Journal of Membrane Science 492 (2015) 164172

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Journal of Membrane Science

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

Performance of an integrated granular media Ultraltration

membrane process for drinking water treatment
Wenzheng Yu n, Nigel J.D. Graham
Department of Civil and Environmental Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ, UK

art ic l e i nf o a b s t r a c t

Article history: The accumulation of residual coagulant ocs and microbial substances on the surface of ultraltration
Received 18 March 2015 (UF) membranes are major contributors to membrane fouling that reduces process performance.
Received in revised form Previous approaches to reduce fouling (e.g. addition of an oxidant or disinfectant) have been only
17 May 2015
partly successful in reducing the formation of a cake layer and material deposits within membrane
Accepted 18 May 2015
Available online 6 June 2015
pores. In this study the performance of an integrated granular media UF membrane process has been
evaluated in which a hollow-bre UF module was embedded within a sand layer in order to prevent
Keywords: fouling material reaching the UF surface (forming a cake layer). The evaluation involved comparing two
Ultraltration laboratory-scale UF systems, operated in parallel for 74 days, with one incorporating the sand layer
Sand layer
(CSUF, coagulation-sand layer ltration-ultraltration), and the other without (CUF, coagulation-
Membrane fouling
ultraltration), serving as a reference conventional process. The results showed that the incorporation
Coagulation
Water treatment of the sand layer successfully prevented the formation of any signicant cake layer on the membrane
surface and substantially reduced inner membrane fouling, which lead to a much reduced trans-
membrane pressure (TMP) increasing rate. The difference in performance was principally attributed to
microbial growth and the release of extracellular polymeric substances (EPS) which was much greater in
the conventional CUF system. Thus, in the CUF system, the deposition of coagulation ocs (consisting of
precipitated nano-scale primary particles) and bacteria on, and within, the membrane produced
substantial reversible and irreversible fouling. In contrast, the deposited material (ocs) in the sand
layer of the CSUF system was easy to be washed away, resulting in fewer bacteria in the sand layer, and a
much reduced production of biopolymer and other EPS, and their accumulation by the UF membrane.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction
Membrane technology has been developed and applied exten-
sively in drinking water treatment, but difculties still remain in
its use and particularly with regard to membrane fouling. Pre-
treatment involving chemical coagulation or coagulationhydrau-
lic occulation has been shown to be an effective and low-cost
approach, not only to improve general water quality, but also to
control membrane fouling [1,2], such as by the use of polyalumi-
num chloride [3].
However, unseparated ocs, or those formed after the coagula-
tion process, will approach the surface of the membrane and form
a cake layer, and many experimental studies and practical opera-
tions have indicated that cake layer formation is the main cause of
membrane fouling [46]. As well as the direct physico-chemical
effect of ocs, the presence of bacteria on the surface of the ocs or
n
Corresponding author. Tel.: 44 2075946121; fax: 44 2075945934.
E-mail addresses: w.yu@imperial.ac.uk (W. Yu),
n.graham@imperial.ac.uk (N.J.D. Graham).
near the membrane surface, may induce membrane fouling after a
long period of operation through the release and accumulation of
extracellular polymeric substances (EPS) in the cake layer or
membrane pores. It has been shown that the increased adsorption
of EPS onto a membrane results in a signicant decrease in
permeate ux, and EPS production may inuence sludge deposi-
tion (and the attachment rate) and subsequently affect the
biofouling propensity of the membrane [7,8]. It has also been
observed that the accumulation of biopolymer clusters in the
sludge mixture of a membrane bioreactor (MBR) facilitates the
formation of a sludge fouling layer on the membrane surface, thus
causing serious fouling [9]. Furthermore, as the thickness of the
bio-cake grows, an anoxic and endogenous environment may
develop in the lower parts of the bio-cake layer, ultimately leading
to cell lysis and release of polysaccharides [10,11].
Therefore, the removal of ocs more effectively before they
reach and attach to the membrane surface, and/or the avoidance of
a cake layer developing, should mitigate membrane fouling.
Several methods/treatments prior to membrane ltration have
been investigated and reported in the literature recently. One
method involved changing the characteristics of the membrane

