Desalination 316 (2013) 146–153

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Desalination
journal homepage: www.elsevier.com/locate/desal

Bio-fouling reducers for improving the performance of an aerobic submerged

membrane bioreactor treating palm oil mill effluent
Adhi Yuniarto a, Zainura Zainon Noor a,⁎, Zaini Ujang a, Gustaf Olsson b, Azmi Aris a, Tony Hadibarata a
a
Institute of Environmental and Water Resource Management (IPASA), UniversitiTeknologi Malaysia, 81310 Johor Bahru, Malaysia
b
Department of Industrial Electrical Engineering and Automation (IEA), Lund University, Box 118, SE-22100 Lund, Sweden

H I G H L I G H T S

► PAC and zeolite were added as bio-fouling reducer (BFR).

► The addition of BFR in ASMBR increases effluent qualities.
► The addition of BFR in ASMBR decreases bio-fouling propensity.
► PAC shows better performance than zeolite in the enhancement of ASMBR system.

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

Article history: A bench scale aerobic submerged membrane bioreactor (ASMBR) was used to treat diluted palm oil mill ef-
Received 18 October 2012 fluent (POME). For further improving the effluent quality and reduction of bio-fouling, powdered activated
Received in revised form 3 February 2013 carbon (PAC) and zeolite were used as bio-fouling reducers (BFR). We compared the performances of
Accepted 4 February 2013
ASMBR without BFR (called BFR0) with ASMBR using BFR, namely 2 g/L PAC (BFR1), 4 g/L PAC (BFR2) and
Available online 15 March 2013
2 g/L zeolite (BFR3) for a period of about 70 days. Each system with BFR showed distinct performances by
Keywords:
producing higher effluent quality as compared with BFR0. On average, the systems with and without BFR re-
Aerobic submerged membrane bioreactor moved COD by 97.5–98.5% and 95.2%, respectively. The ASMBR with BFR also produced permeate with aver-
Bio-fouling reducer age residual color between 16 and 26 Pt-Co, as compared to 80 Pt-Co by BFR0. The addition of BFR increased
Palm oil mill effluent the critical flux from 20 LMH (BFR0) to 36, 42 and 30 LMH (BFR1, BFR2, and BFR3). Furthermore, the ASMBR
systems with BFR formed lower operational trans-membrane pressure (TMP), lowered the concentration of
soluble microbial products (SMP) and increased the concentration of EPS.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction (POME). About 0.9–1.5 m 3 of POME is generated from every metric

Oil palm (Elaeisguineensis) is the leading agricultural industry in
Malaysia, covering about three million hectares of the cultivated
area and the hectarage has increased 70 fold since the 1960s. The
17.56 million metric ton of total crude palm oil (CPO) production
has made Malaysia one of the largest producers and exporters of
palm oil in the world, accounting for 43% of the world's total palm
oil production and 49% of total palm oil exports [1]. Malaysian palm
oil industries also provide 11% of the world's total production of oils
and fats and 26% of export trade in the oils and fats market [2,3]. In
2009, there were 418 crude palm oil mills, 59 refineries, 57 down-
stream industries and 18 oleochemical plants [1].
Unfortunately, this important economic activity generates an
enormous amount of liquid effluent, known as palm oil mill effluent
⁎ Corresponding author at: Institute of Environmental and Water Resource Management
(IPASA), UniversitiTeknologi Malaysia, 81310 Johor Bahru, Malaysia. Tel.: +60 7 5535485;
fax: +60 7 5581463.
E-mail address: zainurazn@utm.my (Z.Z. Noor).
ton of CPO produced [4]. In terms of fresh fruit bunches (FFB), it
amounts to about 0.7 m 3 POME per metric ton FFB processed. This
means that 418 palm oil mills in Malaysia produce more than 40 mil-
lion cubic meters of POME annually. With very high content of or-
ganics, the colloidal suspension of raw POME is a thick brownish
color liquid and is discharged at a temperature at about 90 °C. It is
fairly acidic with pH ranging from 4.0 to 5.0. The POME characteristics
and standard discharges limit set by the Malaysian Department of En-
vironmental are summarized in Table 1.
Various POME treatment schemes currently used by the Malaysian
palm oil industry were listed and discussed in detail by Wu et al. [5].
However, the application of these technologies is often still difficult to
adhere to strict regulations. Therefore, the investigations and the appli-
cation of new techniques and technologies, either as primary, secondary
or tertiary treatment, are still needed. One of the most promising novel
technologies in wastewater treatment system is the membrane bioreac-
tor (MBR), a process involving membrane filtration combined with mi-
crobial degradation [6]. Many studies have been devoted to use MBR to
treat high strength wastewater such as from food industry and textile

