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Desalination
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Removal of heavy metal ions by nanoltration

B.A.M. Al-Rashdi a, D.J. Johnson a, N. Hilal a, b,
a
Centre for Water Advanced Technologies and Environmental Research (CWATER), Multidisciplinary Nanotechnology Centre, Swansea University, Swansea, SA2 8PP, UK
b
Masdar Institute of Science and Technology, P. O. Box 54224, Abu Dhabi, UAE

a r t i c l e i n f o a b s t r a c t

Article history: This study describes the rejection of heavy metal ions using a commercial nanoltration membrane (NF270).
Received 21 March 2012 The effect of feed pH, pressure and metal concentration on the metal rejections and permeate ux and in
Received in revised form 17 May 2012 some cases permeate pH was explored. The results showed that with all metals examined (except As (III)),
Accepted 19 May 2012
when the feed pH is below the isoelectric point, the rejection increased. NF270 rejected almost 100% of cop-
Available online xxxx
per ions at low concentrations, but decreased to 58% at the highest concentration examined. Using 1000 mg/L
Keywords:
concentration level, pH = 1.5 0.2 and 4 bar the rejection was 99%, 89% and 74% for cadmium, manganese
Heavy metals and lead respectively. However at pH above the isoelectric point the average rejections decreased. NF270
Nanoltration membrane was unable to retain As(III). The metals caused a ux decline due to membrane fouling in the order of sever-
Rejection ity: Cu2+ > Cd 2+ Mn2+ > Pb2+ As3+. The correlation between adsorbed amounts of the metals onto
Permeate ux NF270 with the normalised ux shows that as the amount increased the normalised ux decreased, except
Feed pH for arsenic that had a higher deposited amount and higher ux. The RMS roughness as obtained by AFM
Membrane fouling showed that roughness was decreased by membrane fouling.
Membrane characterisation
2012 Elsevier B.V. All rights reserved.
Membrane ltration
Water purication
Atomic force microscopy
AFM

1. Introduction of feed pH on the removal of some heavy metal and permeate ux

Heavy metals are a serious environmental contaminant because
they are environmentally persistent, have high toxicity and have a
tendency to accumulate in body tissues [1]. Because of this, environ-
mental regulations compel industries to reduce the concentration of
heavy metals in their waste water to within safe levels.
In recent years, the use of nanoltration membranes (NF) has in-
creased rapidly in the chemical, petrochemical, biotech and desalina-
tion industries, since the NF technology overcomes operational
problems that are associated with conventional techniques. Several
successful studies have been reported which have used NF mem-
branes as tools for heavy metal removal [1,2]. Most commercial NF
membranes are thin-lm composites made of synthetic polymers
containing charged groups which can make them effective in the sep-
aration of charged metals from water. Additionally, the separation in
NF occurs due to solution diffusion as well as sieving, the Donnan effect,
dielectric exclusion and electromigration, which also makes it useful in
the separation of both charged and uncharged organic solutes [3].
The feed pH can change the nature of the membrane surface
charge and pore size, as well as that of dissolved metal species and
therefore can affect the membrane separation efciency. The effect
Corresponding author. Tel.: + 44 1792606644; fax: + 44 1792295676.
E-mail address: N.Hilal@Swansea.ac.uk (N. Hilal).
using NF membranes has been studied and explained previously
[47]. However, the investigation of several different heavy metals
on the same membrane, under the same conditions gives much infor-
mation about the membrane and its suitability at different conditions
(i.e. pH, metal ions, feed pressure and concentration). The NF270
membrane has been studied before for the retention of copper [8,9]
and manganese [10]. In this work retention of ve metal solutions
(Cd(II), As(III), Cu(II), Mn(II), Pb(II)) was investigated using the
NF270 membrane. The effect of the following factors on membrane
separation was studied: pressure (35 bar), initial feed concentration
(1002000 mg/L) and pH (1.505) of the solution. In this study ux
reduction with these metals also was studied and explained
according to the measured surface roughness (RMS) values and the
amount of each metal deposited onto the membrane surface.
2. Materials and methods
2.1. Materials and apparatus
All chemicals used in this research were of analytical grade and all
metal solutions were prepared by dissolving the appropriate mass of
each metal in high purity Milli-Q water (18.2 M cm), except for ar-
senic which was prepared in boiled acidied or alkalised Milli-Q
water (5 mL for 1 L solution). The arsenic trioxide is insoluble at