http://dx.doi.org/10.1016/j.memsci.2015.05.032
0376-7388/& 2015 Elsevier B.V. All rights reserved.
 W. Yu, N.J.D. Graham / Journal of Membrane Science 492 (2015) 164172
surface, such as through modication of the membrane surface
with anti-adhesion and anti-bacteria properties [1214], as well as
by use of a quorum quenching enzyme (acylase) and fungal
inoculation on the membrane surface [15,16]. A second approach
was to change the characteristics of the ocs, such as by adding
anionic coagulant aids [17], and polyelectrolytes [5] and occu-
lants [18,19], as well as through controlling residence times
[20,21]. A third approach is that of removing established cake
layers, such as by adding suspended carriers [22,23], moving
media [24] and support media [25]. In addition, providing a
sufcient supply of oxygen [10,26], gas bubbling [27] and the use
of ultrasound [28] have been proposed as alternative methods.
To-date there have been very few investigations of the benets
of UF membrane pre-treatment by ltration, and the ndings of
these are contradictory. One recent study reported that pre-
ltration alone (without pre-coagulation) improved ultraltration
performance, as indicated by a ux increase and reduction of
fouling rate [29], whereas an earlier study [30], also without pre-
coagulation, found that pre-ltration (1.5 m pores glass-bre
lters) had little effect on ultraltration. A further study showed
that either slow sand ltration, or coagulation, before ultraltra-
tion could mitigate membrane fouling [31]. A novel alternative
process involving the combination of coagulation and ultraltra-
tion within a sand bed has not been considered previously and this
approach is the subject of the study reported here. In this
arrangement the conventionally separate stages of oc sedimenta-
tion, deep bed sand ltration and UF membrane can be combined
into a single treatment unit process, thereby saving land area and
capital cost. In addition, the direct contact between the sand layer
and the UF membrane can fundamentally change the nature of the
external and internal accumulation of deposits that cause mem-
brane fouling. Thus, this paper summarizes some preliminary
results of a laboratory study of the performance of a UF membrane
placed within a sand layer receiving coagulated model water,
particularly in terms of reducing external and internal membrane
fouling. The results have shown that the novel arrangement, while
simple, can substantially improve the UF membrane performance.
The sand layer appears to concentrate coagulant ocs, EPS and
other pollutants before the membrane, thereby reducing the rate
of membrane fouling.
2. Materials and methods
2.1. Synthetic raw water and coagulant
A synthetic raw water was used for the tests in order to
simplify the study and provide sample consistency and reprodu-
cibility. A small quantity of settled waste water was added to the
local (London, United Kingdom) tap water with a volumetric ratio
of 1:50, as well as 5 mg/L humic acid (International Humic Acid
Substance Society, USA), to represent a micro-polluted raw water.
Table 1
Water qualitya of raw water and UF inuentsb/ltrates.
Parameter Raw water CUF inuent
UV254 (cm  1) 0.117 70.018 0.053 7 0.016
DOC (mg/L) 4.805 70.423 3.1797 0.325
Turbidity (NTU) 6.13 70.56 2.05 7 0.18
SS (mg/L) 4.2 70.8 47.2 7 3.2
Al (mg/L) 0.009 70.003 0.083 7 0.012
NH4 N (mg/L) 0.282 70.103 0.0777 0.018
NO3 N (mg/L) 5.43 70.22 5.65 7 0.17
pH 8.15 70.06 7.79 7 0.09
a
The values shown in table are averages for all the measurements taken every 7 days (10 times).
b
Inuent within membrane tank, immediately after occulation units.
165
The settled waste water and humic acid can represent types of
organic matter which are typically difcult and easy to be
removed by coagulation, respectively, and the waste water pro-
vides bacteria representative of surface water contaminated by
microorganisms from efuent discharges. Prior to mixing with the
waste water and humic acid solution, the tap water was left over
night to ensure the complete decay of residual chlorine. The
characteristics of the synthetic raw water are listed in Table 1.
During the course of the experimental program the temperature of
the water was maintained at 2072 1C (room temperature).
2.2. The UF treatment systems
A schematic illustration of the experimental set-up involving
the coagulation-UF processes with and without a sand layer
(CSUF/CUF) around the submerged membrane module (dead end
mode), operated in parallel, is given in Fig. S1 (Supporting
information). Synthetic raw water was fed into a constant-level
tank to maintain the water head for the membrane tanks. An
optimal dose of Al2(SO4)3 coagulant (0.15 mM, calculated as Al)
was continuously added into the rapid mixing units; the alum
