Journal of Membrane Science 303 (2007) 4–28

Review article

Fouling strategies and the cleaning system of NF membranes

and factors affecting cleaning efficiency
Ahmed Al-Amoudi a,b , Robert W. Lovitt a,∗
a Centre for Complex Fluids Processing, Multidisciplinary Nanotechnology Centre, School of Engineering,
University of Wales, Swansea SA2 8PP, UK
b Saline Water Conversion Corporation (SWCC), Saline Water Desalination Research Institute, Saudi Arabia

Received 17 January 2007; received in revised form 25 May 2007; accepted 6 June 2007
Available online 14 June 2007

Abstract
Nanofiltration membranes play an important role in the desalination of brackish and seawater as well as membrane mediated waste water
reclamation and other industrial separations. Fouling of nanofiltration (NF) membranes is typically caused by inorganic and organic materials
present in water that adhere to the surface and pores of the membrane and results in deterioration of performance (reduced membrane flux) with a
consequent increase in costs of energy and membrane replacement.
Natural organic matter (NOM) fouling of NF membranes involves interrelationship between physical and chemical interactions and is described
in this review. Inorganic fouling due to scale formation of sparingly soluble inorganic salts occurs whenever the ionic salt concentration stream
exceeds the equilibrium solubility. Scale formation takes place by homogenous or heterogeneous crystallization mechanisms. Biofilm formation
also becomes an issue when its thickness and surface coverage reduces permeability.
There are two strategies that are usually employed to minimize the effect of fouling. The first group includes minimizing of fouling by using
adequate feed pretreatment, membrane treatment and membrane modification. The second group involves membrane remediation by chemical
cleaning which is carried out to restore membrane fluxes.
A large number of chemical cleaning agents are commercially available, and the commonly used ones fall into six categories: alkalis, acids,
metal chelating agents, surfactants, oxidation agents and enzymes. In general, these cleaning agents do improve the membrane flux to certain
extent. Combination of these chemical agents has also been tried in order to improve the flux restoration. Even though, many of these cleaning
agents can restore the flux over 100% (enhanced flux), they can also impair the selectivity of the membrane reducing of the product water quality.
There are many traditional assessment methods for cleaning and at present these are being supplemented by methods using modern surface
analysis techniques. These are being now rapidly developed to give a more precise assessment and a better understanding of cleaning processes.
Generally, cleaning is assessed by flux, zeta potential measurement, atomic force microscope (AFM) and Fourier transforms infrared technique
(FTIR). Atomic force microscope and related techniques are particularly employed in order to evaluate the cleaning efficiency and other surface
phenomena.
There are several factors that can affect the chemical cleaning process which include temperature, pH, concentration of the cleaning chemicals,
contact time between the chemical solution and the membrane and the operation conditions such as cross-flow velocity and pressure. The role of
temperature and pH in cleaning are membrane dependent. These factors play very important role in flux recovery. A critical review of these factors
is also presented.
It appears from the literature that only very few papers on cleaning of NF membrane to regenerate membrane performance have been published
up to date, and there is an urgent need for extensive research work to investigate fouling mechanisms in order to obtain fundamental understanding
of fouling to provide more feasible, cost-effective cleaning and performance restoration procedures. This also provides further strategies for the
avoidance of fouling through better pretreatment and more appropriate membrane fabrication and modification.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Cleaning agents; Nanofiltration membrane; Cleaning efficiency; Fouling

∗ Corresponding author. Tel.: +44 1792 295709.

E-mail addresses: Aalmoudi@swcc.gov.sa, 310981@swan.ac.uk
(A. Al-Amoudi), r.w.lovitt@swansea.ac.uk (R.W. Lovitt).

0376-7388/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2007.06.002
 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28 5

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2. Fundamentals of NF separation and selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3. Fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.1. Inorganic fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1.2. Organic fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.1.3. Biofouling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2. Operational aspect of NF and fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3. Primary location for specific types of fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.4. Fouling minimization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.4.1. Coagulation followed by filtration–sedimentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.4.2. Scale inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.4.3. Membrane prefiltration and membrane modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.4.4. Sonication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4. Membrane cleaning. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.1. Remediation of the membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.2. General considerations and costs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.3. Assessment of cleaning agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.3.1. Type of cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.3.2. Cleaning mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.3.3. The impact of cleaning on NF permeate quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.4. Methods of assessing the cleaning effectiveness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.4.1. Flux measurement (non-destructive) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.4.2. Atomic force microscopy (AFM) (destructive method) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.4.3. Fourier transform infrared technique (FTIR) (destructive method) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.4.4. Zeta potential measurements (non-destructive) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.5. Factors affecting chemical cleaning efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.5.1. Effect of cleaning solution pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.5.2. Effect of ionic strength of the cleaning solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.5.3. Effect of cleaning solution concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.5.4. Effect of cross-flow velocity (hydrodynamic shear) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.5.5. Cleaning duration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.5.6. Cleaning frequency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.5.7. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.5.8. Effect of pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5. Discussion and conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

1. Introduction tion for shortages in conventional water resources and has

acknowledged as sustainable and effective process by rep-
Water scarcity is a major political and economic problem in utable institutions such as the World Bank [3]. This can be
the many parts of the world especially in the arid regions such as achieved either by thermal processes involving evaporation
the Middle East, Southern Europe, North and mid Africa, Aus- or by membrane filtration involving separation of ions from
tralia and many states of America such as California, Florida, water.
New Mexico, etc. The shortage in natural fresh water supply As water demand increases, environment and safety regula-
for domestic purposes is most acute for the Arabian Penin- tions are becoming more stringent, greater research efforts have
sula countries – Saudi Arabia, Kuwait, Bahrain, Qatar, United been put into the improvement of membrane processes. During
Arab Emirates, Oman and Yemen – where demand for water the past decade a variety of water treatment membranes has been
increases annually at a rate of 3% or more [1]. In addition, developed [4]. These membranes have been vastly improved in
the rapid further reduction of subterranean aquifers, and the the area of water flux, salt rejection, and especially in their abil-
increasing salinity of these non-renewable sources will con- ity to maintain high performance levels at substantially lower
tinue to exacerbate the water shortage problems in many areas operating pressures than their predecessors [5]. Despite these
of the world. Desalination techniques are capable of provid- improvements, a decline in membrane performance over a period
ing the solution [2]. “Desalination” or “Desalinization” refers resulting from membrane fouling that leads to a decrease in water
to water treatment processes that remove salts from saline flux across the membrane and increased salt passage through the
water. Desalination has already become an acceptable solu- membrane [6,7].
6 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
The membrane can be considered the heart of a desalina-
tion plant where the cost of membrane unit is about 20–25%
of the total capital cost [8]. Consequently, it is very important
to be familiar with factors involved in reduction of membrane
performance and longevity, in particular membrane fouling.
The factors affecting NF separation that can also play an
important role in membrane fouling and cleaning are as follows:
• Membrane properties such as surface roughness pore size dis-
tribution, membrane thickness, membrane charge type and
charge density.
• The chemistry of the treated solution such as solute compo-
sition, the size, geometry and the charge of the components,
the concentration of ions, the pH and the fouling potential of
the solution and its interaction with membranes.
• The operation design of the NF systems, their—capacity,
dimensions and flow.
• The processes environment—temperature and pressure.
This review focuses on the type of foulants that leads to
flux reduction of fresh water obtained from desalination plant:
explanations of desalination processed and their mechanism
of fouling are also reviewed to give clear understanding of
the cleaning processes. The main objective of this review is
to address the key factors in maintaining and restoring the
plant performance and the factors that affect the cleaning
efficiency.
2. Fundamentals of NF separation and selectivity
Nanofiltration (NF) membranes are mainly utilized for
softening brackish waters. The separation characteristics of
nanofiltration (NF) stand between ultrafiltration (UF) and
reverse osmosis (RO) and the membrane selectivity has often
been attributed to the interchange of both molecular siev-
ing mechanisms characteristic of ultrafiltration and diffusion
mechanisms characteristics of RO. NF membranes are usu-
ally made of polyamide based Thin Film Composites (TFC),
which are relatively close to RO membranes in chemical
structure. However, a key distinguishing feature of RO mem-
branes is their higher rejection of both monovalent and
divalent ions, the NF membranes are typically character-
ized by lower rejection of monovalent ions, but maintaining
higher rejection of divalent ions and higher flux than that
of RO membranes. In general NF membranes have relatively
high charge and also pores in the order of about 1 nm [9].
Consequently both, charge effects and sieving mechanisms
influence the rejection behavior of solutes in NF membranes
[10].
Generally, the basic chemical structure of the synthetic poly-
mers used in the preparation of RO, UF and NF membranes are
almost same apart from the pore size of the membranes. There-
fore overlap of properties of RO and UF with NF in terms of
both transport phenomena and consequent fouling is common
in the area of water treatment. Consequently the cleaning pro-
cesses for the RO and UF are also similar for NF membrane.
Hence, this literature review sometimes considers UF and RO
membranes and their fouling or/and cleaning system in order to
elaborate the points where lack of information on NF fouling
and cleaning exists.
The forces of the interaction between the membrane sur-
face and particles in solution are important in understanding
the fouling phenomena. The normal basis for quantify-
ing particle–surface interaction is DLVO theory where the
particle–surface interactions in aqueous environments could be
predicted by the summation of van der Waals and electrostatic
double layer forces. The Fig. 1 is a schematic description of
the DLVO interaction profiles and the summation of these two
forces. There are several important features about this diagram:
Unlike the double layer interaction, the van der Waals interaction
potential is largely insensitive to variations in pH and electrolyte
concentration.
Reducing the interaction between the particles and the mem-
brane as much possible can reduce the fouling phenomena. This
can be achieved when the critical values (flux and pressure)
arise as a balance between the hydrodynamic force driving
solute towards the pore and the electrostatic forces opposing
this motion. Critical flux stems from the concept that the higher
the flux the stronger is the drag force towards the membrane,
the stronger concentration polarization and the higher the com-
paction of particles. Critical flux is defined as the limiting flux
value below which a flux decline over time does not occur [11].
A number of parameters influenced this critical flux have been
discussed in detail and can be found elsewhere [12]. It is main-
tained that if one operates below the critical flux the fouling can
be avoided or minimized.
Fouling is common to all types of membrane separation. The
type of fouling various from Microfiltration (MF) membrane
processes where hydrodynamic force can predominate to RO
membrane processes where hydrodynamic forces have minor
effects compared to the forces associated with particles and their
interaction with the membrane surface.
3. Fouling
3.1. Background
To devise effective cleaning strategies a thorough understand-
ing of membrane fouling and it causes is required and first part
of the review is therefore dedicated to the nature of fouling and
fouling processes membrane fouling is an extremely complex
phenomenon that has not been defined precisely. In general the
term is used to describe the undesirable formation of deposits
on membrane surfaces. This occurs when rejected particles are
not transported from the surface of the membrane back to the
bulk stream.
The foulants are typically colloidal materials of one sort or
another and these properties and interaction with the membrane
dominate fouling/cleaning processes. Colloids are defined as
fine suspended particles in the size range of a few nanometres to
a few micrometers. Examples of common colloids sized foulant
include inorganic (clays, silica salt, and metal oxides), organic
(aggregated natural and synthetic organic), biological (bacteria
and other micro-organism) [7,13–18]. Champlin [19] reported
 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28 7

Fig. 1. Schematic energy versus distance profiles of DLVO interaction profiles (a) Surfaces repel strongly; small colloidal particles remain ‘stable’. (b) Surface
come into stable equilibrium at secondary minimum if it is deep enough; colloids remain’ kinetically ‘stable’. (c) Surfaces come into secondary minimum; colloids
coagulate slowly. (d) The ‘critical coagulation concentration’. Surfaces may remain in secondary minimum or adhere; colloids coagulate rapidly. (e) Surfaces and
colloids coalesce rapidly. [10].

that removing of the particles size of down to 1 ␮m may not be
sufficient to avoid fouling in many cases. Not only do MF and
UF process sometimes fail to remove all colloids below a few
hundred nm in diameter but also conventional processes used to
pre-treat NF feed water fail to remove sub-micron colloids [10].
The high concentration of the rejected ions in the membrane
surface could encourage aggregation of dissolved matter in to
colloidal sized particles. More to the point, the influenced of
salt retention and concentration polarization in the vicinity of
the membrane surface screens electrostatic particle–membrane
and particle–particle interactions allowing colloids to foul the
membrane.
The sites fouling of membrane can be divided into exter-
nal surface fouling (build-up of a cake/gel-like layer on the
upstream face of a membrane) and pore blocking fouling [20].
In a dead-end filtration system, the latter is divided into three
types: complete pore blocking (blocking a pore by a particle with
approximately the same as the pore size), incomplete pore block-
ing (intermediate fouling) and standard pore blocking (gradual
pore narrowing and constriction by particle that is much smaller
than the pore size) [21]. The flux decline of NF membrane is
mainly attributed to the pore blocking and it is observed in
dead-end and the cross-flow filtration systems.
Vrouwenvelder and Kooij [22] showed that diagnosis of the
type/cause of fouling is an essential first step aiming at control-
ling fouling. Autopsy gives conclusive information and further
understanding about the types and extent of fouling in the mem-
brane filtration plant and provides specific ways for reduction
and control of fouling. The tools which have been developed
for diagnosis, prediction, reduction, and control of fouling have
proven their value in controlling fouling in practice. An overview
of the tools is shown in Table 1 [23].
A set of coherent tools has been developed for (i) Determining
the fouling potential of the feed water. (ii) Analyzing the fouling
of NF and RO membranes. The tools presented can be used to
(a) assess the cause of fouling, (b) further define criteria for
feed water to predict and minimize the risk of fouling and (c)
evaluate cleaning strategies. Appropriate use of these tools can
provide strategies for cleaning to reduce the operational costs of
membrane plants (Table 1) [23].
When fouling takes place on the membrane surfaces its causes
flux decline leading to an increase in production cost due to
increased energy demand, chemical cleaning, reduction in mem-
brane life expectancy and additional labor for maintenance.
The types of NF Fouling can be classified on the basis of
fouling material into three types [22–25]:
8 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28

1. inorganic fouling due to deposition on membrane surface of

Brine stage module with a single

spiral wound membrane element

Optimizing recovery, acid dose

inorganic scales (mainly BaSO4 , CaSO4 CaCO3 ),

Continuous on-line monitor-

2. organic fouling due to natural organic material (NOM) found
in the process stream (humic acids, protein and carbohy-

and anti-scalant dose

drate), and
3. biofouling due to microbial attachment to membrane sur-
ScaleGuard

face followed thereafter by their growth and multiplication

in presence of adequate supply of nutrients in the pretreated
Scaling

feed or nutrients that deposited on membrane surfaces.