0011-9164/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2012.05.022

Please cite this article as: B.A.M. Al-Rashdi, et al., Removal of heavy metal ions by nanoltration, Desalination (2012), doi:10.1016/
j.desal.2012.05.022
2 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx
room temperature and required boiling in order to dissolve. For a
multicomponent solution arsenic was dissolved rst in boiling Milli-
Q or tap water. After cooling all other metals were added sequentially,
after the previous metal had completely dissolved. Copper nitrate
Cu(NO3)2 3H2O, lead nitrate Pb(NO3)2, arsenic trioxide As2O3, man-
ganese nitrate Mn(NO3)2 4H2O, cadmium nitrate Cd (NO3)2 4H2O,
sodium hydroxide and nitric acid (6972%) were all obtained from Fi-
scher Scientic, UK. The pH was measured using a calibrated pH
metre (Jenway, model 3540). Concentrations of metal ion in synthetic
and treated solutions were examined using a Varian AA 240FS Atomic
Adsorption Spectrometer (AAS). Calibration curves of the tested
metals were constructed with different concentration. The instru-
ment was calibrated regularly and calibration was veried before
each sample set. Higher concentration metal solutions were diluted
to prevent blocking of the AAS sensor. Standard solutions of each
metal were prepared from a stock solution of 1000 mg/L. The
1000 mg/L stock solution of each used metal was prepared following
the procedures described in Ref. [11].
2.2. Membrane ltration experiments
For the membrane permeability, ux, fouling and rejection studies
a cross-ow stainless steel nano-ltration unit was used (Fig. 1). This
nanoltration unit was equipped with one membrane module with
an effective membrane area of 0.00076 m 2 which can be operated in
the pressure range of 1 to 5 bar. The nanoltration unit consisted of
a feed tank (capacity of 5 L), a membrane module, a high-pressure
pump (Tuthill Pump Co. of California) and two pressure gauges. The
feed and retentate ow rates were measured at the inlet and outlet
of the membrane module by two ow metres (MPB Industries,
Kent, England) with minimum and maximum ow rate of 0.4 L/min
and 4 L/min, respectively. In this work, the feed and retentate ow
rates were maintained at 0.4 L/min. Three valves (Ham-Let, UK;
H6800 for valve 1, H300SSLR1/4RS for both valve 2 and valve 3)
were placed at locations (see Fig. 1) in order to control the uid ow.
Experiments on membrane ltration were carried out using com-
mercial NF270 nanoltration membrane (Dow membrane) at room
temperature that ranged from 22 to 25 C. The NF270 membrane is
a polyamide membrane; the active layer of NF270 is a very thin
semi-aromatic piperazine-based polyamide layer with a microporous
polysulfone supporting layer [10,12]. NF270 pore size, pore size dis-
tribution using solute transport method and the membrane surface
roughness using AFM was investigated and presented in a previous
paper [13]. The surface charge at different pH and the isoelectric
point of NF270 have been noted by many researchers previously
[8,1416]. The membrane surface is positively charged when solution
pH is less than 3.34 and negatively charged when the solution pH is
Fig. 1. Schematic diagram of cross ow NF ltration unit.
Please cite this article as: B.A.M. Al-Rashdi, et al., Removal of heavy metal ions by nanoltration, Desalination (2012), doi:10.1016/
j.desal.2012.05.022
higher. This trend arises in thin-lm composite membranes from the
dissociation of various functional groups (typically carboxyl) located
on the surface of the membrane with increasing pH and pendant
amino groups [17]. In all ltration experiments, the membrane was
immersed in deionised water before being used in any experimental
work and each membrane was pressurised at 5 bar for at least
2 hours using pure water to avoid any compression effects during
measurements and also to establish leak tightness.
2.3. Permeability of NF270
Water ux measurements were carried out with high purity Milli-
Q water (resistivity 18.2 M cm). From ltration tests at different
transmembrane pressures (1.55 bar) at ambient temperature with
membrane area of 0.00076 m 2, the pure water permeability was de-
termined. The pressure was varied between highest pressure at
5 bar down to lowest pressure of 1.5 bar. The trans-membrane pres-
sure and volumetric ow rate were adjusted using the concentrate
outlet valve and variable speed key of the pump. Pure water ux at
certain pressure can be dened as:
Q
Jv 1
A
where:
Jv permeate ux (L/m 2 h)
A effective membrane area (m 2)
Q volume ow rate (L/h).
However, in this study, the pure water ux was determined by
weighing the obtained permeate during a predetermined time using
an electronic balance (Precisa, Model XB3200C) connected to a com-
puter. By plotting membrane ux (Jv) for a variation of applied pres-
sure (P), the membrane permeability (pure water permeability), Lp
can be obtained from the slope of the straight line as follows:
Jv
Lp 2
P
2.4. Heavy metal retention using NF270
In the experiments of heavy metal removal (Cu(II), Mn(II), Pb(II),
Cd(II) and As(III)), an initial volume (approximately 500 mL) of the
metal solution was pumped and circulated without agitation through
the membrane module (Fig. 1). Permeate was continuously collected
 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx
in a beaker until 50 g of the permeate had been acquired, at which
point the experiment was stopped. The permeate ux was deter-
mined by weighing the obtained permeate during the experiment
as mentioned in Section 2.3. Final permeate ux (i.e. when the per-
meate mass = 50 g) was used in discussion of the results unless oth-
erwise stated. The experimental conditions used to study the effect
of pressure, metal concentration (Cmetal), and pH (adjusted using
1 M NaOH or 1 M HNO3) of metal solutions are summarised in
Table 1. A fresh piece of the NF270 membrane was used in each ex-
periment. Solute separation or removal can be represented by rejec-
tion factor (R):
Cp
R 1
Cb
where Cp is concentration of solute in permeate and Cb is an average
bulk concentration of solute in the feed (Cf) and concentrate/
retentate (Cr).
Cf Cr
Cb
2
2.5. Determination of membrane solute adsorption/deposition
Solute adsorption experiments on NF270 membrane were carried
out inside a closed bottle by measuring the metal concentration be-
fore and after 24 hours contact time with the membrane. During the
experiments the bottles were shaken regularly to prevent settling.
The volume and the initial concentration of metal solution were
500 mL and 1000 mg/L, respectively. The effective surface area (A)
of the membrane was 25 cm 2. The effect of water evaporation and ad-
sorption of the solute onto the recipient walls were determined
through a blank experiment. The adsorption amount Q (mg/m 2)
was determined using [12]:
h
 i
C i C eq C i C blank  V
Q 5
A Based on the calculation described by Ferguson [21] and using Ksp
where Ci, Cblank and Ceq are the initial, blank and equilibrium concen-
trations in mg/L or mol/L, respectively.
2.6. Atomic force microscopy (AFM)
All AFM measurements were performed using a Multimode AFM
with Nanoscope IIIa controller (Veeco, USA) using manufacturer sup-
plied software. All measurements were made using tapping mode in
air at room temperature and were performed using TESP type cantile-
vers (nominal spring constant 2080 N/m) (Bruker AXS). Roughness
parameters for all images were calculated using the instrument soft-
ware, with all values being the mean value of at least three images
taken from different areas on the sample surface. The roughness pa-
rameters were the root mean squared roughness (RMS), roughness
average (Ra) and the percentage surface difference. An explanation
Table 1
Membrane experimental conditions.
Exp. Cmetal (mg/L) pHmetal Pressure (bar)
1 1000 5 5, 4, 3
2 1000 3.3 4
3 1000 1.5 4 0
4 100 5 4
5 500 5 4
6 2000 5 4
Please cite this article as: B.A.M. Al-Rashdi, et al., Removal of heavy metal ions by nanoltration, Desalination (2012), doi:10.1016/
j.desal.2012.05.022
3
of how these parameters are calculated can be found in the following
references: [13,18].
3. Results and discussion
3.1. Effect of applied pressure
3.1.1. Membrane permeability
Pure water ux measurements as a function of trans-membrane
pressure (TMP) for membrane NF-was carried out. Using Eq. (2),
the membrane permeability (Lp) was found to be 13.2 L/m 2 h bar
(Fig. 2) which is similar with that found by others [12,15]. Moreover,
Semiao and Schafer [16] found that this membrane has permeability
3
of about 18 L/ m 2 h bar. All of these permeability results indicate that
NF270 membrane is a loose NF membrane.
3.1.2. Permeate ux
Fig. 3(ae) shows the uxes of NF270 using ve different metals as
a function of pressure. With all metals the permeate ux increased
with increasing pressure. As pressure increases, convective transport
4 and concentration polarisation become more important [19]. Fig. 3c
for cadmium (Cd) reveals that change in the permeate ux remains
linear with increasing pressure, which indicates insignicant concen-
tration polarisation. A similar observation was made for arsenic.
However with copper, lead and manganese the increase in ux is
not linear with the rise of pressure, which shows a quantity of con-
centration polarisation.
The permeate uxes for all metal solutions were lower than the
corresponding pure water ux, 60 L/m h, 33 L/m h and 23 L/m h,
with pressure 5, 4 and 3 bar, respectively (Table 2). This can be
taken as an indication of membrane fouling and/or due to osmotic
pressure build up caused by the retained salt [4,9]. A similar reduction
in permeate ow using a similar range of pressure was observed by
Chaabane et al. [20]. The metals ranked by the order which they cau-
sed membrane fouling is Cu 2+ > Cd 2+ Mn 2+ > Pb 2+ As 3+. This
may be due to the formation of a cake layer of copper hydroxide pre-
cipitate Cu(OH)2 (s). The measured pH of the retentate was around 6,
which is indeed higher than the pH at which precipitation occurs.
constant at 25 C and for 1000 mg/L copper solution, copper hydrox-
ide precipitation starts at pH = 5.24. On the other hand, the pH of pre-
cipitation of the other metals (Mn, Cd and Pb) was higher than that
found in the retentate solution; thus these metals tend to diffuse
through the membrane. The metal hydroxide complexes and forma-
tion of insoluble hydroxides at certain pH were also reported by
70
y=13.201x-13.557
60
R= 0.9402
50
Flux (L/m.h.bar)
40
30
20
10
0
1 2 3 4 5 6
Pressure (bar)
Fig. 2. Water ux as a function of transmembrane pressure (membrane NF270).
4 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx