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http://dx.doi.org/10.1016/j.desal.2013.02.002
 A. Yuniarto et al. / Desalination 316 (2013) 146–153 147

Table 1 remove natural and synthetics color [24–28]. Lee et al. [29] reported
Characteristics of raw combine POME and its standard discharge limit by Malaysian De- that the addition of zeolite into membrane bioreactor produced more
partment of the Environment (2006).
rigid, stable and strong sludge flocs that could reduce the membrane
Parameters Concentrations (mg/L) Standard limit (mg/L) fouling by forming a less compressible cake layer on membrane surface.
pH 4.2–5.1 5–9 Latest studies have considered another two important factors to mem-
BOD 31,000–34,000 100 brane fouling propensity, i.e. bound extracellular polymeric substances
COD 62,000–67,000 – (EPS) and soluble microbial products (SMP) [30,31]. Studies have also
Suspended solids 20,500–24,000 400
pointed out the positive relation between membrane fouling reducing
Total nitrogen 870–910 150
Ammoniacal nitrogen 36–46 – process with increasing of critical flux and production flux [14,32]. Crit-
Oil and grease 1800–2100 50 ical flux definition and its determination were not discussed here but
Temperature 85–91 45 more details on these subjects can be found mostly in [33–35].
Except pH and temperature, all other parameters are in mg/L, temperature in °C. The objective of this study is to assess the performance of Aerobic
Submerged Membrane Bioreactor (ASMBR) system with and without
[7], showing the possibility to treat POME using MBR system. Studies on the addition of BFR in treating diluted POME on a long term opera-
the application of MBR in treating POME in lab scale have been done re- tional time and various loading conditions. The focus of this paper is
cently. The studies included the application of ultra-filtration mem- to compare the removal efficiencies of organic content (as COD), re-
brane [8], microfiltration membrane [9], anaerobic membrane system sidual color of effluent, membrane fouling propensity through
[10], and hybrid anaerobic–anoxic–aerobic system [11]. However, this SMP-EPS concentrations and trans membrane pressure (TMP) pro-
membrane separation technology for treating POME has never been ap- files, and determination of critical flux enhancement of the used
plied at industrial scale. This is mainly due to the high concentration of membrane.
suspended organics which will potentially cause membrane fouling and
degradation. 2. Material and methods
Several studies have shown that the addition of bio-fouling reducer
or flux enhancement, which are mostly flocculants or adsorbent, is one 2.1. Configuration of ASMBR
of the strategies to lower the fouling propensity in MBR [12–15]. Mean-
while, the direct addition of activated carbon into the submerged MBR The laboratory ASMBR set-up (Fig. 1) consists of an acrylic tank
could maintain or improve the organic removal efficiency without the with an effective volume of 20 L. Single commercial flat sheet mem-
need for the membrane to be cleaned for longer operation time brane module (Kubota, Japan) was immersed vertically in the tank.
[16–22]. Akram and Stuckey [21] concluded that the addition of PAC This hydrophilized high-density chlorinated polyethylene (CPE)
might improve the flux and organic removal efficiency of a submerged membrane [36] have an effective filtration area of 0.1 m 2 with nomi-
anaerobic MBR. Zeolite have been used as cation exchange, molecular nal pore size of 0.4 μm. The air was fed into the reactor with a
sieving, catalyst and sorption media. The application of zeolite in fine-bubble diffuser installed beneath the membrane to provide ade-
water and wastewater treatment has been reported as promising quate oxygen to maintain the aerobic conditions for biomass growth,
methods [23], including zeolites application as an adsorption media to as well as to scour cake accumulation on the membrane surface. This

Fig. 1. The ASMBR system configuration.

