characterization of membrane
The morphology of the membrane was analyzed via scanning elec-
tron microscopy (SEM, model: SEM-5800, JEOL, Japan). The cross-
sectional sample was first dipped and cracked in liquid nitrogen and
then coated by a gold film to ensure higher conductivity. Also, energy
dispersive X-ray spectroscopy (EDX) was applied to identify the ele-
ments and their percentage in the membrane. X-ray diffraction (XRD,
PW1730, Netherlands) analysis in the scan range of 10–80° (step
size = 0.05 and counting time = 1 s) was used to characterize the
membrane structure. The FTIR spectra of membrane was measured in
the transmission mode by Fourier transform infrared spectroscopy
(FTIR Avatra, USA) in the range of 500–4000 cm−1 at a resolution of
4 cm−1. To examine surface roughness (Ra) of the prepared membrane,
atomic force microscopy (AFM, Ara Research Co., model No. 0101/A,
Iran) was applied.
2.4. UF experiments
Experiments were performed at 25 ± 3 °C (room temperature)
using a dead-end UF cell, with an effective membrane area of 12.4 cm2
and feed volume of 500 mL. Before each experiment, the membrane was
soaked in deionized water for 24 h and then compacted at a pressure of
1 bar for almost 1 h with deionized water. The filtration system con-
sisted of a 500-mL feed tank, a nitrogen gas cylinder, a stainless-steel
flat membrane module, valves, and pressure gauges (Fig. 1). The feed
solution was prepared by dissolving the predetermined amounts of CPC,
arsenate, and nitrate in 300 mL of deionized water. The solution pH was
adjacent by 0.1 M HNO3 or NaOH. A magnetic stirrer was used to stir
the solution for 1 h at a constant speed of 300 rpm (≈31.42 rad/s) to
obtain an efficient mixture. Then, it was settled for 30 min to facilitate
micelle formation. The aqueous solution was subjected to the UF
membrane. 30 min after the onset of the experiment, the experimental
processes were terminated, and the permeate samples were collected
and analyzed. The MEUF experiments were designed to study the ef-
fects of some operating parameters (concentration of CPC, TMP, and
pH) on the permeate flux and removal of pollutants and surfactant re-
jection. All experiments were repeated 3 times and their average was
reported. After each experiment, to recover the membrane perme-
ability, it was washed with 0.1 M NaOH at 1 bar pressure for 30 min and
then rinsed twice with deionized water [2,40]. Subsequently, the water
flux was assessed to ensure that it was within 95% of the initial water
flux.
The following equation was used to measure the removal of anions
or rejection of CPC (R, %) and permeate flux (J, L/m2/h) [53,54].
Cp
R= 1 × 100
Cf (1)
J = V /(A t ) (2)
where Cf and Cp represent the anion concentrations in the feed and
P. Bahmani et al. Journal of Water Process Engineering 27 (2019) 24–31

Table 1
Physicochemical properties of the surfactant (cetylpyridinium chloride).
Molecular Formula C21H38ClN
Molecular Structure

Molecular Weight 339.99 g/mol

CAS (Chemical Abstracts Service) Number Anhydrous: 123-03-5, Monohydrate: 6004-24-6
CMC (Critical Micelle Concentration) 0.9 mM
Melting Range 80–84 °C
EINECS (European Inventory of Existing Commercial Substances) 204-593-9
Number
RTECS (Registry of Toxic Effects of Chemical Substances) Number UU4900000
Appearance Solid (white crystalline powder)
Density 0.47 g/mL (powder form)
Chemical Stability Stable under normal conditions
Solubility Soluble in water, freely soluble in chloroform, ethanol, and insoluble in ethers, acetone and
hydrocarbons
pH Value 5.0–5.4 (10 g/L, H2O, 20 °C)

Fig. 1. Schematic diagram of the dead-end apparatus.

permeate solutions (mg/L), respectively, V denotes the total permeate

water volume (L), A is the membrane effective area(m2), and t re-
presents the operation time (h).
Flame atomic absorption spectrophotometry (Varian spectra AA
200) and ion chromatography (IC, Metrohm 882 Compact, Switzerland)
were performed to determine the concentrations of As(V) and nitrate,
respectively in the feed and permeate samples [55,56]. The CPC con-
centration was measured by a UV–vis spectrophotometer at 258 nm [1].
Also, pH was determined using a pH meter (3510, Jenway).