dose corresponded to near zero zeta potential of resulting ocs.
The rapid mix speed was 200 rpm (184 s  1) in the mixing units
with a hydraulic retention time (HRT) of 1 min, which then
reduced to 50 rpm (23 s  1) in the three occulation tanks, each
having a HRT of 5 min. After the occulation tanks the ow passed
directly into the membrane tanks. Each tank contained a sub-
merged polyvinylidene uoride (PVDF) hollow-ber UF membrane
module (Tianjin Motimo Membrane Technology Co. Ltd, China)
with a nominal pore size of 0.03 m and a surface area of 0.025 m2
(inner diameter0.7 mm, and outer diameter 1.1 mm). For the
CSUF tank, the membrane module was placed within a sand layer
(sand size is around 0.5 mm), retained by a stainless steel mesh
(pore size is 0.256 mm), such that the ow passed through the
sand (approximately 1 cm deep) before ultraltration.
The UF permeate was continuously collected by a suction pump
at a constant ux of 20 L/(m2 h), operated in a cycle of 30 min
ltration and 1 min backwash (40 L m  2 h  1). For each backwash,
air was supplied to each reactor immediately below the membrane
modules at 100 L/h (air: water 200:1). The HRT of the membrane
tanks was maintained at 0.5 h and accumulated sludge was
released every 3 days. The integrity of the sand layer was
unaffected by the routine backwashing throughout the experi-
mental period as the backwash rate was very low, and the aeration
only contacted the outer surface of the sand layer, held by the
stainless steel mesh. During the 74 days of the CUF/CSUF opera-
tion, the CUF membrane was taken out and washed by sponge on
two occasions, at day 35 and day 59; while for the CSUF process
only one cleaning operation was required (day 59), which involved
removing the UF membrane from the sand layer and subsequent
washing of the sand (similar to the backwashing of sand lters in
CSUF inuent CUF ltrate CSUF ltrate
0.050 70.010 0.048 7 0.006 0.0457 0.008
2.929 70.283 3.0577 0.246 2.792 7 0.198
1.98 70.21 0.0770.03 0.067 0.03
36.8 7 2.2
0.037 70.011 0.0727 0.022 0.032 7 0.008
0.064 70.019 0.0427 0.019 0.034 7 0.022
5.71 70.13 5.687 0.23 5.747 0.26
7.7770.04 7.78 7 0.05 7.80 7 0.04
166 W. Yu, N.J.D. Graham / Journal of Membrane Science 492 (2015) 164172
conventional water treatment plants); more details of the cleaning
are provided in the supporting information.
2.3. Extraction and measurements of EPS from cake layer and sludge
At the end of the UF operation, the fouled membrane modules
were taken out from the membrane tanks. The foulant materials
on the membrane surface (cake layer) or in the sand layer were
carefully scraped off with a plastic sheet, and analyzed by the
following methods to characterize the contents of external mem-
brane fouling. The ocs/sludge in the sand layer was washed and
separated by 1 min ultrasound. The extraction of internal fouling is
described later.
A heating and extraction method [32] was modied to extract
the loosely bound EPS (LB-EPS) and tightly bound EPS (TB-EPS)
from the cake layer, sand layer and sludge, and to make sure the
EPS was not released from bacterial cells. Sludge suspension and
cake layers were rst dewatered by centrifugation (Model 5417C,
Eppendorf, Germany) in a 20-mL tube at 3000g for 5 min. The
concentrate liquor was recovered for water quality analysis. The
sludge pellet in the tube was re-suspended in 10 mL phosphate
buffer saline (PBS) solution, and the sludge suspension was then
ultrasonically treated (Nusonics, USA) for 1 min (0.8 W/cm2).
Without any delay, the suspension was then sheared by a vortex
mixer (Vortex- Genies 2, Mo Bio laboratories, Inc., USA) for
15 min, followed by centrifugation at 3000g for 10 min. The
organic matter in the supernatant was readily extractable EPS,
and was regarded as the LB-EPS of the biomass. For extracting the
TB-EPS, the sludge pellet left in the centrifuge tube was re-
suspended in PBS solution to its original volume (10 mL), ultra-
sonically treated for 3 min, and heated to 80 1C in a water bath for
30 min. Then the mixture was centrifuged at 10,000g for 15 min.
After the membrane surface was wiped with a sponge,
0.01 mol/L NaOH was used for extraction of internal foulants and
the bers were soaked for 24 h at 20 1C in the alkaline solution
according to the method described by Kimura et al. [20] and Yu
et al. [33]. The extracted organic matter was then subjected to the
following chemical analyses.
The absolute polysaccharide content in the bound EPS (LB-EPS
plus TB-EPS) was measured by the phenolsulfuric acid method
with glucose as the standard [34]. A modication of the Bradford
method [35] called the Coomassie procedure (Pierce Chemical),
was used to quantify the absolute concentration of proteins, with
bovine serum albumin (Sigma) as the standard. Polysaccharide