3.1.1. Inorganic fouling

Scale formation at the membrane surface is serious problem
Dead end equipment

and resulting from the increased concentration of one or more

Particulate fouling
potential of water

species beyond their solubility limits and their ultimate precip-

overview of tools available for determining the fouling potential of feed water and fouling diagnosis of NF and or membranes used in water treatment adopted [90]

itation onto the membranes [26]. In order to avoid scaling, it

Particulate
MFI-UF

is very important to operate NF systems at conditions lower

than the critical solubility limits, unless the water chemistry and
physical conditions are adjusted to prevent the type of precipita-
tion. Currently, due to the complexity of the problem, there is no
reliable way to predict the limiting concentration level at which
Specific Oxygen Consumption

determining active biomass in

Non-destructive method for

there is no a risk of scale formation with a given membrane sys-

Biofouling formation rate

tem and treated water. Similarly, specific antiscalant treatments

are hard to define with confidence [27]. Schafer et al. [10], have
membrane systems

reported that scaling (scale formation) or precipitation fouling,

Rate (SOCR)

occurs in a membrane process whenever the ionic product of

Biofouling

a sparingly soluble salt in the concentration stream exceeds its

equilibrium solubility product.
The term ‘membrane scaling’ is commonly used when the
precipitate formed is a hard scale on the surface of the mem-
brane. Scaling usually refers to the formation of deposits of
Assimilable organic carbon (AOC),

inverse-solubility salts such as CaCO3 , CaSO4 ·xH2 O, silica,

Biofouling by determining the
Biofilm monitor of biofouling

Predictive and prevention of

and calcium phosphate. Inorganic scale formation can even lead

(growth) potential of water

to physical damage of the NF membrane, and it is difficult to

cylinder (glass) surface

restore NF membrane performance due to the difficulties of scale

removal and irreversible membrane pore plugging [10]. The
formation rate

greatest scaling potential species in NF membrane are CaCO3 ,

Biofouling

CaSO4 ·2H2 O and silica, while the other potential scaling species
are BaSO4 , SrSO4 , Ca(PO4 )2 , ferric and aluminium hydroxides
[26,28]. Calcium sulphate precipitates in six different phases,
dihydrate (so-called gypsum), two hemihydrates and three anhy-
drites, although at ambient temperatures (about 20 ◦ C), gypsum
Zeta potential, Contact angle, NMR and

chemical and physical properties of the

Biofouling, inorganic, compounds and

SEM, EDX, XRD, FTIR, AFM„ XPS,

membrane. This confirmed with water

Comparison of fouled and un fouled

is the most common. The other phases are the product of gyp-
Chemical analysis of the foulant by

treatment properties provide likely

system isolate the differences both

sum dehydration at relatively higher temperature, whereas the

Integrated diagnosis (autopsy)

calcium carbonate precipitates in three phases: calcite, valerite

and aragonite.
The most common crystal of calcium carbonate is calcite.
TOC, ICP,HPLC etc.

It is widely accepted that the crystallization (precipitation) of

causes of fouling

salts that takes place on the NF membrane surface requires at

least two stages, a nucleation stage and a crystal growth from
particles

supersaturated solution. It is important to be familiar with the

mechanism of scale formation in order to avoid flux reduction
through membrane. Gilron and Hasson [27,29–31] considered
Fouling diagnosis

that the flux decline was due to the blockage of the membrane
surface by lateral growth of the deposits on the membrane (het-
Comment

erogeneous crystallization (two phase)) whereas Pervov [29–31]

Method
Table 1

reported that the flux decline was due to the crystal formation
Tools

that took place in the bulk solution followed by crystal deposition

 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28 9

Fig. 2. Scale formation mechanisms in NF membrane (a) show homogenous precipitation in the liquid phase while (b) show heterogeneous precipitation between
liquid phase and solid surface phase and the factor effect the crystallizations [28].

on the surface of the membrane (homogenous crystallization).
Clearly, this process will be a mixture of these two extremes and
will be affected by membrane morphology and process condi-
tions. Fig. 2 represents homogeneous and heterogeneous modes
of crystallization [30]. Her et al. [8,32], reported that if the sur-
face of the solid substrate matches well with the crystal and
the interfacial energy between the two solids is smaller than
the interfacial energy between the crystal and the solution, then
nucleation may take place at a lower saturation ratio on a solid
substrate surface (heterogeneous crystallization) rather than in
the solution (homogenous crystallization) [8,32]. When the bulk
phase becomes supersaturated due to the increasing of concen-
tration polarisation layer, it is possible that both mechanisms of
crystallization simultaneously occur in NF system [30].
Aluminium oxide, inorganic salts, clays, sand and biologi-
cal surfaces can also act as suitable substrates for crystallization
[33]. Dydo et al. [8] have reported that most researchers indicate
that the gypsum scale precipitates as a bulk phase precipitation
process (homogenous crystallization) rather than on membrane
surface (heterogeneous crystallization). Lee et al. [30] has
also demonstrated that the homogeneous crystallization in the
retentate is a more important mechanism than heterogeneous
crystallization of the membrane fouling and flux decline [30].
Hasson et al. [27] have reported that the effect of CaSO4 scaling
in RO and NF membranes on the flux decline was a function of
the super-saturation level on membrane surface and in the bulk.
Various physical and chemical parameters that affect the
crystallization process within a membrane system and include
temperature [34,35], pH [36], flow velocity, permeation rate
[37], types of pretreatment [38], salt concentration and concen-
tration polarization [30,39–42], membrane type, materials [37]
and metal ions [43]. In addition to these parameters, NOM has
also been considered to affect various forms of scaling [44].
These factors also have been summarized as to whether they
increase or decrease the scaling, in Table 2 and more informa-
tion can be found elsewhere [45]. It can be drawn from this
table that there are several factors either alone or combined with
each other play an important role in crystallization and subse-
quent cake formation. However, this is further complicated by
the nature of mixed solutions of how these alter substantially
the solubility product, strength and morphology of precipitates
from those in pure state. When the structure of the precipitate is
10 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28

Table 2
scaling factors [38]
Value Crystallization Cause

Ionic strength High Increased Solubility and supersaturating

CP High Increased Solubility and supersaturating
Co-precipitation Presence Increased Changing structure of the precipitate
pH Higher Increased Solubility decreased
Pressure Higher Increased Increasing CP and Osmotic pressure at membrane surface
(solubility and supersaturating)
Velocity (flow rate) Higher Decreased Higher wall shear rate
Temperature Higher Increased Solubility decreased
Surface morphology Higher Increased Valley blocking

altered so are the intramolecular forces holding the precipitate
together [40].
3.1.2. Organic fouling
In general, NF membrane are used in water treatment as
alternative processes for the removal of natural organic mat-
ter NOM that cause contamination, taints and color and are
vehicles for other materials that bind to these substances [46].
Organic fouling could cause either reversible or irreversible
flux decline. The reversible flux decline, due to NOM fouling,
can be restored partially or fully by chemical cleaning [24].
Whereas the irreversible flux decline can not be restored at
all even by rigorous chemical cleaning is applied to remove
NOM [47]. Membrane fouling in the presence of NOM can
be influenced by: membrane characteristics [25,48–52], includ-
ing surface structure as well as surface chemical properties,
chemistry of feed solution including ionic strength [51,53], pH
[48,50,51,54–58]; the concentration of monovalent ions and
divalent ions [50,51,54,59,60]; the properties of NOM, including
molecular weight and polarity [25,49,52,61,62]; the hydrody-
namics and the operating conditions at the membrane surface
including permeate flux [25,51,63–65], pressure [47,50,66],
concentration polarization [50], and the mass transfer proper-
ties of the fluid boundary layer. These factors either increased
or decrease the fouling rate have been summarized in Table 3
and more information can be found elsewhere [45]. As it can be
seen the Table 3 that the chemical (Ionic strength, NOM frac-
tion, etc.) and physical parameters, such as pressure, velocity,
and permeate flux, play a major role in NOM fouling at NF
membrane surface.
Humic substances in aquatic environments are considered
to be the major fraction of NOM, are refractory anionic
macromolecules of low to moderate molecular weight. Humic
substance contains both aromatic as well as aliphatic compo-
nents with primarily carboxylic (carboxylic functional groups
account for 60–90% of all functional groups) and phenolic
functional groups [67]. As a result, humic substances gen-
erally are negatively charged in the pH range of natural
waters [18]. Nilson and DiGiano found that only the large
molecular weight fraction of NOM contributed to the layer
formation. In addition, while studying the effect of NOM prop-
erties on fouling of NF membranes, they fractionated NOM
into hydrophilic and hydrophobic components. They found
that the hydrophobic fraction was the major factor causing
permeate flux decline while the hydrophilic fraction had rel-
atively small effect [68]. The hydrophobic fraction of NOM
tends to adsorb more than hydrophilic fraction of NOM to the
membrane surface. The hydrophobicity of the NOM increases
with increasing molecular weight [18,68]. Jucker and Clark
have also observed the same trend [69]. The fouling effect of
divalent ions on high molecular weight of NOM was more pro-
nounced than with low molecular weight of NOM. Braeken
[70] et al. have reported that hydrophobicity and molecular
size play an important role in retention of dissolved organic
compounds. Hydrophobicity is the most important parame-
ter determining the retention of molecules with a molecular

Table 3
Natural organic matter fouling factors [38]
Value NOM fouling Rate Cause

Ionic strength concentration Increased Increased Electrostatic repulsion

pH High pH Increased Hydrophobic forces
Low pH Increased Electrostatic repulsion
Divalent cations Presence Increased Electrostatic repulsion and bridging between NOM and
membrane surface
NOM fraction Hydrophobic Increased Hydrophobicity
Hydrophilic Decreased
Molecule or membrane Charge High charge Increase Electrostatic repulsion
CP High Increased
Surface morphology Higher Increased Valley blocking
Permeate flux (High recovery) Higher Increased Hydrophobicity
Pressure Higher Increased Compaction
 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
Fig. 3. Conceptual sketch of the swollen membrane matrix for different ionic
environments (a) thick electrical double layer at high pH and low ionic strength
and (b) thin electrical double layer at high ionic strength and low pH) [51].
weight below the molecular weight cut off (MWCO) of the
membrane, presumably binding on or in the membrane sur-
face.
The apparent membrane surface structured in the solution is
a function of pH and ionic strength. Fig. 3 shows the potential
impact of high and low ionic strength on membrane structure. At
high ionic strength, the membrane pore size was found to exhibit
larger pore size compared at low ionic strength. The forces that
control secondary and tertiary structure of NOM are also altered
with increasing salt concentration, and results the slow restruc-
turing or transition of the NOM particles [57,71]. For example,
the NOM particles can stretch to more linear chains at low
concentrations, low ionic strengths and at neutral pH because
of higher intermolecular repulsion. Whereas a rigid, compact,
spherocolloidal macromolecule is found at high ionic strength,
low pH and high solution concentration when intramolecular
charge shielding acts to neutralize functional groups (Fig. 4)
[53].
The pH also has a major effect on the fouling behavior of
humic acids. Typically humic acid contains carboxylic acid
groups that lose their charge at acidic pH. At low pH (<4)
macromolecules of humic acid have a smaller macromolecular
configuration due to increased hydrophobicity and reduced inter-
chain electrostatic repulsion and hence these macromolecules
pass more easily through the membrane pores (size exclusion)
[51,53]. Mika et al. showed that at pH 4–5 the membrane and
humic acid are almost uncharged and that these conditions pro-
mote fouling [48].
Consequently, NOM fouling at high pH is possible when the
calcium concentration is high can precipitates and the NOM
adsorbs on the calcite surface [58,64]. Schafer has also indi-
cated that the precipitation of a calcium-organic complex is
co-precipitated or absorbed occurs at pH 10. He concluded that
deposition of calcium increases with pH so more organics are
absorbed on the calcite surface [50]. As a results, the Ca2+
and Na+ rejection of the membrane were decreased by foul-
11
Fig. 4. Conceptual sketch of hypothetical macromolecular endpoints from
polyelectrolyte solution theory: (A) high pH, low ionic strength, low solute
concentration; (B) low pH, high ionic strength, high solute concentration [51].
ing [54–57]. The same result and trend have found by Manttari
and his group [48].
This phenomenon has also elegantly demonstrated by using
non-contact AFM imaging in high and low salt environment.
Bowen et al. [72] concluded that High electrolyte concentra-
tions give the sharpest images with the best definitions of the
pores in case of Ultrafiltration membrane (ES625). At the high
ionic strength (10−1 M) the isopotential lines follow the pore
entrance more closely than at the low ionic strength, not only was
the image obtained in 10−3 M solution less sharp, but also the
mean pore size determined was greater than at the higher ionic
strengths and also greater than the value obtained in air (Fig. 5).
This behaviour will also occur with NF membrane system.
Thorsen showed that the most critical particle sizes for NOM
fouling fall in the range 0.1–1.5 ␮m [73]. In a more detailed
study, Hong and Elimelech investigated the role of chemical
and physical interactions in natural organic matter (NOM) foul-
ing of NF membranes. The role of solution ionic strength, pH,
and divalent cations in NOM membrane fouling, as well as
the fouling mechanisms involved, are reproduced in Fig. 6. of
these chemical factors, the presence of divalent cations, such
as calcium and magnesium, has a marked effect on NOM foul-
ing by allowing ionic bridging between NOM molecules. In
addition, it was shown that rapid membrane fouling occurs
at high permeation rates, even under chemical conditions not
favorable for fouling, such as low ionic strength, low levels
of divalent cations, and high pH. Therefore the rate of foul-
ing is controlled by the interplay forces in the solute particles
between permeation drag and electrostatic double layer repul-
sion. NOM fouling of NF membranes involves both physical
and chemical interactions. The addition of a strong chelating
agent (EDTA) to feed water reduces NOM fouling signifi-
cantly by removing free and NOM-complexed calcium ions
[51].
A more complete understanding of the fouling factors of
NOM and membrane characteristics could build the foundation
12 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28

