Desalination 315 (2013) 3336

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

Application of nanoltration for reuse of municipal wastewater and quality analysis

of product water
Samuel Bunani a, Eren Yrkolu a, Gkhan Sert b, mran Yksel a, Mithat Yksel c, Nalan Kabay c,
a
b
c

Ege University, Faculty of Science, Department of Chemistry, 35100 Izmir, Turkey

Ege University, Faculty of Fisheries, 35100 Izmir, Turkey
Ege University, Faculty of Engineering, Department of Chemical Engineering, 35100 Izmir, Turkey

H I G H L I G H T S
Reuse of bio-treated municipal wastewater
Application of nanoltration for wastewater reuse
Best product water quality with NF-90 membrane

a r t i c l e

i n f o

Article history:
Received 8 August 2012
Received in revised form 13 October 2012
Accepted 14 November 2012
Available online 8 December 2012
Keywords:
Irrigation
Membrane technology
Municipal wastewater
Nanoltration (NF)
Water reuse

a b s t r a c t
In this study, the municipal wastewater treated by biological methods was used for further treatment by
nanoltration method for wastewater reuse. For this purpose, different nanoltration (NF) membranes,
such as CK, NF-90, and NF-270 were employed. The quality analysis of product water was carried out using
various analytical techniques. The results revealed that the NF-90 membrane can produce the best water
quality compared to other two membranes. The CK membrane showed also a good rejection property after
NF-90 membrane but its big inconvenience is that it gave a lower water ux. Despite the good water ux
by NF-270, the permeate quality obtained with this membrane was not as good as obtained with the
NF-90 and CK membranes.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Globally, the water resources in various regions and countries are
expected to face unprecedented pressures in the coming decades as a
result of continuing population growth and uneven distributions of
population and water. The concentration of populations within urban
areas further exacerbates the disparity between water demand and
regional water availability [1].
Wastewater can be an alternative water resource which can decrease the demands for fresh water. Some municipalities and industries are dealing with high salt concentration in their wastewaters.
Saline efuents are conventionally treated through physicochemical
means, as biological treatment is strongly inhibited by salts [2].
Most of such systems involve anaerobic or aerobic biological treatment. Biological treatment systems offer the best alternative to
treat wastewaters containing carbonaceous organic and nitrogen

Corresponding author. Tel.: +90 232 3112290; fax: +90 232 3887776.
E-mail address: nalan.kabay@ege.edu.tr (N. Kabay).
0011-9164/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.desal.2012.11.015

matter [3]. However, high salt content in wastewater is known to

signicantly reduce the treatment efciency of conventional activated sludge, anaerobic, nitrication and denitrication processes
[4,5].
In order to attain the environmental standards, membrane technologies provide an important solution in wastewater discharge, reuse and
recovery of water, recycling valuable components from the waste
streams [6]. Those membrane technologies are namely nanoltration
(NF) and reverse osmosis (RO) that can be used as advanced treatment
technologies. NF falls between ultraltration and reverse osmosis and
its separation characteristics are based on sieve effect. But most
commercial NF membranes are also charged, so ion rejection by NF
membranes results from the combination of electrostatic and steric
interactions associated with charge shielding, Donnan exclusion and
the degree of ion hydration [7,8].
In this study, different kinds of NF membranes were investigated for assessing their performance in rejection of contaminants
that are not removed by biological treatment of municipal wastewater. The product water quality was compared with irrigation
water standards in order to assess its reusability in agriculture for
irrigation.

34

S. Bunani et al. / Desalination 315 (2013) 3336

2. Materials and methods

Table 1
Characteristics of the NF membranes.

