Journal of Membrane Science 493 (2015) 539548

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Journal of Membrane Science

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

Combined colloidal and organic fouling of FO membranes: The

inuence of foulantfoulant interactions and ionic strength
Machawe M. Motsa a,c,n, Bhekie B. Mamba b, Arne R.D. Verliefde c
a

Department of applied chemistry, University of Johannesburg, P.O Box 17011, Doornfontein 2028, South Africa
College of Engineering, Science and Technology, University of South Africa, P.O Box 392, Pretoria 003, South Africa
c
Department of Applied Analytical and Physical chemistry, University of Gent, Coupure links 653, B-9000 Ghent, Belgium
b

art ic l e i nf o

a b s t r a c t

Article history:
Received 30 December 2014
Received in revised form
12 June 2015
Accepted 20 June 2015
Available online 9 July 2015

In this work we determined the exact foulantfoulant interactions during combined membrane fouling
in forward osmosis (FO). FO fouling tests were performed using sodium alginate and colloidal silica (STZL, 139 nm) as model foulants. The fouling potential of each foulant and their mixture was investigated
using feed solutions containing xed concentrations of Na and Ca2 (total ionic strength of 0.5 M).
Changes on the foulant surface charges upon mixing with cationic species were monitored using zeta
potential analysis. The inter-foulant interactions were determined by conducting sequential fouling experiments (the membrane was fouled by each foulants in alternating sequences) as well as Quartz Crystal
Microbalance with Dissipating monitoring (QCM-D). Fouling tests with the mixture of alginate and silica
colloids resulted in a ux decline trend very similar to that of alginate alone, an observation attributed to
the primary effect of alginate during the gel layer formation. QCM-D analysis revealed that alginate
macromolecules adsorb onto the surface of silica colloids and thus inuencing the subsequent colloid
colloid interactions resulting in a cake layer with similar hydraulic resistance to that formed by alginate
alone. There was no evidence of synergistic effects when alginate and silica colloids co-existed mixed in
same feed matrix. It was also found that inter-foulant interactions were governed by non-electrostatic
forces because at seawater level ionic strength there was excessive reduction of the Debyle length and
electric double layer (EDL) such that normal electrostatic forces were greatly suppressed and short range
non-electrostatic forces became dominant. The Extended-Derjaguin-Landau-Verwey-Overbeek (XDLVO)
approach was used to understand foulant membrane interactions during fouling and it could not compliment the ux decline trends observed from fouling with combined foulant feed stream. The newly
proposed approach of determining combined fouling, whereby the membrane was fouled with the two
different single foulants in alternating sequences revealed that gel layer hydraulic resistance, hindered
colloid back diffusion and cake enhanced osmotic pressure (CEOP) were responsible for ux loss during
combined alginatecolloid fouling.
& 2015 Elsevier B.V. All rights reserved.

Keywords:
Alginate
Combined fouling
Flux decline
Sequential fouling
Silica colloids

1. Introduction
During any membrane-based ltration process, fouling of all
kinds (colloidal deposition, organic adhesion, formation and
growth of bacterial biolms and precipitation of sparingly soluble
minerals) impedes membrane performance, resulting in generally
higher water production costs [1,2]. FO is no exception to this
phenomenon and though fouling in FO is moderate and reversible
compared to RO processes. However, the coupled presence of
fouling and the unique concentration polarisation phenomenon
n
Corresponding author at: Department of Applied Analytical and Physical
Chemistry, University of Gent, Coupure links 653, B-9000 Ghent, Belgium.
Fax: +32 9 264 6242.
E-mail address: mxolisimachawe.motsa@UGent.be (M.M. Motsa).

http://dx.doi.org/10.1016/j.memsci.2015.06.035
0376-7388/& 2015 Elsevier B.V. All rights reserved.

have catastrophic effects on permeate ux.

Earlier studies have focused on investigating the fouling behaviour of FO membranes by single, well-characterized foulants
with homogeneous physico-chemical properties [37]. And they
have demonstrated that membrane fouling by single foulants is
strongly dependent on foulant properties (type, size and surface
charge density), feed solution chemistry (pH, total ionic strength
and concentration divalent cations), membrane orientation and
operational conditions such as cross-ow velocity and operational
ux [812]. However, the experimental insights obtained from
studies conducted with single foulants cannot be correctly applied
to water and wastewater treatment systems where fouling is almost always caused by more than one type of foulant, with different physicochemical characteristics (i.e. colloidal materials and
dissolved organic macromolecules) [1,11].