30
35 (a) (b)

30 25

25 20

Flux (L/m.h)
Flux(L/m.h)

20
15
15
10
10

5
5
Exp.1 EXP.2 Average EXP.1 EXP.2 Average

0 0
2 3 4 5 6 2 3 4 5 6
Pressure (bar) Pressure (bar)
30 (c) 40 (d)
35
25
30
20 Flux (L/m.h)
Flux (L/m.h)

25

15 20

15
10
10
5
5 EXP.1 EXP.2 Average
Exp.1 EXP.2 Average

0 0
2 3 4 5 6 2 3 4 5 6
Pressure(bar) Pressure(bar)
40 (e)
35

30
Flux (L/m.h)

25

20

15

10

5
Exp.1 EXP.2 Average
0
2 3 4 5 6
Pressure(bar)

Fig. 3. Effect of pressure on nal permeate ux of NF270 membrane with (a) Cu(II), (b) Mn(II), (c) Cd(II), (d) Pb(II) and (e) As(III) (experimental conditions: 1000 mg/L, pH = 5,
collected permeate = 50 g).

Ozaki et al. [22]. Moreover Pb 2+ has a higher mobility and diffusion
coefcient than that of with Cd 2+ and Mn 2+ [23].
Brandhuber and Amy [24] conrmed that small and uncharged
As(III) was easily passed through a loose NF membrane with a similar
ux as observed for water. This can explain the higher permeate ux
and the lower difference between pure water ux and the ux when
arsenic solution was used in this study (Table 2).
It is evident from Fig. 3 that sometimes there is a clear difference
between experiment 1 and experiment 2 (even though the conditions
were the identical). However, with each experiment a different sec-
tion of the NF270 membrane was used. Thus the differences in the re-
sults may indicate heterogeneity of the membrane surface. The use of
different samples of membrane in each experiment may represent
nearly the actual permeate ux or rejections of the membrane.

Please cite this article as: B.A.M. Al-Rashdi, et al., Removal of heavy metal ions by nanoltration, Desalination (2012), doi:10.1016/
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 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx 5

Table 2
Final permeate ux and percentage ux reduction of NF270 membrane for some metals with different parameters.

Metals Cu(II) Mn(II) Cd(II) Pb(II) As(III)

Parameters Flux (L/m h) Flux Red.% Flux (L/m h) Flux Red.% Flux (L/m h) Flux Red.% Flux (L/m h) Flux Red.% Flux (L/m h) Flux Red.%

Pressure (bar) 3 9.0 61 12.9 44 12.7 45 18.1 21 17.9 22

4 22.0 33 21.7 34 21.0 36 21.8 34 25.4 23
5 25.3 58 26.3 56 29.0 52 33.8 44 33.6 44
Feed pH 1.5 15.7 52 14.5 56 21.0 36 24.8 25 32.6 1.1
3.3 14.9 55 23.8 28 22.6 32 21.8 34 20.8 37
5 22.0 33 21.7 34 21.0 36 21.8 34 25.4 23
9.3 32.8 0.53
Concentration (mg/L) 100 29.8 10 29.6 10 24.5 9 29.6 10 31.5 4.4
500 23.4 29 26.4 20 25.5 23 27.0 18
1000 22.0 33 21.7 34 21.0 36 21.8 34 25.4 23
2000 11.1 66 21.6 35 18.2 45 20.3 38 20.6 38

Fig. 4 presents the permeate ux for the NF270 membrane plotted
against time for different pressure values during the treatment of
1000 mg/L copper solution. When the pressure was 3 or 4 bar the

permeate ux (Jv) reduction in (J0 J v J  100) compared with that
0
of pure water (J0) (Fig. 5) was 61% for 3 bar pressure and 33% for
4 bar pressure. When 5 bar pressure was applied, the reduction was
higher, 58%. In the case of 3 bar pressure, the drop in the ux starts
from the beginning (t = 1 min) whereas with 4 and 5 bar pressures,
this drop occurred after 1 minute and decreased to an almost con-
stant value in the later stage. However the initial ux (t = 1 min) is
not the same as that of pure water at 5 bar pressure. Obviously with
3 bar pressure the permeate ux was less and thus more time was
needed to collect 50 g permeate (about 8 hours). In order to moder-
ate the effects of fouling and the time, pressure of 4 bar was kept in
the latter experiments.
3.1.3. Rejection
Concentration polarisation, which increased with increasing pres-
sure, results in a decrease in retention. However, convective transport
causes an increase in retention. The counteracting contributions of in-
creased convective transport and increased concentration polarisation
result in a nearly constant retention value [19]. Fig. 6ad reveals that
all used metals have an effect on both concentration polarisation and
convective transport but with some variations. For example, the rejec-
tion of copper at pressure = 3 bar was 96% (average of Exp.1 and
Exp.2) and then decreased to 90% at both pressures 4 bar and 5 bar
which implies that concentration polarisation followed by both con-
vective transport and concentration polarisation had occurred.
When the applied pressure was increased, the manganese rejection
increased slightly (29% to 36%). Cadmium and lead behaved different-
ly: when the pressure was increased from 3 bar to 4 bar, the rejections
increased, but when the pressure increased further to 5 bar then the
rejection decreased. However, all these changes in rejection were
small; thus they might be considered nearly constant. With increased
pressure, rejection increased or decreased slightly. The small differ-
ences between Cu, Cd, Pb and Mn rejection as the pressure increased
can be attributed to the water permeation rate becoming greater at
higher pressure, or to the solute diffusion rate which would not be
expected to be affected signicantly by higher pressure because it is
mainly controlled by the solute concentration [4]. The average rejec-
tions of Cd, Cu, Pb and Mn were 63, 92, 54 and 33%, respectively. The
reason for higher copper removal and lower manganese removal
might be credited to the formation of metal hydroxide precipitate as
discussed in Section 3.1.2.
Other explanations for the experimentally determined rejection
sequence are:
i) The diffusion coefcients of cations Pb 2+, Cd 2+, Cu 2+ and Mn 2+
in water at 25 C are 1.89 10 5, 1.438 10 5, 1.428 10 5 and
1.424 10 5 cm 2/s, respectively [23]. The order of diffusion coef-
cients is inversely reected in the rejection sequence except for
manganese which might oxidise to Mn 3+. Similar trends with NF
were observed in the literature for different ions [5]
ii) The ionic radius of cations Pb 2+, Cd 2+, Cu 2+ and Mn 2+ are 133,
97, 72 and 80 pm [25], respectively. Tansel et al. [26] reported
that ions with lower ionic radius tend to hold their hydration
shell (i.e. are strongly attached to water molecules) thus would
be more removed by membrane. Copper has a comparatively

50 P= 3 bar P= 4 bar P= 5 bar

P= 3 bar P= 4 bar P= 5 bar 70

60
40

50
Flux(L/m.h)

Flux (L/m.h)

30
40

20 30

20
10
10

0 0
1 101 201 301 401 1 101 201 301 401
Time(min) Time (min)

Fig. 4. Permeate ux with time at different pressure, experimental conditions: metal Fig. 5. Change in pure water ux observed over time for several different pressure
concentration = 1000 mg/L copper, pH = 5 0.2, collected permeate = 50 g. values.