Fig. 5. numerically calculated isopotential lines at the entrance to a membrane pore of diameter 0.1 I.tm. (a) In 10–1 M solution, (b) in10–4 M solution. The pore size
distribution obtained from AFM images at various concentrations. The line BC is the front of the membrane, CD is the internal pore wall, FE is the axis of symmetry
along the centre of the pore (due to symmetry, only a half section is shown), AB and AF are the natural boundaries in the solution and DE is a natural boundary in
the pore. The front surface and pore wall of the membrane have a normalised potential of 1.0. [60].

required to figure out the mechanisms of NOM fouling dur- NOM fouling in order to maintain the flux. In addition to solute
ing driven-pressure membrane applications. A systematic and characteristics, a comprehensive understanding of membrane
comprehensive study is still needed in order to identify key properties is also needed to predict solute–membrane interac-
parameters that could be used effectively for the prediction of tions and eventually NOM fouling. Clearly there is scope to

Fig. 6. Schematic description of the effect of solution chemistry on the conformation of NOM macromolecules in the solution and on the membrane surface and
the resulting effect on membrane permeate flux. The NOM fouling described in the diagram is applicable for permeation rates above the critical flux. The difference
between the two chemical conditions shown becomes less clear at very high permeate flux. At low permeate flux (below the critical flux), no significant fouling is
observed for both conditions [22].
 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28 13

improve processes and membrane by understanding the nature

NOM–membrane interaction.