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M.M. Motsa et al. / Journal of Membrane Science 493 (2015) 539548

This work takes fouling studies in FO a step further toward realworld situations where different types of foulants co-exist. The
extensively used sodium alginate (as model organic foulant) was
mixed with colloidal silica (as model foulant representative of
suspended colloidal matter). The co-existence of organic foulants
and silica particles in the presence of divalent cations has been
discussed in several studies on NF/RO fouling, but may lead to an
even more complicated and unique fouling behaviour in FO
membrane processes due to the additional occurrence of the ICP
phenomenon [1315].
Several studies conducted on NF and RO processes have revealed that poly-dispersed suspensions form cake-layer structures
with resistances different than mono-dispersed solutions and that
the interactions between foulants can be correlated to ux decline
behaviour. Contreras et al. [16] evaluated the fouling behaviour of
nanoltration membranes using foulants representative of proteins, polysaccharides and inorganic colloidal foulants in water
and wastewater. They hypothesised that three mechanisms were
responsible for enhanced membrane ux decline when combined
foulants were used: 1) increased hydraulic resistance of the mixed
cake layer structure; 2) hindered silica colloids back diffusion in
the concentration polarisation layer in the presence of sodium
alginate and 3) changes in colloid surface properties due to organic
adsorption. Cake-enhanced osmotic pressure (CEOP) was also
found to have a dominant effect on permeate ux loss when silica
colloids and NOM co-existed in the same feed solution [17]. In
another work involving silica colloids and NOM by Li and Elimelech [18], permeate ux loss was also attributed to hindered back
diffusion of silica colloids in the presence of the complexed NOM.
Amongst the few efforts studying combined fouling in FO
processes, Lui and Mi determined the effects of combined fouling
by alginate and gypsum in forward osmosis processes. A synergistic effect between alginate fouling and gypsum scaling was
observed, mainly through aggravated gypsum scaling in the presence of alginate molecules due to cake-enhanced concentration
polarisation (CECP). In addition, alginate molecules acted as nuclei
in gypsum crystal growth thus signicantly increasing the gypsum
crystal size and accelerating deposition [19]. In another recent
study on FO by Kim et al. [20], the propensity of combined organic
and colloidal fouling in forward osmosis under various solutions
chemistries (pH, and calcium ion concentrations) was investigated.
The obtained ndings demonstrated synergistic effects for combined fouling with alginate and silica colloids, where the overall
ux decline was more severe with combined foulants compared to
the sum of the individual contributions of alginate and silica colloids alone.
All these studies have clearly demonstrated that permeate ux
loss during the ltration of feed solutions bearing organic and
colloidal foulants is mainly due synergistic effects of the mixture
that promote CEOP which in turn greatly reduce the effective
driving force. However, the interfoulant (foulantfoulant) interactions that inuence the synergy between different foulant species are not clearly dened. The interactions between the membrane and these complex mixtures, particularly at seawater level
ionic strength where the surface properties of foulants and
membrane maybe greatly altered compared to low ionic strength
environments. According to our knowledge, this is the rst effort
to describe the fouling mechanisms during combined colloidal and
organic fouling at seawater level ionic strengths.
Therefore, the objective of this study was to identify and determine the exact key interactions between organic and colloidal
foulants (alginate and silica colloids) when co-existing in the same
feed solution. The impact of the resulting inter-foulant interactions
on permeate ux during seawater desalination using FO membranes was determined by conducting a series of fouling tests.
Membrane and foulant interfacial free energies were determined

using advanced contact angle measurements; the data was then

processed using the Extended-Derjaguin-Landau-Verwey-Overbeek (XDLVO) approach to gain more insight into fouling mechanisms. The observed feed water ux decline trends of the
complex foulant mixtures were compared to those obtained with
single foulants. In addition, we focused on membranefoulant and
foulant-deposited-foulant interactions by proposing a new method of investigating combined fouling, whereby the membrane was
fouled with the two different single foulants in alternating sequences and the fouling trends observed were compared to
those observed for combined fouling.

2. Material and methods

2.1. Membrane and characterisation
The commercially available cellulose triacetate (CTA) membrane used in this study was supplied by Hydration Technologies
Inc. (Albany, OR). The CTA membrane was chosen for this work
due to its extensive characterisation in previous applications, thus
making it ideal for our new investigations of characterizing fouling
at seawater level ionic strength. It has been found to have a total
thickness of approximately 50 mm [19,21]. It was previously tested
and recorded a salt rejection of above 95%, a pure water permeability (A) of 0.44 70.12 L m  2 h  1 bar  1 and a salt permeability
coefcient (B) of 0.261 70.026 L m  2 h  1 [20]. The membrane
structural factor (S) is a parameter that describes the effect of
membrane support thickness, porosity and tortuosity on mass
transport in the support layer, and is around 481 mm [22,23]. The
membrane was stored in ultrapure water at 4 C prior to use.
2.2. Model foulants and their characterisation
Colloidal silica (Snowtex ST-ZL) was used as a model foulant
representative of suspended colloidal matter and was supplied by
Nissan Chemical Industries, Tokyo, Japan. The data supplied by the
manufacturer specied an average particle size of 100 nm. The
supplied colloidal suspension contained 40% w/w amorphous silica and 60% w/w water. Alginic acid (provided as sodium alginate)
was used as a model organic foulant to represent common polysaccharides which are the main constituents of organic matter in
wastewater and seawater. This model foulant was provided by
Sigma-Aldrich, St Louis, MO, United States, and was received in
powder form. The molecular weight of the alginate was about 12
80 kDa. An alginate stock solution of 2 g L  1 was prepared by
dissolving alginate powder in deionised (DI) water, after which
this solution was mixed vigorously for 24 h, and thereafter kept at
4 C.
Dynamic light scattering experiments were performed to analyse the particle/aggregate size of silica colloid and alginate as well
as their mixture using a Malvern photon correlation spectrometer
(Malvern Instruments, UK). A concentration of 0.5 g L  1 (instead of
the 0.2 g L  1 used for fouling experiments) was used for alginate
aggregate size determination, to enhance instrument detection. It
is worth mentioning that this increase in concentration did not
signicantly alter the obtained values as proven by other experiments performed with 0.3, 0.75 and 1 g L  1 alginate concentrations. The foulant zeta potentials (for silica colloids and alginate)
when exposed to the different electrolyte solutions were calculated from the measured electrophoretic mobility, obtained using
a Malvern Zetasizer300 HS series (Malvern Instruments, UK). The
concentration of alginate was again increased to 0.5 g L  1 during
this analysis to enhance instrument detection.