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6 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx

Fig. 6. Effect of pressure on rejection (a) Cu(II), (b) Mn(II), (c) Cd(II), (d) Pb(II) using NF270 membrane. Experimental conditions: metal concentration = 1000 mg/L, pH = 5 0.2,
collected permeate = 50 g.

small ionic radius and hence will be more easily rejected. Pb will
be easily permeated because of the relatively loose hydration
shell. However with loose and charged NF membranes size exclu-
sion is not the main mechanism to explain rejection. Charge exclu-
sion and metal deposition play very important roles which cannot
be ignored.
Rejection of As(III) by NF270 was very small and occasionally the
rejection was below the level of detection. The rejection of As(III) at
different pressures ranged from 0 to 11%. However, this result was
expected because NF270 is a loose nanoltration membrane. Many
researchers [6,24,27] found that rejection of As(III) by loose NF mem-
brane was very small compared with As(V); thus they recommended
oxidation of As(III) to As(V) prior to use of loose NF membrane to re-
move arsenic from water.
3.1.4. Permeate ux and metal rejection
The relation between permeate ux and metal rejection of Cu 2+,
Cd 2+, Mn 2+, and Pb 2+ for NF270 in pressure range 35 bar is
shown in Fig. 7. It is interesting to note that the highest ux was
obtained for lead. For copper the rejection fell off with increasing
permeate ux. An almost linear relationship (R 2 = 0.963) was found
to relate the permeate ux to Cu(II) rejection. On the contrary, for
manganese as the permeate ux increased the rejection was found
to increase with a linear relationship (R 2 = 0.99). For both cadmium
and lead, at higher and lower uxes the metal rejections were similar.
This result suggests that these metals are rejected by different
mechanisms.
3.2. Effect of feed pH on NF270 performance
3.2.1. Permeate ux
Fig. 8(ae) shows the ux of NF270 as a function of feed pH for
1000 mg/L cadmium, arsenic, copper, manganese and lead solutions.
It can be seen that the ux varied over the used pH range depending
on the metal tested. In general, the change of ux with feed pH was
small (average ux for all used metals ranged from 14 L/m 2 h to
25 L/m 2 h). With the manganese solution the maximum ux was at
pH = 3.3 0.2 (at or close to the iso-electric point of the membrane).
Childress and Elimelech [28] and Qin et al. [29] found a similar result;
maximum permeate ux was found to be at the isoelectric point.
However, with the copper solution (Fig. 8a) the maximum ux occurs

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 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx
Cu(II) Mn(II) Cd(II) Pb(II)
120
y = -0.3927x+99.367
100 R = 0.9627
80
%Rejection
60
40
20 y = 0.5111x + 22.281
R = 0.9903
0 jection of arsenite As(III) increased with the increase of pH from 50%
0 10 20 30 40
Flux(L/m.h)
Fig. 7. Relation between permeate ux and Cu(II), Mn(II), Cd(II) and Pb(II) rejection.
Experimental conditions: 1000 mg/L metal solution, pressure 35 bar, pH = 5 0.2.
at pH = 5 0.2 (22.0 4 L/m h) and the minimum ux occurred
at both pH = 1.5 0.2 (16 0.83 L/m h) and 3.3 0.2 (15.0
2.3 L/m h). With As(III) solution, the minimum ux occurs at
pH= 3.3 0.2 (21 4 L/mh) (Fig. 8e). Wang et al. [4] reported that
the permeate ux was minimal around the isoelectric point of the
membrane. With the lead solution, as well as the cadmium solution,
the permeate ux was nearly constant as the pH increased. Childress
and Elimelech [28] proposed mechanisms to explain the ux at the iso-
electric point: the pore size changes with pH due to i) the expanding or
shrinking of the cross linked-membrane polymer network, ii) the
lowest electroviscous effect and iii) the highest net driving force due
to lowest osmotic pressure at the membrane surface. Wang et al. [4]
explained the minimum permeate ux in terms of concentration
polarisation and membrane fouling. In addition, Ballet et al. [7]
explained the effect of decreasing permeate ux with changes in pH
due to shrinking of the skin layer which result from the differences of
the hydration of the ionised groups of the membrane.
3.2.2. Rejection
Fig. 9(ad) presents the effects of feed pH on the Cu, Mn, Cd and
Pb rejections. Generally, as the pH increased from pH = 1.50 to
pH = 5 0.2, the rejections of these metals decreased. For instance,
the average rejection of cadmium was 99% and 68% at pH = 1.50
0.2 and 5 0.2 respectively. The decrease in removal as the pH in-
creased can be caused by the membrane charge. As mentioned previ-
ously, the isoelectric point (IEP) of NF270 is in the range 3.34 and it
is negatively charged in solution above pH = 4 and positively charged
in solution less than pH = 4. At pH = 1.50 the membrane is positive;
thus the retention of these cations would be higher because of charge
repulsion. Moving to pH = 5 the membrane becomes negative; thus
the cations would more easily permeate the membrane and thus re-
tention would be less. For example, retention of manganese ion at
pH = 1.50 was 89% while at pH = 5 the retention decreased to 33%
only (Fig. 9b) which can be considered as a big change, proving that
pH plays an important role in manganese removal using NF mem-
brane. A similar result for manganese removal in acidic medium has
previously been reported [10]. Similar trends of high at pH values
below the isoelectric point and low rejection at pH values above the
IEP for NF membrane was reported by Wang et al. and Ballet et al.
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j.desal.2012.05.022
7
[4,7]. As discussed in Section 3.2.1, the permeate ux at the IEP
could be the minimum or the maximum; this discussion can also be
used to explain the rejection. For example Wang et al. [4] explained
the higher rejection at IEP as at this point the electrostatic interaction
between the membrane and the ions was zero. Therefore the ions did
not easily permeate the membrane. In this study this occurs with cop-
per solution where the rejection at pH = 1.50 0.2 and pH = 3.3 0.2
was similar at 100%. However, shrinking of the skin layer of the mem-
brane as explained by [7,28] causes a higher permeate ux and lower
rejection. This happened with lead and manganese, where the rejec-
tion at the IEP was 59% and 26%, respectively.
At all pH values studied, the rejection of copper was higher
than for the other metals. The order of metal rejections with NF270
was Cu > Cd > Mn > Pb at pH = 1.50 0.2, Cu > Cd > Pb > Mn at pH =
3.3 0.2 and pH = 5 0.2. Higher rejection of copper by the same
membrane, NF270, was also reported by Tanninen et al. [9] and
Ortega et al. [10].
With As(III) the feed pH appears to have very little effect at pH 5
and below. At pH = 1.50, 3.3, 5 and 9.30 the rejection was 12%, 12%,
13% and 5%, respectively. However, Urase et al. [6] found that the re-
at pH 3 to 89% at pH 10. At pH 10, most of the arsenite is in monova-
lent anion form (H2AsO3) while at lower pH values most of the arse-
nite is in neutral solute H3AsO3 because the pKa of arsenite is 9.1. The
decrease of As(III) at pH = 9.30 in this work might be attributed to the
decrease of the arsenic deposition on membrane surface due to simi-
lar charge, as will be discussed later.
3.2.3. Permeate pH
Differences in permeate pH relative to feed pH can give informa-
tion about the passage of protons through the membrane. During
the ltration of copper and cadmium solution (pH = 1.5), the perme-
ate pH decreased to about 1.45 and 1.47 respectively, which indicates
a greater passage of protons compared with Cu and Cd ions. This neg-
ative proton retention when the pH of the feed solution is lower than
the isoelectric point has been studied by others [10,28]. This was
explained in terms of mobility and ionic size; hydrogen ions have a
higher ionic mobility and smaller size. With the other metals, Mn,
Pb and As(III), and at the same feed pH, positive rejections of protons
occurred (permeate pH was 1.60, 1.56 and 1.75 for Mn, Pb and As re-
spectively). Qin et al. [29] reported the same outcome; positively
charged membrane resulted in higher permeate pH. Protons did not
easily pass through the NF membrane for feed pH values below the
isoelectric point due to the electrostatic repulsion between the pro-
tons and the positively charged membrane surface. The results
showed that the effect of pH depends mainly on the nature of the sur-
face ionic groups of the membrane and changes of the speciation in
solution which is in agreement with data reported in the literature
[7]. When the feed solution has a pH of around 5, the permeate pH de-
creased for all metals in the range 4.50 to 4.80 except for As(III)
where the permeate pH increased to 6.50.
3.3. Effect of metal concentration on NF270 performance
3.3.1. Permeate ux
Fig. 10(ae) illustrates the effect of metal concentration (100 to
1000 mg/L) on permeate ux of NF270. It is clear from this gure that
the permeate ux declines with increasing concentration for all investi-
gated metals. The explanation for this is that it might be due to: (i) de-
crease of the effective membrane pore size due to adsorption or
deposition of solute on the membrane surface [4,30] and (ii) increase
in osmotic pressure [4]. Using 2000 mg/L of each metal results a ux
of 11.1 4, 21.6 3, 18.2 3, 20.3 0.86 and 20.6 0.31 L/m 2 h for
Cu(II), Mn(II), Cd(II), Pb(II) and As(III), respectively. Thus the copper
was the metal that most blocked or fouled the membrane compared
8 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx

30
30 (a) (b)
25
25

20
20
Flux (L/m.h)

Flux (L/m.h)
15 15

10 10

5 5
EXP.1 EXP.2 Average EXP.1 EXP.2 Average

0 0
0 2 4 6 0 2 4 6
Feed pH Feed pH

30
(c) 40
(d)
25 35

30
20
Flux (L/m.h)
Flux (L/m.h)

25

15
20

15
10

10
5
EXP.1 EXP.2 Average 5
EXP.1 EXP.2 Average

0 0
0 2 4 6 0 1 2 3 4 5 6
Feed PH Feed pH

40
(e)
35

30
Flux (L/m.h)

25

20

15

10

5
Exp.1 EXP.2 Average

0
0 2 4 6 8 10
Feed pH

Fig. 8. Effect of feed pH on nal permeate ux of NF270 membrane with (a) Cu(II), (b) Mn(II), (c) Cd(II), (d) Pb(II) and (e) As(III) (experimental conditions: 1000 mg/L,
pressure = 4 bar, collected permeate = 50 g.).

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120 (a) 100 (b)

90
100
80
70

Rejection (%R)
80
Rejection (%R)

60
60 50
40
40
30
20
20
EXP.1 EXP.2 Average 10 EXP.1 EXP.2 Average
0 0
0 2 4 6 0 1 2 3 4 5 6
Feed pH Feed pH

120 (c) 90 (d)

80
100
70

Rejection (%R)
80 60
Rejection (%R)

50
60
40

40 30

20
20
10
EXP.1 EXP.2 Average EXP.1 EXP.2 Average
0 0
0 2 4 6 0 1 2 3 4 5 6
Feed pH Feed pH

Fig. 9. Effect of feed pH on rejection of (a) Cu (II), (b) Mn (II), (c) Cd (II) and (d) Pb (II) using NF270 membrane. Experimental conditions metal concentration = 1000 mg/L,
pressure = 4 bar, collected permeate = 50 g.

with other used metals. The relationship of copper concentration levels
to permeate ux was almost linear.
3.3.2. Rejection
The rejection of cadmium, copper, lead, manganese and arsenic
at different feed concentrations (1002000 mg/L) is shown in
Fig. 11(ae). For cadmium, copper and lead, at low concentration
the rejection was higher and as the concentration of the metal solu-
tion increased the rejection decreased. NF270 can reject Cu complete-
ly at 100 and 500 mg/L and only 58% at a concentration of 2000 mg/L
at 4 bar. Nevertheless the rejections at higher concentration of 1000
and 2000 mg/L have higher standard deviation 14 and 20, respective-
ly. For cadmium and lead ions, the rejection at 100 mg/L was 83
3.5% and 79 4.5% and at 2000 mg/L the rejection was 57 2.8%
and 58 3.5%, respectively. The trend of decreasing rejection as
metal concentration increased was also reported in the literature for
the same membrane NF270 but with different metals [31].
Nevertheless, Tanninen et al. [8] found that the rejection of 25 g/L
Cu using NF270 was 99.5%. In this work the rejection even for
2000 mg/L was small. This might be attributed to different experi-
mental condition of pressure and pH.
Using Mn solution, the rejection was smaller than that of Cu(II),
Cd(II) and Pb(II). Approximately 100 mg/L manganese solution re-
sults only in a 45 2.8% rejection. At a concentration level of
500 mg/L, the rejection decreased to 28 0.71%. However from 500
to 2000 mg/L, the rejection then increased very slightly (Fig. 11b).
When arsenic solution was used the rejection was lower than all
other metals studied: 7 1.3% for 100 mg/L and 30 3% for
2000 mg/L. As the As(III) feed concentration increased the rejection
increased. The poor retention of As(III) by NF270 might be ascribed
to the neutral molecules of As(III) in aqueous solution at the used
pH (pH = 5). Increasing of As(III) retention as As(III) feed concentra-
tion increased was also found by Ref. [32]. Refs. [4] and [33] explained
the increasing of rejection as feed concentration increased by the ad-
sorption of the solute on the membrane surface.
3.4. Roughness of NF270 with different metals
AFM images at scan area 1 m 1 m for NF270 membrane ltered
1000 mg/L metals Cu(II), Cd(II), Pb(II), Mn(II), As(III) at pH = 5 and
Cu(II) at pH = 1.50 are shown in Fig. 12. NF270 with different ltered
metals and with different pH (copper) shows different topographies.
NF270 membranes fouled with different metals (Cu, Cd, Mn, Pb and
As) were scanned using AFM tapping mode in air, in order to compare
their roughness with that of unused NF270 and with each other. Mea-
surements were made at scan sizes of 1, 5, 20 and 50 m. In order to
see the effect of pH, Cu(II) was ltered at two pH values; 1.50 and 5.
For NF270 fouled membranes, the data for average roughness (Ra),
root mean square roughness (RMS) and surface area difference (%)
are presented in Table 3. Due to the effect of image size on various
roughness parameters the surface roughness, RMS and Ra should be
compared for identical scan sizes. As shown in Table 3 and Fig. 13