and protein concentration were measured at least three times.
2.4. EEM and SEC
EPS extracted from the cake layer and sludge was also mea-
sured by three-dimensional excitation-emission matrix (EEM)
uorescence spectrometry and size exclusion chromatography
(SEC). Fluorescence measurements were conducted using a spec-
trouorometer (PerkinElmer, LS 55, USA) at an ambient tempera-
ture of 25 1C. Further details of the method can be found in
previous research reported elsewhere [36,37].
As suggested by Myat et al. [38], SEC-UV254 might be used to
identify aggregated biopolymers, combined with other character-
ization techniques. SEC was carried out to determine the apparent
molecular weight (MW) distribution of UV-active substances in
the waters from the two systems, as well as the organic matter
(EPS) extracted from the cake layers and sludges. SEC was
performed using a BIOSEP-SEC-S3000 column (Phenomenex, UK)
(7.8 mm  300 mm) as well as the Security Guard column xed
with a GFC-3000 disc 4 mm (ID). A solution of 10 mM sodium
acetate (Aldrich, USA) was used as the mobile phase. Analysis
using High Performance Size Exclusion Chromatography (HPSEC)
was achieved on the HPLC system (Perkin-Elmer, USA) using the
following instrumentation: Series 200 pump, UV/vis detector
operated at a wavelength 254 nm and autosampler. The ow
rate was set at 1 mL/min, and the injection volume of water
samples was 100 L. Prior to operation, the mobile phase was
purged at a volumetric ow rate of 2 ml/min in order to clear any
residual and wash out the column of any contaminants. Polystyr-
ene sulfonate (PSS) standards (American Polymer Standard Corp.,
U.S.) of molecular weights 33,500, 14,900, 6530, and 1100 Da. were
employed to calibrate the relationship between the MW and the
retention time.
2.5. Other analytical methods
Fouled membrane bers were cut from the two membrane
modules, and the foulant layer attached on the membrane surface
was retained on the membrane surface. The fouled membrane
samples were then platinum-coated by a sputter and observed
under high resolution eld emission gun scanning electron micro-
scope (FEGSEM, LEO Gemini 1525, Germany). Also, the nature of
the materials on the fouled membranes was analyzed by Fourier
Transform infrared spectroscopy (FTIR, Spectrum 400, PerkinEl-
mer, USA) with Quest ATR Accessory (SPECAC Ltd, UK).
The UV absorbance at 254 nm, UV254, of 0.45 m ltered
solutions was determined by an ultraviolet/visible spectrophot-
ometer (U-3010, Hitachi High Technologies Co., Japan). Dissolved
organic carbon (DOC) was determined with a total organic carbon
(TOC) analyzer (TOC-VCPH, Shimadzu, Japan). Residual aluminum
after 0.45 m membrane ltration was measured by inductivity
coupled plasma optical emission spectrometer (ICP-OES, Optima
7300 DV, PerkinElmer, USA). Residual turbidity measurements
(Hach 2100, USA) were made for samples in the two membrane
tanks. The concentrations of NH4 N and NO3 N were determined
by the APHA standard colorimetric/spectrometry methods [39],
and the concentrations of bacteria were determined as the
Heterotrophic Plate Count (HPC) by the recommended method
involving the use of yeast extract agar [40].
3. Results and discussion
3.1. TMP developments in CUF and CSUF systems
As the membrane ux was xed at a constant value (20 L/
m2 h), membrane fouling was indicated by the increase in TMP.
The comparative increase in TMP for the CUF and CSUF streams are
shown in Fig. 1. There was no detectible, additional pressure loss
caused by the 1 cm sand layer in the CSUF system at the start of
process operation, as expected at such a low ltration rate.
Comparing the two types of pretreatment, the additional preltra-
tion by the sand layer after coagulation produced a membrane
fouling rate that was substantially lower than that of only
coagulation pre-treatment. In particular, the initial (rst 15 days)
increase in TMP of the CUF membrane was rapid (15 kPa), while
there was no measurable increase for the CSUF membrane.
Subsequently, although there was an increase of TMP in the CSUF
system, the increase was dramatically slower than that of the CUF
system. Thus, before the CUF membrane required washing (at day
35), the rate of TMP increase of the CUF membrane was nearly ve
times that of the CSUF membrane, indicating the signicance of
membrane protection (oc capture) by the 1 cm sand layer.
After physical cleaning of the CUF membranes (membrane was
taken out and cleaned by high pressure tap water) at day 35 and
day 59, a much greater initial TMP was found (6.5 kPa and 7.5 kPa),
which may be related to the difculty of removing the cake layer
on the CUF membrane, and other organic contaminants.
 W. Yu, N.J.D. Graham / Journal of Membrane Science 492 (2015) 164172 167