M.M. Motsa et al. / Journal of Membrane Science 493 (2015) 539548

Table 1
The various feed solutions, their composition and corresponding draw solutions.
Feed
solutions

Solution
Solution
Solution
Solution

Feed composition

DS concentration (MNaCl)

Total ionic
strength
(mM)

1
2
3
4

Alginate
Silica colloids
Alginate Silica colloids
Alginate 0.476 M NaCl 0.008 M
CaCl2
Solution 5 Silica colloids 0.476 M
NaCl 0.008 M CaCl2
Solution 6 ST-ZL Silica
colloids Alginate 0.476 M
NaCl 0.008 M CaCl2

1.8

500

3.5

2.3. Feed and draw solution chemistries

Sodium alginate, a representative of polysaccharides in wastewater and seawater, has been previously identied as a major organic foulant [24]. It is also known to form highly arranged complexes in the presence of divalent cations resulting in severe
membrane ux decline [25]. Therefore the feed solutions in this
study contained xed concentrations of cationic species (0.476 M
Na and 0.008 M Ca2 ). The concentrations of alginate and ST-ZL
silica colloids in the feed waters for the fouling experiments were
xed at 200 mg L  1 and 1 g L  1 respectively for both single and
mixed feed solutions. The total ionic strength of the feed solutions
was xed at 0 and 0.5 M as listed in Table 1 and the corresponding
draw solution concentrations were adjusted accordingly to give
similar initial uxes (see Table 1). The differences in the degree of
internal concentration polarisation (ICP) and external concentration polarisation (ECP) due to the different feed concentrations
were the reason for the large deviation among the draw solutions.
No further pH adjustments were conducted; the solutions were
tested at their ambient pH (6.90 70.45). No large pH variations
were observed during the experiments.
2.4. Forward osmosis membrane test unit and fouling protocol
The FO membrane fouling tests were performed using a benchscale cross-ow system; a detailed description of the FO unit is
given elsewhere [12]. During ltration the draw solution typically

541

becomes diluted due to water permeation and gradually decreases

in concentration which tends to reduce the osmotic drive force.
Therefore, an easy method to estimate the changes in draw solution concentration was developed using a conductivity metre
(Consort, Model C931, Belgium). A programme-controlled (LabVIEW software) 3-way valve was installed on the DS return tube
just before it enters the draw solution tank (Fig. 1). The valve
temporally directs (at set intervals) the draw solution into a lter
funnel containing dry solid salt (NaCl) after being triggered by a
decline in draw solution conductivity. The dissolved salt then
dripped into the bulk draw solution to correct the dropping solution conductivity and maintain constant draw solute
concentration.
The electrolyte solution resulting from the dissolved NaCl
(which was used as a draw and a feed solution) enabled the use of
conductivity to monitor ionic concentration via conductivity
measurements. However, due to the non-ideal nature of solution
especially at our working concentrations; the effective (measured
ionic concentration) is usually lower than the real concentration,
thus this method was the closest estimation of the ionic strength
of the feed and draw solution.
The membrane performance with respect to fouling resilience
was tested in two manners: 1) by traditional fouling of the
membrane with the single foulants and their mixtures (combined
fouling), and 2) by fouling the membrane in alternating sequences
of the two foulants, as well as their mixture. Traditional fouling
tests with single foulants and their mixture were performed over a
24 h period while sequential fouling tests were conducted over
two 24 h segments (48 h). All fouling experiments were conducted
with the membrane oriented with the active layer facing the draw
solution (PRO mode) to aggravate membrane fouling and clearly
distinguish fouling mechanisms. A new membrane coupon was
used for each experiment and prior to each fouling experiment, a
baseline experiment was performed using a feed solution of MilliQ with similar ionic strength but lacking the foulant. During the
experiment, the draw and feed solutions were circulated on each
side of the membrane at a ow of 7.0 cm s  1 counter-current
conguration. An electronic balance (Defender, Ohaus, USA) connected to a data-logging system was used to record the water ux
at pre-determined time intervals. The average water ux values of
experimental runs were then normalised to the initial water ux.
The initial permeate ux was constant at 15.84 70.75 L m  2 h  1
for all conducted experiments.

Pump

Feed
tank

FO membrane cell
FO membrane

1
4

Pump

Magnetic stirrer

Balance

Relay board
Conductivity meter
PC
1. Draw solution tank, 2. Filter funnel with salt, 3. 3-way valve, 4. Draw over-flow vessel
Fig. 1. Illustration of the laboratory-scale FO test unit.

