Journal of Membrane Science 289 (2007) 231240

Pre-treatments to reduce fouling of low pressure

micro-filtration (MF) membranes
Rolando Fabris a, , Eun Kyung Lee b , Christopher W.K. Chow a ,
Vicki Chen b , Mary Drikas a
a

Co-operative Research Centre for Water Quality and Treatment, Australian Water Quality Centre,
SA Water Corporation, PMB 3, Salisbury, SA 5110, Australia
b UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering and Industrial Chemistry,
University of New South Wales Sydney, NSW 2052, Australia
Received 20 April 2006; received in revised form 27 November 2006; accepted 1 December 2006
Available online 8 December 2006

Abstract
Despite the fact that natural organic matter (NOM) is significantly smaller than the pore size of microfiltration (MF) membranes, fouling due
to organic compounds has emerged as a problematic issue for both potable water and wastewater membrane filtration. Pre-treatment of the feed
water can be a useful strategy for reduction or mitigation of these fouling effects. The aim of this investigation was to evaluate various combined
pre-treatment methods for reducing NOM fouling of laboratory scale micro-filtration (MF) membranes, including treatment with adsorbents such
as MIEX (MIEX is a registered trademark of Orica Australia Pty. Ltd.) and powdered activated carbon (PAC) as well as coagulation with
alum. High performance size-exclusion chromatography (HPSEC) was applied to determine molecular weight (MW) distribution and proved to
be a simple analytical technique, capable of detecting the onset of fouling by observation of the >50,000 Da colloidal peak in the water sources
examined. Results obtained showed that treatments that reduce the majority of bulk water dissolved organic carbon (DOC) of all MW ranges,
including colloidal (very high MW) material successfully prevented short-term fouling of MF, where treatments that removed most of the DOC
but did not remove the colloidal components, were unable to prevent fouling.
2007 Elsevier B.V. All rights reserved.
Keywords: Microfiltration; MIEX ; NOM; PAC; Fouling

1. Introduction
Fouling of membranes by natural organic matter is a significant issue for the efficiency of membrane filtration in both
potable and wastewater treatment systems. As membrane filtration has grown in prevalence, the issue of flux decline due
to fouling has determined the direction of significant research
in the field. While inorganic fouling is as much an issue, it is
the complex and often unknown composition of NOM and a
lack of understanding of the fouling mechanisms that has driven
the need for scientific investigation to address the causes and
possible means of mitigation.
Microfiltration (MF, pore sizes between 0.1 and 10 m) is
typically used as a clarification process for the removal of par-

Corresponding author. Tel.: +61 8 8259 0314; fax: +61 8 8259 0228.
E-mail address: rolando.fabris@sawater.com.au (R. Fabris).

0376-7388/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2006.12.003

ticulate material. This may be as a polishing step following a

conventional treatment or as a pre-treatment before a more retentive membrane process such as nanofiltration (NF) or reverse
osmosis (RO). It is worth noting that dissolved organic carbon (DOC) is not typically retained by MF due to the pore
sizes involved being much larger than component molecules;
however DOC is nevertheless involved in both short and long
term fouling. Research has shown that only a small portion of
the total NOM is responsible for irreversible fouling including
high molecular weight (MW) polysaccharides, colloidal material, low MW proteins and amino sugars [14], however highly
aromatic hydrophobic acids that make up the majority of typical
natural water NOM also cause significant flux decline through
reversible fouling [5]. Recent research has highlighted the influence of organic colloids in the fouling of MF membranes [610]
and shows that of the fractional components of NOM in a water
source, the colloids cause the most significant flux decline [9].
Colloidal fouling also appears independent of solution pH but

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R. Fabris et al. / Journal of Membrane Science 289 (2007) 231240