22
14
21 Raw water
12 2.0 Humic acid
Wash CUF effluent

UV254 adsorbance (mV)

20 CSUF effluent

Temperature ( C)
10 Wash

o
100
TMP (kPa)

19 1.5 Building
8 CUF 80 Biopolymer
CSUF
blocks
18 60
6 Temperature
Sand 1.0 40
Low MW
4 Wash 17 20
organic matter
0
2 16
0.5 1000000 100000 10000

0 15
0 10 20 30 40 50 60 70 80 A

Time (Day) 0.0

1000000 100000 10000 1000 100 10
Fig. 1. Variation of TMP with different pretreatment conditions over a period of
approximately 74 days (20 L m  2 h  1) (In the UF ltration experiments, the Molecular Weight (Dalton)
membrane ux of the CUF and CSUF streams were both set at a constant value of
20 L m  2 h  1 in a cycle of 30 min ltration/1 min water backwash (40 L m  2 h  1);
2000
CUF membrane was washed by sponge at day 35 and day 59; the sand layer around
the CSUF membrane was washed at day 59, but there was no sponge wash for the
membrane).

Bacteria concentration (mL )

1500

Furthermore, in addition to some residual cake layer on the
surface of the membrane, there may have been blockage of the
pores by other materials, causing the greater degree of irreversible
membrane fouling. In marked contrast, the increase in TMP of the
CSUF membrane over the 59 days of operation was only 2.2 kPa.
Washing of the sand layer at day 59 resulted in a much lower TMP
(1.7 kPa). In this case it was assumed that the low membrane
fouling was mainly caused by the residual ocs in the sand layer
after the long operation time, and with only minor internal
membrane fouling. Throughout the period of operation the water
temperature increased no more than 2 1C, which was not signi-
cant to the process performance.
In summary, it was evident that the internal and external
membrane fouling in the CUF process was much greater than the
CSUF process. In view of this enhanced performance arising from
the pre-ltration with the sand layer, further detailed investiga-
tion was undertaken concerning the nature of the ocs in the sand
layer and cake layer, and the extent of bacterial activity in the two
membrane systems.
3.2. Organic matter and bacteria concentration in membrane tanks
As established in our previous research results, a low amount of
precipitate solids of coagulants cause little membrane fouling [41].
Instead, the activities of bacteria and the inuence of organic
matter are believed to be the main factors of fouling, including the
role of EPS. The EPS in the cake layer may transfer to the
membrane pores after a long operation time, as well as from the
feed water.
Size exclusion chromatograms (molecular weight) of the cor-
responding samples were produced to further characterize the
dissolved organic matter (DOM) (Fig. 2a). The MW distributions
obtained from the chromatograms displayed signicant differ-
ences in the feed and efuent samples (there was little difference
between tank samples and efuent samples), particularly in the
range of large molecules identied as biopolymers. As previously
reported, part of the EPS can be removed by the coagulation
process [42]. However, the residual EPS was higher in the CUF tank
than that in CSUF tank. Some similar results indicated by EEM
analysis can be found in the supporting information (Fig. S2). The
EPS properties can be linked to the microbial community and its
activity [43], and thus the higher EPS concentration in the CUF
-1
1000
500
0
Raw water Tank Tank Effluent Effluent
CUF CSUF CUF CSUF
Fig. 2. MW distributions of DOM (a), and bacteria concentrations (b), in the two
membrane systems at day 50.
indicated that the activity of bacteria in the CUF was greater than
in the CSUF.
The presence of viable bacteria (HPC) was investigated for the
two membrane systems and was found to increase in both
membrane tanks as the period of operation increased (Fig. 2b).
Although the total bacteria concentration increased in both mem-
brane tanks, it was much lower in the CSUF tank. The result
showed that the ocs were difcult to adhere in the sand layer
than onto the membrane surfaces, which caused fewer bacteria to
be present on the surface of particles (ocs) in the CSUF mem-
brane tank as the backwash process can remove retained ocs in
each backwash cycle. These results clearly indicated that a higher
concentration of EPS was produced by greater bacterial activity in
the CUF tank.
As drinking water sources are often polluted by NH4 , such as in
China [44], its removal efciency was also discussed here.
Although there were some differences between the bacteria
concentration in the two systems, there were little differences in
NH4 transformation between them (Table 1). Nearly all NH4
appeared to be converted to NO3 in both membrane tanks, with
very low concentrations of NH4 in the efuent water, which
indicated that the bacterial concentration was sufciently high to
transfer NH4 to NO3 in the two systems. Therefore, the existence
of the sand layer did not change the transformation efciency of
NH4 to NO3 (Table 1), and both processes were able to treat the
NH4 effectively.
168 W. Yu, N.J.D. Graham / Journal of Membrane Science 492 (2015) 164172