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M.M. Motsa et al. / Journal of Membrane Science 493 (2015) 539548

2.5. Contact angle measurements

Contact angle measurements were used to determine the surface free energy components of the CTA membrane and foulants
using the Young-Dupr equation (Eq. (1)). This equation links the
contact angle of a drop liquid placed on a solid surfcace wit the
surface tension components of the liquid, according to van Oss
[26]

l(1 + cos ) = 2( sLW l LW +

s+ l +

sl + )

(1)

where:

m =

is the measured contact angle,

LW is the Lifshitzvan der Waals free energy component,
is the electronacceptor component,
 is the electron donor component; subscripts s and l designate the solid and liquid phases, respectively.
Surface tension components of a membrane can be determined
by measuring contact angles between the membrane and three
well-characterized probe liquids with known surface tension
components, such as deionised water, glycerol and diiodomethane.
The contact angles due to these probe liquids were measured on
ltered lawns of alginate, silica colloids and their mixture using a
computerised Krss DSA 10-MK2 (Krss, Germany) contact angle
goniometer. A full description of how the contact angle analysis
was conducted can be found in the Appendix.
The total interfacial free energies (interfacial free energy of
cohesion and adhesion) per unit area between solid materials
1 and 2 immersed in liquid medium 3 were determined from the
sum of the Lifshitzvan der Waals (LW) and acidbase (AB) components as expressed by Eq. (4)
LW
G132
=2

3LW

AB
G132
= 2 3+

water that was pumped across the sensors for 1 h. The temperature in the ow chambers was set at 18 C and the solution were
kept at 22 C in a water bath.
Adsorption is indicated by changes in the vibration frequency
of the piezoelectric quartz-crystal sensor and the amount of organic foulant macromolecule adsorbed can be calculated from the
frequency change using the Sauerbrey equation (Eq. (5)) [27],
which relates the mass change per unit area at QCM electrode
surface to the observed change in oscillation frequency of the
crystal

1LW

1 +

1+2

)(

2LW

3LW

3 + 2 3

(2)

1+ +

2+

12+

TOT
LW
AB
G132
= G132
+ G132

3+

)
(3)
(4)

TOT
If surfaces 1 and 2 are the same, then G131
indicates the interfacial free energy of cohesion. The interfacial free energy of
cohesion, G131, describes energetic favourability of a solid material (1) interacting through a liquid medium (3) with itself (1).
Cohesive free energy offers insight into particles stability as well as
particle deposition onto surfaces already covered by the same
particles. The interfacial free energy of adhesion, G132, describes
the attraction or repulsion of solid material (1) interacting with
another solid material (2) through a liquid medium (3). The adhesive free energy relates to adsorption and adhesion of dissimilar
materials.

2.6. Measurement of alginate adsorption on silica colloids

The adsorption of alginate macromolecules on silica was studied using quartz crystal microbalance with dissipating monitoring (QCM-D) technique with silica sensors (Q-Sense, Sweden). The
silica-coated quartz crystal sensors were used to simulate the
surface of the silica particles. The same ionic strength (0.5 M) and
foulant concentration (200 mg L  1) used for cross-ow fouling
tests was used for the adsorption studies. Prior to analysis ultrapure water was pumped across the sensors for 15 min at 0.5 mL/
min after which the foulant solution was introduced. At
t100 min, the desorption step was initiated using ultrapure

CQCM
n

(5)

where:
CQCM is the mass sensitivity constant (17.77 ng cm  2 Hz  1 at
f 5 MHz).
f is the change in the resonance frequency.
n is the overtone number (n has values 1, 3, 5,).
CQCM is a constant independent of the overtone number/order,
n.

3. Results and discussion

3.1. Characterisation of model foulants
The resulting foulant sizes and surface charges after both foulants were mixed with the elevated concentrations of Na and
Ca2 are presented in Table 2. Both alginate and colloidal silica
recorded negative zeta potential values, indicating their negative
surface charge. The colloidal silica exhibited a slightly more negative charge (  54 mV) compared to alginate (  47 mV) in the
absence of cations. The presence of cationic species (Na and
Ca2 ) substantially reduced the surface charge of both foulants
and their combination, mainly through surface charge neutralization. However, the extent of neutralization was not the same
for both foulants, with alginate being mostly neutralised; recording  8.85 versus the 14.2 mV for the colloids. This could be due
to the fact that the amount of silica colloids (1 g L  1) used for
purposes of this study was too high to be completely neutralised.
A similar observation was made when the silica and alginate coexisted, the particles' surface charges was reduced from  72.15 to
 15.2 mV. According to the literature, the addition of salts, particularly calcium salts, to alginate-containing solutions should result in the formation of a highly organised gel-type conformation
that should increase both the alginate aggregate size [28]. The
signicant increase in size was evident from the measured hydrodynamic diameter of alginate in the presence of Ca2 as listed
in Table 2. The size and charge results of the combined or mixture
of the two foulants should be viewed with reservation since the
Table 2
Measured zeta potential and hydrodynamic diameters for alginate and silica colloids in different solution conditions.
Sample

Zeta potential (mV)

Hydrodynamic diameter (nm)

ST-ZL
ALG
ST-ZL ALG
*ST-ZL (0.5)
*ALG (0.5)
*ST-ZL ALG (0.5)

 54.4
 47.5
 72.15
 14.2
 8.85
 15.2

139.9
66.02
184.9
156.35
535.4
177.8

ST-ZL: Model silica colloids. ALG: Alginate.