increases in the presence of divalent metal ions such as calcium

[9,10].
Strategies to reduce fouling can include reducing flux, careful membrane material selection and pre-treatment (coagulation,
adsorption). Reduction of the flux can in some cases prevent the
onset of fouling altogether, however in an application where a
target daily flux is required this will necessitate additional surface area (i.e. membrane modules) thereby increasing both the
plant footprint and capital cost. The benefits of longer filtration
cycles and less chemical cleaning may not justify the additional
expense in a purely economic sense but may become viable if
environmental sustainability is an important consideration [11].
Membrane materials will have a significant effect on the fouling
capacity for any particular compound as well as the reversibility. Many different polymer membranes are available with either
a hydrophilic or hydrophobic surface, thereby changing their
interaction with potential foulants [1,12]. The microstructure of
the membrane will determine the uniformity of the pore size
and also the resistance to fouling with track-etched membranes
having much greater resistance to fouling than sponge-like membranes with large pore openings and irregular pore size [13].
Pre-treatment of the process stream to either remove or
modify potential foulants is an effective method for reduction of flux decline and is usually easy to implement where
membrane filtration is retrofitted into an existing conventional
treatment plant. The most popular pre-treatment is coagulation/flocculation followed by either traditional rapid sand
filtration or direct filtration, where flocculated water is flowed
directly onto the membrane, forming a porous, low density cake
on the surface that is easily removed by scouring or backwashing
[1416]. It is generally accepted that reduction of overall DOC
reduces the potential for fouling, however remaining recalcitrant NOM may still be available to foul the membrane. Kimura
et al. [4] remarked that pre-coagulation alone does not mitigate
irreversible fouling, only reversible fouling. To remove these
additional recalcitrant components, other technologies must be
employed, such as oxidative or absorptive processes. While
there is extensive literature on the use of adsorbents to reduce
NOM levels, studies of the effects of adsorption treatments on
membrane fouling examine mostly activated carbon application [1722] and little on other adsorbents such as ion-exchange
resins [23]. In most cases, the carbon is applied directly within
the membrane reactor and may not provide sufficient contact
time to fully exploit the capacity of the carbon [24]. In addition, the accumulation of the carbon on the membrane surface
may create difficulties in partitioning the sources of any resultant
fouling [25]. Ease of implementation may also be a consideration with adsorbents such as activated carbon being the easiest to
add to an existing coagulation plant with minimal modification.
The aim of this investigation was to evaluate various pretreatment methods for reducing NOM fouling of MF membranes
for potable water treatment, focussed on combining adsorption
using magnetic ion exchange resin (MIEX ) with coagulation
using alum or adsorption with powdered activated carbon (PAC)
and varied combinations of all three. MIEX typically removes
DOC over a broad range of molecular weights while alum has
been shown to be effective for higher molecular weight com-

pounds [2628]. While most means of evaluating membrane

fouling are destructive or require the removal of the membrane from the system, it was hoped that the contributions of
various organic carbon species to the fouling could be evaluated using high performance size exclusion chromatography
(HPSEC) applied to the process stream waters.
2. Materials and methods
2.1. Source waters
Source waters chosen for this investigation were both well
characterised by the authors and also known to cause significant
fouling without treatment. Source waters were also selected to
provide low and high range levels of DOC to assess the impact on
pre-treatment and membrane fouling. The Myponga Reservoir
is located about 50 km south of Adelaide, Australia. The water
from Myponga Reservoir is sourced via surrounding catchment
and is generally considered a high colour and high DOC source
(62 Hazen units (HU) and 11.7 mg/L, respectively). Woronora
Dam, in contrast, is considered a low colour, low DOC source
water (3 HU and 2.2 mg/L, respectively) and is sourced from the
catchment area of the Woronora River, serving the residents of
Sydneys southern suburbs, NSW, Australia.
2.2. Pre-treatments
The combined treatments protocol (Fig. 1) was based on a
three-step treatment utilising adsorbent technologies and minimal chemical addition that was developed in a previous study
[29]. Magnetic ion exchange resin (MIEX ) is a macroporous
anion exchange resin specifically developed for the removal
of NOM in drinking water treatment. Detailed description is
available elsewhere [3032]. Jar tests were performed on a sixpaddle gang stirrer (SEM Pty. Ltd., Australia) in 2 l gator jars
(B-KER2 , Phipps & Bird, USA). Myponga Reservoir water
was treated with 10 mL/L of MIEX by stirring at 100 rpm
for 20 min. Settled water was decanted and filtered through an
11 m pore size filter (Whatman International, UK) to remove
resin fines. The filtered water was contacted with 40 mg/L

Fig. 1. Pre-treatment protocol for membrane fouling experiments.

R. Fabris et al. / Journal of Membrane Science 289 (2007) 231240

of a coal-based, steam-activated powdered activated carbon

(PAC) (PICA, Australia) by stirring at 100 rpm for 30 min. A
20,000 mg/L Al2 (SO4 )3 18H2 O solution was used to dose coagulant at 40 mg/L to flocculate the PAC and/or the remaining
natural water turbidity. For coagulation treatment, samples were
flash mixed at 200 rpm for 1 min followed by 14 min of slow
mixing at 25 rpm and 15 min of settling before samples were
gravity filtered through 11 m pore size paper filters (Grade 1,
Whatman International Ltd., UK). MIEX contacted water was
also coagulated without prior PAC treatment. For all combined
treatments, the treated water was filtered through an 11 m pore
size filter to remove remaining MIEX and/or PAC, thereby
minimising any further adsorption before the membrane experiments could commence. Samples were taken at the intermediate
treatment steps to enable partitioning of the contribution to the
fouling of remaining NOM components.