148 A. Yuniarto et al. / Desalination 316 (2013) 146–153

Table 2 The operational parameters for each experiment are shown in

ASMBR operation system. Table 4. The HSL experiment (Run 2) was carried out at about
Parameters Specification 15 LMH for a period of 5 days after 15 days of Run 1 experiment.
After the end of the HSL run, the ASMBR was set back to operate in
Reactor tank 1
Effective reactor size (LWH, mm) 250 × 200 × 400 the initial condition (Run 1) for 5 days before the organic shock load-
Effective volume aerobic tank (L) 20 ing (OSL) run (Run 3). The OSL run was conducted for 5 days with
Aeration system Micro-bubble diffuser VOLR 72 g COD/m 3 d. By the end of the OSL run, the ASMBR was
Aeration rate (L/min) 6
again operated at the initial conditions for several days to observe fur-
MLSS (mg/L) 9000–10,000
MLSS (mg/L) 6000–7000 ther fouling propensity.
SRT (days) 20 The critical flux was determined after each experiment completed
Dissolved oxygen (mg/L) >2 by using another new membrane. The determination of critical flux of
pH 6.8 ± 0.3 membrane followed the approach proposed by Le Clech et al. [33].
Temperature (°C) 25
The comparison of critical flux of the ASMBR systems was done
Membrane material Chlorinated polyethylene
Membrane size (mm) 210 × 297 using a flux step height of 2 LMH with step duration of 15 min. The
Membrane effective area (m2) 0.1 membrane was then cleaned by washing it with tap water; the cake
Membrane pore size (μm) 0.4 and bio layer on the membrane surface were gently scrubbed using
Membrane manufacturer Kubota Inc.
a spoon. Then, the membrane was soaked with 0.5% w/w of NaOCl so-
Membrane average clear water flux (LMH) 22
Membrane operation flux (LMH) 10 lution for approximately 24 h and washed again using tap water.
Suction operation mode to relaxation mode (min) 5:1
2.3. Wastewater characteristic and analytical methods

air sparging was controlled with a flow meter. The influent flow rate
was controlled by a water level float sensor set in the reactor. The
constant permeate flux was maintained with a variable speed peri-
staltic pump. In addition, the flux was manually measured using a cal-
ibrated cylinder and a stopwatch daily. The pump speed adjustment
was made when the flux deviated from its intended value. A pressure
transducer (PG-30 Copal Elect.) was used to measure the TMP and the
data were recorded using a data logging system. Table 2 shows the
detailed operational condition of ASMBR systems.
2.2. Experimental conditions
The ASMBR was seeded with activated sludge obtained from a
palm oil wastewater treatment plant near Kahang Johor–Malaysia.
After a steady-state condition had been achieved, the experiments
were started. The reactor was operated at room temperature and
was maintained at neutral pH. The membrane flux of the ASMBR
was kept constant at about 10 L/m 2 h (LMH), which was the opera-
tional flux of the system and the reactor's HRT was 20 h (called Run
1) except at the hydraulic shock loading (HSL) experiment. The volu-
metric organic loading rate (VOLR) was equal to 24 g COD/m 3 d ex-
cept during the organic shock loading (OSL) run. At the end of each
experiment, the ASMBR was emptied and the sludge was settled
and dried before disposal. In addition, a new membrane sheet was
used for every experiment.
The experiment was initially conducted by operating the ASMBR
without BFR (called BFR0), and then followed by three different dos-
ages of the bio-fouling reducers, called BFR1, BFR2 and BFR3 (Table 3).
The dosages of BFR were determined based on the result of the pre-
liminary study [9]. The BFR were dried in an oven at 105 °C for 24 h
prior to being introduced into the ASMBR.
The raw POME was a fresh POME obtained from the sludge pit
after de-oiling tank of a local palm oil mill near Kahang Johor–Malay-
sia. To treat raw POME in an aerobic environment is very difficult and
anaerobic treatment is usually applied. For this reason, the raw POME
was diluted by a factor of about 65 times (based on Total COD) before
it was fed in to the aerobic system. It should be emphasized that the
composition of the various POME components in the feeds then
remained the same as in raw POME. The feed preparation and deter-
mination of its quality were done on a daily basis in a 35 L feed tank.
The characteristics of the feed are shown in Table 5.
Laboratory experiments conducted for this study were carried out
at the Environmental Engineering Lab, Faculty of Civil Engineering,
UniversitiTeknologi Malaysia. The biomass quantity was regularly
tested for MLSS and MVLSS. The COD (as total COD) concentration
was analyzed according to standard methods [37] immediately after
the samples were collected. Carbohydrate and protein fractions of
SMP and EPS were analyzed using heating method [38,39]. The resid-
ual color was measured with a spectrophotometer (HACH/DR5000)
using Pt-Co scale.
3. Results and discussion
3.1. Comparison of organic removal
POME consists of complex forms of organic acids. The fatty acids
composition (C8–C20) of each of this fraction is different from one an-
other and contribute to a high value of pollution load in POME [1,40].
In this experiment, total COD represented the total organic com-
pounds in POME. The difference of COD on influent and permeate
was calculated as organic removals performance of the ASMBR.
Fig. 2 shows that all systems with and without BFR, on their