*

0.5 M feed ionic strength.

M.M. Motsa et al. / Journal of Membrane Science 493 (2015) 539548

Normalized flux (J/Jo)

1.0
0.8
0.6
0.4
Baseline
ST-ZL SC
ALG
Combined

0.2
0.0
0

10

15

20

25

15

20

25

Time (h)

1.2

Normalized flux (J/Jo)

1.0
0.8
0.6
0.4
Baseline
ST-ZL SC
ALG
Combined

0.2
0.0

10
Time (h)

Fig. 2. (a) Permeate ux decline curves due to fouling with single foulants (ST-ZL
colloidal silica, 1 g L  1and alginate, 200 mg L  1) and their combination without
addition of mono and divalent salts. The draw solution was adjusted to give similar
ux to that of fouling in the presence of background electrolytes. Fouling experiments were performed in PRO mode at a cross-ow velocity of 4.0 cm s  1 for 24 h.
(b) Permeate ux decline curves due to fouling with single foulants and their
combination in the presence of 476 mM NaCl and 8 mM CaCl2. The membrane area
was deemed representative and fouling experiments were performed once.

colloidal silica was the most active light-scattering species during

DLS analysis, mainly due to the particle concentration, size and
shape; therefore the recorded particle size of the mixed foulants of
177.8 nm could have been highly inuenced by the silica colloids
since it was close to that of silica alone (156.35 nm).
3.2. Membrane fouling behaviour caused by single and combined
foulants
When the membrane was fouled with both foulants and their
mixture in the absence of abundant cationic species, no severe
fouling was observed and all foulants resulted in almost identical
fouling proles (Fig. 2a). However, when calcium ions together
with a high concentration of sodium ions (0.476 M) were added,
clear distinctions in fouling rates were observed between the
different foulants (Fig. 2b). Fig. 2b also shows that during the
earlier stages of ltration the baseline experiment (without a
foulant) exhibited a similar ux loss rate as the ST-ZL colloids. This
observed ux loss was mainly caused by the increased feed solution concentration which then reduced the effective driving force.

However, after about 8 h of ltration, the silica colloid permeate

ux trend deviate from that of baseline indicating continual loss in
permeate ux was noticed over the entire ltration period. On the
other hand, alginate fouling was distinct resulting in a high initial
ux loss rate compared to that of the baseline experiment indicating that ux loss was mainly due to foulant deposition. In
most studies on combined fouling, tests involving the mixture of
alginate and silica colloids resulted in severe permeate ux decline
[29]. This observation has mainly been attributed to the synergy
between the two foulants manifested through increased fouling
rate compared to that of single foulants. However, interestingly, in
this study, when the two foulants co-existed in the same feed
stream, they exhibited a fouling trend very similar to that of alginate alone (Fig. 2b), contradicting several observations made in
RO studies that reported a clear synergy between the two foulants
at lower ionic strength [18,20]. This deviation in fouling behaviour
is mainly due to the structures of the fouling layers resulting from
the different membrane processes. In FO, the lack of hydraulic
pressure allows for the formation of relatively loose cake layer
where foulant deposition is dependent on permeation drag, while
the RO process results in a compact and cohesive fouling layer that
has more resistance to permeate ow, resulting in higher ux
decline rates. It also indicates that the resulting gel layer due to
combined alginatesilica fouling had a similar hydraulic resistance
to that of alginate alone and the alginate aggregates had a primary
role in the cake layer formation during combined fouling.
One over arching observation was that despite the different
initial ux loss rates for alginate, ST-ZL silica colloids, after 20 h
uxes were similar for all the three feed solutions. We therefore,
hypothesise that this is due to the fact that at this point the
permeate ux had dropped to such low levels due to fouling and
ICP that the existing permeate drag is no longer sufcient to cause
foulant deposition on the membrane. As a result, the ux levels off
(around 4 L h  1 m  2) regardless of the feed type resulting in the
stable ux point observed from 20 h. We hypothesise that this is
more or less comparable to the limiting ux observed in pressure-driven membrane applications.
It has been reported that organic fouling is highly inuenced by
the presence of Ca2 ions in the feed stream [28] and the ux loss
trends shown in Fig. 3 clearly indicate the effect of calcium ions on
alginate during combined alginatesilica fouling. Severe permeate
ux loss was observed with the addition of calcium ions due to gel
layer formation. The obtained results of combined alginatesilica
colloids fouling are complex and have important implications on

1.2
1.0
Normalized flux (J/Jo)

1.2

543

0.8
0.6
0.4
0.2
0.0

10

15

20

25

Time (h)
Fig. 3. Permeate ux decline as a function of time for membranes fouled with a
mixture of alginate and ST-ZL colloidal silica with and without 8 mM Ca2 . The
total ionic strength was xed at 0.5 M.