233

shown in Fig. 2. The flat sheet configuration consisted of a deadend cell containing a 0.22 m pore size hydrophilic flat PVDF
membrane (GVWP from Millipore) with 15.2 cm2 area. The cell
was operated in unstirred mode at 30 kPa. The pure water flux
for the flat sheet membrane at 30 kPa was 1974 59.3 L/(m2 h)
(65.8 1.98 L/(m2 h kPa)). The submerged hollow fibre (SHF)
module consisted of 10 fibres (30 cm length) of 0.2 m pore
size hydrophilic PVDF (US Filter), potted in-house. The lower
end of the bundle was fixed and blocked while suction was
applied in the lumen of the fibres from the top of the bundle. At 100 L/(m2 h), the measured transmembrane pressure
(TMP) was 0.62 0.02 kPa for pure water (161.3 L/(m2 h kPa)).
In both configurations, the TMP and flux were monitored using
a pressure transducer and an electronic balance connected to a
computer.
2.4. Instrumental analyses

2.3. Membrane congurations

A flat sheet and a hollow fibre submerged configuration were
utilized in the experiments. Schematics of the filtration set-up are

Analysed parameters included turbidity, true colour, ultraviolet absorbance at 254 nm (UV254 ), DOC, molecular weight
distribution by high performance size exclusion chromatography

Fig. 2. Schematic of (a) dead-end unstirred filtration set-up in constant pressure and (b) submerged hollow fibre filtration set-up in constant flux.

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R. Fabris et al. / Journal of Membrane Science 289 (2007) 231240

(HPSEC) and scanning electron microscopy (SEM). Turbidity was determined using a Hach 2100AN turbidimeter (Hach,
USA) and is expressed in nephelometric turbidity units (NTU).
Samples for true colour, UV254 and DOC were filtered through
0.45 m membranes. True colour was measured using a 5 cm
quartz cell at 456 nm and calibrated against a Platinum/Cobalt
standard [33]. UV254 was measured through a 1 cm quartz cell
and DOC was measured using a Sievers 820 Portable TOC
analyser (Ionics, USA). HPSEC was analysed using a Waters
Alliance 2690 separations module and 996 photodiode array
detector (PDA) at 260 nm (Waters Corporation, USA). Phosphate buffer (0.1 M) with 1.0 M NaCl was flowed through a
Shodex KW802.5 packed silica column (Showa Denko, Japan)
at 1.0 mL/min. This column provides an effective separation
range from approximately 100 Da to an exclusion limit of
50,000 Da. Apparent molecular weight was derived by calibration with poly-styrene sulphonate (PSS) molecular weight
standards of 35, 18, 8 and 4.6 kDa. Electron microscopy was
performed using a Hitachi S900 field emission scanning electron
microscope (Hitachi Science Systems, Japan).
2.5. Membrane fouling
The fouling behaviour of membrane filtration can be
described by the resistance-in-series model, which is based on
Darcys law. For constant pressure filtration, the resistance-inseries model is expressed as:
J=

P
(Rm + Rf )

(1)

where J is the filtrate flux, P the transmembrane pressure, the

permeate viscosity, Rm the membrane resistance, and Rf is the
total foulant resistance. Rf is the sum of hydraulically reversible
(Rrev ) and irreversible (Rirrev ) fouling resistances:
Rf = Rrev + Rirrev

(2)

The resistance of a clean membrane was determined by filtering pure water until steady state was attained. The feed was
then changed to pre-treated water and the filtrate flow rate was
monitored in order to determine Rf . At the end of filtration, the
filtration cell was emptied and the membrane was gently rinsed
in situ three times with 50 mL of pure water to remove the concentration polarisation layer contributing to reversible fouling