Table 3
BFR systems and characteristics.

System Type of BFR Doses (g/L) Size Quality, content Manufacturer

BFR0 None None – – –

BFR1 PAC 2 4 mm mesh Analytical, Charcoal Powder Fisher Scientific, Ltd.
BFR2 PAC 4 4 mm mesh Analytical, Charcoal Powder Fisher Scientific, Ltd.
BFR3 Zeolite 2 4 mm mesh Commercial, Powder, Harta Semarak, Sdn. Bhd.
SiO2 63.4%
AlO3 9.2%
CaO 4.1%
FeO3 1.9%
MgO 1.1%
Others 20.3%
 A. Yuniarto et al. / Desalination 316 (2013) 146–153 149

Table 4
100
Operation condition and parameter for ASMBR system.

Parameter Run 1 (Initial) Run 2 (HSL) Run 3 (OSL)

Membrane flux (LMH) 10 15 10 95

VOLR (g COD/m3 d)

COD Removal (%)

24 36 72
HRT (h) 20 13.33 20
Duration (days) 15, 5, 43–45 5 5
90

63–74 days of operation, achieved excellent organic removals, more BFR0

than 95% on average. Nonetheless, BFR0 needed longer time
(11 days) to achieve constant organic removals than other systems
(8, 4 and 4 days, respectively). Meanwhile, BFR2 produced higher or-
ganic removal than others from the beginning of operation. The rea-
son was apparently that a higher concentration of BFR would result
in larger surface areas which allowed more organic materials to be
absorbed.
On day 15–20, the systems received higher VOLR as a result of the
HSL. BFR0 responded initially by decreasing its performance, before
the organic removal rate tended to increase back to the initial perfor-
mance. This condition could also take place in the ASMBR systems
with BFR, as there were no significant changes in organic removal
efficiencies.
Also, as indicated in Fig. 2, as the volumetric organic loading rate
(VOLR) was set back to the initial level, the organic removal of all
ASMBR systems achieved almost the same level with the initial condi-
tion. In the Run 3 experiment in which the ASMBR systems were sub-
ject to an organic shock loading (OSL) and much higher VOLR, a
decline of organic removals in BFR0 was observed. However, the sys-
tem was slowly restored to produce higher organic removals. With
the addition of BFR, the organic removals just slightly declined and
then recovered to the initial performance. It seems that the systems
with BFR had better performance while handling shock loading, par-
ticularly if it was because of hydraulic shock. The simultaneous activ-
ities of high density of biomass and adsorption of BFR could be
considered as the main reason for those trends [17].
BFR2 had double concentration of PAC compared to BFR1. There
were no significant differences in terms of organic removal efficien-
cies, even though it removed almost all organic content in the bulk
solution. Zeolite in BFR3 also gave good performance in terms of or-
ganic removal as compared to PAC in BFR1 and BFR2.
3.2. Comparison of effluent residual color
BFR1
85
BFR2
BFR3
80
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Operation Time (days)
Fig. 2. Organic removal efficiency.
batch reactor [43]. Syalfani et al. [24] reported the removal of organics
and color in dye wastewater using granulated activated carbon (GAC)
and zeolite in column filter. Damayanti et al. [11] founded that PAC
and zeolite removed SMP by 58% and 42%, respectively in hybrid
membrane bioreactor. However, no such a review/report about the
comparison of PAC and zeolites performances in removing color in
wastewater has been found. Since PAC have larger surface areas due
to its smaller particle size, PAC should have greater adsorption capac-
ity than GAC.
In this study, the ASMBR system without BFR produced the
highest residual color, about 80 Pt-Co, as shown in Fig. 3. Brownish
water, which was produced during the early stage of Run 1 experi-
ment, gradually became clearer after 11 days of operation. On the
other hand, the ASMBR systems with BFR1 and BFR2 produced less
color effluent after 3 days, and they remained constant in the range
of less than 22, 23 and 40 Pt-Co, respectively. This was most likely
due to the adsorption of the small molecule materials onto the BFR
surface or BFR-biomass surface, in accordance with the results
reported by previous studies [29,44,45]. The addition of PAC (BFR1
and BFR2) increases the removal of low molecular weight organics
by adsorption, acts as a supporting medium for attached bacterial
growth, and influences the bacterial population [46]. Lee et al. and
Suzuki et al. found that a large portion of organics smaller than