NF tests were performed by using a cross-ow at-sheet membrane test unit (SEPA CF-II, GE) for the ltration of the conventionally
bio-treated municipal wastewater. The ow sheet of the membrane
ltration system was shown in Fig. 1.
In this study, three different types of NF membranes were used.
Two of them namely NF-270 and NF-90 (Dow-FilmTech) are thin
lm polyamide membranes with a surface negatively charged and
one is cellulose acetate membrane, CK (GE-Osmonics). The membrane characteristics were summarized in Table 1.
The bio-treated municipal wastewater was obtained from the discharge line of the Cili Municipal Wastewater Treatment Plant, Izmir
city, Turkey in which wastewater is biologically treated by conventional treatment processes.
In the quality analyses of feed and product water; TDS, conductivity,
salinity and temperature measurements were performed by portable
Mettler Toledo type conductivity meter. The pH was measured by a portable digital pH meter (WTW pH 315i/SET) and bicarbonate was determined by titration analysis. The analyses of chloride and sulfate ions
were carried out using ion chromatography equipment (Shimadzu IC
10 Ai Model) and TOC was measured by a TOC analyzer (Shimadzu
TOC-VCPH Model). The concentrations of Na+, K +, Ca2+ and Mg2+
ions were measured by an Atomic Absorption Spectrophotometer
(Varian 10 Plus Model). Turbidity measurement was performed with
a portable turbidimeter (Micro TPI Field Portable Turbidimeter). All
other parameters such as COD, phosphate-P, nitrate-N, nitrite-N,
ammonium-N, color and silica were measured with a colorimeter
(Spectroquant Nova 60, Merck Model). Feed characteristics were listed
in Table 2.
The membranes were investigated at 10 bar of applied pressure
during 6 h of operation. Before the set-up of the experiment, membranes were soaked in the ultrapure water for 24 h for conditioning.
The permeate samples were collected after each 30 min in the initial
2 h period and after each 2 h for the last 4 h period. During sampling,
the permeate ow rate was also measured. The concentrate ow rate
was maintained constant as 96 L/h during the experiment. This value

Designation

Manufacturer

Polymer

MWCO

T-max
(C)

P-max
(bar)

pH
range

CK
NF-270
NF-90

GE Osmonics
Dow FilmTech
Dow FilmTech

CAa
PTFCc
PTFCc

150 Dab
200300 Da1
200 Da2

30
45
45

31
41
41

38
310
310

a
b
c

Cellulose acetate.
Estimated based on salt rejection [9], 1[10], 2[11].
Polyamide thin-lm composite.

was chosen as the optimum ow rate from our previous studies. Permeate and concentrate streams were circulated back to the feed tank
to keep the composition of the feed constant during the test period.
Rejection (R) performance and permeate ux (Jv) of the different
membranes were derived from the following equations:


cp
R% 1
 100

 co
2
Jv L=hm V=S t
where Cp, Co, V, S, and t are concentration of the permeate, concentration of the feed, volume of the permeate, membrane area and time,
respectively.
3. Results and discussion
Conventionally bio-treated municipal wastewater was further treated by using NF membranes. As the three NF membranes tested have different properties; their performances were also obtained as different.
Regarding to the membrane pore size; the more effective membrane
was NF-270 with a permeate ux which rises up to 81 L/h m2. The
membranes NF-90 and CK showed a permeate ux up to 49.3 L/h m 2
and 26.6 L/h m 2, respectively. However, except for the CK membrane;
the two other membranes showed some decline in ux after a certain
time which may be caused by fouling or scaling on membrane surface.
The ux vs. time plots for three membranes are shown in Fig. 2.

Fig. 1. The ow sheet of the membrane ltration test system.

Table 2
Feed characteristics.
Parameter

Value (minmax)

Parameter

Value (minmax)

TDS (mg/L)
EC (S/cm)
T (C)
pH
Salinity (psu)
Turbidity (NTU)
Si (mg/L)
COD (mg/L)
Color (Hazen)
TC (mg/L)
IC (mg/L)
TOC (mg/L)

31103908
62257816
22.924.8
7.928.39
3.444.17
0.130.39
10.512.9
20.130.5
21.128.3
88.090.6
73.476.9
11.816.5

Na+ (mg/L)
Ca2+ (mg/L)
K+ (mg/L)
Mg2+ (mg/L)
NH4N (mg/L)
HCO3 (mg/L)
SO42 (mg/L)
Cl (mg/L)
PO4P (mg/L)
NO3N (mg/L)
NO2N (mg/L)

1003.51090.5
138220
96.8105
134150
0.090.11
408440
236299
17891848
2.052.28
8.4011
0.200.22

Salinity Rejection (%)

S. Bunani et al. / Desalination 315 (2013) 3336

100
90
80
70
60
50
40
30
20
10
0

35

CK
NF270
NF90
0

100

200

300

400

Time (min)
Fig. 4. Salinity rejection vs. time plots for the NF membranes.