only, while avoiding significant disturbance of the NOM fouling

layer. The pure water flux of the membrane was then re-evaluated
for the determination of irreversible foulant resistance. Rf treat is
defined as the calculated total foulant resistance of the treated
water.
3. Results and discussion
3.1. Pre-treated water quality
When comparing water quality data for the various pretreatments (Table 1), it is clear that MIEX was very effective
as a primary treatment for colour, UV absorbance and DOC
removal. Although initial water turbidity was not high for
either water source, treatments that reduced turbidity to around
0.1 NTU in both source waters included alum coagulation, as
the absorbents are largely incapable of turbidity removal and
in some cases (especially PAC) increase the visually apparent
treated water turbidity prior to filtration. Reported reductions
(Table 1) in turbidity for the adsorbent treatments were predominantly due to the subsequent filtration step, as partitioning of
the adsorbents and natural water turbidity was not practically
feasible. Coarse (11 m) filtration was also deemed necessary
to the pre-treatment procedures as the focus of the investigation was not to observe the effects of particles and DOC, as
in direct or contact microfiltration, but rather the more isolated
effects of the dissolved organic species on fouling of MF membranes. Full combined treatment produced treated water with
less than 1.0 mg/L DOC for both Myponga and Woronora source
water (>80% DOC removed). It is worth noting that despite
large differences in both DOC and traditional water quality
parameters, both Myponga Reservoir and Woronora Dam water
had been shown to produce significant short term fouling of
MF membranes. Both waters also contained detectable quantities of very high MW colloidal NOM. This multi-component
peak, seen at the exclusion limit of the column (50,000 Da), is
believed to be composed of some NOMmetal complexes [28]
and complex amino sugars from bacterial cell walls and other
biological sources [34,35]. The organo-metallic complexes are
usually indicative of low residence time in the catchment, which
prevents significant natural photo-oxidation or biodegradation,
and are not generally detected following conventional treatment
or extended storage. The amino sugar component however, has

Table 1
Treated water quality parameters for pre-treated Myponga Reservoir and Woronora Dam
Sample

Code

pH

Turbidity (NTU)

Colour (HU)

UV254 (cm1 )

DOC (mg/L)

Myponga Raw
Myponga MIEX
Myponga MIEX /Alum
Myponga MIEX /PAC
Myponga MIEX /PAC/Alum

MR
MM
MMA
MMP
MMPA

7.8
6.9
6.5
7.3
6.6

1.95
0.66
0.12
0.24
0.14

65
6
1
2
0

0.432
0.054
0.037
0.013
0.007

11.7
3.4
2.8
1.0
0.9

Woronora Raw
Woronora MIEX
Woronora MIEX /Alum
Woronora MIEX /PAC
Woronora MIEX /PAC/Alum

WR
WM
WMA
WMP
WMPA

6.7
6.5
4.8
6.6
4.7

0.69
0.28
0.07
0.25
0.07

3
1
2
1
0

0.035
0.013
0.021
0.005
0.005

2.2
1.2
1.1
0.4
0.4

R. Fabris et al. / Journal of Membrane Science 289 (2007) 231240

235

Fig. 3. Pre-treatment DOC molecular weight distributions by HPSEC for Myponga Reservoir. Code: R, Raw; M, MIEX ; A, Alum; P, PAC.

generally proved to be more difficult to remove. For the purposes

of this paper, colloidal material is defined as the component of
the source water organic matter of apparent molecular weight
greater than 50,000 Da that is detectable by UV absorbance.
MIEX treatment reduced a broad range of UV-absorbing
components (Figs. 3 and 4), especially high and medium MW
DOC (100010,000 Da) but was not effective for very high MW
colloidal NOM. Coagulation with alum removed the remaining high MW NOM and all detectable colloidal material. PAC
removed low to medium MW DOC (3001000 Da) when used
after MIEX contact but little additional colloidal material. Typically it is observed that most absorbents are ineffective for
removal of colloidal components. This could be explained by
their inability to take dissolved colloidal material into the pore
structure due to physical size, as well as possible stearic hindrance on the adsorbent surface.

3.2. Flat sheet fouling experiments

The foulant resistance as a function of permeate volume is
shown in Fig. 5 for raw and treated waters. For the untreated
waters, Myponga water being higher in colour and DOC fouls
the membrane more readily than Woronora water. The MIEX
treatment of Woronora water resulted in detrimental filtration
performance. The broken MIEX resin fines in the sub-micron
range may not have been completely removed by the 11 m
post-treatment filtration and interacted with NOM to form a
dense NOM-MIEX cake layer, resulting in the higher Rf than
raw water. The MIEX treated Myponga water, in contrast,
resulted in reduced fouling compared to the raw water. The
greater foulant load with regards to the untreated Myponga water
may have masked any additional fouling from MIEX fines.
The ratio (Rf treat /Rf ) is plotted against (Rf ) and summarizes the

Fig. 4. Pre-treatment DOC molecular weight distributions by HPSEC for Woronora Dam. Code: R, Raw; M, MIEX ; A, Alum; P, PAC.