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M.M. Motsa et al. / Journal of Membrane Science 493 (2015) 539548

membrane ux decline during seawater treatment, thus motivating the exploration of a new approach of investigating inter-foulant interactions where the membrane was fouled with each single
foulant in alternating sequences. Further discussions and observations made on this approach are discussed in detail in Section
3.4.
It is also worth mentioning that the feed ionic strength played a
signicant role in the observed ux loss. The high feed stream
ionic strength (0.5 M) greatly reduced the Debye length and
electric double layer (EDL) such that the effect of normal particle
particle electrostatic forces was largely suppressed and shortrange non-electrostatic interactions became dominant [30]. The
excessive reduction in repulsive forces amongst foulant particles
results in the formation of a more densely packed cake layer on
the membrane surface, which consequently causes a greater resistance to permeate ow (this is later explained using the Extended DerjaguinLandauVerweryOverbeek approach (XDLVO))
[31]. Thus, the permeate ux loss at seawater level ionic strength
can be partly attributed to the signicant role of the non-electrostatic forces between the foulants and the membrane, as well as
between the on-coming foulant particles and the already deposited cake layer [32,33].
3.3. Interfacial surface free energies
Further insight (elucidate) into the membrane fouling process
was attained by computing the surface free energies for the
membrane and foulants using measured contact angles of diiodomethane, glycerol and the salt solution containing Na and
Ca2 . The resulting interfacial energies are displayed in Table 3.
Alginate exhibited the most negative energy of cohesion
(  22.07 mJ m  2) suggesting that the macromolecules would rather form an interface among themselves (strong hydrophobic
attraction) in the feed solution, rather than forming an interface
with water. This also implies that alginate is more likely to be
deposited on a membrane surface already covered with alginate
aggregates [34,35]. On the other hand, the ST-ZL colloidal silica
exhibited a strongly positive energy of cohesion ( 25.19 mJ m  2)
implying that the colloids would rather form large interfaces with
water other than aggregating, and as such indicating that for the
silica colloids, the critical coagulation concentration has not been
reached and colloidal particle deposition onto the membrane
could only be prompted by the presence of a strong permeate drag
force. The computed energy of cohesion for the alginatesilica
colloids mixture was  2.51 mJ m  2. This energy valuewhen
compared to that of the single foulantssuggests that inter-foulant
interactions of foulants were partly dominated by alginate. There
were weak hydrophobic attraction forces amongst alginate and
silica colloids as shown by the weakly negative cohesion energy
value.
Similar observations were made with the energy of adhesion;
alginate had the most negative value, the colloids recorded a
strong positive energy value, while the energy value for the mixture of alginate and silica colloids was slightly negative. This
means that during the initial stages of membrane fouling the alginate macromolecules would attach spontaneously upon
Table 3
Interfacial free energy of cohesion and adhesion for alginate, colloidal silica and
their mixture.
Foulant

Energy of cohesion,
G131 (mJ m  2)

Energy of adhesion,
G132 (mJ m  2)

Initial ux decline rate (h  1)

ALG
ST-ZL
ALG ST-ZL

 22.07
24.19
 2.51

 20.16
16.74
 2.82

0.127
0.0319
0.129

deposition onto the membrane surface, leading to a high initial

permeate ux loss rate as shown in Fig. 2b and Table 3.
As already indicated by the strong positive adhesion energy,
the silica colloids will only be deposited on the membrane surface
under conditions of high permeate drag force [36,37]. This was
supported by the low ux decline rate (high permeation rate) at
the initial stages of fouling experiments (Table 3) as well as the
positive energy of adhesion (16.74 mJ m  2).Unlike the alginate or
colloidal silica, the adhesion energy value for the mixture of alginate and colloidal silica was slightly negative (  2.82 mJ m  2)
implying that the afnity for the membrane surface was low. It
could then be suggested that permeation drag forces were dominant in the deposition of the combined alginatesilica aggregates
resulting in a higher initial ux decline rate as that observed
during alginate fouling. This is further complemented by the size
of the primary foulant (alginate; Table 2). This implies that the
contact angle approach followed in this work could not accurately
dene foulantmembrane interactions of multi-component feed
streams. In addition, interactions energies determined for the
mixture from ltered lawns might not reect full foulant behaviour in FO applications. Therefore, more insight is required to
understand the exact foulantfoulant interactions when alginate
co-exists with silica colloids. An attempt to address this was made
in the next sections.
3.4. Sequential membrane fouling
3.4.1. Inter-foulant interactions and cake layer formation
In a bid to further elucidate possible inter-foulant interactions
during combined organic and colloidal fouling, we applied a new
approach of investigating membrane fouling. In this approach, the
membrane was fouled with the two foulants (colloidal silica and
alginate) in alternating sequences. Therefore, the second fouling
trend was greatly inuenced by the cake layer developed during
the rst fouling run.
There was a signicant jump in permeate ux when switching
from one foulant species to another. This curious regain in ux was
only due a mismatch in the feed ionic strengths, that is, the subsequent fresh feed's ionic strength was lower compared to the
previous feed and as such the osmotic driving force was increased
temporally restoring permeate ux. The effect of the ionic strength
differences is investigated in detail in the next section. However,
directly after the start of the second fouling runs, there was a
conspicuous decline on the regained permeate ux to an almost
stable ux points marked i, ii and iii in Fig. 4 for ALGST-ZL SC, STZL SCALG and combinedcombined sequences. This sharp
permeate ux loss might be attributed to increase in gel layer
resistance and cake-enhanced osmotic pressure (CEOP) due to the
high concentration of salt at the membrane surface that severely
reduces effective osmotic pressure. The combined alginatecolloid
feed had the steepest slope indication that the formed gel layer
could enhance CEOP [38]. Another striking observation was that
the stable ux points (ux levelling-off point) were different for
the three sequences: the ST-ZL SCALG sequence recorded no
further ux decline below 40% of the initial ux, 50% was the
stable ux point for the reverse sequence (ALGST-ZL SC) and the
combinedcombined sequence was stable at 37% (more or less
comparable to ST-ZL SCALG). These observations reveal that
during combined alginatecolloid fouling hindered colloid back
diffusion, hydraulic resistance and CEOP play a major role in
permeate ux loss while hydraulic resistance and CEOP were the
main mechanisms during alginate fouling.
3.4.2. Inuence of Ionic strength on foulant deposition during sequential ltration experiments
In order to investigate the inuence of feed ionic strength on