3.3. EPS in the cake layer and sand layer
The information from SEC analyses was also used to characterize
the EPS of the sludge/ocs from the CSUF sand layer and the CUF
cake layer (Fig. 3), and different peaks were analyzed according to
the approach used by Huber et al. [45]. It can be seen that the LB-
EPS biopolymers (105104 Da) in the CUF cake layer were much
greater than the ocs/sludge from the sand layer (Fig. 3a). These
results suggest that there were low levels of bacteria present in the
sand layer ocs, which in turn produced low concentrations of
biopolymer. In contrast, greater bacteria concentrations developed
in the CUF cake layer as the process operation proceeded, leading to
greater quantities of EPS. The results were consistent with the
section 2.3, fouling material from within the membranes were
extracted by NaOH and analyzed by EEM and SEC. In addition, the
membranes after washing by sponge were examined by FTIR
spectroscopy.
The characteristics of EEM uorescence spectra of internal
membrane foulants were slightly different from those of the
external foulants, as indicated in Fig. 5(a) and (b). Peaks A and C
represent humic acid type materials, which is consistent with the
0.010

Protein concentration (g/g SS)

impact of the regular removal of ocs/sludge from the CSUF sand 0.008
layer during the back wash process, where the solids were easier to
be removed than the cake layer on the CUF membrane surface. 0.006
Also the results given in Fig. 3b conrmed that the concentra-
tion of TB-EPS with MW larger than 500 Da was much higher in
the cake layer from the CUF system than the sand layer ocs of the 0.004
CSUF system, especially for the MW range between 104 and 105.
These results indicate again that a higher concentration of EPS was
0.002
produced by greater bacterial activity in the CUF cake layer.
Therefore, the existence of high concentrations of EPS may result
in their escape from the cake layer and entry into the membrane 0.000
pores, causing both external and internal membrane fouling. CUF CUF CSUF flocs CSUF
In addition to the SEC method for EPS measurement, the cake layer sludge in sand layer sludge
absolute concentration of EPS was also measured in the cake layer
and sludge (protein and polysaccharides). Comparing the EPS
0.10
Polysaccharides concentration (g/g SS)

content in the sludge and cake layer/sand layer of the two systems,
the amount of total protein in the CUF cake layer was substantially
higher (approximately twice) than that in the CUF sludge and the
0.08
CSUF sludge and sand layer (Fig. 4), indicating the accumulation of
proteins within the membrane cake throughout the operating
period (note that sludge was removed from the membrane tanks 0.06
every 3 days). The variation of polysaccharide quantities extracted
from the cake layer, sand layer ocs and sludges in the two
membrane systems was very similar to that of protein, with the 0.04
greatest concentration present in the CUF cake layer. Overall, the
results further conrmed the correspondence between the higher 0.02
EPS concentration (proteins and polysaccharides) in the CUF cake
layer and the greater extent of external membrane fouling.
0.00
3.4. Internal membrane fouling CUF CUF CSUF flocs CSUF
cake layer sludge in sand layer sludge
As well as the existence of external fouling, the development of Fig. 4. The concentration of protein (a) and polysaccharide (b) in the cake layer
internal fouling was also investigated in this study. As described in (CUF), sand layer (CSUF), and sludges of the membrane tanks.