90

Color Rejection (%)

80

Jv (L/hm)

70
60
50
40
30
20

CK
NF270
NF90

10
0
0

100

200

300

100
90
80
70
60
50
40
30
20
10
0

CK
NF270
NF90
0

100

200

300

400

Time (min)

400

Fig. 5. Color rejection vs. time plots for the NF membranes.

Time (min)
Fig. 2. Volumetric ux vs. time plots for the NF membranes.

100
90
80
70
60
50
40
30
20
10
0

COD Rejection (%)

Conductivity Rejection (%)

Conductivity was rejected by the NF-90 membrane up to 89%

while for the other membranes the rejection was achieved up to
70.6% (by CK) and 52.6% (by NF-270). Conductivity rejection vs.
time plots for the NF membranes are given in Fig. 3. The reason of
this result may be the charge effect which in addition to sieving effect
with membrane pore size; played also a great role in retention of
parameters that contribute in conductivity. The charge effect is due
to electrostatic interactions between the ion and the membrane,
and so it only appears with charged membranes.
Salinity rejection was in the similar order with conductivity rejection given by the three membranes. NF-90 performed a rejection of
salinity up to 90.3% followed by CK membrane with a salinity rejection of 73%. On the other hand, salinity rejection for NF-270 was
only 50.8%. Fig. 4 shows salinity rejection vs. time plots for the NF
membranes.

CK
NF270
NF90
0

100

All of the three membranes showed similar capacity in rejection

of color. The NF membranes CK, NF-270 and NF-90 were able to reject
color with an average of 90%, 90.6 and 91.7%, respectively as it shown
in Fig. 5. It could be seen that even the NF-270 membrane with larger
pore size was effective in color rejection.
COD is rejected highly by the NF-90 membrane with an average
rejection of 86.6% and with an average of 81% by the NF-270 membrane while the CK membrane achieved only a rejection up to
76.4%. Although the NF-90 and NF-270 membranes have larger pore
size than the CK membrane, they showed a better performance for
COD rejection than the latter. This can be due to rejection of ionic
species contributing to an increase in COD that are rejected by the
two charged membranes by repulsion effect. COD rejection vs. time
plots are shown in Fig. 6.
According to Fig. 7, TOC was rejected by the three membranes
with a little difference. Thus, NF-270 showed a good rejection with
an average TOC rejection of 88% followed by NF-90 with an average
of around 86%. The CK membrane revealed a rejection up to 79.8%
as shown in Fig. 7. From those results, it can be said that TOC rejection

200

300

Time (min)
Fig. 3. Conductivity rejection vs. time plots for the NF membranes.

400

100
90
80
70
60
50
40
30
20
10
0

CK
NF270
NF90
0

100

200

300

Time (min)
Fig. 6. COD rejection vs. time plots for the NF membranes.

400

S. Bunani et al. / Desalination 315 (2013) 3336

TOC Rejection (%)

36

100
90
80
70
60
50
40
30
20
10
0

the NF-90 membrane. According to the obtained results, it was concluded

that NF could be a potential method to reuse biologically treated municipal wastewater for irrigation purposes.
Acknowledgment
CK
NF270
NF90
0

100

200

300

400

Time (min)

This work was partly supported by Ege University Scientic

Research Project (EU-2011-FEN-089). We acknowledge Izmir Metropolitan Municipality Directorate-ZSU-ili Wastewater Treatment
Plant for bio-treated wastewater samples. We acknowledge Dr. Markus
Busch and Mr Eduard Gasia Bruch, Dow Chem. for sending us some of
the NF membrane samples. We thank M. Akay for AAS analyses and
G. Serin for TOC analyses.

Fig. 7. TOC rejection vs. time plots for the NF membranes.