3.1.3. Biofouling
Biofouling is a term used to describe all instances of foul-
ing where biologically active organisms are involved [74]. This
is distinct from NOM fouling caused by contaminated organic
matter that may be derived from biological systems. Membrane
biofouling is caused by bacteria and to a lesser degree, fungi and
other eukaryote microorganisms [75]. Biofouling is a dynamic
process of microbial colonization and growth, which result in the
formation of microbial biofilms. Biofilm formation invariably
precedes biofouling, which becomes an issue only when biofilms
reach thickness and surface coverage that may cause problems
such as declined normalized flux and/or increase in normal-
ized pressure drops during NF or RO operation [22,76]. Many
products from biofilms have been shown to enhance inorganic
precipitation through enhanced nucleation and crystallization
kinetics, e.g. carbonate and silicates. Biofouling can be con-
trolled by (1) removal of degradable components from the feed
water, (2), ensuring the relative purity of the chemicals dosed
and (3) performing effective cleaning procedures. Also, it has
been reported that cleaning procedures applied when fouling is
not a problem might delay biofilm formation [77]. The surface
of the membrane offers good site for microbial colonization as
it concentrates nutrients for growth.
Fig. 7. Membrane arrays—straight and tapered brine stage (a) straight brine
stage one pressure vessel contained six element in series), (b) tapered brine
3.2. Operational aspect of NF and fouling staging in the ratio of 2:1 each presser vessel have six membrane elements),
(c) tapered brine staging in the ratio of 3:2:1 each presser vessel contained four
From the mechanisms of fouling process above, many oper- membrane elements) and (d) tapered brine staging in the ratio of 4:2:1 each
ating procedures have a direct impact on fouling of membranes. pressure vessel contained four elements).
This section reviews the effect of membrane process design on
fouling. In most cases flux rate is considered as a key design ments per stage in order to maintain the same or high recovery
parameters for membrane system and reflect membrane produc- will involve the following constraints [10,82]:
tivity. The two factors that lead to deterioration the flux rate
are fouling and concentration polarization. In order to over- 1. The flow rate should not exceed the maximum flow rate per
come these shortcomings the membrane array is to be introduced element, qmax , to avoid large axial pressure drops which could
[21,67,78–81]. An appropriate membrane array was considered cause membrane element damage such as telescoping.
in designing membrane treatment system in order to reduce the 2. There is a lower limit on the flow rate per element, qmin , in
effects of both concentration polarization and to minimize the order to control concentration polarization and scaling.
membrane fouling. Typically, membrane systems use multiple 3. There is a maximum recovery for each stage as well as overall
parallel modules so that the plant performance in terms of the maximum recovery in order to minimize the fouling.
product quality and recovery remain identical for a single mod-
ule (Straight brine stages; typically a single module contains 3.3. Primary location for specific types of fouling
six elements). In the tapered systems (Tappered brine stages;
membrane array design 2:1, 3:2:1, 4:2:1), the feed stream is When reviewing the major causes of NF membrane fouling
passed through the first module (or parallel set of modules) and and associated mechanisms, it is very important to understand
is divided two streams. These streams are the product and the where the fouling takes place in membrane system in order to
reject stream, the reject stream from first module (or parallel set arrange the module and optimize fluid handling (see section
of modules) is passed through as feed to the second module (or above). Typically the fouling typically takes place either in the
set of modules). Here the velocities are boosted at each stage by lead element (first element in the pressure vessel) where parti-
decreasing the number of modules in parallel. Thus it is possible cles became entrapped on the surface or in the end element (last
to obtain a high recovery while still avoiding the worst effects element in the same pressure vessel) where salts are highly con-
of fouling and concentration polarization (Fig. 7). centrated). Usually organic and metal oxide fouling take place in
The membrane arrangements are designed with the aim of the first stage of lead element, metal oxide and colloids deposit
minimizing fouling and reducing concentration polarization by early in the process as drag forces are relatively high. However,
increasing number of stages and reducing the number of ele- organic fouling usually occurs heavily in the feed side of the
14 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
Table 4
where fouling occurs first, adapted from hydranautics technical service bulletin
tsp [82]
Type of foulant Most susceptible stage of NF/RO
Scaling/silica Last membrane in last stage
Metal oxides First membranes of first stage
Colloids First membranes of first stage
Organic First membranes of first stage
Biofouling (rapid) First membranes of first stage
Biofouling (slow) Throughout the whole installation
module. While biofouling can be found throughout the filtration
stages, however, rapid biofouling was found mostly in the feed
side as a result of particle and nutrient attachment [83].
In general, scaling and silica fouling take place in the brine
side membrane elements when the concentration of inorganic
salts exceeds the solubility limit. The types of the foulants and
where they usually cause fouling in typical NF/RO systems are
summarized in Table 4 [83].
There are two strategies in order to minimize the effect of
fouling, and these can be classified into two major groups min-
imization and remediation. Both of the strategies are practiced
in membrane process industries.
3.4. Fouling minimization
It is possible to avoid or control fouling to certain extent by
using adequate pretreatment such as coagulation/precipitation,
or slow sand filtration and membrane surface modification.
3.4.1. Coagulation followed by filtration–sedimentation
Conventional coagulation filtration pretreatment was
designed to remove most of the potential foulant materials
from the pretreated feed by prefiltration and more rarely by
sedimentation. The degree of the pretreatment, however, is
dependent on the raw water quality, particularly its content of
organic (including biological) and inorganic suspended matter.
Coagulant and coagulant aids can be added in a pretreatment to
increase separation efficiency. Several studies were have been
carried out on the pretreatment side in order to remove the
foulant materials by optimizing the operational conditions of
the pretreatment process such as flow rate, backwash frequency,
pH, etc. [84,85]. Howe and Clark [86], reported studies that
were focused on the effect of coagulation on the fouling
by dissolved and particulate colloidal matter. Tests with and
without prefiltration were able to provide a comparison between
the effect of particulate versus dissolved and colloidal matter.
Usually, less than 20% of the fouling in their experiments
could be attributed to particulate matter. They concluded that
when the water was treated with coagulant, the fouling usually
decrease after prefiltration and suggested that the coagulated
particulate matter was able to form a dynamic layer material
on the membrane surface. Thus, the fine particles could remove
materials that would otherwise foul the membrane. When
the dynamic layer was eliminated by prefiltration the fouling
actually worsened [86]. Earlier work [87] on surface water
pretreatment reducing Ca2+ and Mg2+ to very low level was
achieved using a complex multi-stage process of coagulation
and flocculation using lime; mechanical bed filtration; weak
cation ion exchange and deep-cartridge filtration, were success-
ful in obtaining pretreated water with Ca2+ and Mg2+ under the
detection limit.
3.4.2. Scale inhibitors
Another approach is to avoid scale formation the addition
of scale inhibitors. It is obvious that scaling intensity depends
upon the chemical composition of feed water; therefore water
with a high scaling potential requires treatment using scale [30].
The chemical species, such as lime and soda or caustic soda are
added to hard water in order to remove or reduce the hardness
ions. Alkaline chemical additives are added to hard water to
raise the pH in order to convert bicarbonates to carbonates and
then calcium and magnesium are removed from water as CaCO3
and Mg(OH)2 prior to filtration. Zero hardness water can not be
achieved due to the limited solubility of CaCO3 and Mg(OH)2 .
3.4.3. Membrane prefiltration and membrane modification
The application of microfiltration (MF) as well as ultrafiltra-
tion (UF) as NF prefilters has emerged in the last decade as an
efficient method in pretreating surface water [88]. Both UF as
well as MF membranes offer good physical barrier to colloids,
suspended particles as well as microbes. Both MF and UF mem-
brane can be used ahead of desalination units and have capability
of filtering out particles in the ranges “between” 0.005 ␮ to 0.1 ␮
(UF) whereas 0.1 ␮ to 3 ␮ (MF) [63].
Attempts have been made to modify membrane surfaces in
order to make them less vulnerable to fouling. In some cases,
the surface roughness increases membrane fouling by increasing
the rate of attachment onto the membrane surface and hence the
membranes with a rough surface is more prone to fouling than
membrane with a smoother surfaces [50,51]. Colloidal inter-
actions are also important in fouling and charged components
tend to cause fouling because of electrostatic attractions between
charged components and the membrane (see above). Develop-
ment of membranes with lower surface charge or surface charge
similar to that of the foulant, with hydrophilic character may
help solve these specific problems [89].
3.4.4. Sonication
The effect of the particle concentration on the ultrasonic con-
trol of the membrane fouling was investigated by Chen et al. [90].
The basic principle of operation is that ultrasound removes par-
ticles from the surface by causing particle movement in or near
membrane. In this experimental work it was concluded that the
ultrasound reduced ceramic membrane fouling by silica parti-
cles during cross-flow filtration. At low particle concentrations,
there was a little membrane fouling in the presence of ultra-
sound. However, the permeate recovery of the ultrasound treated
membrane decreased with an increased in particle concentration.
At low particle concentrations (lower than 0.8 g/L) the particle
concentration effect was more apparent when the membrane
was far away from the cavitation region. However, at higher
 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
particle concentrations of greater than 0.8 g/L the effect of par-
ticle concentration was more pronounced when the membrane
sonifacation power was close to the cavitation region.
Standard water treatments, carried out in order to solve
specific pretreatment problems, could lead to further fouling
problems. Walton [91], outlined some of these problems as fol-
lows:
• The use of certain phosphate anti-scalants stimulates biolog-
ical activity in both the internal and external environments.
• The use of organic biocides to control biological growth often
results in organic slime formation and subsequent after growth
activity and colloidal entrapment.
• The use of flocculants to control particulate matter results in
colloidal iron or aluminium floc fouling, especially in associ-
ation with organic slimes.
• The introduction of oxygen or oxidants into anaerobic sys-
tems results in iron and sulphur precipitation and potential
stimulation of iron hydroxide slime-production.
• Addition of minerals acid anti-scalant can produce avail-
able CO2 allowing biological growth, especially algae and
autotrophic bacteria.
• The use of activated carbon for dechlorination and/or organic
removal results in an excellent substrate for bacterial growth
producing fouling byproduct; it can also absorb polyelec-
trolyte and organic antiscalants.
4. Membrane cleaning
4.1. Remediation of the membrane
Remediation is usually conducted by chemical cleaning for
nearly all membrane processes and application. However, the
frequency of the chemical cleaning could range from a routine
daily process such as in whey processing to long term annual
processes such as in desalination plant according to occurrence
of fouling [89]. In general, much of the decline in membrane per-
formance can be corrected by cleaning the membrane. Cleaning
can be defined as “a process where material is relieved of a
substance, which is not an integral part of the material”, [92].
Physical cleaning methods include for example: hydrodynamic
forward or reverse flushing, permeate back pressure, air spurge
and automatic sponge ball cleaning. These methods depend on
a mechanical treatment to dislodge and remove foulants from
the membrane surface. Application of these methods usually
results in a more complex control and design of equipment.
The physio-chemical cleaning methods use mechanical clean-
ing methods with the addition of chemical agents to enhance
cleaning effectiveness [93].
Adequate pretreatment and appropriate membrane selection
as mentioned above can slow the fouling rate, but the membrane
cleaning is an essential step in maintaining the performance of
the membrane process. The ideal cleaning processes should not
only be effective against several foulants, but gentle to the mem-
branes so as to maintain and restore their characteristics. The
optimal (the least membrane damage and maximal effective-
ness of cleaning) choice of the cleaning agent is a function of
15
membrane material as well as foulants. Fu et al. [94] noticed
that two NF membranes with different properties (TS 80 and
NT47450), fed by the same feed water, required different clean-
ing processes. The results of cleaning procedures are sometimes
very difficult to determine using only flux recovery data. It is of
interest to know in what way the cleaning agent interacts with
the membrane and whether it actually modifies the membrane
surface structure and chemistry in such a way that fouling is pre-
vented. It has been noticed that cleaning often increases the flux
of the virgin membrane [95]. The chemical reactions between
the chemical agents and the foulant takes place either by chang-
ing the morphology of the foulant or by altering the surface
chemistry of fouling layer in order to remove the foulants from
the membrane surfaces [96]. Kosutic and Kunst [97], concluded
that an irreversible change in the porous structure of NF mem-
brane was observed as a result of the chemical cleaning. Cleaning
may make the pore surfaces more hydrophilic and charged by the
adsorption of the chemical agent [98]. Chemical cleaning proce-
dures and commercial membrane cleaning products are almost
specified by membrane manufacturers [96,99].
4.2. General considerations and costs
In any membrane processes, the need for proper and periodi-
cal cleaning is essential regardless of the type feed be; seawater,
brackish water, wastewater or industrial water. The objective of
the cleaning processes is to restore membrane performance when
it falls below the expected permeate yield typically by about
10%, or feed pressure increase by about 10% and/or differential
pressure increase by 15–50% [24]. Membrane replacement is a
necessary part of the plant operation that is needed to main-
tain the quality of the product water to the protocol agreed
with membrane manufacturers as well as to meet the design
productivity when the cleaning processes fail to restore the
declined flux [100]. Usually about 10% of the membrane is
annually replaced in order to maintain the targeted product qual-
ity as well as quantity. It has been reported that the cost of the
membrane replacement is about 2–3% of product water cost
from Jeddah SWRO Plant at power cost $ 0.1 kWh−1 (water
cost = 1.473 $/m3 ) [101]. Although, there are a number of clean-
ing techniques such as physical or chemical or combination of
both, only the chemical cleaning methods are widely used by
NF and RO industries for membrane cleaning and regeneration.
The complexity and detailed understanding of cleaning pro-
cesses has not yet been addressed by many researchers and
is needed for a clear knowledge of these processes. Although
cleaning is intended to restore the flux, it often deteriorates prod-
uct quality and increases the cleaning frequency affecting plant
availability. For example, cleaning processes sometimes takes
1–2 days to complete in large plants [24]. Desalination plant
availability is usually designed to be in the range of 90–97%
and varies according to the type of water being treated. How-
ever, this percentage can be reduced if the cleaning frequency
is increased, but the costs routine of plant maintenance, the
additional manpower utilization and energy consumed during
cleaning processes can increase the overall cost of water pro-
duction. In general, the chemical consumption of the plant per
16 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
year is about 0.3–1% of total water treatment cost, neverthe-
less, the chemical consumption of the cleaning process per year
is much higher than the annual chemical consumption for the
overall RO process (conditioning etc.,) [102]. These general cost
figures exclude the additional facilities, manpower and energy
consumed for cleaning.
It is well recognized that the energy cost of the plant is about
50–60% from the total water cost [101–103]. Moch [102] stated
that “power, itself, can be a half to three quarters of the opera-
tional and maintenance costs”. In general the cleaning process
increases the overall system energy efficiency, regardless of the
energy consumed during the cleaning. For example by reducing
the net driving pressure will be reduced after cleaning by about
10–30% which is quiet considerable energy saving, especially
during the plant operation [24].
4.3. Assessment of cleaning agents
4.3.1. Type of cleaning
A large number of chemical cleaning agents are commercially
available, and commonly used ones fall into six categories: alka-
lis, acids, metal chelating agents, surfactants, oxidizing agents
and enzymes [104,105]. Commercial cleaning products are usu-
ally mixture of these chemicals but the actual composition is
often not clearly specified. Table 5 [106] shows the chemical
cleaning agent recommended by various membrane manufactur-
ers. The table gives the details of chemicals and its concentration
to be used for different type foulants. The choice of the pre-
ferred cleaning product depends on feed characteristics. For
example, acid cleaning is suitable for the removal of precipi-
tated salts, such as CaCO3 , while alkaline cleaning is used to
remove adsorbed organics [89]. When surfactant is introduced
on the membrane surface in order to restore the membrane flux,
surfactant adsorption is possible from hydrophobic interactions
between the hydrophobic portion of the membrane surface and
hydrophobic tails of the surfactant. In spite of increased electro-
static repulsion between the negatively charged membrane and
anionic surfactant, even at a low surfactant concentration may
adsorb on to a negative-charged surface due to an ion exchange
mechanism leading to a higher concentration of surfactant near
to membrane surface compared to bulk solution, which may
induce a micellization process at the membrane solution inter-
face [107]. On the other hand, cationic surfactant could lead
to a reduction in membrane permeability owing to membrane
modification with a cationic surfactant [108,92].
As mentioned earlier, NF membranes are extremely vulner-
able to natural organic matter (NOM) fouling, especially in
the presence of divalent cations [109,50,51]. Characterization
of NOM-fouled membranes by contact angle, zeta potential,
and attenuated total reflection-fourier transform infrared (ATR-
FTIR) spectroscopy as well as molecular weight distribution
measurements demonstrated that colloidal material with hetero-
geneous characteristics with variable area of hydrophobicity and
charge membrane [104]. These materials are typified by humic
acids, fulvic acids, proteins and peptides. Typically, NOM tend
to have higher hydrophobic fraction of about 75% compared
to about 20% of hydrophilic fraction in water such as Orange
county ground water. While Horsetooth reservoir surface water
(HT-SW) found to have high fraction of hydrophilic NOM of
about 65% compared to about 27% of hydrophobic NOM frac-
tion. Lee reported that a caustic solution was more effective than
citric acid for fouled membrane with the hydrophobic fraction
of NOM. On the other hand, chemical cleaning agents were
not able to clean fouled membrane by hydrophilic fraction of
NOM, because of lack of electrostatic repulsion between NOM
acids and the negatively charged membrane surface [104]. This
was due to high ionic strength of the feed solution masking the
membrane surface charge.
In general, alkaline cleaning recovers the flux, while the
introduction of alkaline chelating agent further increases the
flux. Liikanen et al. [109] reported that alkaline chelatant such
as EDTA increased the flux more than plain alkaline cleaning
(NaOH) due to membrane charge increase in EDTA alkaline
environment, which makes the membrane more open. Liika-
nen et al. concluded that alkaline and chelating cleaning agents
increased membrane flux, but they reduced the ion retention,
whereas acidic cleaning could be used in order to recover mem-
brane ion retention. In a recent study, Li et al. [110] noticed that
combined simultaneous process of NaOH with sodium dodecyl
sulfate (SDS) demonstrated greater cleaning power and cleaning
efficiency by about more than 100% compared to that of single
cleaning with each of NaOH or SDS alone. This is also true when
two step method in which SDS cleaning step was performed
after caustic treatment [111]. Jacques et al. [112] reported that
hydrochloric acid cleaning showed better results than citric acid
in removal of the iron deposition on the membrane surface [32].
Song [51,113] reported that sequential use of both caustic and
acid cleaning was more effective, in terms of high flux recov-
ery, than caustic or acid alone in removing both acidic and basic
fractions of NOM. Also he reported that the caustic cleaning
was found to more effective than acid cleaning in removal of
the NOM foulants. This is a result of the presence of hydroxyl
ions in caustic solutions, which could promote disruption of the
foulant layer by these mechanisms: (i) increasing ionic strength,
(ii) increasing solubility of NOM foulants, (iii) increasing pH.
Increasing the pH should result in an increased negative charge
of NOM, because of deprotonation of the carboxyl and pheno-
lic groups. Conversely, decreasing negative charge of NOM has
been observed as a result of adsorption of sodium ions to NOM
during cleaning with [81,113]. EDTA and SDS were also used
as effective cleaning agents in order to remove virtually or all of
the NOM foulant material [51,114]. The acid cleaning is effec-
tive in removal of precipitated salts (scaling) from the surface
of the membrane and from the pore [10].
The polyamide thin film membrane (TFM) is very sensitive
to disruption by the oxidising agent. Powerful oxidation agents
have not been used in order to regenerate membrane perfor-
mance because of oxidation agent typically causes irreversible
damage to these membranes. However, there is a procedure
based on a patented chemical cleaning using NaOCl where a
known concentration is prepared and recirculated through the
membrane cells for 20 min at pH > 10, while chlorine oxidation
effects were almost negligible [115]. This cleaning procedure at
high pH was effective to remove the organic foulant materials
Table 5
chemical cleaning agents recommend by different manufacturers
Type of foulant Type of membranes
DuPont B-10
CaCO3 HCl at pH 4, citric acid
(2%w) pH 4 (NH4 OH),
Nutek-NT 600 (5%w),
citric acid
(2%w) + Na2 EDTA
(2%w), pH 4 (NH4 OH)
CaSO4 /BaSO4 Citric acid (2%w) pH 8
/SrSO4 /CaF2 (NH4 OH), EDTA
(1.5%w), pH 7–8
(NaOH/HCl), sodium
hydrosulfite, Na2 S2 O4
(1%w)
SiO2 NaOH, pH 11, Biz
(0.5%w), pH 11 (NaOH)
Metal oxides Citric acid (2%w) pH 4
(NH4 OH), sodium
hydrosulfite, Na2 S2 O4
(1%w), citric acid
(2%w) + EDTA (2%w)
pH 4 (NH4 OH), v
Inorganic colloids HCl at pH 4, citric acid
(2%w) pH 4 (NH4 OH),
NaOH, pH 11, Biz
(0.5%w), pH 11 (NaOH),
Drewperse 738 (1%w),
SHMP (1%w)
Biological matter Formalin (0.25–2%w)
followed by Biz
(0.25%w)
Organics NaOH, pH 11, Biz
(0.5%w), pH 11 (NaOH),
SHMP (1%w)
Flow rate velocity as high as possible, pressure as lowest as possible, temperature does not exceed manufacturer recommendation (<45 ◦ C).
FilmTec FT-30 Fluid System Nitto Denko Toyobo Toray
HCl (0.2%w), phosphoric acid, Citric acid (1%w), pH Citric acid (2%w) pH 4 Citric acid (1–2%), pH 2.5-4
H3 PO4 (0.5%w), citric acid 2.5 (NaOH) (NH4 or NaOH), ultrasil 70
(2%w), pH 4, sulfamic acid, 0.5% pH 2-2.5, peracetic acid
NH2 SO3 H (0.2%w) 100–200 ppm
HCl (0.2%w), phosphoric acid, Sodium
H3 PO4 (0.5%w), Citric acid tripolyphosphate,STP
(2%w), pH 4, sulfamic acid, (2%w) + Na4 EDTA
A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
NH2 SO3 H (0.2%w) (0.85%w), pH 10 (H2 SO4
NaOH (0.1%w) + Na2 EDTA – - Citric acid (2%w) pH 4
(0.1%w), pH 12, max 30 ◦ C (NH4 OH)
Phosphoric acid, H3 PO4 Citric acid (1%w), pH Citric acid (2%w) pH 4 Citric acid (2%w) pH 4 -
(0.5%w), sodium hydrosulfite, 2.5 (NaOH) (NH4 OH)
Na2 S2 O4 (1%w), sulfamic acid,
NH2 SO3 H (0.2%w)
NaOH (0.1%w) + sodium - Sodium Citric acid (2%w) pH 4 -
dodecylsulfate Na-DSS tripolyphosphate,STP (NH4 OH)
(0.05%w), pH 12, max 30 ◦ C (2%w) + Na4 EDTA
(0.85%w), pH 10 (H2 SO4
NaOH (0.1%w) + Na2 EDTA Sodium Sodium Tripolyphosphate, 1–5 ppm chlorine, pH Sodium lauryl sulfate 0.2%
(0.1%w), pH 12, max 30 ◦ C, tripolyphosphate, STP STP (2%w) + Na4 EDTA 6.5–7.5, Formalin pH 10-11 by NaOH, ultrasil
NaOH (0.1%w) + sodium (1%w) + trisodium (0.85%w), pH 10 (H2 SO4 ), (0.5–2%w) 10 0.7% pH 10-11
dodecylsulfate Na-DSS phosphate, TSP Sodium Tripolyphosphate,
(0.05%w), pH 12, max 30 ◦ C, (1%w) + EDTA STP (2%w) + sodium dodecyl
sodium tripolyphosphate, STP (1%w) pH 10–11 benzene sulfonate (0.25%w),
(1%w) + trisodium phosphate, (HCl) pH 10 (H2 SO4
TSP (1%w) + EDTA (1%w)
NaOH (0.1%w) + Na2 EDTA Sodium Sodium 1–5 ppm chlorine, pH -
(0.1%w), pH 12, max 30 ◦ C, tripolyphosphate, STP tripolyphosphate,STP 6.5–7.5, formalin
NaOH (0.1%w) + sodium (1%w) + trisodium (2%w) + Na4 EDTA (0.5–2%w)
dodecylsulfate Na-DSS phosphate, TSP (0.85%w), pH 10 (H2 SO4 ),
(0.05%w), pH 12, max 30 ◦ C, (1%w) + EDTA sodium tripolyphosphate,STP
Sodium tripolyphosphate, STP (1%w) pH 10–11 (2%w) + sodium dodecyl
(1%w) + trisodium phosphate, (HCl) benzene sulfonate (0.25%w),
TSP (1%w) + EDTA (1%w) pH 10 (H2 SO4 )
17
18 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
Fig. 8. Schematic illustration of the change in the organic fouling layer structure by EDTA (a) compact fouling layer formed in the presence of Ca2+ . (b) Loose
structure of the fouling layer after EDTA addition [117].
from membrane surface [78]. Hydrogen peroxide also used as
oxidizing cleaning agent at high pH in order to clean the mem-
brane from NOM. A combination of both Cl2 and H2 O2 at high
pH were noticed that had remarkable increased in the product
flux [78].
4.3.2. Cleaning mechanisms
It is reported that the presence of Ca2+ with humic acid
increased the fouling rate of humic acid on the membrane
surfaces. Li and Elimelech [116], reported that the proposed
mechanisms of chemical cleaning with EDTA in order to clean
membrane from NOM (humic acid). Since EDTA forms a strong
complex with Ca2+ , humic acid molecules associated with Ca2+
ions are replaced by EDTA via a ligand exchange reaction.
EDTA cleaning agent does reduce the intermolecular Ca2+ -
humic acid complexes and humic acid molecules can be more
easily rinsed off the membrane surface as illustrated in Fig. 8.
The proposed mechanisms of SDS solubilization of Ca2+ -
humic acid fouled surface at low, moderate and high
concentration are illustrated in Fig. 9. Low concentration of
SDS is not sufficient to break the intermolecular bridging formed
between humic acid and Ca2+ . When moderate concentration of
SDS is used, more SDS molecules partition into the foulant layer
results in breakup of some Ca2+ binding. Once the SDS concen-
tration exceeds the critical mycella concentration CMC, it is then
strong enough to break up all the Ca2+ -induced bridges, result-
ing in the dissociation of humic acid to the aqueous phase (as
indicated by the zero adhesion with SDS shown in Fig. 10). Chil-
dress and Elimelech [117], explored the mechanisms of chemical
cleaning with SDS and dodecyl trimethylammonium bromide
(DTAB, cationic surfactant) at high pH and low pH. Fig. 11
shows the differences in SDS adsorption at low pH and high pH.
At low pH of 3, the membrane initially has a slight positive and
adsorption occurs as a result of electrostatic attraction between
the positively charge membrane surface and the negative charged
polar head of surfactant ions. The surfactant ions start asso-
ciating with each other and form surfactant aggregates when
the concentration of SDS increases causing dramatic change in
the surface charge potential. At pH 8 the membrane has nega-
tively charge and the adsorption will be a result of hydrophobic
interaction between membrane surface charge and surfactant
tail. When the SDS concentration increases, the membrane sur-
face becomes slightly more negative due to a larger number of
adsorbed surfactant molecules. Schematics of adsorption mech-
anisms of DTAB molecules onto membrane surface are shown
in Fig. 12. As the concentration increases the membrane surface
charge become more positive due to hydrophobic interactions
at low pH. At high pH of 8, the adsorption occurs between the
membrane surface and charge polar head of the surfactant will
be due to electrostatic attraction. Hemi-micelle formation may
take place at the very high concentrations [117].
In all cases the cleaning process depends on the type of foulant
deposited on the membrane surface, and for a successful clean-
ing of fouled membranes, identification of the type of foulant is
essential which is done by extensive analysis of the foulants. A
destructive autopsy, which can provide a scientific foundation
on which to optimize the cleaning procedure, is done as a last
resort, when cleaning fails to restore membrane performance.
4.3.3. The impact of cleaning on NF permeate quality
An impact of cleaning on NF permeate quality has also been
observed. According to Liikanen et al. who performed anal-
ysis for alkalinity, hardness and conductivity found that the
permeate conductivity generally increased after cleaning [118].
 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28 19