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R. Fabris et al. / Journal of Membrane Science 289 (2007) 231240

Fig. 5. Fouling profile (foulant resistance) vs. permeate volume of (a) untreated
and treated Myponga Reservoir water and (b) untreated and treated Woronora
Dam water. Code: R, Raw; M, MIEX ; A, Alum; P, PAC.

benefits of multiple pre-treatment in terms of reduced foulant

resistance in Fig. 6. For this investigation, Rf treat is defined as
the total foulant resistance at a permeated volume of 1000 mL
of pre-treated water. A ratio (Rf treat /Rf ) of less than 1.0 indicates
the relative benefit of treatment in terms of reduced fouling.
Comparison with the observations of the molecular weight
distribution by HPSEC showed that MF alone had no effect
on molecular weight components in the 3008000 Da range
that encompassed the majority of the UV absorbance (data not
shown). This was entirely expected as these components are too
small to be retained by a 0.2 m pore size membrane. However,
examination of the >50,000 Da response consistently showed a
decrease with increasing permeate volume (Figs. 7 and 8). While
the designated 500 and 1000 mL samples were both representative of specific time periods during the filtration, the permeate

and retentate samples were collected at the termination of the

experiment and therefore represent averaged water quality. This
means that they contain material from both before, and after the
onset of fouling. In interpretation of the fouling behaviour of the
various pre-treated waters, observation of the molecular weight
distribution would tend to propose two fouling theories. Either
the colloidal material is directly involved in the membrane fouling and therefore becomes less abundant in the permeate with
increasing volume filtered, or the membrane fouling by other
components causes increased retention of the colloidal material. Both theories are valid if based only on the HPSEC data,
however TMP increases were only apparent in treated waters
where the colloidal material was still present indicating that the
colloidal DOC was directly involved in the short-term fouling
observed. This further confirms the findings of Lee et al. and
Chen et al. [6,36]. The data presented in Figs. 7 and 8 also show
that in most cases, the amount of colloidal DOC detected in
the permeate exceeded the amount in the retentate. This phenomenon can also be explained by the proposed fouling theory.
While the colloidal DOC in the permeate is distributed throughout the solution, following the onset of fouling, the majority of
colloidal DOC in the retentate is immobilised on the surface of
the membrane (fouling layer) and is therefore less abundant in
the bulk aqueous solution.
Waters pre-treated with MIEX + alum showed greatly
reduced membrane fouling in parallel with high removal of
colloidal DOC. This is supported by SEM of the membrane surface after fouling and washing (Fig. 9) which shows the surface
foulants are clearly reduced with pre-treatment and that alum
provided a significant improvement. In comparing coagulation
and MIEX pre-treatment for ultrafiltration, Son et al. [37] also
observed that MIEX was less effective for reduction of fouling
due to lesser removal of high MW organic matter. For the treatments that included PAC, some residual particulates from PAC
can also be seen which is consistent with the obtained resistance
data and the work of Matsui et al. [24] with submicrometre PAC
on microfiltration. After washing of the membrane surface to
remove retained material and the filter cake (Table 2), the amount
of fouling material in absolute terms was clearly reduced,
however the reversible component as a percentage of the original resistance decreased with pre-treatments despite an overall
decrease in total resistance. This suggests that although several
Table 2
Percentages of reversible resistance after flat sheet filtration

Fig. 6. Foulant resistance benefit analysis of pre-treatments for Myponga (M)

and Woronora (W) water (ratio < 1.0 is a benefit). Code: R, Raw; M, MIEX ;
A, Alum; P, PAC.

Sample

Code

Rf treat (1/m)

%Rf reversible

Myponga Raw
Myponga MIEX
Myponga MIEX /Alum
Myponga MIEX /PAC
Myponga MIEX /PAC/Alum

MR
MM
MMA
MMP
MMPA

1.15 1012
5.16 1011
4.20 109
1.05 1011
7.22 109

60.9
46.4
44.6
53.9
21.5

Woronora Raw
Woronora MIEX
Woronora MIEX /Alum
Woronora MIEX /PAC
Woronora MIEX /PAC/Alum

WR
WM
WMA
WMP
WMPA

4.68 1011
6.73 1011
7.71 109
1.55 1011
8.74 109

44.8
42.9
72.6
31.6
33.9

Rf , foulant resistance; Rf treat , foulant resistance at 1000 mL permeated volume.