3. Results and discussion

3.1. UF membrane characterization

The top surface and cross-sectional SEM morphology of prepared

membrane are presented in Fig. 2a and b. Prepared membrane had a
symmetric structure. The structure morphology of the membrane is
associated with the rate of phase inversion in a water bath [57]. This
membrane has a top thin layer that functions as a selective barrier film
Fig. 2. SEM images of (a) top surface, and (b) cross-section in the poly-
for the solute. This layer was supported by a finger-like sub-layer,
acrylonitrile (PAN) membrane.
containing macro voids and microspores, which increase the membrane

26
P. Bahmani et al.
Fig. 3. (a) XRD spectra of the PAN membrane, (b) FTIR spectra of the PAN membrane, (c) EDX spectra of the PAN membrane, and (d) 3D AFM images of the PAN
membrane with magnification of 40 μm.
mechanical strength.
XRD patterns of UF membrane is presented in Fig. 3a. PAN mem-
brane has diffraction peaks at 2θ = 16.7° relating to the crystal plane of
PAN [58]. The FTIR spectra of PAN membrane are shown in Fig. 3b.
The peaks of stretching vibration at 2246 cm−1 indicate the symme-
trical C^N stretching at 2929 cm−1 for CeH stretch, while the peaks at
1731 and 1664 cm−1 refer to C]O stretch. CeO stretch is observed at
1037 cm−1. The EDX spectrum of the UF membrane was shown in
Fig. 3c, which represents the weight percentage of the elements in the
membrane structure such as carbon (C), nitrogen (N), and oxygen (O).
Fig. 3d presents 3D AFM images of the prepared membrane. According
to Fig. 3d, the dark and bright areas indicate the valleys and the peaks
on the membrane surface, respectively, with a magnification of 40 μm
and surface roughness (Ra) of 88.84 nm.
27
Journal of Water Process Engineering 27 (2019) 24–31
3.2. Effect of CPC concentration on removal efficiency and permeate flux
Fig. 4a indicates the effects of feed CPC concentration on the re-
moval efficiency of As(V) and NO3–. The initial As(V) and
NO3–concentrations were respectively set at 1000 μg/L and 100 mg/L.
The system performance in As(V) and NO3– removal was investigated at
25 °C, pH of 7–8, and TMP of 1 bar. Fig. 4a shows that As(V) and NO3–
removal efficiency increased with an increase in the surfactant con-
centration; this could be attributed to the concentration polarization.
During this process, CPC concentration increased on the membrane
surface and formed a gel layer adjacent to or on the membrane surface
where micelles were formed to bind to anion molecules and CPC con-
centration reached CMC. According to Fig. 4a, with a further increase in
CPC concentration (> 5 mM), anion rejection decreased which could be
due to reduced aggregation and mean size of micelles at higher CPC
levels. Also, active binding sites did not increase by increasing the feed
CPC concentration [59]. Samper et al. [36] confirmed this
P. Bahmani et al. Journal of Water Process Engineering 27 (2019) 24–31