Fig. 10. Interaction forces between the CML colloid probe and the SRHA fouled
membrane surface in the presence of various chemical cleaning agents. The
test solution contained 20 mg/l SRHA, cleaning chemical as indicated 1 mM
NaHCO3 , 1 mM CaCl2 and NaCl to adjust the total ionic strength to 10 mM. the
solution pH during the measurements was fixed at 8.1 [117].

Fig. 11. Schematic of adsorption of sodium dodecyl sulfate (SDS) molecules

into the membrane surface [118].

Fig. 9. Mechanism of humic acid solubilization by SDS (a) low SDS concen-
tration allows association of humic acid (b) moderate SDS concentration allow
partial breaking, and (c) SDS concentration exceeding the CMC allowing solubi-
lization of humic acid. The binding sits shows are solely for illustration purposes
[117].
of surface analysis such as atomic force microscopy (surface
characterization by visualization and measurement of the sur-
face characteristics), FTIR and zeta potential. The three types
of measurement are complementary.

Al-Amoudi et al. [24] also recognized that the increase in perme-

ate conductivity after each chemical cleaning specifically after
high pH cleaning when it was carried out in commercial NF
plant at UmmLujj. However, the acid cleaning following high
pH cleaning assisted in partial restoration of the ions reten-
tion property of membrane [24,118]. This suggests that acidic
cleaning had a role in preserving the membrane ion retention
capability, probably by making the membranes tighter by charge
neutralisation.

4.4. Methods of assessing the cleaning effectiveness

There is several assessment methods of cleaning have been

used and well established in order to evaluate cleaning efficiency. Fig. 12. Schematic of adsorption of sodium dodecyl trimethyl ammonium bro-
The most common methods are flux measurements, or forms mide (DTAB) molecules into the membrane surface [118].
20 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
4.4.1. Flux measurement (non-destructive)
Flux measurement is a direct assessment of fouling and clean-
ing process and can be made in the applied situation. There is
typically a linear relationship between the flux decline and the
deposited mass indicating that the flux decline is due to NF foul-
ing resulting from deposition heterogeneous crystallization [30].
Typically the product water flux declines drastically at higher
permeation rates in the presence of NOM refers and relates to
the transport processes driven by the hydrodynamics force that
acts perpendicular to the membrane surface [18,64].
It is important to establish effectiveness of a particular
cleaning protocol. The clean water flux can be measured and
compared to the flux of the original steady state process. The
water flux recovery (WFR) can be calculated [118] as:
Jc
WFR = (1)
J0
where Jc is the flux after cleaning and J0 is the flux of the virgin
membrane. The measurement of initial flux and the flux after
cleaning has to be carried out at the pressure and temperature.
Several authors [119,4,17] have proposed the comparison of
the hydraulic resistance of the cleaned membrane, Rcw , and the
intrinsic hydraulic resistance of the membrane to evaluate the
cleaning efficiency. Permeate flux data was used to evaluate the
hydraulic resistance of the membrane (R), according to Darcy’s
law:
P
R= (2)
μJ
and
Ruf = Rm + Rf = Rm + Rif + Rrf (3)
where P is the transmembrane pressure; J the permeate flux;
and Ruf , Rm and Rf , respectively, Ruf is the total resistance
of the intrinsic hydraulic resistance of the membrane plus the
total resistance of the total fouling membrane (Rf ), the intrinsic
hydraulic resistance of the membrane (Rm ), the fRres is residual
resistance after cleaning, and the resistance due to membrane
fouling, which combines reversible (Rrf ) and irreversible (Rif )
phenomena. The variation of membrane resistance is depicted in
Fig. 13. Cleaning can be assumed to be complete when Rcw ≈ Rm
allowing for experimental error (Fig. 13) [120].
Cleaning efficiency (ERW ) can be determined as
 
Rif − Rres
ERW = × 100 (4)
Rif
Both WFR and ERW have been used as a measure of clean-
ing efficiency. There is no difference between the above two
methods. However, the hydraulic resistances give a more details
to understandings fundamental to the flux. By knowing the
membrane hydraulic resistance and other fouling resistance, an
understanding of some fouling properties could be obtained.
The efficiency of membrane cleaning is mostly evaluated by
flux measurements [121]. Song et al. reported that the chemical
cleaning agents tested could not achieve complete flux recov-
ery as a result of residual foulants were strongly embedded in
the concavities of membrane surface [113]. However, Zhu et al.
Fig. 13. Graphical depiction of resistance in filtration, rinsing and cleaning
[121].
concluded that most of cleaning agents used improved the mem-
brane flux after fouling and some of them even restored the flux
up to about 95%. Recently, Al-Amoudi and Lovitt et al. [95]
from the results of the permeability of the fouled NF-DK mem-
brane before and after cleaning showed that the cleaning process
restored the declined flux close to its original value. Moreover,
it was also found that the SDS cleaning agents triple the perme-
ability of the virgin membrane. These results suggest that the
chemical cleaning does have a major effect on the flux of NF
membrane as well on its surface properties. It has been noticed
that cleaning often increases the flux and even the permeability
of the virgin membrane.
4.4.2. Atomic force microscopy (AFM) (destructive method)
There are now many new surface analysis techniques avail-
able for assessing membrane fouling and cleaning processes that
based on the visualization of the surface of membrane down to
the nanometer scale [122]. These images allow the assessment of
surfaces and pore by direct measurement of surface morphology
in air and in liquid (process relevant) environment. Analysis of
these images can be carried out in a number of ways, the most
useful being various measurement and/or dimension of pores
[122–124]. Atomic force microscopy can be used as good tool
to evaluate chemical cleaning procedures performance. Using
AFM it was showed that there was an accumulation of the par-
ticles in the valleys of rough membranes causing more severe
flux decline than smooth membranes [125]. Song et al. [113]
reported that significant difference between the surface mor-
phologies of the virgin and fouled membrane is recognized by
AFM. Here the root mean square (RMS) surface roughness of a
virgin membrane was about 48 nm whereas; RMS of the fouled
membrane was about 124 nm. This increase in surface rough-
ness was observed as a result of the presence of humic acid
with calcium on the negatively charged membrane surface. Also,
workers reported that, RMS of cleaned fouled membrane was
about 40 nm compared the virgin of about 48 nm. This decrease
in surface roughness was possibly due to the presence of resid-
 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
Fig. 14. Scanning electron microscope image of a silicon collide probe [128].
ual foulants within the concavities of the membrane surface after
cleaning. Warczok et al. [111] recently reported that it is possi-
ble to determine from AFM images the mean pore distribution
and roughness so indicating whether the cleaning procedure was
correctly designed or not.
The AFM colloid probe which is powerful technique, has
been used to measure the force of interaction between colloid
particles and the surface of the membrane. Using AFM it is possi-
ble to directly measure the force of interaction in process relevant
environments where the cantilever tip of AFM is brought in a
contact with membrane surface.
The most commonly used AFM tips for force measurement
are the sharp silicon tips which provide high resolution when
measuring surface topography and force in a process relevant
environment, However, attaching a sphere to a tipless AFM
cantilever has been used to quantify the surface interactions
between a sphere and a flat surface as well as different material
(Fig. 14). These so called colloid probes give a known geometry
when approaching or leaving the surface. These probes typi-
cally are about 1–5 ␮m diameter whose surfaces can be treated
with many materials including foulants. With different foulants
as probe coatings in liquid medium of different salt solutions
or cleaning solution, this technique allows an assessment of
the foulant membrane interactions and the chemical cleaning
processes [126,127].
The study of the electrical double layer interaction between
a particle and membrane by AFM also allows assessment of
the propensity of the surface to fouling when in use. Force
measurement in conjunction with colloid probe technique also
allow a direct quantification of membrane fouling through the
measurement adhesive force when the probe is retracted from
the surface after contact has been made [128]. Adhesive force
measurements were performed utilizing carboxylate modified
latex (CML) Colloid probe in the presence of various chemical
cleaning agents in order to look into the effect of chemical clean-
ing on foulant–foulant interactions in the fouling layer. Fig. 10
shows that the adhesive forces were measured with and without
chemical cleaning agent addition. The eliminated adhesive force
was in the presence of EDTA and SDS gave rise to a complete
flux recovery. While the remaining adhesive force with NaOH
addition indicates a poor cleaning efficiency, although, the adhe-
21
sive force was reduced significantly by NaOH compared to that
without chemical cleaning addition.
4.4.3. Fourier transform infrared technique (FTIR)
(destructive method)
FTIR technique is used to investigate the membrane surface
properties and the cleaning efficiency. Her et al. used FTIR
techniques in combination with other techniques to study pre-
cipitation scaling attributed to inorganic scales such as CaCO3
and CaSO4 [32]. Zhu and Nystrom [21] have used the FTIR
technique to characterize the chemical cleaning efficiency.
They concluded from the FTIR results that the fouling notably
changed the FTIR spectrum. New peaks appeared and foul-
ing obscured some of the peaks of the polysulfone membrane.
The results clearly showed that not all of the fouling had been
removed by cleaning. Song et al. [113] reported using FilmTec
NF-70 membrane that from the FTIR results of virgin, fouled
and cleaned membrane that the peak intensity of the virgin
were eliminated or severely attenuated due to coating by NOM
foulant, whereas the peaks intensity of caustic cleaned mem-
brane tend to be slightly close to the peak intensity of the virgin
membrane.
The cleaning agent may not remove the NOM completely
from the membrane surface by using EDTA. This is supported
by FTIR spectra measurements for virgin membranes, fouled
membrane and cleaned membrane with and without preoxidiz-
ing water where fouled membrane, exposed to preoxidized water
and cleaned with caustic solution, had better peak recovery com-
pared to the fouled membrane exposed to raw water and cleaned
with caustic solution [113].
4.4.4. Zeta potential measurements (non-destructive)
The electrokinetic properties of a membrane reveal the elec-
trical characteristics of the membrane surface. Membrane elec-
trokinetic properties are determined by streaming potential or
electro-osmosis that involves the relative motion of charged sur-
face and an electrolyte solution, with the results often expressed
in term of membrane Zeta potential [129], which is defined as the
potential at the surface of shear. By measuring streaming poten-
tial with solutions of different pH, the membrane surface isoelec-
tric point can be measured. Streaming potential is determined
by measuring the electrical potential difference when there is
relative motion between a fluid containing charged species and
charged surface caused by hydrostatic pressure gradient.
The interaction of organic and inorganic colloidal substances
with membrane surfaces in aqueous media is dependent on the
electrostatic properties of both membrane surface and foulant
material. Therefore, study of membrane surface characteristics
and its interaction with fouling materials is critical area of mem-
brane fouling research. The effect of surface characteristics has
generally been overlooked in efforts to select optimal (the best
pretreated quality) pretreatment schemes and operating con-
ditions for various membrane separation processes. The zeta
potential measurements method can be used not only to evalu-
ate the surface charge of the NF membrane but also to play an
important role in the selection of the NF membrane to be used
in the treatment of water [51,130].
22 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
Recently, workers [95] concluded that using different types of
NF membranes (virgin and fouled) were characterized with zeta
potential before and after chemical cleaning agents. Results sug-
gest that the cleaning does have a major effect on surface state
properties. However, the mechanisms vary from one agent to
another; chemical reactions modify membrane surface proper-
ties (surface charge) not only between cleaning agent and virgin
membrane but also between cleaning agents and fouled mem-
brane. The study also revealed that SDS cleaning agent has the
highest effect on surface charge for both virgin and fouled NF
membranes.
4.5. Factors affecting chemical cleaning efficiency
Cleaning mainly involves the dissolution of the material from
the membrane surface and several factors could affect the chemi-
cal cleaning process. These are: temperature, pH, concentration
of the cleaning chemicals, contact time between the chemical
solution and the membrane and operation conditions such as
cross-flow velocity and pressure [131].
4.5.1. Effect of cleaning solution pH
The pH of cleaning solution affects the recovered permeate
flux of fouled membrane with humic acid. Li et al. reported that
cleaning efficiency of EDTA depend critically on the pH of the
solution as a result of deprotonation of functional groups. For
example, at high pH 11 all carboxylic groups are deprotonated
while at low pH only two or four carboxylic groups molecule
are deprotonated. Ang et al. [132] reported that the influence of
solution pH on EDTA cleaning efficiency had remarkable effect.
They have shown that the cleaning efficiency increased notice-
ably (from 25% to 44%) with increasing pH from 4.9 to 11.0 in
the case of EDTA and all carboxylic functional groups of EDTA
are deprotonated. The gel layer was broken down more easily
at pH 11 compared to lower pH. On the other hand, solution pH
has very little effect on SDS cleaning because of the pKa of the
sulfate functional group of SDS is at 2.12, implying that SDS is
already in its ionic form at ambient and elevated pH values [132].
It was concluded that the cleaning solution pH is a governing
factor affecting chemical reaction between deposited foulants
and EDTA, whereas the chemical reaction between deposited
foulant and SDS is less influenced by cleaning solution pH.
4.5.2. Effect of ionic strength of the cleaning solution
High ionic strength of the NaCl solution alone or in a com-
bination with chemical agent has been found to have an effect
on the chemical cleaning system. Lee reported that the recover-
ing flux of hydrophilic NOM fouled membrane was carried out
effectively by high ionic strength of NaCl (0.1 M), whereas the
citric acid, caustic, and SDS surfactant were not effective to clean
the hydrophilic NOM. This could be due to reduced charges of
the membrane surface and NOM acids leading to double layer
compression and charge screening. Also, it is possible that Cl−
ions replaced the foulants of hydrophilic NOM associated with
Horsetooth surface water (HT-SW) [104]. A combination of high
ionic strength and caustic solution were more effective than the
acid and SDS solutions for removal hydrophobic of NOM on
fouled membranes [104]. Lee [81] concluded that additional
benefits from the higher cross-flow velocity and the longer clean-
ing duration were negligible for high ionic strength cleaning.
However, Tran et al. [81] concluded that the cleaning efficiency
was found to be superior at higher ionic strengths.
4.5.3. Effect of cleaning solution concentration
Li et al, reported that at 1 mM (millimole) concentration of
SDS had minor effect on the recovered flux, and a similar observe
also was made by Lee [104]. These results indicate poor cleaning
efficiency by SDS at this concentration, when an ultrafiltration
membrane was fouled by surface or ground water NOM. A SDS
concentrations of about 10 mM or higher, cleaning completely
recovered the initial cleaned membrane water flux. On the other
hand, Bartlertt et al. [86] noticed that for UF ceramic and the
sintered stainless steel membrane systems, increasing the con-
centration of NaOH above the optimum value do not improve the
cleaning process but rather reduced the cleaning efficiency. Li
et al. [110] reported that increasing the concentration of surfac-
tant such as CTAB from 0.1 to 0.5 wt.% had an adverse effect
on cleaning, possibly due to adsorption of excess surfactants
onto membrane surface during the cleaning. In their recent work,
Chen et al. [133] noticed that a significant factor affecting chem-
ical cleaning of both UF and RO membranes is the high pH and
the concentration of cleaning solution. Ang et al. [132], reported
that cleaning efficiency with EDTA and SDS cleaning increased
with increasing cleaning agents concentration. They concluded
that cleaning with SDS above CMC is critical factor for efficient
SDS cleaning, allowing adequate chemical reaction between
SDS and the foulant to break down an alginate gel network.
Therefore, to better understand the cleaning mechanisms, the
“stoichiometry” between the cleaning agent concentration and
amount of foulant on the membrane surface must be considered.
4.5.4. Effect of cross-flow velocity (hydrodynamic shear)
Hydraulic cleaning conditions such as cross-flow velocity
play important role in membrane flux recovery. Lee [104]
reported that in an experiment carried out using fouled UF
membrane cleaned with caustic chemical cleaning at low and
high cross-flow velocity, he found that the cleaning efficiency
increased at high cross-flow velocity compared to low cross-
flow velocity, for 1 h duration time [104]. On the other hand,
Bartlett et al. [86] noticed that an increase in cross-flow velocity
while cleaning seems to have minimal effect on membrane flux
fouled with whey protein, for 30 min. The main cause of min-
imal effect on flux recovery is attributed to the duration of the
cleaning and the effect of duration time will be explained in the
next section. The cleaning efficiency increased with increasing
cross-flow velocity when only the chemical reaction between the
foulant and cleaning agents has to be high enough to produce a
favorable reaction. Otherwise, an increase in cross-flow velocity
which result an increase in the shear rate dose not enhance the
mass transfer of foulant in the fouling layer to the bulk solution
[132]. It can be concluded that the chemical reaction between of
the cleaning agent with deposited foulants and associated mass
transfer phenomena are quite important in membrane cleaning
[132].
 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28 23