M.M. Motsa et al. / Journal of Membrane Science 493 (2015) 539548

545

1.2

0.8

Normalized flux

Normalized flux (J/Jo)

1.0

0.6
i
ii

0.4
iii
Baseline
ST-ZL SC - ALG
ALG - ST-ZL SC
Combined-Combined

0.2
0.0
0

10

20
Time (h)

30

40

Time (h)

Fig. 4. Sequential membrane fouling experiments with single foulants in alternating sequences. A fresh feed solution with an ionic strength of 0.5 M was used for
the subsequent fouling run. Fouling conditions were kept the same as in previously
conducted experiments.

the partial ux recovery and whether the real ux decline in the

consecutive fouling experiments was due to CEOP or hydraulic
resistanceor a combination of both, another series of experiments were carried out whereby the ionic strength of the second
feed solution was adjusted to the same value as the feed solution
at the end of the rst fouling run, by matching the conductivity of
the feed solution at the start of the second fouling run to that of
the nal conductivity value of the rst fouling run through the
addition of sodium chloride.
Unlike what was observed in the previous section (Fig. 4), no
ux was regained for the fouling sequence of ALGST-ZL SC and
combinedcombined. The ux decline trends followed a clear
continuation from the previous experiments. This provides evidence that the temporal regain in ux observed in the previous set
of experiments for these combinations of foulants was mainly due
to the low ionic strength of the new feed. In contrast, a large
proportion of permeate ux (about 80%) was recovered when a
second feed of alginate was used to foul the membrane already
covered by colloidal silica. This suggests that alginate might have
an abrasive effect of on the colloidal silica already deposited, an
observation that serves as proof that alginate adsorbs on the silica
colloids (and subsequently tearing the silica layer off the membrane surface leading to a signicant period of permeation ux
recovery). Further proof of alginate's abrasive effect on the silica

Fig. 6. Consecutive membrane fouling experiments performed with colloidal silica.

The feed solution was adjusted to the same ionic strength as that of the previous
feed solution.

layer is provided by Figs. 5 and 6. When silica is used instead of

alginate in the second fouling run to further foul the silica-fouled
membrane (after correcting the ionic strength), no permeate ux
recovery is observed but a continual ux decline until the stable
ux point. This shows that it is through specic adsorption of alginate onto the silica, that the combined fouling layers are formed.
This could also be an indication why the fouling trends mainly
seem to follow the characteristics of the alginate.
The interaction between alginate macromolecules was probed
using QCM-D and the results are shown in Fig. 7. After the injection of the alginate solution (at t 15 min) there was a rapid
change in the frequency to  59 Hz an indication of alginate adsorption on the silica. This was supported by the signicant rise in
dissipated energy after the introduction of alginate (Fig. B1). This
observation interaction between the two model foulants is completely different from what has been previously reported at low/
moderate ionic strength which suggests that the extreme reduction in Debyle screening length allowed for non-electrostatic interactions between alginate and silica colloids.

500

Areal mass of alginate (ng/cm 2)

1.2

Normalized flux (J/Jo)

1.0
0.8
0.6
0.4
0.2
0.0

ST-ZL SC - ALG
ALG - ST-ZL SC
Combined - Combined

10

20
Time (h)

30

40

Fig. 5. Sequential membrane fouling experiments with single foulants in alternating sequences. The feed solution was adjusted to the same ionic strength as the
previous feed solution. Fouling conditions were kept the same as in previously
conducted experiments.

400

300

200

100
A

0
0

20

40

60

80

100

120

140

160

Time (min)
Fig. 7. Areal mass of the adsorbed alginate layer on the silica particle surface as a
function of time. Stage A: ultrapure water; stage 2: introduction of 200 mg L  1 in
0.5 M ionic strength; stage 3: desorption with ultrapure water.