higher than that of NO3– at the same value of CPC because of the lower
initial concentration of As(V) and also the higher valence of As(V). The
same results were obtained by Beak et al. [62] who reported that the
removal of chromate was higher than that of nitrate because the higher
valence of chromate resulted in higher binding.
According to Fig. 4b, the permeate flux reduced as the feed CPC
concentration increased. At CPC concentrations below CMC, most CPC
molecules can be found as free monomers, which have a smaller size
than the pore diameter; monomers can move through the membrane
easily under these conditions; therefore, the permeate flux is high. As
CPC concentration increased, concentration polarization took place
adjacent to or on the surface of membrane; the membrane pores were
blocked in a short period, which resulted in membrane fouling, in-
creased hydraulic resistance, and reduced flux. At all concentrations of
CPC, the permeate flux was lower than the flux of pure water (63.1 L/
m2/h) (data not shown); it can be because of the presence of CPC and
anions in the feed solution. As mentioned above, due to the higher
removal of arsenate compared to nitrate, the permeate flux of nitrate
was greater than that of arsenate. Reduction in membrane permeability
is generally associated with surfactant deposition in the membrane pore
or on the membrane surface [42].

3.3. Effect of CPC concentration on CPC rejection

Fig. 4c indicates CPC rejection in terms of CPC concentration. CPC

rejection increased by increasing the feed CPC concentration and then
decreased. When CPC concentration increased to 5 mM, CPC molecules
at the membrane surface formed micelles, and rejection of CPC for both
arsenate and nitrate reached more than 96%. At higher concentration of
CPC (8 mM), the CPC rejection decreased. As discussed earlier, when
CPC concentration increased, the mean micelle size decreased; they
might break into mono, di, and trimmers, leading to the crossing of
more micelles through the membrane [63]. However, the permeate CPC
concentration was lower than the surfactant CMC (0.9 mM) at con-
centrations higher than 5 mM (8 mM). This is in fact a positive finding
since surfactant leakage into the permeate is an important MEUF
parameter due to minimization of environmental issues and costs.

3.4. Effect of CPC concentration on simultaneous removal of arsenate and

Fig. 4. (a) Effect of cetylpyridinium chloride (CPC) concentration on As(V) and
nitrate
NO3– removal efficiency (As(V) concentration = 1000 μg/L, NO3– concentra-
tion = 100 mg/L, pressure = 1 bar, pH = 7–8), (b) effect of CPC concentration
on permeate flux (same conditions given in part (a)), and (c) effect of CPC
Fig. 5a indicates the simultaneous removal of As(V) and NO3– re-
concentration on CPC rejection (same conditions given in part (a)). lative to CPC concentration. The removal efficiency of As(V) in the
presence of NO3– was similar to removal efficiency without NO3–. This
result showed that NO3– does not inhibit the binding of As(V) to ca-
phenomenon. Also, similar results were reported by some other re-
tionic micelles since binding of NO3– to CPC micelles is related to the
searchers [41,43]. Theoretically, no micelles were formed at CPC con-
electrostatic attraction of negative charges of NO3– to the positively
centrations below CMC (0.9 mM); therefore, no NO3– removal occurred.
charged head of CPC [41]. However, rejection of As(V) decreased by
Nonetheless, the rather high removal of As(V) (49.3%) was observed.
3–4% at low CPC concentrations, compared to the As/CPC system. This
This unanticipated rejection can be attributed to the negative mem-
result was supported by the findings reported by Iqbal et al. [44], which
brane charge, leading to arsenate repulsion (Donna exclusion effect)
showed a minor decline (4–8%) in the removal of arsenate with nitrate
[60,61].
and phosphate. On the other hand, As(V) decreased the removal of
As the CPC value increased from 0.1 mM to 5 mM, the rejection of
NO3–, compared to the NO3–/CPC system considering the binding
As(V) and NO3– increased from 49.3% to 96.9%and from 0.3% to
competition on micelles sites. In the presence of NO3–, As(V) bound to
90.5%, respectively. This shown that negative charged anions bound
CPC micelles, preferentially to NO3–. Beak et al. reported that rejection
with cationic surfactant micelles and removed from the aqueous solu-
of ferricyanide with valence of 3 was higher than that of chromate with
tion by UF membrane. The cationic surfactant micelles formed in
valence of 2. Considering the ion valences, ferricyanide showed a
aqueous phase can be bind with anionic arsenate species based on the
greater binding power than chromate for binding on ODA surfactant
absolute electrostatic potential and the high surface charge density. In
micelles [37].
the next step, the created micelles can be separated during UF because
their size are physically too large to pass through membrane pores. In
3.5. Effect of pH on removal efficiency and permeate flux
CPC concentration of 5 mM, removal efficiency of As(V) and NO3–
reaches below MCL (0.01 mg/L and 11.3 mg/L for arsenate and nitrate,
The solution pH value has been identified as a most important factor
respectively). Tanhaei et al. [41] removed 5 mg/L aniline and 10 mg/L
during MEUF process [38]. The effect of feed pH on As(V) and NO3–
nickel from aqueous solution after they were entrapped with SDS mi-
removal is presented in Fig. 5b. As pH increases from 3 to 11, removal
celles by UF membrane. As shown in Fig. 4a, the rejection of As(V) was
efficiency of As(V) and NO3– increased from 81.2% to 99.7% and from