As mentioned, POME has a brown/red dark color due to the pres-

ence of the carotenes [41]. By nature, carotenes are fat-soluble and or
less soluble in water. It is well-known that this color is difficult to re-
140
move by biological treatment due its properties and structures. The
existence of residual color in final discharge water raises an aestheti- BFR0
120 BFR1
cal problem to the water body around palm oil mills. BFR2
Generally activated carbon showed good performance since it BFR3
used as an adsorbent of several compound in red palm oil wastewater 100
Residual Color (PtCo)

i.e. color, organic, and inorganic compounds [42]. Significant role of

PAC on color removal was reported by Aziz et al. in hybrid sequencing 80

Table 5
60
Characteristics of the feed.

Parameter Range (mg/L, except pH) 40

Run 1, Run 2 Run 3

COD 1000 ± 107 3000 ± 86 20

Total suspended solids 680 ± 35 2000 ± 45
Total N 14 ± 2 38 ± 3
0
Total P 3.2 ± 1.3 8 ± 0.5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Ammoniacal nitrogen 0.8 ± 0.2 2.2 ± 0.4 Operation Time (days)
Oil and grease 21 ± 2.2 53 ± 3.9
pH 6.8 ± 0.2 6.7 ± 0.4
Fig. 3. Residual color of effluent.
150 A. Yuniarto et al. / Desalination 316 (2013) 146–153
membrane pore size were adsorbed by adsorbent and then completely
separated by the membranes [29,47].
BFR1 and BFR2 had better performance in removing color than
BFR3. It might be due to better nature composition and greater surface
area of BFR1 and BFR2. In Run 2 and Run 3 experiments, significant in-
crease of residual color was observed on the system without BFR. It
was apparent that this system was sensitive to the VOLR shocks, in
terms of color removal, even though the organics removal was just
slightly affected by the shocks.
3.3. Comparison of TMP profiles
Fig. 4 shows the change in TMP over time at a constant flux,
according to Table 3, for the experiments without BFR and with BFR.
During the Run 1 experiment, BFR0 produced higher TMP than the
others. The TMP promptly rose to a level around 22 mbar after the
operation was started. The increase of TMP gradually took place dur-
ing the experiment, indicating significant fouling on the membrane.
During Run 2 and Run 3 experiments, the TMP of BFR0 jumped due
to higher VOLR, and then the TMP decreased to the level slightly
above the level before these shock loading experiments, indicating
an irreversible fouling on the membrane surface. The system was
likely more sensitive towards HSL than OSL, in term of TMP value.
From day 30 to 72, the TMP increased gradually from 32 to
120 mbar, without significant jump on TMP. On day 62, MLSS was ad-
justed by wasting the sludge, as it was exceeding 10 g/L. This process
did not affect its TMP profile.
On the other hand, despite the addition of BFR, there was still a
gradual TMP rise but the values continued to be lower than that with-
out BFR. It was noticed that BFR3 produced the lowest rising of TMP,
followed by BFR1 and BFR3 throughout the experimental period. The
ASMBR with BFR produced lower TMP on the end of experiment,
namely 73 mbar (after 74 days), 43 mbar (after 68 day) and
68 mbar (after 63 days), respectively, as compared to the ASMBR
without BFR. During the shock loading experiment, the systems
with BFR also showed sudden TMP increase and TMP recovery, none-