4.5.5. Cleaning duration
Hydraulic cleaning conditions, such as cleaning duration,
may play important role for flux recovery at actual plants. Longer
cleaning time at lower velocity was found more effective in
order to remove the NOM foulants from membrane surfaces
[104]. In some applications, a cleaning time for 15 min is enough
[134], while in other applications of membranes more time is
needed for cleaning about 1 h [135] or even longer to reach
their maximal cleaning effect in order to restore the membrane
performance [24]. In a recent study, Li et al., [110] noticed
that increasing cleaning time from 10 to 20 min for surfactant
(SDS, CTAB) had greater power on cleaning efficiency. Ang
et al., [132], in the case of RO membrane reported that, the
cleaning efficiency of EDTA increased dramatically when the
cleaning time increased from 15 to 60 min. the cleaning effi-
ciency of SDS at low concentration with cleaning time of 15
or 60 min was not incorrigible. In other words, a longer contact
time did not contribute to enhancing cleaning efficiency. Unless
there was a favorable chemical reaction between the foulant
and cleaning agents in the fouling layer there will be little to
reduce the foulant–foulant interaction [132]. The duration of
chemical cleaning at different operation conditions has not been
discussed to any depth in the literature. However, the few papers
on cleaning of NF membrane have been published up to date
suggest that shorter filtration cycles and hence more frequent
but longer cleaning procedures are beneficial as fouling layers

Fig. 15. Schematic representation for effective cleaning of organic-fouled RO membranes. Across-linked fouling layer is formed on the membrane surface in presence
of calcium ions, which bind to organic foulants and form bridges between adjacent foulant molecules. During cleaning, the cleaning agent reacts with the foulants
in the fouling layer yielding loosened foulants. These reaction products are removed from the fouling layer to the bulk solution through the hydrodynamics/mass
transfer. Thus, Efficient cleaning can be achieved through the coupling between the chemical reaction and mass transfer along with the optimization of cleaning
conditions responsible for the favourable chemical reaction and mass transfer [133].
24 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
become compact with time and are more difficult to remove
[24,78,133,134].
4.5.6. Cleaning frequency
Typical cleaning frequencies for full-scale nanofiltration sys-
tems treating ground water are 3 months to 2 years, with typical
an average of 6 months [112,116]. For surface water the range
may vary from once per week to once per 3 months. Cleaning
frequencies for full-scale nanofiltration system treating seawater
are in the range of 4–6 months [24]. Cleaning frequency plays
an important role in the lifetime of the membrane. Increasing
cleaning frequency could lead deterioration of the cross-linking
network of the membrane surface properties by making the
chemical interaction between the cleaning solution molecules
and surface functional groups of the membrane stronger [136].
Moreover, it has been noticed that cleaning processes often
increases the flux even of the virgin membrane by making the
pore more open or altering the membrane surface properties
[96,97,99].
The cleaning interval depends on the foulant amount on the
membrane surface which is indicated by the decrease in flux
or increase in operating pressure. The amount of cleaning is
therefore a function of cleaning duration and the frequency. A
combination of these factors can give widely varying method as
such need optimization.
4.5.7. Effect of temperature
The temperatures of the chemical cleaning solution may
also play an important role in chemical cleaning system. Gen-
erally increased temperature increases the cleaning efficiency
presumably by increasing transport processes and solubility of
the material. However, the sensitivity of membrane materials
usually prohibits the use of very high temperature. Gener-
ally, membrane manufacturers recommend chemical cleaning
should be carried out at lower than 45 ◦ C. Bartlett et al., noticed
that for the sintered stainless steel membrane and ceramic
membrane, further increases in temperature above the opti-
mum value reduced chemical cleaning efficiency [86]. Li et al.,
[110] reported that preheating the cleaning solution up to about
42 ◦ C had a significant impact on increased water flux recovery
compared to 25 ◦ C where increased cleaning temperature was
favorable for desorption of deposits from the membrane surface.
Chen et al., [133] noticed that one significant factor which can
affect chemical cleaning of both UF and RO membranes is the
cleaning temperature. Ang et al., [132] shown that, the cleaning
efficiency increased dramatically with increasing temperature
from 20 to 40 ◦ C in the case of RO membrane. Both the rate of
the chemical reaction of EDTA with deposited foulants and the
diffusive transport of foulant from the fouling layer to the bulk
solution increased as temperature was increased.
4.5.8. Effect of pressure
Operating pressure is often related to the hydrodynamics of
the system and should be maintained very carefully. Cleaning
is to be carried out a minimum pressure in order not onto force
the foulant layer onto the surface making it more adhesive. On
the other hand, Bartlett et al., [86] reported that ‘these results
demonstrate that any applied pressure during cleaning will not
result in maximum cleaning efficiency, while there is surface
deposits present. The same trend was observed by Sayed [134].
This topic was not covered well in literature and further exper-
iments are needed to find out the relationship of the operating
pressure on effectiveness of cleaning.
When reviewing the above major factors of NF membrane
cleaning efficiency, it is very important to understand that mem-
brane cleaning involves both chemical and physical interactions.
The relationship between the coupled effect of dissolution of
material from the membrane surface caused by chemical reac-
tions between the cleaning agents and the foulants and the
subsequent mass transfer of the dissolved or loosened foulant
materials into the bulk solution (Fig. 15) [132]. The effectiveness
of cleaning in terms of chemical reactivity depends on the type of
cleaning solution, cleaning solution pH, cleaning chemicals con-
centration and ionic strength while mass transfer of the foulant
from the fouling layer to the bulk solution was mainly controlled
by the cross-flow velocity and pressure, whereas cleaning time
and temperature affects both the mass transfer and chemical
reaction.
5. Discussion and conclusion
This review is focused on the types of membrane fouling
processes that lead to deterioration of the plant performance
and there subsequent recovery using membrane cleaning pro-
cesses. Different types of inorganic fouling and organic fouling
have been addressed in this study. Fouling problems lead to
higher operation costs, higher energy demand, reduce life time
of membrane and increasing cleaning frequency. Our work also
reveals that membrane chemical cleaning methods are widely
implemented in order to regenerate the membrane performance,
even though some cleaning methods have potential limitations.
The success of chemical cleaning methods depends on many
factors such as nature of the foulant type of cleaning agents,
temperature, pH, concentration of the cleaning chemicals, con-
tact time between the chemical solution and the membrane and
operation conditions such as cross-flow velocity and pressure.
These factors affect the outcome of the cleaning procedure and
therefore need thorough investigation in order to establish the
optimum cleaning system. Conventional assessment of cleaning
by flux measurement has been used in the last decades in order to
optimize and evaluate the cleaning procedures. At present there
are several modern surface analysis techniques that can assist
precisely and rapidly in optimizing the cleaning processes.
Fouling is a complex processes largely governed by empiri-
cal rules due to poor understanding of processes involved. The
main drawback is the poor prediction of fouling rate in the mem-
brane system as a result of limited understanding of the organic
fouling and the lack of knowledge concerning the NF module
operating conditions at which the crystallization or the scale pre-
cipitation associated with inorganic fouling occur. The use of
modern surface analysis is required to improve our understand-
ing on mechanisms of fouling or to closely understand how these
foulant materials get deposited on membrane surfaces. Never-
theless, it is fundamental to obtain the molecular basis of these
 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28 25