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P. Bahmani et al. Journal of Water Process Engineering 27 (2019) 24–31

Fig. 6. Effect of transmembrane pressure (TMP) on As(V) and NO3– removal

efficiency (As(V) concentration = 1000 μg/L, NO3– concentration = 100 mg/L,
pH = 7–8), and (b) effect of TMP on permeate flux of As(V) and NO3– (same
conditions given in part (a)).

resulting in reduced flux [66]. In the all experiments, pH was set in 7–8,
because at this pH removal efficiency of anions was effective.

3.6. Effect of operating pressure on removal efficiency and permeate flux

Fig. 6a is present the effects of TMP on removal efficiency of As(V)

and NO3–. The removal efficiency decreased with TMP, which can be
Fig. 5. Effect of CPC concentration on simultaneous removal of As(V) and attributed to lower compact of micelles at high pressure [67,68].
NO3–(As(V) concentration = 1000 μg/L, NO3– concentration = 100 mg/L, Therefore, anions molecules are extracted from micelles complex and
pressure = 1 bar, pH = 7–8), (b) effect of pH on As(V) and NO3– removal ef- pass through the membrane [41]. Based on the findings, the removal
ficiency (same conditions given in part (a) except pH), and (c) effect of pH on
efficiency of As(V) and NO3– decreased from 98.9% to 86.2% and from
permeate flux of As(V) and NO3– (same conditions given in part (a) except pH).
90.5% to 82.1% as TMP increased from 1 to 2 bar. Also, according to
Fig. 6b, the permeate flux is greater at higher TMP due to a higher
68.5% to 98.1%, respectively. At pH < 6.9, arsenate ions are available driving force, which resulted in increased mass transport across the
in form of mono-ionic (H2AsO4), while at pH ≥ 6.9, di-ionic (HAsO4−2) membrane. As TMP increased from 1 to 2 bar, the permeate flux in-
species of arsenate is dominant. Therefore, at high pH, di–ionic species creased from 11.1 to 23.4 L/m2/h for As(V) and from 35.6 to 41.2 L/
of arsenate can bind to more micelles, which resulted in the increased m2/h for NO3–. Similar results were reported by Schwarze et al. [66],
removal efficiency of As(V). This finding is consistent with a study by who indicated that an increase in pressure caused a flux increase.
Gecol et al. [64], who showed that the removal efficiency of As(V) was
enhanced by increasing pH from 5.5 to 8. Fig. 5b shows that by in-
3.7. Removal mechanism according to Donnan effect and steric hindrance
creasing pH from 3 to 11, the removal efficiency of NO3– increased. It
can be due to the fact that at low pH, HNO3 was formed, which could
The arsenic (As) and nitrate (NO3–) removal depend on the mem-
cross the membrane easily, while at higher pH, hydroxyl ions in the
brane sieving mechanisms: (i) Donnan effect (named after the American
solution increased, and the membrane surface became negatively
physicist Josiah Willard Gibbs and the British chemist Frederick G.
charged, leading to the formation of a strong complex between micelles
Donnan, and also known as the Donnan law, Donnan equilibrium, or
and membrane surface. It can result in increased removal efficiency of
Gibbs–Donnan equilibrium) and (ii) steric hindrance (prevention or
NO3–. The previous studies supported these results [65].
retardation of inter- or intramolecular interactions due to the spatial
As presented in Fig. 5c, by increasing pH, the permeate flux reduced
structure of a molecule). The NO3– ion has a negative charge and As is
due to the structural change of micelles. Based on the findings, by in-
also converted into arsenate (As(V)) in solution, which has a negative
creasing pH from 3 to 11, the permeate flux of As(V) and NO3– de-
charge. In contrast, the membrane is modified with cationic surfactant
creased from 35.2 to 3.4 and from 61.6 to 10.4 L/m2/h, respectively.
and therefore has a positive charge. Hence, the membrane repels po-
Previous studies showed that smaller micelles are formed at low pH
sitively charged ions from surface of membrane. Consequently, the
rather than high pH. Therefore, presence of bigger micelles at higher pH
concentration of positive ions increases in the solution. So, due to
led to the formation of a denser layer on the surface of the membrane,
Donnan exclusion, NO3– and As ions will be less close to the surface of