theless the values were not significant.
The properties and the concentration of BFR might be the main
reason for these low-rising TMP. These were possibly due to the ad-
sorption of colloids and dissolved organics, including SMP. Further-
more, the addition of BFR held up the development of bio-film layer
onto membrane surface by producing a layer of high porosity and bet-
ter permeability onto the membrane surface [21,29]. It is suggested
140
BFR0
120 BFR1
BFR2
BFR3
100
TMP (mbar)
80
RUN3
60
RUN2
40
20
0 0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Operation time (days)
Fig. 4. Trans membrane pressures profiles.
that BFR also acted as a pressure-shock buffer in the shock loading
experiments.
3.4. Comparison of SMP and EPS
The influence of microorganism metabolites, such as SMP and EPS,
on membrane fouling is essential for understanding and controlling
membrane fouling [48]. EPS are complex mixture of macromolecular
polyelectrolytes (i.e. polysaccharides, protein, nucleic acids, and humic
compounds) participating in the formation of microbial aggregates
and consist of insoluble materials (sheaths, capsular polymers, con-
densed gel, loosely bound polymers, and attached organic material);
whereas, SMP are considered also as soluble part of EPS (i.e. soluble
macro-molecules, colloids, and slimes) released into the solution from
substrate metabolism and biomass decay [30,31,49]. EPS and SMP
were measured as carbohydrate fraction (EPSc and SMPc) and protein
fraction (EPSp and SMPp). Higher SMP concentrations in the solution
led to higher membrane fouling rates, due to higher pore blocking and
reduced the cake porosity by filling the void spaces between the cell
particles in the cake layer [50]. Hydrophilic SMPc were most likely the
major foulants [30]. Higher EPS concentrations in the sludge enhance
bioflocculation, resulted in the development of larger and more perme-
able flocs and then tended to reduced membrane fouling as a result of
reduced hydraulic resistance. Meanwhile, higher hydrophobicity of
EPSp was more likely to enhance the attachment of flocs on the mem-
brane surface and increased the fouling propensity than hydrophobic
EPSc.
Fig. 5 illustrates the carbohydrate and protein concentrations of
SMP and EPS normalized to biomass in the reactor (as MLVSS) over
the experiment period of each variation. These results confirmed
that the concentration of SMP (both SMPc and SMPp) in bulk solution,
which was regarded as soluble cellular components released during
cell lysis, decreased. These could be due to adsorptions process [15],
and/or lost during synthesis by biomass [39], and/or already attached
onto membrane surface as bio-layer [21], and/or discharged out
trough membrane pores as a organic content in effluent [30]. Consid-
ering the lower organic content in the effluent (as discussed above), it
might expected that this decrease of SMP in bulk solution after the
addition of BFR was not because of the SMP discharged out in effluent.
In Table 6, the concentration of hydrophilic SMPc in the bulk solu-
tion after the addition of BFR1, BFR2 and BFR3 have decreased by 34.5,
SMPc EPSc SMPp EPSp
80
70
60
SMP or EPS (mg/g MLVSS)
50
40
30
20
10
BFR0 BFR1 BFR2 BFR3
Type of BFR
Fig. 5. Concentration of SMP and EPS in the reactor.
 A. Yuniarto et al. / Desalination 316 (2013) 146–153 151