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M.M. Motsa et al. / Journal of Membrane Science 493 (2015) 539548

4. Conclusions
The fouling trend obtained from combined alginatecolloids
feed was very similar to that of alginate alone, an indication that
the combined foulant gel layer had the same hydraulic resistance
as that of alginate alone. It was also revealed that alginate had a
primary effect on the cake layer formation during combined
fouling; that is the presence of alginate resulted in faster permeate
ux decline. The new approach of sequential fouling experiments
and QCM-D analysis provided proof of the adsorption of alginate
onto the surface of silica particles surfaces which led to altered
colloidcolloid interactions. There was no clear evidence of synergy between alginate and the silica colloids during combined
fouling, since combined fouling layer had the same characteristics
as the alginate fouling layer. Hindered colloid back diffusion in the
presence of alginate gel layer and cake enhanced osmotic pressure
were most likely the mechanisms responsible for the observed
ux decline during combined fouling. There was no clear evidence
of synergy between alginate and the silica colloids during combined fouling, since combined fouling layer had the same characteristics as the alginate fouling layer. The feed ionic strength also
inuenced permeate ux loss, manifested through the excessive
reduced Debyle screening length and electric double layer forces
such that the electrostatic forces were suppressed and only nonelectrostatic forces became dominant in foulantfoulant and

foulantmembrane interactions.
The contact angle approach used in this work could not clearly
dene foulantmembrane interactions of combined foulants feed
streams. The new approach of sequential fouling experiments revealed that alginate adsorbs on silica colloids, and it is most likely
through this specic adsorption that combined fouling results in
fouling layers with similar characteristics to that of the alginate
fouling layer. This study has brought different insights into the
interpretation of combined fouling behaviour, though improvements could be made in developing newer models that could account for the surface interaction during combined fouling.

Acknowledgements
This research work was nancially supported by the University
of Ghent, Belgium through BOF Special Research fund (Account No.
B/12493/01 iv1) and the DST/Mintek Nanotechnology Innovation
Centre (DST/NIC), South Africa (Cost centre No. 05.15.075885.15).

Appendix A. : Scanning electron microscopy (SEM)

Scanning electron microscopy (SEM) was used to determine the
macro-scale surface morphology of the different fouling layers and

Fig. A1. SEM micrographs of FO membrane surface fouled with: (a) ST-ZL colloidal silica, (b) alginate and their mixture (c, d). The feed solution ionic composition was made
up of 476 mM NaCl 8 mM CaCl2.

M.M. Motsa et al. / Journal of Membrane Science 493 (2015) 539548

the obtained micrographs showed the appearance of the different

cake layers after fouling the FO membrane surface with the different single foulants and their mixtures. The silica resulting silica
colloids cake layer is shown in Fig. A1a, while the alginate fouling
layer showed is displayed by Fig. A1b. When the two foulants were
mixed, a crumb-like cake layer was formed that appeared to be
made up of layers of alginatesilica aggregates (Fig. A1 c and d).

Appendix B. : Contact angle measurements

The surface tensions of alginate due to the different electrolyte
solutions were determined by rst dissolving it in ultrapure water
and deposited onto a NF membrane using a dead-end membrane
ltration system for a period of 8 h a method which was also
implemented by Jin et al. [39]. The ltered lawns of alginate were
then allowed to dry for 12 h in a dessicator. Contact angle measurements of the different salt solutions, deionised water and
diiodomethane were then performed using the sessile drop
method.
However when determining the clean membrane surface tensions two methods were employed: (1) sessile drop on a dry
membrane surface and (2) sessile drop measurement on a hydrated membrane surface as previously conducted by Botton and
workers, [40] on their work with NF membranes.
After drying the membrane samples in a sealed desiccator for
12 h, they were then attached to a glass slide and a minimum of 10
drops were measured per membrane sample for all three probe

547

liquids. The average contact angle was used for computation of

surface tensions and interfacial free energies. The hydrated
method aimed at delaying water evaporation during contact angle
measurement as well as simulating the liquidmembrane contact
during the ltration process. Membrane samples were placed on a
wet lter paper to curb the effect of water evaporation. Sessile
drops of the three probe liquids were placed on the hydrated
membrane surface with the contact angle measured within seconds. Drops were placed at intervals of 35 min for a period of
about 1.5 h. For each membrane sample a minimum of 10 drops
were measured. Measuring the liquid drop contact angle on the
dry CTA membrane gave an over-estimation of the contact angles
since the contact angle is quantied while the membrane is still
wetting leading to higher values that are not accurate representatives of the membrane surface tensions. Therefore only
the sessile drops on the hydrated membrane surface were used for
the computation of membrane surface tensions.

Appendix C. : Alginate adsorption onto silica particles

The interactions between foulants (alginate and silica colloids)
were studied with QCM-D and the resulting frequency shifts and
dissipated energy are shown in Fig. B1a. To relate the observed
changes in dissipation, D to changes in frequency, f, we plotted the
Df (dissipationfrequency) plot shown Fig. B1b and it reveals that
the density of points is smaller near the origin. An indication of
faster kinetics at the beginning and it slows down as the frequency
shift is reduced.

22

10

References

20

18
-10

14

Frequency (Hz)

-20

12

-30

10
-40

8
6

-50

Dissipation (1E-06)

16

-60

2
-70

0
-2

-80
-20

20

40

60

80

100

120

140

160

180

Time (min)
20

15

10

-5
0

-20

-40

-60

-80

f (Hz)

Fig. B1. Frequency shifts corresponding to interactions between alginate and silica
particles, (a) change in frequency and dissipation as a function of time during the
adsorption and desorption analysis of alginate and (b) Df plots showing dissipation against frequency.

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