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10 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx

35
35 (a) (b)
30
30

25
25

Flux (L/m.h)
Flux (L/m.h)

20 20

15 15

10 10

5 5
EXP.1 EXP.2 Average
EXP.1 EXP.2 Average
0 0
0 500 1000 1500 2000 2500 0 500 1000 1500 2000 2500
Concentration (mg/L) Concentration (mg/L)
40
40 (c) (d)
35
35

30 30

25 25
Flux (L/m.h)

Flux (L/m.h)

20 20

15 15

10 10

5 5
EXP.1 EXP.2 Average
EXP.1 EXP.2 Average
0 0
0 500 1000 1500 2000 2500 0 500 1000 1500 2000 2500
Concentration (mg/L) Concentration (mg/L)
40
(e)
35

30
Flux (L/m.h)

25

20

15

10

5
Exp.1 EXP.2 Average
0
0 1000 2000 3000
Cocentration (mg/L)

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 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx 11

120
(a) 50 (b)
45
100
40

80 35

Rejection (%R)
Rejection (%R)

30
60 25

20
40
15

10
20
5 EXP.1 EXP.2 Average
EXP.1 EXP.2 Average
0 0
0 500 1000 1500 2000 2500 0 500 1000 1500 2000 2500
Concentration (mg/L) Concentration (mg/L)
90 (c) (d)
90
80
80
70
70
60
Rejection ( %R)
Rejection (%R)

60
50
50
40
40

30 30

20 20

10 10
EXP.1 EXP.2 Average EXP.1 EXP.2 Average
0 0
0 500 1000 1500 2000 2500 0 500 1000 1500 2000 2500
Concentration (mg/L)
Concentration (mg/L)
35 (e)
30

25
Rejection (%)

20

15

10

5
Exp.1 EXP.2 Average
0
0 500 1000 1500 2000 2500
Cocentration (mg/L)

Fig. 11. Effect of initial concentration on rejection of (a) Cd, (b) As(III), (c) Cu(II), (d) Mn(III) and (e) Pb(II) using NF270 membrane. Experimental conditions: pH = 5 0.2,
pressure = 4 bar, 50 g permeate.

Fig. 10. Effect of initial concentration on permeate ux of NF270 membrane with (a) Cu (II), (b) Mn(II), (c) Cd(II), (d) Pb(II) and (e) As(III). Experimental conditions: pH = 5 0.2,
pressure = 4 bar, 50 g permeate.

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12 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx

Fig. 12. AFM images after ltering sample 1) Pb(II), 2) As(III), 3) Cu(II), 4) Cd(II), 5) Cu(II) and 6) Mn(II), about 1000 mg/L at pH = 5 0.2 except sample 3 at pH = 1.5 0.2.

(RMS), at larger scan sizes (20 m and 50 m) the variation between
images taken on the same sample was very high for some metals and
the virgin membrane. Thus 5 m 5 m was chosen for comparison.
Table 3 also shows that as the scan size was increased the Ra and
RMS values increased except for Pb(II) (which might be due to the
large deviation of 26%). Some studies [34] found that the surface
area increases as the roughness increases; however this trend was
not observed in this study. The higher roughness parameter of virgin
NF270 (Fig. 13) indicates that this membrane is expected to have rel-
atively high fouling on its surface because foulant particles could ac-
cumulate in the valleys on the membrane surface due to higher
local ux over valley regions [3537]. Virgin NF270 membrane with
image scans size 5 m (except for As(III)), 20 m and 50 m has
higher roughness values compared with fouled membrane. NF270
membrane fouled with Pb and Mn has the lowest observed RMS
roughness. The permeate ux reduction (Table 2) at pH = 5, ranged
from 23 to 36%. In contrast the membrane used to lter the 5 compo-
nent mixed solution had a higher RMS value 10 5 nm.
Song et al. [38] and Zahrim et al. [39] reported that fouled mem-
brane exhibits high surface roughness compared with the virgin
membrane. However, it is not the case with the metals carried out
in this work. In this study some surfaces fouled with metals such as
copper, as shown in Tables 2 and 3, have lower surface roughness,
although their permeate ux reduction in some condition such as
pH = 5 and pressure = 3 bar was high (61%). Hobbs et al. [17] found
similar results; some fouled membrane shows lower average rough-
ness although it suffered more ux decline (fouling); thus, surface
area difference was used instead of RMS as a measure of surface
roughness.
At 5 m, RMS value for NF270 membrane used to lter copper at
pH = 1.50 and that for copper at pH = 5, the difference was insigni-
cant. While at 20 m, NF270 membrane used to lter copper at
pH = 1.50 has higher RMS roughness (27.15 8 nm) than that for
copper at pH = 5 (6.79 0.18 nm). This means that the pH inuences
the surface roughness of the membrane. At lower pH, the membrane
pores might expand [28] so more metal ions may be retained within
the membrane pores, thus higher RMS and permeate ux reduction
(52%).
3.5. Depositions of metals on NF270 membrane
The high ux nanoltration membrane (NF270) has been found to
adsorb or deposit high quantities of micropollutants, such as hor-
mones [16] and organic compounds [30]; thus the deposition or ad-
sorption of the used metals in this study on the surface of
nanoltration membrane (NF270) has been investigated in this work.

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 B.A.M. Al-Rashdi et al. / Desalination xxx (2012) xxxxxx 13

Table 3
800
Some surface characteristics of fouled NF270 membrane.