1.0 30
Humic acid Building
0.9 blocks
UV254 adsorbance (mV)
UV254 adsorbance (mV)

CUF cake layer 25

0.8
CSUF flocs in sand layer Low MW
0.7
20 organic matter
Humic acid
0.6
0.5
15
0.4 Building
blocks
0.3 Biopolymer Low MW 10
0.2 organic matter Biopolymer
0.1 5 CUF cake layer
0.0 CSUFflocs in sand layer

-0.1 0
1000000 100000 10000 1000 100 10 1000000 100000 10000 1000 100 10 1
Molecular Weight (Dalton) Molecular Weight (Dalton)
Fig. 3. MW distributions of (a) LB-EPS and (b) TB-EPS extracted from the cake layer of CUF or ocs retained in the sand layer of CSUF (methods can be found in Section 2.3).
 W. Yu, N.J.D. Graham / Journal of Membrane Science 492 (2015) 164172 169

450 450
3 3 2
2 22 2
4 2
Excitation Wavelength (nm)
4 2
6
7

Excitation Wavlength (nm)

400 3
5 4
6 400 5
45 9
15 8 4 12
4 5 6 5
7
C C
5
48 6 6 350 237 65 7
350
3 8
76 7 B 14 11
10 6
5 10
5 4 13 A 4 3 8 A B11
2 12
300 3 15 300 2 11
1 15 5 10
1 T1 2 1 T1 4
1
1
3
250 250

200 200
250 300 350 400 450 500 550 250 300 350 400 450 500 550
Emission Wavelength (nm) Emission Wavelength (nm)

18
Humic acid 1.4
new membrane
16 CUF CSUF membrane
1.2
UV254 adsorbance (mV)

CSUF CUF membrane

14
Absorbance 1.0
12
10 Building 0.8
blocks 0.6
8
Biopolymer Low MW
6 0.4
organic matter
4 0.2
2
0.0
0
-0.2
1000000 100000 10000 1000 100 10 2000 1800 1600 1400 1200 1000 800 600
-1
Molecular Weight (Dalton) Wavelength (cm )
Fig. 5. EEM uorescence spectra of inner membrane fouling for CUF (a) and CSUF (b) (peak values shown expressed in absorbance units); MW distributions of DOM (c) and
FTIR spectra (d) of the two membranes.

humic acid present in the raw water [33]. From the EEM uores- 1640 and 1542 cm  1 may correspond to CQO and NH bonds
cence spectra of the two fouled membranes (Fig. 5a and b), there [46], and although they increased for both membranes, the
was a very low intensity of peak T1 (protein-like material) evident increase level was much lower for the coagulation-sand layer
from the inner membrane fouling material compared to the much ltration pretreatment (CSUF). The organic matter contained
greater intensities for the humic-like substance peaks (C and A). CQO bonds, such as carboxylic acid, may complex with Al
The occurrence of peak B is believed to be from the overlapping of (OH) and adsorbed in the membrane pores. Also the NH peak
peaks A and C as was evident in the material of both membranes. may be ascribed to proteinaceous material adsorbed in the
The intensity of all three principal peaks (A, C and T1) in the CSUF membrane pores, produced by bacteria (within the EPS). In
membrane pores was much lower than that from the CUF contrast, the intensities of PVDF absorption peaks at 763, 870,
membrane, which was consistent with the accumulation of less 1016, 1174, and 1400 cm  1 corresponding to CF2 and CH2 chemical
humic-like materials and EPS in the CSUF membrane. bonds are reduced in the two membrane systems, most likely
The SEC results also clearly indicated that less organic matter through adsorption of organic substrates [47]. It is evident from
was retained or adsorbed in the CSUF membrane pores, compared Fig. 5d that the decrease of the peaks for the coagulation-sand
to the CUF system, with a lower concentration of biopolymer and layer ltration pretreatment was much less than for only coagula-
humic-like materials (Fig. 5c). The higher concentration of EPS, as tion pretreatment, which meant that more organic substrate was
well as humic-like materials, in the CUF was consistent with the adsorbed on the CUF membrane. These results further show the
higher internal fouling resistance, indicated by the greater TMP benet of the sand ltration process in reducing the adsorption
development of the CUF system observed (Fig. 1). These results and accumulation of organic contaminants within the membrane
conrmed that the presence of the sand layer in the CSUF system pores (internal fouling).
lead to a much reduced cake layer, and consequently signicantly
less EPS and humic acid was adsorbed within the membrane 3.5. SEM images of fouled membrane structure
pores. The results also indicated that the organic matter in the
membrane pores most likely originated from the cake layer, both In order to support the results indicating that membrane
from the effect of bacterial activity and desorption. fouling can be mitigated by preventing ocs accumulating on the
The nature of the internal membrane fouling was further surface of the UF membrane, and forming a cake layer, SEM images
examined by FTIR analyses. As illustrated in Fig. 5d, the peaks at were obtained and can be seen in Fig. 6. The SEM images showed
170 W. Yu, N.J.D. Graham / Journal of Membrane Science 492 (2015) 164172