References
is not only related with sieving mechanism but also other mechanisms such as charge effect which can intervene in its rejection.
Product water qualities obtained by different nanoltration membranes were compared with irrigation water standards in Table 3. The
feed characteristics were also listed for each membrane. From Table 3,
it can be seen that the NF-90 membrane produced a good water quality according to the irrigation standards for all of the analyzed parameters except for potassium. The qualities of product water obtained
with the CK and NF-270 membranes were also generally good for irrigation standards. However, these membranes were not able to reduce
some parameters to the levels exhibited by the NF-90 membrane. The
difference in performance of the membranes observed during this
work is attributed to the properties of the investigated membranes.
Those properties are pore size given here by MWCO, membrane surface which is charged for some and not for others and the structure
or composition of the active layer of the NF membranes.

4. Conclusions
Conventionally bio-treated municipal wastewater was further treated
by NF membranes using 10 bar of applied pressure and a concentrate
ow rate maintained at 96 L/h. The product water quality obtained was
different for each membrane. The best water quality was obtained with

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the treatment of sh processing saline wastewater, Desalination 246 (2009) 389396.
[3] F. Kargi, A.R. Dincer, Salt inhibition effects in biological treatment of saline wastewater in RBC, J. Environ. Eng. 125 (1999) 966971.
[4] F. Kargi, A. Uygur, Biological treatment of saline wastewater in an aerated percolator unit utilizing halophilic bacteria, Environ. Technol. 17 (1996) 320325.
[5] F.J. Ludzack, D.K. Noran, Tolerance of high salinities by conventional wastewater
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[6] M. Marcucci, G. Nosenzo, G. Capannelli, I. Ciabatti, D. Corrieri, G. Ciardelli, Treatment and reuse of textile efuents based on new ultraltration and other membrane technologies, Desalination 138 (2001) 7582.
[7] P.Y. Pontalier, A. Ismail, M. Ghoul, Mechanisms for the selective rejection of solutes
in nanoltration membranes, Sep. Purif. Technol. 12 (1997) 175181.
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(2008) 318330.
[10] M. Nystrm, S. Butylina, S. Platt, NF retention and critical ux of small hydrophilic/
hydrophobic molecules, Mem. Technol. 10 (2004) 58.
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(2005) 227234.
[12] R.S. Ayers, D.W. Westcot, Water quality for agriculture, in: FAO Irrigation and
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Table 3
Comparison feed/permeate characteristics for the NF membranes with irrigation water standards.
Membrane

CK

Parameter

Feed
Average

Permeate
Average

Feed
Average

Permeate
Average

Feed
Average

Permeate
Average

TDS (mg/L)
Conductivity (S/cm)
pH
Salinity (psu)
Turbidity (NTU)
Na+ (mg/L)
Ca2+ (mg/L)
K+ (mg/L)
Mg2+ (mg/L)
NH4N (mg/L)
HCO3 (mg/L)
SO42 (mg/L)
Cl (mg/L)
PO4P (mg/L)
NO3N (mg/L)
NO2N (mg/L)
Si (mg/L)
COD (mg/L)
Color (Hazen)
TOC (mg/L)

3908
7815
8.13
4.17
0.15
1018
195
80.3
134
0.11
408
299
1848
2.10
8.55
0.22
10.5
30.5
21.1
16.5

1150
2300
7.60
1.16
b0.01
353
7.12
30.7
4.80
0.07
57.2
b0.05
572
b0.05
5.63
0.07
4.75
7.18
2.10
3.34

3055
6108
8.39
3.44
0.29
1025
138
105
144
0.10
415
236
1789
2.28
11.0
0.20
12.9
29.8
21.6
11.8

1690
3380
8.20
1.69
0.11
584
57.5
47.2
22.3
0.08
85.5
b0.05
1038
b0.05
8.00
0.09
7.90
5.90
2.00
1.41

3150
6303
8.34
3.51
0.39
1091
218
96.8
150
0.11
440
261
1834
2.28
8.65
0.21
12.5
30.5
22.3
13.7

340
690
7.59
0.34
0.02
134
0.54
14.5
0.41
0.06
31.0
b0.05
206
b0.05
3.75
0.06
4.07
4.49
1.85
1.70

a
b

[13].
No standard.

NF-270

NF-90

Irrigation water
standards [12]

02000
03000
6.008.50
01.94a
00.20
0920
0400
02.00
060.0
05.00
0610
0960
01065
02.00
010.0
NSb
NSb
NSb
NSb
NSb