Fouled membrane Image size RMS* Ra* Surface 700

area diff. %*

Adsorped amount, Q (mg/m)

(m) (nm) SD* (nm) SD* (%) SD*
600
Pb 1 2.47 0.10 1.91 0.03 2.67 0.23
5 4.52 0.16 3.30 0.15 3.44 1.07
500
20 22.39 25.88 11.01 9.76 1.42 0.87
50 15.02 7.22 7.65 2.97 0.53 0.34
As 1 2.78 0.23 2.18 0.16 5.77 1.17 400
5 20.68 14.30 17.56 12.37 3.12 1.80
20 38.04 30.31 29.46 25.78 2.10 1.41
50 54.89 26.61 41.48 23.09 0.47 0.13 300
Cu, PH = 1.5 0.02 1 2.51 0.14 1.97 0.13 3.85 0.39
5 4.71 0.80 3.68 0.55 1.57 0.23 200
20 27.15 8.25 20.05 7.08 1.47 0.01
50 63.38 28.31 47.09 28.05 0.34 0.08
Cd 1 2.94 0.08 2.29 0.07 4.09 0.24 100
5 4.81 0.95 3.81 0.77 1.97 0.42
20 9.60 6.83 7.10 4.73 1.01 0.25
0
50 38.75 24.80 17.42 7.83 0.33 0.13
Cu-pH = 5 0.02 1 2.83 0.45 2.23 0.36 5.10 0.86 As,pH=5 Cu,pH=5 Cu,pH=1.5 Cd,pH=5 Pb,pH=5 Mn,pH=5
5 4.76 0.17 3.73 0.15 6.38 1.33
20 6.79 0.18 5.29 0.09 2.11 0.22 Fig. 14. The deposited amount of As(III), Cu(II), Cd(II), Pb(II), Mn(II) onto NF270 membrane
50 33.80 34.68 15.85 13.90 0.37 0.09 surface at pH=50.02 and pH=1.500.02. Experiment condition: metal con-
Mn 1 4.94 2.41 3.55 1.70 3.86 0.55 centration=1000 mg/L, 500 mL solution and 25 cm membrane surface area.
5 5.97 1.74 4.15 0.45 5.39 0.88
20 8.37 1.79 6.01 0.88 2.06 1.07
50 20.01 7.87 13.14 5.17 0.61 0.09 associated error bars for As(III) (215.5 9.00 mg/m) make it doubt-
Mixed 1 2.54 0.30 2.01 0.08 1.06 0.39 ful whether this could be considered a signicant result. Representing
5 10.18 5.43 4.53 1.10 2.64 1.79 this data without arsenic gives a correlation R 2 = 0.70. Comparable
All values were taken the average to three different images. SD standard deviation. correlation was also demonstrated by Van der Bruggen et al. [40].
Fig. 14 also shows that the adsorption or deposition of copper onto
the NF270 surface at pH = 1.50 was higher than at pH = 5, despite the
Fig. 14 presents the adsorbed amount, Q (mmol/m) of metals membrane being positive at pH = 1.50 which suggests that repulsion
Cu(II), Mn(II), Pb(II), As(III) and Cd(II) at pH = 5 0.2 and at pH = will occur between copper cations and the membrane surface.
1.50 0.2 for Cu(II). The adsorption order of the used metals According to the effect of ionic strength, as explained by Li et al.
at pH = 5 onto NF270 membrane is Cu 2+ > Cd 2+ > As 3+ > Mn 2+ > [41], the presence of nitrate groups from the acid HNO3, NO3, reduces
Pb 2+. Investigation of the relation between the adsorbed amount the repulsion between the Cu 2+ ions and the membrane surface and
and atomic mass of the used metals shows no correlation between between the copper cations leading to an accelerated accumulation of
them. Similar results were also reported by Van der Bruggen et al. copper on the membrane surfaces. Another suggested explanation is
[40]. However, lead (Pb), with a larger atomic mass, has a lower ad- that at acidic conditions the membrane shows greater stretching;
sorption and less fouling. On the other hand correlation between this has been speculated to cause greater pore opening and easier
the adsorbed amount of the metals onto NF270 with the normalised penetration of metal aggregates [42].
ux (i.e. the permeate ux (Jv) divided by the pure water ux (J0)), The relation between metal rejections and the adsorbed or depos-
is given in Fig. 15. The correlation shows that as the adsorption in- ited amount of the metals onto the NF270 membrane surface is
creased the normalised ux decreased, except for arsenic which has shown in Fig. 16. It appears that as the metal deposition within or
a higher deposited amount and higher ux. However the large onto the membrane surface increased, the rejection increased. This

300 135
1m1m 5m5m 20m20m 50m50m

250 115
RMS Roughness (nm)
RMS Roughness (nm)

200 95

150 75

100 55

50 35

0 15

-50 -5
0 1 2 3 4 5 6 7 8 0 1 2 3 4 5 6 7 8

Fig. 13. Root mean square (RMS) and roughness calculated from 5 m 5 m AFM images 1) virgin NF270, 2) Pb(II), 3) As(III), 4) Cu (II) at pH = 1.50 0.2, 5) Cd(II), 6) Cu(II)
pH = 5 0.2 and 7) Mn(II).

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0.9 (a)
As(III)
Pb(II)
Normalized Flux

0.6 Cd(II) Cu(II),1.5

Mn(II)
Cu(II),5

0.3

0
0 200 400 600 800 1000
Adsorbed amount (mg/m)
0.9
(b) Fig. 16. The effect of adsorbed/deposited amount of some metals onto NF270 mem-
y = 0.7339x -0.059 brane on their rejections.
Pb(II) R= 0.6974

Zahrim et al. [44] reported that membrane fouling can be classi-

Cd(II)
Normalized Flux

0.6 ed as reversible and irreversible. Reversible fouling can give a ux

Cu(II),1.5
Mn(II)
Cu(II),5
0.3
0 of irreversible fouling described by Zahrim et al. [44], the deposi-
-200 0 200 400 600 800 1000
Adsorbed amount (mg/m)
Fig. 15. The effect of adsorbed amount on the average permeate ux of NF270 mem-
brane using different metals.
relation can be correlated to a linear function with R 2 = 0.86. Nghiem
and Schfer [43] stated that if the pore size of the membrane is larger
than solute molecules, breakthrough of the rejection can be observed
when the membrane adsorption sites are saturated. Semiao and
Schafer [16] found that adsorption onto NF membrane caused lower
retention when steric interactions take place. However, adsorption
or deposition of the materials onto the membrane is highly depen-
dent on the membrane material used and the ltered material prop-
erties such as size, hydrophobicity, acid dissociation constant (pKa),
ability for hydrogen bonding and other possible interaction mecha-
nisms [16].
For arsenic (III) the uncharged and small arsenic(III) easily pass
through the loose NF270. Thus sieving or size exclusion and charge
exclusion mechanism with this metal was unexpected. However
some of the As(III) may be retained within the membrane valleys
which might explain the rejection mechanism of NF270 for As(III)
and which is indeed very low. Calculating the removal of arsenic by
adsorption onto NF270 gives 10% and that actually the range of the
arsenic(III) rejections that was found in this study.
Evaluation of the results of deposited or adsorbed amount of each
metal onto NF270 surface with the results of the surface roughness
(Table 3) demonstrates that membrane that fouled with manganese
and lead and which has lower surface roughness, has lower adsorbed
amounts of metal. The metals that were highly adsorbed by NF270
may lead to a higher measured surface roughness.
reduction of up to 18%, whereas irreversible fouling can produce per-
meate ux reduction of 2646%. Concentration polarisation, gel layer
formation and osmotic pressure are the expected mechanisms for re-
versible fouling while cake layer formation, adsorption and pore
blocking are the known mechanisms for irreversible fouling. Based
on this criteria, the permeate ux reduction of the used metals as
represented in Table 2 shows that both types of reversible (perme-
ate ux reduction 18%) and irreversible fouling (permeate ux
reduction = 2646%) were present. Also, based on the mechanisms
tion results of the used metals, such as copper and cadmium onto
NF270 as described above gives indication of irreversible fouling.
Moreover, the membrane properties, the operating parameters
and the type of wastewater can be the main factors which affect
membrane fouling [44]. As well as cake ltration a study by Wang
and Tarabara [45] showed that 53% of ux declines during the
rst stage of ltration can be attributed either to intermediate
blocking of relatively more permeable areas of the membrane
skin, or to cake formation or a combination of both mechanisms.
The membrane used in this study, NF270, was previously characterised
[13] as having a membrane pore size of 0.40 nm, which might be blocked
to some extent depending on the ions or the particles found within the
used metal solution.
3.6. Multi-component solutions
3.6.1. Permeate ux
For both multi-component solution (Cu 2+, Mn 2+, Cd 2+, Pb 2+ and
3+
As ) prepared using tap water or Milli-Q water, the ux was slow at
less than 4 L/m 2 h. Flux reduction reached 90% as compared with
water alone. This observed ux reduction is also very high compared
with that for each single metal solution (Table 2). This pronounced
decrease in ux might be attributed to cake layer formation and ad-
sorption of the metal hydroxide species on the membrane surface
[46]. In addition Van Der Bruggen et al. [47] and Ozaki et al. [22]
found that the ux reduction can be ascribed to osmotic pressure:
high ionic concentrations have a strong inuence on osmotic pres-
sure, since a large part of the ions are retained by the membrane.
The concentration difference on both sides of the membranes gives
rise to an osmotic pressure.