R. Fabris et al. / Journal of Membrane Science 289 (2007) 231240

237

Fig. 7. Impact of flat-sheet micro-filtration fouling on retention of high molecular weight colloidal NOM using (a) Myponga Reservoir water, (b) Myponga MIEX
treated water and (c) Myponga MIEX and PAC treated water.

pre-treatments were very effective for reduction of short term,

surface fouling (cake formation), there still remains some pore
blocking constituents that can contribute to longer term fouling.
Treatment of both water sources with MIEX + PAC + alum
showed higher Rf treat than MIEX + alum treatments alone
(Table 2). This indicates that at high levels of treatment, the benefit of removing additional low MW organic material by PAC
may be overweighed by the detrimental effects of PAC fines
in short term fouling of MF. Similarly, for a low DOC water
source like Woronora, the detrimental effect of MIEX resin
fines on the fouling may be more significant than the reduction
of DOC due to the treatment. This highlights the need to tailor
pre-treatment strategies for an individual water source.
3.3. Submerged hollow bre experiments
For the submerged hollow fibre experiments at 100 L/(m2 h),
the waters that were analysed were both untreated source waters,
the MIEX + alum treated and MIEX + PAC + alum treated
waters. It was intended that the SHF experiments would test if
the successful treatments from the flat-sheet experiments would

also prevent fouling in a more practical application and at higher

fluxes. Pre-treatments that failed to prevent short term fouling in
the flat-sheet experiments were not applied. For the two treated
water conditions, the set flux was maintained at the same TMP
for the duration of the filtration (2.5 L, 4 h), indicating that the
treated waters failed to foul the hollow fibre bundle. The accumulated filtration resistances at a permeated volume of 1000 mL are
shown in Fig. 10. The observed fouling behaviour during SHF
filtration was similar to that of dead-end unstirred cell filtration
at constant pressure shown in the previous section. However,
the fouling resistances were less. One reason may be that the
higher fluxes obtained with constant pressure filtration (approximately 300 L/(m2 h)) in the flat sheet configuration produced
more fouling.
As a result, it can be assumed that the low fouling potential of
the applied treated waters extended to volumes and fluxes greater
than those applied to the flat-sheet fouling experiments. The raw
source water experiments were both terminated after 1.5 L of
the planned 2.5 L total volume of water was filtered as applied
increases in TMP were unable to maintain the desired flux due
to the onset of fouling. HPSEC scans of the colloidal peak reveal

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R. Fabris et al. / Journal of Membrane Science 289 (2007) 231240

Fig. 8. Impact of flat-sheet micro-filtration fouling on retention of high molecular weight colloidal NOM using (a) Woronora Dam water, (b) Woronora MIEX
treated water and (c) Woronora MIEX and PAC treated water.

Fig. 9. Electron microscopy of Woronora (W) and Myponga (M) flat-sheet membrane after fouling and rinsing. Code: R, Raw; M, MIEX ; A, Alum; P, PAC.

R. Fabris et al. / Journal of Membrane Science 289 (2007) 231240

239

Fig. 10. Transmembrane pressure (TMP) during submerged hollow fibre (SHF) filtration of (a) Myponga Reservoir and (b) Woronora Dam water. Code: R, Raw;
M, MIEX ; A, Alum; P, PAC.

Fig. 11. Impact of submerged hollow fibre microfiltration fouling on retention of high molecular weight colloidal NOM using (a) Myponga Reservoir water and (b)
Woronora Dam water.

that by the 1000 mL sampling point, retention of colloidal material was very high in both raw water sources with low levels in the
permeate (Fig. 11). The pre-treatment with MIEX + alum and
MIEX + PAC + alum, successfully prevented short-term fouling of microporous SHF. The addition of PAC treatment slightly
increased the fouling resistance as was also observed in the flat
sheet experiments; however, the SEMs of flat sheet membranes
indicate that the presence of PAC fines may contribute to this
additional resistance.
4. Conclusion
In the application of the combined treatment protocol, it was
expected that the removal of selective components of the source
organic matter by the various treatment steps would allow the
effects of the residual organic material on fouling of MF to
be more easily observed. It was shown that treatments that
reduced the majority of bulk water DOC of all MW ranges,

including colloidal (very high MW) material (MIEX + Alum,

MIEX + PAC + Alum) successfully prevented short-term fouling of MF, where as treatments that removed most of the
DOC (MIEX + PAC) but did not remove the colloidal components, were unable to prevent fouling. HPSEC proved to be
a non-destructive analytical technique, capable of detecting a
significant contributor to membrane fouling by observation of
the >50,000 Da colloidal organic material in the water sources
examined. Although it cannot provide sufficient information to
be used exclusively in the evaluation of membrane fouling, the
ability to apply HPSEC analysis to an operating system without removal of the membrane makes it potentially attractive as
a monitoring method.
References
[1] L. Fan, J.L. Harris, F.A. Roddick, N.A. Booker, Influence of the characteristics of natural organic matter on the fouling of microfiltration membranes,
Water Res. 35 (18) (2001) 44554463.