29
P. Bahmani et al.
the membrane, so that their separation increase. This phenomenon
improves their removal efficiency.
Regarding the steric hindrance, the membrane is made up of poly-
acrylonitrile, a macromolecular with molecular weight of 100 kDa. This
macromolecule has several functional groups that will be charged due
to pH changes. Therefore, due to the steric hindrance phenomenon, it
prevents the ions getting close to the surface of the membrane and
increase the efficiency.
4. Conclusions
This study examined the performance of MEUF process in the re-
moval of As(V) and NO3– from aqueous solutions using a prepared PAN
membrane and CPC as the cationic surfactant. The PAN UF membrane
was produced by a phase inversion process and used in a dead-end cell
system. The influence of CPC concentration, solution pH, and TMP was
studied on the membrane performance in terms of permeate flux and
removal efficiency of As(V) and NO3–, as well as rejection of CPC.
Increasing the CPC concentration from 0.1 to 5 mM, the removal
efficiency of As(V) and NO3– increased from 49.3% to 96.9% and from
0.3% to 90.5%, while the permeate flux reduced from 36.6 to 10.2 L/
m2/h and from 54.2 to 33.3 L/m2/h, respectively. The reduced flux can
be attributed to the concentration polarization and gel layer of CPC.
Increasing the CPC concentration to 8 mM, removal of As(V) and NO3–
decreased, which can be related to reduced mean micelle size and mi-
celle aggregation at higher concentrations of CPC.
The concentration of CPC in the permeate was maintained below
the CMC of CPC for preserving the concentration polarization layer. In
addition, feasibility of simultaneous removal of As(V) and NO3– by
MEUF was investigated. The presence of As(V) ions in the solution
decreased the removal efficiency of NO3–, whereas NO3– removal was
not majorly influenced by As(V); therefore, As(V) preferentially binds
on CPC micelles since its binding power on CPC micelles exceeds that of
NO3–. This result shows that the prepared PAN membrane could pro-
duce a high-quality permeate at concentrations below the MCL of As(V)
and NO3– (0.01 mg/L and 11.3 mg/L, respectively) under optimal
conditions (CPC concentration = 5 mM, pH = 7–8, and TMP = 1 bar).
Conflict of interest
The authors declare that they have no conflict of interest.
Acknowledgments
This study was extracted from a PhD thesis project which was
supported by Kurdistan University of Medical Sciences
(IR.MUK.REC.1394.57) and approved by the Environmental Health
Research Center. Hereby, we extend our gratitude to the sponsors of
this study.
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