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3.6.2. Retention of the metals
The effect of 5 component (metal) concentrated mixtures was in-
vestigated. In order to mimic the real solution tap water was used to
prepare a mixture solution. Fig. 17 illustrates the removal of Cu, Cd,
Mn, Pb and As from their mixtures prepared using tap water and
Milli-Q water with approximately 1000 mg/L of each metal. The mea-
sured pH of both solutions was about 2.35. A difference in retention
between the single solution of each metal and their mixture was ev-
ident. The retention of copper and lead in single solution was 100%
and 69% respectively, whereas with the 5 metal solution the retention
decreased to 40% and 5.8%, respectively; the difference was about
60%. Also the retention of Cd decreased but the difference was
about 19%. On the other hand, the retention of Mn in both single
and mixed solutions was similar. The different rejection observed be-
tween multicomponent solution and single solution was also
reported by other authors [26,29]. On the other hand, Qdais and
Moussa [48] found that the efciency of NF membrane was similar
for both single solution of copper (200 mg/L) and cadmium
(200 mg/L) and a mixture of both. However the total concentration
of both metals in the mixture was 500 mg/L. To the best of the au-
thors' knowledge, no other study of high concentrated multi-
component solutions using NF membrane has been reported.
Fig. 17 also shows that retention of the metals was slightly depen-
dent on the water used. Copper, manganese, cadmium and lead re-
tention differences were only 4%, 8%, 5%, and 6% respectively. For
copper and lead their rejections using tap water were higher than
using Milli-Q water. The reverse was observed for manganese and
cadmium. Ozaki et al. [22] found that the rejection of heavy metals
tends to decrease as the feed concentration of other ions increased.
They explained this decrease in rejection in terms of the Donnan ef-
fect; negative anions present in the feed solution can easily pass
through the membrane and counter ions are also forced to pass
through the membrane to maintain electro-neutrality around the
membrane, and in terms of osmotic pressure that increased due to
the presence of other co-ions. This explanation leads to the sugges-
tion that the concentration of the co-ions present in tap water was
small or/and their mobility was high; thus their effects were small.
Contrarily Sato et al. [49] found that the removals of arsenic by NF
membranes were not affected by the source of water composition.
80 75
72
70 67 67
Tap Water
60
MilliQ Water
50
% Retention
44
40
40
30
20
10
5.8
0.99 0.62
0.01
0 salt rejection in nanoltration membrane, Desalination 167 (2004) 369376.
Cu(II) Cd(II) Mn(II) Pb(II) As(III)
Fig. 17. Retention of Cu, Cd, Mn, Pb and As from their mixtures prepared using tap
water and Milli-Q water, 1000 mg/L of each metal, pH = 2.35 0.2.
Please cite this article as: B.A.M. Al-Rashdi, et al., Removal of heavy metal ions by nanoltration, Desalination (2012), doi:10.1016/
j.desal.2012.05.022
15
4. Conclusions
In this study and with all used metals (except arsenic), when
the feed pH was lower than the isoelectric point of the NF mem-
brane the rejection was higher due to electrostatic repulsion and/or
adsorption/deposition of metal onto the membrane. These indicate
that Donnan exclusion and/or adsorption mechanisms play an impor-
tant role. NF270 membrane rejected almost 100% of copper ions in
1000 mg/L copper solution with all used pressures (35 bar) and
pHs (1.505) which demonstrates the suitability of NF270 for copper
rejection. However NF270 membrane rejection effectiveness de-
creased as the concentration of copper concentration reached
2000 mg/L.
Using 1000 mg/L level concentration at pH = 1.50 and 4 bar pres-
sure, NF270 removed about 99%, 89% and 74% of cadmium, manga-
nese and lead, respectively. NF270 is a loose membrane; thus it
failed to reject As(III). With all metals used the permeate ux in-
creased with the rise of pressure. With Cd(II) and As(III) the perme-
ate ux remains linear with increasing pressure, which indicates
insignicant concentration polarisation. With copper, lead and man-
ganese metals the increase in ux was not linear with the rise of pres-
sure, which shows that a quantity of concentration polarisation may
have occurred. With increasing the pressure, results increased or de-
creased metals rejections. However, all these changes in rejection
were small.
The reduction of permeate ux might be attributed to a number
of causes, such as adsorption of soluble metal hydroxide species on
the membrane surface, formation of a cake layer of metal hydroxide
precipitate, concentration polarisation, and osmotic pressure. The
order of the metals which caused a ux decline due to NF270 fouling
was Cu 2+ > Cd 2+ Mn 2+ > Pb 2+ As 3+. The correlation between
adsorbed amounts of the metals onto NF270 with the normalised
ux shows that as the amount increased the normalised ux de-
creased, except for arsenic that has higher deposited amount and
higher ux. The difference in NF270 retention between the single so-
lution and multicomponent solution was about 60% for both copper
and lead, 19% for cadmium and similar for manganese. The type of
water used to prepare the 5 components solution had a slight effect
on the metal retentions. Difference in retention for copper, manga-
nese, cadmium and lead was only 4%, 8%, 5%, and 6% respectively.
Acknowledgments
B.A.M. Al-Rashdi would like to thank the Ministry of High Educa-
tion in Sultanate of Oman for funding her PhD.
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