240

R. Fabris et al. / Journal of Membrane Science 289 (2007) 231240

[2] B. Kwon, S. Lee, J. Cho, H. Ahn, D. Lee, H.S. Shin, Biodegradability

DBP formation and membrane fouling potential of natural organic matter:
characterisation and controllability, Environ. Sci. Technol. 39 (3) (2005)
732739.
[3] N. Her, G. Amy, H.R. Park, M. Song, Characterizing algogenic organic
matter (AOM) and evaluating associated NF membrane fouling, Water Res.
38 (6) (2004) 14271438.
[4] K. Kimura, Y. Hane, Y. Watanabe, Effect of pre-coagulation on mitigating irreversible fouling during ultrafiltration of a surface water, Water Sci.
Technol. 51 (67) (2005) 93100.
[5] L. Fan, J. Harris, F. Roddick, N. Booker, Fouling of microfiltration membranes by the fractional components of natural organic matter in surface
water, Water Sci. Technol.: Water Supply 2 (56) (2002) 313320.
[6] V. Chen, A.G. Fane, S. Madaeni, I.G. Wenten, Particle deposition during
membrane filtration of colloids: transition between concentration polarization and cake formation, J. Membr. Sci. 125 (1) (1997) 109122.
[7] A.I. Schafer, A.G. Fane, T.D. Waite, Fouling effects on rejection in the
membrane filtration of natural waters, in: Proceedings of the Conference
on Membranes in Drinking and Industrial Water Production, vol. 1, October
2000, Desalination Publications, LAquila, Italy, 2000, ISBN 0-86689-0602, pp. 411420.
[8] B. Kwon, S. Lee, M.B. Gu, J. Cho, Minimisation of membrane organic
fouling and haloacetic acids formation by controlling amino sugars and/or
polysaccharide-like substances included in colloidal NOM, Water Sci.
Technol.: Water Supply 3 (5) (2003) 223228.
[9] N. Lee, G. Amy, J.-P. Croue, Low-pressure membrane (MF/UF) fouling
associated with allochthonous versus autochthonous natural organic matter,
Water Res. 40 (12) (2006) 23572368.
[10] A.R. Costa, M.N. de Pinho, M. Elimelech, Mechanisms of colloidal natural
organic matter fouling in ultrafiltration, J. Membr. Sci. 281 (12) (2006)
716725.
[11] K. Parameshwaran, A.G. Fane, B.D. Cho, K.J. Kim, Analysis of microfiltration performance with constant flux processing of secondary effluent,
Water Res. 35 (18) (2001) 43494358.
[12] T. Thorsen, Concentration polarisation by natural organic matter (NOM)
in NF and UF, J. Membr. Sci. 233 (12) (2004) 7991.
[13] H.H.P. Fang, X. Shi, Pore fouling of microfiltration membranes by activated
sludge, J. Membr. Sci. 264 (12) (2005) 161166.
[14] T. Leiknes, H. Odegaard, H. Myklebust, Removal of natural organic matter
(NOM) in drinking water treatment by coagulation-microfiltration using
metal membranes, J. Membr. Sci. 242 (12) (2004) 4755.
[15] M.-H. Cho, C.-H. Lee, S. Lee, Influence of floc structure on membrane
permeability in the coagulation-MF process, Water Sci. Technol. 51 (67)
(2005) 143150.
[16] A.W. Zularisam, A.F. Ismail, R. Salim, Behaviours of natural organic matter
in membrane filtration for surface water treatmenta review, Desalination
194 (13) (2006) 211231.
[17] M. Pirbazari, V. Ravindran, B.N. Badriyha, S.-H. Kim, Hybrid membrane filtration process for leachate treatment, Water Res. 30 (11) (1996)
26912706.
[18] K. Konieczny, G. Klomfas, Using activated carbon to improve natural water
treatment by porous membranes, Desalination 147 (1) (2002) 109116.
[19] C.-W. Li, Y.-S. Chen, Fouling of membrane by humic substance: effect of
molecular weight and powder-activated carbon (PAC) treatment, Desalination 170 (1) (2004) 5967.
[20] S. Mozia, M. Tomaszewska, A.W. Morawski, Studies on the effect of humic
acids and phenol on adsorption-ultrafiltration process performance, Water
Res. 39 (23) (2005) 501509.