Table 6
SMP and EPS concentrations changes in the reactor after the addition of BFR.
Concentrations SMP/EPS changes as compared to BFR0 (%)
SMPc SMPp
BFR0 – –
BFR1 (−) 34.5 (−) 22.3
BFR2 (−) 43.3 (−) 40.0
BFR3 (−) 6.7 (−) 36.1
Note: sign (−) indicate decreased by, while sign (+) indicate increased by.
43.3 and 6.7%, respectively, as compared to SMPc in BFR0. However it
was noticed that the concentrations of SMPc did not significantly re-
duce after the addition of higher concentration of BFR (on BFR1 and
BFR2). Meanwhile, BFR3 only reduced a small part of SMPc. The sys-
tems with BFR1, BFR2 and BFR3 showed the capability to reduce the
protein part of SMP by 22.3, 40.0 and 36.1%, respectively. It was no-
ticed the PAC in BFR1 and BFR2 has better performance to decrease
hydrophilic SMPc, while zeolite was better in reduction of SMPp.
The increases of EPS (both EPSc and EPSp) on BFR2 system, compared
to BFR1 system, indicated that the system with higher concentration of
PAC in BFR2 produced flocs which had better structure and/or formation
as confirmed by lower rise of TMP in Fig. 4. The concentration of EPSc in
the system with BFR2 (increased by 53.0%) indicated that this system
has higher possibility to form bigger and better flocs structure. However,
the higher concentration of EPSp in this system (increased by 45.9%)
would lead the bigger and permeable flocs attached the onto membrane
surface, increased the cake resistance, and then might increase the
membrane fouling propensity. The EPS concentrations of BFR3 was
lower than BFR1 system, indicated that properties of zeolite had affected
to the biomass properties to form permeable flocs.
At the end of all experiments, it was observed that the cake forma-
tion on the membrane surface has occurred in all ASMBR system.
EPSc EPSp
However, it was found that the cake formation only occurred in few
– –
spots on the membrane surface. Especially in the spots that did not
(+) 30.9 (+) 28.7
(+) 53.0 (+) 45.9 get air scouring and the water turbulence due to aeration. It was no-
(+) 29.0 (+) 19.1 ticed also that these cake layer was easy to clean using clear water
during membrane washing. Furthermore, a thin bio-layer was found
on BFR0 system, indicating the attachment of hydrophobic SMPc to
form biological layer led to membrane fouling [31,51]. On the systems
with BFR, bio-layer was even thinner on BFR3 or even imperceptible
on BFR1 and BFR2. It should be noted that not only the cake formation
but also the bio-layer was not happened uniformly on the entire flat
membrane surface.
The ASMBR without BFR had more organic material deposit onto the
membrane surface. This resulted in cake accumulation and develop-
ment of bio-layer, hence led to higher propensity of membrane fouling.
Lee et al. [29] stated that an increase in particle size may reduce the
probability of the particle to pass through membrane pores and also en-
hanced particle movement from the membrane surface to the bulk so-
lution. The addition of BFR with adsorption capacity to the ASMBR
system changed the BFR-biomass flocs size and changed its behavior
to attract more soluble organic matter to attach or stay in bulk solution.
Consequently, this slowed down the bio-layer development onto mem-
brane surface, and reduced the bio-fouling [44,52]. The BFR can also be a
medium for biomass to attach, grow and develop bigger flocs. As men-
tioned by Akram and Stuckey [21], BFR was effective in adsorbing high
molecular weight (MW) of SMP by making the size of BFR-biomass flocs

(a) (b)
80
48 80
48
70 44
70 44
40 40
60 60
36 36
TMP BFR0 TMP BFR1
32
TMP (mbar)
TMP (mbar)

Flux (LMH)
Flux (LMH)

50 Flux BFR0 50 Flux BFR1 32

28 28
40 24 40 24
30 20 20
30
16 16
20 12 20 12
8 8
10 10
4 4
0 0 0 0
0 1 2 3 4 5 6 7 8 0 1 2 3 4 5 6 7 8 9 10 11 12
Time (hours) Time (hours)

(c) (d)
120 60 80
48
110 56
52 70 44
100
48 40
90 TMP BFR2 60
Flux BFR2
44 36
80 40 32
TMP (mbar)

TMP (mbar)
Flux (LMH)

Flux (LMH)

36 50
70 28
32
60 40 24
28
50 24 20
30
40 20 TMP BFR3 16
16 Flux BFR3
30 20 12
12
20 8
8 10
10 4 4
0 0 0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 0 1 2 3 4 5 6 7 8 9 10
Time (hours) Time (hours)