processes. More to the point, the use of AFM and other modern
technique can assist in reaching the target of understanding foul-
ing phenomena. The direct force measurement between micro-
scopic surfaces as function of distance in controlled environment
became possible with development of the surface force apparatus
[137]. The fabrication of AFM colloidal probe will undoubtedly
be used as one of the powerful technique for providing a deeper
understanding of membrane–fouling interaction process. It also
can be used to directly measure the interaction between surfaces
of different materials in various aqueous solutions and that can
assist particularly in understanding and addressing the complex-
ity of the fouling materials attachment, removal and movement
in and around the membrane surfaces [122].
In general, chemical cleaning is conducted mainly to remove Fig. 16. Venn diagram of factors influencing operational membrane processes.
the fraction of NOM foulant or to remove the scale formation
from NF membrane surfaces or to clean the NF membrane sur-
and changed membrane surface properties as well as membrane
faces from both of them in order to regenerate the membrane
surface functionality [95].
performance. There are two types of force that can be applied
Generally, modern surface analysis techniques can assist not
during cleaning, the adhesive force that keep the foulant on the
only in selecting the membrane materials with correct surface
membrane surface and a hydrodynamic shearing force required
properties during the membrane casting and grafting process, the
in removing the foulant from the membrane surface to the bulk.
aim being to avoid and/or reduce the foulant materials adhesion
However, in reality the dynamic process associated with move-
on the membrane surface. A better understanding membrane
ment of foulant material in and around the membrane surfaces
functionality in relation to adsorption–desorption phenomena
is critical during the cleaning processes.
on the membrane surface will also be obtained. Modern instru-
It is difficult to obtain clear strategies in both membrane
mentation will lead to a systematic more predictable view of the
design and avoidance of fouling. Nevertheless, there are several
fouling and cleaning processes. This understanding is funda-
ways to avoid the fouling of membranes and can be classified
mental to providing novel method and materials for membrane
into three groups: (i), changing operating conditions, (ii), mod-
manufacture, feed water conditioning and optimal operational
ification of the membrane and (iii), modification of the feed
systems. Manipulating membrane surface characteristics with
by adding antifoulants prior to filtration system (pretreatment)
chemical and physical aspect of feed water and operation con-
[66]. Until now these avoidance strategies do not stop the fouling
ditions can directly lead to optimized systems with minimized
on surface of the membrane, however, they reduce the fouling
fouling and (Fig. 16) effective cleaning systems.
rate on membrane surfaces and so reducing the frequency and
Extensive research work is certainly needed to investigate
duration of cleaning, both have substantial effect on membrane
and explore new ideas and techniques in the field of membrane
productivity and longevity.
cleaning and restoration. It is in the interest of the NF mem-
There are several chemical cleaning agents used directly to
brane industry that the importance of membrane cleaning be
remove foulant material and an understanding of the roles in
recognized and be addressed with more time and effort being
chemical has been developed. The broad mechanism of clean-
devoted to understand fouling mechanisms and develop more
ing agents have been inferred from the coupling effect of these
feasible cost-effective, cleaning and restoration procedures for
chemical reaction between the cleaning agents and the foulant
each type of fouling. Apart from this, new membranes which
and the mass transfer of the loosened foulant to the bulk and
avoid fouling have to be developed in order to reduce cleaning
this has lead to improve formulation. Indeed formulations of
processes and their costs. Fundamental parameters that affect the
cleaning agents have been developed for specific foulants.
condition of feed water treatment and operation of the membrane
The adsorption–desorption phenomena are very important
system are very important and have to be given more time sub-
in cleaning processes. The surface charge will not only be
sequently to prevent or reduce fouling and cleaning processes.
dependent on the coverage of foulants but also on adsorption
Physical and physio-chemical cleaning methods have not been
phenomena associated the use of cleaning agents. The adsorp-
given much needed emphasis in order to evaluate the effective-
tion phenomena of the cleaning agents are varying and depend
ness of these methods. These methods could be economically
on interaction between the membrane and the cleaning agent
attractive but need more investigation.
concentration. The precise chemistry and morphology of the
active membrane layer also significantly affect the adsorption
phenomena. The active layer of the membrane may consist of References
several sub-layers to give a complex composite structure that
can significantly alter rejection and adsorption properties of the [1] A. Al-Rewiali, et al., Performance Evaluation of SWCC SWRO Plants,
Research centre and development, Jubail, 2000, pp. 1–30.
surface. Indeed, the cleaning agent may change the membrane [2] T.G. Temperely, The Coming of Age of Desalination. in Proceeding of the
surface functionally by allowing chemical changer or by adsorp- IDA World Congress on Desalination and Water Sciences. 1995. United
tion onto the membrane surface so cause permanent modification Arab Emirates, Abu Dhabi: Abu Dhabi Publishing Co.
26 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
[3] T.A. Dabbagh, The Role of Desalination in Sustaining Economic Growth
in the Gulf”, Proceeding of the IDA World Congress on Desalination and
Water Sciences,. 1995. United Arab Emirates, Abu Dhabi: Abu Dhabi
Publishing Co.
[4] R.J. Petersen, Composite reverse osmosis and nanofiltration membranes,
J. Membr. Sci. 83 (1) (1993) 81–150.
[5] Manual, M.T., Manufacturers Technical Manual.
[6] M. Barger, R.P. Carnahan, Fouling prediction in reverse osmosis pro-
cesses, Desalination 83 (1–3) (1991) 3–33.
[7] D.E. Potts, R.C. Ahlert, S.S. Wang, A critical review of fouling of reverse
osmosis membranes, Desalination 36 (3) (1981) 235–264.
[8] P. Dydo, et al., The nucleation kinetic aspects of gypsum nanofiltration
membrane scaling, Desalination 164 (1) (2004) 41–52.
[9] W.R. Bowen, A.W. Mohammad, N. Hilal, Characterisation of nanofiltra-
tion membranes for predictive purposes—use of salts, uncharged solutes
and atomic force microscopy, J. Membr. Sci. 126 (1) (1997) 91–105.
[10] A.I. Schafer, A.G. Fane, T.D. Waite, Nanofiltration—Principle and Appli-
cations, Elsevier Advanced Technology, 2005, pp. 1–543.
[11] R.W. Field, et al., Critical flux concept for microfiltration fouling, J.
Membr. Sci. 100 (1955) 259–272.
[12] P. Bacchin, P. Aimar, R.W. Field, Critical and sustainable fluxes: theory,
experiments and applications, J. Membr. Sci. 281 (2006) 42–69.
[13] E. Van Houtte, et al., Treating different types of raw water with micro- and
ultrafiltration for further desalination using reverse osmosis, Desalination
117 (1–3) (1998) 49–60.
[14] G. Tchobanoglous, et al., Ultrafiltration as an advanced tertiary treat-
ment process for municipal wastewater, Desalination 119 (1–3) (1998)
315–321.
[15] J.J. Porter, Recovery of polyvinyl alcohol and hot water from the textile
wastewater using thermally stable membranes, J. Membr. Sci. 151 (1)
(1998) 45–53.
[16] K. Hagen, Removal of particles, bacteria and parasites with ultrafiltration
for drinking water treatment, Desalination 119 (1–3) (1998) 85–91.
[17] L. Vera, et al., Cross-flow microfiltration of biologically treated wastew-
ater, Desalination 114 (1) (1997) 65–75.
[18] S. Hong, M. Elimelech, Chemical and physical aspects of natural organic
matter (NOM) fouling of nanofiltration membranes, J. Membr. Sci. 132
(1997) 159–181.
[19] T.L. Champlin, Using circulation tests to model natural organic matter
adsorption and particle deposition by spiral-wound nanofiltration mem-
brane elements, Desalination 131 (1–3) (2000) 105–115.
[20] T.V. Knyazkova, A.A. Maynarovich, Recognition of membrane fouling:
testing of theoretical approaches with data on NF of salt solutions con-
taining a low molecular weight surfactant as a foulant, Desalination 126
(1–3) (1999) 163–169.
[21] H. Zhu, M. Nystrom, Cleaning results characterized by flux, streaming
potential and FTIR measurements, Colloids Surf. A: Physicochem. Eng.
Aspects 138 (2/3) (1998) 309–321.
[22] H. Vrouwenvelder, et al., Biofouling of membranes for drinking water
production, Desalination 118 (1998) 157–166.
[23] J. Vrouwenvelder, et al., Tools for fouling diagnosis of NF and RO mem-
branes and assessment of the fouling potential of feed water, Desalination
157 (2003) 361–365.
[24] A.S. Al-Amoudi, A.M. Farooque, Performance, restoration and autopsy
of NF membranes used in seawater pretreatment, Desalination 178 (2005)
261–271.
[25] B. Van der Bruggen, L. Braeken, C. Vandecasteele, Flux decline in
nanofiltration due to adsorption of organic compounds, Sep. Purif. Tech-
nol. 29 (1) (2002) 23–31.
[26] M.R. Wiesner, et al., Committee Report: membrane processes in potable
water, J. AWWA (1992) 59–64.
[27] D. Hasson, A. Drak, R. Semiat, Inception of CaSO4 scaling on RO mem-
branes at various water recovery levels, Desalination 139 (1–3) (2001)
73–81.
[28] K.A. Faller, Reverse osmosis and nanofiltration. in AWWA. 1999. Denver.
[29] A.G. Pervov, Scale formation prognosis and cleaning procedure sched-
ules in reverse osmosis systems operation, Desalination 83 (1–3) (1991)
77–118.
[30] S. Lee, J. Kim, C.-H. Lee, Analysis of CaSO4 scale formation mechanism
in various nanofiltration modules, J. Membr. Sci. 163 (1) (1999) 63–74.
[31] J. Gilron, D. Hasson, Calcium sulphate fouling of reverse osmosis
membranes: flux decline mechanism, Chem. Eng. Sci. 42 (10) (1987)
2351–2360.
[32] M. Alborzfar, G. Jonsson, C. GrOn, Removal of natural organic matter
from two types of humic ground waters by nanofiltration, Water Res. 32
(10) (1998) 2983–2994.
[33] S. Lee, C.-H. Lee, Effect of operating conditions on CaSO4 scale forma-
tion mechanism in nanofiltration for water softening, Water Res. 34 (15)
(2000) 3854–3866.
[34] Z. Amjad, J. Hooley, Influence of polyelectrolytes on the crystal growth
of calcium sulfate dihydrate, J. Colloid Interface Sci. 111 (2) (1986)
496–503.
[35] D.G. Troup, J.A. Richardson, Scale nucleation on a heat transfer surface
and its prevention, Chem. Eng. Commun. 2 (1978) 167–180.
[36] P.G. Klepetsanis, P.G. Koutsoukos, Precipitation of calcium sulfate dihy-
drate at constant calcium activity, J. Cryst. Growth 98 (3) (1989) 480–
486.
[37] X.-L. Wang, C. Zhang, P. Ouyang, The possibility of separating saccha-
rides from a NaCl solution by using nanofiltration in diafiltration mode,
J. Membr. Sci. 204 (1/2) (2002) 271–281.
[38] D.R. Kasper, Pre-and posttreatment processes for membrane water treat-
ment system membrane technology conference proceeding, Baltimor,
1993.
[39] T.H. Chong, S. Yuen, R. Sheikholeslami, Composite Fouling in Seawater
Desalination Precipitation of Calcium Sulfate and Calcium Carbonate,
School of chemical engineering and industrial chemistry, Sydney, 2004,
pp. 1–10.
[40] R. Sheikholeslami, Mixed salts—scaling limits and propensity, Desali-
nation 154 (2) (2003) 117–127.
[41] P. Dydo, M. Turek, J. Ciba, Scaling analysis of nanofiltration systems fed
with saturated calcium sulfate solutions in the presence of carbonate ions,
Desalination 159 (3) (2003) 245–251.
[42] T.H. Chong, R. Sheikholeslami, Thermodynamics and kinetics for mixed
calcium carbonate and calcium sulfate precipitation, Chem. Eng. Sci. 56
(18) (2001) 5391–5400.
[43] S.K. Hamdona, R.B. Nessim, S.M. Hamza, Spontaneous precipitation of
calcium sulphate dihydrate in the presence of some metal ions, Desalina-
tion 94 (1) (1993) 69–80.
[44] D.L. Kronmiller, What every reverse osmosis water system manager
should know, Desalination 98 (1–3) (1994) 401–411.
[45] A. Al-Amoudi, R.W. Lovitt, Natural organic matter (NOM) and scaling
fouling in NF membranes and its factors: a review, Desalination, in press.
[46] P. Fu, H. Ruize, Pilot plant study on ground water natural organic
removved by low pressure, Desalination 102 (1995) 47–56.
[47] A.R. Roudman, F.A. DiGiano, Surface energy of experimental and com-
mercial nanofiltration membranes: effects of wetting and natural organic
matter fouling, J. Membr. Sci. 175 (1) (2000) 61–73.
[48] M. Manttari, et al., Fouling effects of polysaccharides and humic acid in
nanofiltration, J. Membr. Sci. 165 (1) (2000) 1–17.
[49] B. Van der Bruggen, et al., Influence of molecular size, polarity and charge
on the retention of organic molecules by nanofiltration, J. Membr. Sci.
156 (1) (1999) 29–41.
[50] A.I. Schafer, A.G. Fane, T. Waite, Nanofiltration of natural organic matter:
Removal, fouling and the influence of multivalent ions, Desalination 118
(1998) 109–122.
[51] M. Elimelech, et al., Role of membrane surface morphology in colloidal
fouling of cellulose acetate and composite aromatic polyamide reverse