[21] P. Zhao, S. Takizawa, H. Katayama, S. Ohgaki, Factors causing PAC

cake fouling in PAC-MF (powdered activated carbon-microfiltration) water
treatment systems, Water Sci. Technol. 51 (67) (2005) 231240.
[22] R. Thiruvenkatachari, W.-G. Shim, J.-W. Lee, R.B. Aim, H. Moon, A novel
method of powdered activated carbon (PAC) pre-coated microfiltration
(MF) hollow fiber hybrid membrane for domestic wastewater treatment,
Colloids Surf. A: Physicochem. Eng. Aspects 274 (13) (2006) 2433.
[23] S. Khirani, P.J. Smith, M.-H. Manero, R.B. Aim, S. Vigneswaran,
Effect of periodic backwash in the submerged membrane adsorption
hybrid (SMAHS) for wastewater treatment, Desalination 191 (13) (2006)
2734.
[24] Y. Matsui, R. Murase, T. Sanogawa, N. Aoki, S. Mima, T. Inoue, T.
Matsushita, Rapid adsorption pretreatment with submicrometre powdered
activated carbon particles before microfiltration, Water Sci. Technol. 51
(67) (2005) 249256.
[25] H.-N. Jang, D.-S. Lee, M.-K. Park, S.-Y. Moon, S.-Y. Cho, C.-H. Kim, H.S. Kim, Effects of the filtration flux and pre-treatments on the performance
of a microfiltration drinking water treatment system, Water Sci. Technol.:
Water Supply 6 (4) (2006) 8187.
[26] C.W.K. Chow, J.A. van Leeuwen, M. Drikas, R. Fabris, K.M. Spark, D.W.
Page, The impact of the character of natural organic matter in conventional
treatment with alum, Water Sci. Technol. 40 (9) (1999) 97104.
[27] M. Drikas, C.W.K. Chow, D. Cook, The impact of recalcitrant organic
character on disinfection stability, trihalomethane formation and bacterial
regrowth: an evaluation of magnetic ion exchange resin (MIEX ) and alum
coagulation, J. Water Supply Res. Technol. Aqua 52 (7) (2003) 475487.
[28] B.P. Allpike, A. Heitz, C.A. Joll, R.I. Kagi, G. Abbt-Braun, F.H. Frimmel,
T. Brinkmann, N. Her, G. Amy, Size exclusion chromatography to characterize doc removal in drinking water treatment, Environ. Sci. Technol. 39
(7) (2005) 23342342.
[29] R. Fabris, C.W.K. Chow, M. Drikas, Combined treatments for enhanced
natural organic matter (NOM) removal, in: Proceedings of the Enviro 06
Conference, Melbourne, Australia, 911th May, 2006, paper e6174, CDROM and www.enviroaust.net/e6/papers/e6174.pdf.
[30] C. Chow, D. Cook, M. Drikas, Evaluation of magnetic ion exchange resin
(MIEX ) and alum treatment for formation of disinfection by-products
and bacterial regrowth, Water Sci. Technol.: Water Supply 2 (3) (2002)
267274.
[31] P.C. Singer, K. Bilyk, Enhanced coagulation using a magnetic ion exchange
resin, Water Res. 36 (16) (2002) 40094022.
[32] J.Y. Morran, M. Drikas, D. Cook, D.B. Bursill, Comparison of MIEX
treatment and coagulation on NOM character, Water Sci. Technol.: Water
Supply 4 (4) (2004) 129137.
[33] L.E. Bennett, M. Drikas, The evaluation of colour in natural waters, Water
Res. 27 (7) (1993) 12091218.
[34] J.A. Leenheer, Comprehensive assessment of precursors, diagenesis, and
reactivity to water treatment of dissolved and colloidal organic matter,
Water Sci. Technol.: Water Supply 4 (4) (2004) 19.
[35] G. Makdissy, J.-P. Croue, G. Amy, H. Buisson, Fouling of a polyethersulfone ultrafiltration membrane by natural organic matter, Water Sci.
Technol.: Water Supply 4 (4) (2004) 205212.
[36] N. Lee, G. Amy, J.-P. Croue, H. Buisson, Identification and understanding
of fouling in low-pressure membrane (MF/UF) by natural organic matter
(NOM), Water Res. 38 (20) (2004) 45114523.
[37] H.J. Son, Y.D. Hwang, J.S. Roh, K.W. Ji, P.S. Sin, C.W. Jung, L.S. Kang,
Application of MIEX pre-treatment for ultrafiltration membrane process
for NOM removal and fouling reduction, Water Sci. Technol.: Water Supply
5 (5) (2005) 1524.