350

300

250 CUF
CSUF
200
Number

150

100

50

0
<10 10~15 15~20 20~25 25~30 >30
Size (nm)
Fig. 6. SEM images of membranes with different pretreatment: CUF membrane without (a) and with (c) wash, CSUF membrane without (b) and with (d) wash, and of sand
grains (CSUF) before water backwash (e); and open pore size distributions of fouled membranes in CUF and CSUF (f).

that there was a thick cake layer on the surface of the CUF
membrane, which is composed of nano-scale primary particles,
as well as some EPS-like materials (Fig. 6a). In contrast, there was
little indication of a cake layer on the surface of the CSUF
membrane, and only a limited number of small ocs were evident
(Fig. 6b), conrming that suspended ocs in the membrane tank
were prevented by the sand layer from reaching the surface of
membrane. The SEM images also showed the presence of ocs on
the surface of the sand (sand layer) before water backwash
(Fig. 6e). Although in conventional UF operation the applied shear
stress during backwashing is sufcient to remove substantial
proportions of the cake layer and moderate membrane fouling,
the thickness of cake layer progressively increases, leading in turn
to increasing membrane fouling after a long period of membrane
operation. In contrast, the presence of the 1 cm sand layer in the
CSUF was able to retain ocs in the sand layer and prevent them
reaching the surface of the membrane, thus the application of uid
shear stress by backwashing is not needed. According to the EPS
concentration in the sand layer, the bacteria on the ocs were also
prevented by the sand layer, which was much easier to be back-
washed away, causing little EPS reaching the surface of the CSUF
membrane.
After the cake layer was washed and the membranes were
cleaned by sponge, the internal fouling of the membrane was
mainly determined by the blockage of pores. As seen from the SEM
images (Fig. 6c and d), there were few primary particles resident
on the surface of both membranes, but more pores were blocked
by the organic matter in the case of the CUF membrane. This was
 W. Yu, N.J.D. Graham / Journal of Membrane Science 492 (2015) 164172
evident visually and from the statistical number of open pores of
the two fouled membranes, as quantied by the use of Scion Image
software (Fig. 6f). Thus, the results in Fig. 6f indicated more pores
of a wide range of sizes remained open during the treatment
period in the case of the CSUF membrane, compared to the CUF
membrane, which is consistent with the accumulation of more
organic matter in the CUF membrane pores (Fig. 4).
4. Conclusions
The potential benets of enclosing UF membranes within a
sand layer, following coagulation pretreatment, have been inves-
tigated with a principal focus on reducing membrane fouling
effects.
1. Compared to conventional coagulation pretreatment (CUF), the
novel arrangement of pre-ltration by a sand layer after
coagulation (CSUF) produced a membrane fouling rate that
was substantially lower, potentially offering a more efcient
and compact process, as it merge together three separate
treatment steps sedimentation, sand ltration and
ultraltration.
2. SEM images showed that there was a thick cake layer on the
surface of the CUF membrane, which is mainly composed of
nano-scale primary particles. In contrast, there was little cake
layer evident on the surface of CSUF membrane.
3. The presence of EPS/biopolymers in the CUF cake layer was
much greater than in the ocs from the sand layer. This
corresponded to the greater concentrations of bacteria present
in the CUF cake layer as the membrane operation proceeded.
4. Analysis by different methods of internal membrane foulant
material clearly showed that substantially less organic matter
(EPS) was present in the CSUF membrane, compared to the CUF
membrane, with a lower concentration of biopolymers and
humic-like materials.
Acknowledgments
This research was supported by a Marie Curie International
Incoming Fellowship (FP7-PEOPLE-2012-IIF-328867) within the
7th European Community Framework Programme for Dr Wenz-
heng Yu. The authors wish to acknowledge the assistance of
Thames Water Utilities Ltd (wastewater samples) and colleagues
in Imperial College London.
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.memsci.2015.05.
032.
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