osmosis membranes, J. Membr. Sci. 127 (1997) 101–109.
[52] C.R. Bouchard, et al., Study of humic acid adsorption on nanofiltration
membranes by contact angle measurements, Can. J. Chem. Eng. 75 (2)
(1997) 339–345.
[53] K. Ghosh, M. Schnitzer, Macromolecular structures of humic substances,
Soil Sci. 129 (5) (1980) 266–276.
[54] A.I. Schafer, et al., Natural organic matter removal by nanofiltration:
effects of solution chemistry on retention of low molar mass acids versus
bulk organic matter, J. Membr. Sci. 242 (1/2) (2004) 73–85.
 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
[55] A.E. Childress, S.S. Deshmukh, Effect of humic substances and anionic
surfactants on the surface charge and performance of reverse osmosis
membranes, Desalination 118 (1–3) (1998) 167–174.
[56] A.E. Childress, M. Elimelech, Effect of solution chemistry on the surface
charge of polymeric reverse osmosis and nanofiltration membranes, J.
Membr. Sci. 119 (2) (1996) 253–268.
[57] M. Elimelech, W.H. Chen, J.J. Waypa, Measuring the zeta (electrokinetic)
potential of reverse osmosis membranes by a streaming potential analyzer,
Desalination 95 (3) (1994) 269–286.
[58] E. Suess, Interaction of organic compounds with calcium-carbonate. 2.
Organo-carbonate association in recent sediments, Geochimica Et Cos-
mochimica Acta 37 (11) (1973) 2435–2447.
[59] W. Yuan, A.L. Zydney, Humic acid fouling during microfiltration, J.
Membr. Sci. 157 (1) (1999) 1–12.
[60] W. Agui, et al., Removal of dissolved humic substances from water with
a reverse-osmosis membrane, Sci. Total Environ. 118 (1992) 543–550.
[61] C. Bellona, et al., Factors affecting the rejection of organic solutes during
NF/RO treatment—a literature review, Water Res. 38 (2004) 2795–2809.
[62] B. Van der Bruggen, et al., The use of nanofiltration for the removal of
pesticides from ground water: an evaluation, Water Sci. Technol. 1 (2001)
99–106.
[63] M.R. Wiesner, S. Chellam, The promise of membrane technologies, Env-
iron. Sci. Technol. 33 (17) (1999) 360A.
[64] L.F. Song, M. Elimelech, Particle deposition onto a permeable surface in
laminar-flow, J. Colloid Interface Sci. 173 (1) (1995) 165–180.
[65] AWWA membrane technology research committee, C.r., Membrane pro-
cesses in potable water treatment. J. AWWA, 1992. 84 (1): p. 59–67.
[66] I.l. Roux, et al., Use of chitosan as an antifouling agent in a membrane
bioreactor, J. Membr. Sci. 248 (1/2) (2005) 127–136.
[67] P.H. Given, Humic Substances in Soil, Sediment and Water,
Wiley–Interscience, New York, 1985, p. 692.
[68] J.A. Nilson, F.A. DiGiano, Influence of NOM composition on nanofiltra-
tion, J. Am. Water Works Assoc. 88 (5) (1996) 53–66.
[69] C. Jucker, M.M. Clark, Adsorption of aquatic humic substances on
hydrophobic ultrafiltration membranes, J. Membr. Sci. 97 (1994) 37–52.
[70] L. Braeken, et al., Influence of hydrophobicity on retention in nanofiltra-
tion of aqueous solutions containing organic compounds, J. Membr. Sci.
252 (1–2) (2005) 195–203.
[71] M.S. Caceci, A. Billon, Evidence for large organic scatterers (50–200 nm
diameter) in humic-acid samples, Organic Geochem. 15 (3) (1990)
335.
[72] W. Richard Bowen, et al., Atomic force microscope studies of membranes:
force measurement and imaging in electrolyte solutions, J. Membr. Sci.
126 (1) (1997) 77–89.
[73] T. Thorsen, Concentration polarisation by natural organic matter (NOM)
in NF and UF, J. Membr. Sci. 233 (1/2) (2004) 79–91.
[74] H.M. lappin-Scott, J.W. Costerton, Bactierial biofilms and surface foul-
ing, Biofouling 1 (1989) 323–342.
[75] H.C. Flemming, et al., Biofouling—the Achilles heel of membrane pro-
cesses, Desalination 113 (2/3) (1997) 215–225.
[76] H.F. Ridgway, H.C. Flemming, Membrane Biofouling in Water Treatment
Membrane Processes, McGraw Hill, New York, 1996.
[77] N. Hilal, et al., A comprehensive review of nanofiltration membranes:
treatment, pretreatment, modelling, and atomic force microscopy, Desali-
nation 170 (3) (2004) 281–308.
[78] A. Farooque, A. al-Amoudi, A.M. Hassan, Chemical cleaning experi-
ments for performance restoration of NF membranes operated on seawater
feed, in: IDA Conference, Bahrain, 2002.
[79] C. Shankararaman, et al., Effect of pretreatment on surface water nanofil-
tration, J. AWWA 10 (1997) 77–89.
[80] S. Bertrand, I. Lemaitre, E. Wittman, Performance of a nanofiltration
plant on hard and highly sulphated water during two years of operation,
Desalination 113 (1997) 277–281.
[81] M.H. Tran-Ha, D.E. Wiley, The relationship between membrane cleaning
efficiency and water quality, J. Membr. Sci. 145 (1998) 99–110.
[82] J.S. Taylor, E.P. Jacobs, Reverse osmosis and nanofiltration, chapter 9 in
water treatment membrane processes, ed. P.E.O.a.M.R.W.e. J. mallevialle,
1996, McGraw Hill.
27
[83] H. Huiting, J. Kappelhof, T. Bosklopper, Operartion of NF/RO plants
from reactive to proactive, Desalination 139 (2001) 183–189.
[84] A. Maartens, P. Swart, E.P. Jacobs, Feed-water pretreatment: methods to
reduce membrane fouling by natural organic matter, J. Membr. Sci. 163
(1) (1999) 51–62.
[85] A.H. Hassan, et al., Optimization of SWRO pre-treatment—Part I-SDI
measurement. in IDA World congress, 1995, Abu Dhabi.
[86] M. Bartlett, M.R. Birdl, J.A. howell, An experimental study for the devel-
opment of qualitative membrane cleaning model, J. Membr. Sci. 105
(1995) 147–157.
[87] V. Mavrov, et al., Desalination of surface water to industrial water with
lower impact on the environment. Part 2. Improved feed water pretreat-
ment, Desalination 110 (1/2) (1997) 65–73.
[88] A.M. Hassan, et al., A new approach to membrane and thermal sea-
water desalination processes using nanofiltration membranes (Part 1),
Desalination 118 (1–3) (1998) 35–51.
[89] B. Van der Bruggen, et al., Direct nanofiltration of surface water using
capillary membranes: comparison with flat sheet membranes, Sep. Purif.
Technol. 31 (2) (2003) 193–201.
[90] D. Chen, L.K. Weavers, H.W. Walker, Ultrasonic control of ceramic mem-
brane fouling: effect of particle characteristics, Water Res. 40 (4) (2006)
840–850.
[91] N.R.G. Walton, Reverse osmosis pretreatment-injecting a little chemical
control and management, Desalination 82 (1991) 281–300.
[92] G. Tragardh, 71 (1989) 325, Membrane cleaning Desalination, 1989. 71:
p. 325–334.
[93] S. Ebrahim, Cleaning and regeneration of membranes in desalination and
waste water applications, Desalination 96 (1994) 225–238.
[94] R.A. Bergman, Membrane softening versus lime softening in Florida: a
cost comparison update, Desalination 102 (1–3) (1995) 11–24.
[95] A. Al-Amoudi, et al., Cleaning results of new and fouled nanofiltration
membrane characterized by zeta potential and permeability, Sep. Purif.
Technol. 54 (2) (2007) 234–240.
[96] A. Wies, M.R. Bird, M. Nystrom, The chemical cleaning of polymeric
UF membranes fouled with spent sulphite liquor over multiple operational
cycles, J. Membr. Sci. 216 (2003) 67–79.
[97] K. KoSutic, B. Kunst, RO and NF membrane fouling and cleaning and
pore size distribution variations, Desalination 150 (2002) 113–120.
[98] M. Nystrom, H. Zhu, Characterization of cleaning results using combined
flux and streaming potential methods, J. Membr. Sci. 131 (1/2) (1997)
195–205.
[99] S.I. Graham, R.L. Reitz, C.E. Hickman, Improving reverse osmosis
performance through periodic cleaning, Desalination 74 (1989) 113–
124.
[100] M. Abdul-Kareem Al-Sofi, Seawater desalination—SWCC experience
and vision, Desalination 135 (1–3) (2001) 121–139.
[101] R. Osterberg, L. Szajdak, K. Mortensen, Temperature-dependent restruc-
turing of fractal humic acids—a proton-dependent process, Environ. Int.
20 (1) (1994) 77–80.
[102] I. Mooch, A 21st Century study of global seawater reverse osmosis oper-
ating and capital costs, in: IDA Conference, Singapore, 2003.
[103] A.M. Hassan, et al., Performance Evaluation of SWCC-SWRO Plants,
Research Center, Jubail, 2003, pp. 1–59.
[104] H. Lee, et al., Cleaning strategies for flux recovery of an ultrafiltra-
tion membrane fouled by natural organic matter, Pergamon 35 (2001)
3301–3308.
[105] G. Morel, et al., Surfactant modified ultrafiltration of nitrate ions removal,
J. Membr. Sci. 134 (1997) 47–57.
[106] Du-Pont Manual Hand Book.
[107] H. Seungkwan, M. Elimelech, Chemical and physical aspects of natural
organic matter (NOM) fouling of nanofiltration membranes, J. Membr.
Sci. 132 (1997) 159–181.
[108] J. Cho, et al., Characterization of clean and natural organic matter (NOM)
fouled NF and UF membranes and foulants characterization, Desalination
188 (1998) 101–108.
[109] R. Liikanan, J. Yli-Kuivila, R. Laukkanen, Efficiency of various chemical
cleanings for nanofiltration membrane fouled by conventionally-treated
surface water, J. Membr. Sci. 195 (1995) 265–276.
28 A. Al-Amoudi, R.W. Lovitt / Journal of Membrane Science 303 (2007) 4–28
[110] L. Xiufen, et al., Chemical cleaning of PS ultrafilters fouled by the fer-
mentation broth of glutamic acid, Sep. Purif. Technol. 42 (2005) 181–187.
[111] J. Warczok, et al., Concentaion of apple and paer juices by nanofiltration
at low pressures, J. Food Eng. 63 (2004) 63–70.
[112] A.M. Jacques, et al., Integrated multi-objective membrane systems for
surface water treatment: pre-treatment of nanofiltration by riverbank fil-
tration and conventional ground water treatment, Desalination 118 (1998)
239–248.
[113] W. Song, et al., Nanofiltration of natural organic matter with H2 O2 /UV
pretreatment: fouling mitigation and membrane surface characterization,
J. Membr. Sci. 241 (1) (2004) 143–160.
[114] G.S. Murthy, et al., Concentration of xylose reaction liquor by nanofiltra-
tion for the production of xylitol sugar alcohol, Sep. Purif. Technol. 44
(2005) 205–211.
[115] H.A. Fremont, et al., Membrane cleaning process and U.S.P., 1988.
[116] Q. Li, M. Elimelech, Organic fouling chemical cleaning of nanofiltration
membranes: measurements and mechanisms, Environ. Sci. Technol. 38
(17) (2004) 4683–4693.
[117] A.E. Childress, M. Elimelech, Relating nanofiltration membrane perfor-
mance to membrane charge (electrokinetic) characteristics, Environ. Sci.
Technol. 34 (17) (2000) 3710–3716.
[118] R. Liikanen, J. Yli-Kuivila, R. Laukkanen, Efficiency of various chemical
cleanings for nanofiltration membrane fouled by conventionally-treated
surface water, J. Membr. Sci. 195 (2) (2002) 265–276.
[119] G. Daufin, et al., Efficiency of cleaning agents for an inorganic membrane
after milk ultrafiltration, J. Dairy Res. 59 (1) (1992) 29–38.
[120] M.A. Arguello, et al., Enzymatic cleaning of inorganic ultrafiltration
membranes used for whey protein fractionation, J. Membr. Sci. 216 (1/2)
(2003) 121–134.
[121] K.-J. Kim, A.G. Fane, Performance evaluation of surface hydrophilized
novel ultrafiltration membranes using aqueous proteins, J. Membr. Sci.
99 (2) (1995) 149–162.
[122] W.R. Bowen, A. Teodora, G. Austin, The use of atomic force microscopy
to quantify membrane surface electrical properties, Colloids Surf. 201
(2002) 73–83.
[123] N. Hilal, W.R. Bowen, Atomic force microscope study of the rejection of
colloids by membrane pores, Desalination 150 (3) (2002) 289–295.
[124] W.R. Bowen, T.A. Doneva, Atomic Force Microscopy of Membrane,
Madison Avenue, New York, 2002.
[125] E.M. Vrijenhoek, S. Hong, M. Elimelech, Influence of membrane sur-
face properties on initial rate of colloidal fouling of reverse osmosis
and nanofiltration membranes, J. Membr. Sci. 188 (1) (2001) 115–
128.
[126] I. Larson, et al., Direct force measurements between TiO2 Surfaces, J.
Am. Chem. Soc. 115 (1993) 11885–11890.
[127] W.R. Bowen, et al., Atomic force microscope studies of membranes, in:
T.S. Sorensen (Ed.), Surface Chemistry and Electochemistry of Mem-
brane Surfaces, Surfactant Science Series, vol. Chapter 1, Marcel Dekker
Inc., 1999, pp. 1–37.
[128] W. Richard Bowen, T.A. Doneva, Atomic force microscopy studies of
nanofiltration membranes: surface morphology, pore size distribution and
adhesion, Desalination 129 (2) (2000) 163–172.
[129] K. Kontturi, M. Vouristo, Adsorption of globular proteins on polymeric
microfiltration membranes, Desalination 104 (1996) 99–105.
[130] M.D. Afonso, G. Hagmeyer, R. Gimbel, Streaming potential measure-
ments to assess the variation of nanofiltration membranes surface charge
with the concentration of salt solutions, Sep. Purif. Technol. 22/23 (2001)
529–541.
[131] T. Mohammadi, S.S. Madaeni, M.K. Moghadam, Investigation of mem-
brane fouling, Desalination 153–160 (2003) 155.
[132] W.S. Ang, S. Lee, M. Elimelech, Chemical hysical aspects of cleaning
of organic-fouled reverse osmosis membranes, J. Membr. Sci. 272 (1/2)
(2006) 198–210.
[133] J.P. Chen, S.L. Kim, Y.P. Ting, Optimization of membrane physical and
chemical cleaning by a statistically designed approach, J. Membr. Sci.
219 (1–2) (2003) 27–45.
[134] S.K. Sayed Razavi, J.L. Harries, F. Sherkate, Fouling and cleaning of
membranes in the ultrafiltration of the aqueous extract of soy flour, J.
Membr. Sci. 114 (1) (1996) 93–104.
[135] M.J. Munoz-Aguado, D.E. Wiley, A.G. Fane, Enzymatic and detergent
cleaning of a polysulfone ultra-filtration membrane fouled with BSA and
Whey, J. Membr. Sci. 117 (1996) 175–187.
[136] M. Chpman, Bench-scale testing of surfactant modified reverse osmo-
sis/nanofiltration membranes, J. Pellegrino A Zydney 115 (1998) 15–
32.
[137] J.N. Israelachvili, R.K. Tandon, L.R. White, Measurement of forces
between two mica surfaces in aqueous polyethylene oxide solution, J.
Colloid Interface Sci. 78 (2) (1980) 430–443.