Fig. 6. Flux-step result for critical flux determination of (a) ASMBR with BFR0, (b) ASMBR with BFR1, (c) ASMBR with BFR2, and (d) ASMBR with BFR3.
152
bigger, hence increased the organic removals in the ASMBR systems, as
indicated by the data presented in Fig. 2.
3.5. Determination and comparison of critical flux
In this study, the determination of critical flux was carried out to
assess the impact of BFR addition to the critical flux of the membrane
system since in general, fouling propensity is proportionally related
with critical flux [11]. The most common definition of critical flux
was stated by [34], which is a flux below which a decline of flux
with time does not occur; above it fouling is observed, or the “first”
permeate flux at which fouling becomes noticeable [35]. Observation
of critical flux can be done by plotting flux against TMP, to monitor
the change between the constant and non-constant permeability at
the onset of fouling [33]. A step flux of 2 LMH and 15 min duration
was chosen for these experiments. This flux-step method defines
the highest flux for which TMP remains stable as the critical flux [33].
According to Fig. 6a, the ASMBR system without BFR produced a
constant rate of increasing TMP up to 14 LMH, while its rate became
significant at higher fluxes due to fouling. According to Fig. 6b, the ad-
dition of BFR1 produced a relatively constant rate of increasing TMP
for fluxes up to 28 LMH. Higher rate of TMP increments was observed
at higher fluxes. Fig. 6c and d shows that in the ASMBR system with
BFR2 and BFR3, the TMP increment appeared to start higher when
the flux reached 36 and 26 LMH, respectively. By this figure, barely
we could determine the critical flux of the systems, i.e. 14, 28, 36
and 26 LMH, respectively. Fig. 6 also confirms that the TMP values
recorded during the descending phase were just slightly higher than
the values obtained during the ascending phase [26]. These findings
indicated that irreversible fouling had happened in the systems with-
out and with BFR.
The critical flux of the ASMBR system can be determined by using the
raw data of flux-step experiments as discussed above, however the values
are somewhat subjective. Le Clech et al. [26] proposed several numbers of
criteria that could be used to determine the critical flux of the system,
namely dP/dt (rate of TMP increase)= 0, dP/dt b 0.1 mbar/min, ΔPo
(initial TMP increase), Pave(average TMP) and Δ(dP/dt)/ΔJ (second
moment of TMP with respect with flux). Bacchin et al. [28] also pro-
posed to determine the critical flux by plotting dP/dt from the raw data
versus flux. A trend-line could be added to emphasize that the distinction
to be considered is between a low fouling rate and a higher fouling rate
and is not between no fouling and fouling.
Fig. 7 shows the rate of increasing TMP for each flux in the exper-
iments. According to the exponential trend-line drawn, significant in-
crement of dP/dt on BFR0 happened after 20 LMH as a higher fouling
0.20
0.18
0.16
0.14
dP/dt (mbar/min)
0.12
0.10
0.08
0.06
0.04
0.02
0.00
0 5 10 15 20 25 30 35
Flux (LMH)
Fig. 7. dP/dt versus flux for critical flux determination.
A. Yuniarto et al. / Desalination 316 (2013) 146–153
rate, while those trend-lines on the systems with BFR were not show
a significant increment after 25 LMH, which made it difficult to deter-
mine the critical flux.
Therefore, by considering dP/dt b 0.1 mbar/min, we could deter-
mine the values of the critical flux for the ASMBR system with BFR0,
BFR1, BFR2 and BFR3 in Fig. 7 as about 20, 36, 42 and 30 LMH, respec-
tively. Furthermore, it was noticed that the addition of BFR1, BFR2 and
BFR3 had increased the ASMBR critical flux by 80%, 110% and 50%, re-
spectively, higher than the system without BFR. The application of
BFR in the ASMBR system to treat POME will promote the implemen-
tation of higher operational flux, which will result in higher produc-
tion of treated water; higher quality of effluent, prolong the
membrane operational time, prolong the membrane life-span; reduce
the use of chemical agent for cleaning; and could even prevent the
necessity of addition polishing treatment after MBR system.
4. Conclusions
The ASMBR systems with BFR treating POME produced higher ef-
fluent quality, in terms of lower organics content and lower residual
color. After 8 days of operation, the ASMBR with BFR1, BFR2 and
BFR3 removed organic materials (as COD) more than 97%, 98% and
96%, respectively, as compared to BFR0 (over 95% after 11 days). Fur-
thermore, they also produced less residual color, namely lower than
22, 23 and 40 Pt-Co, respectively, as compared to 80 Pt-Co on BFR0.
Furthermore, by acting as a buffer, BFR has also enhanced the capabil-
ity of system (ASMBR with BFR) to cope with sudden change in OLR
and VOLR due to shock loading of the influent. The addition of BFR
in ASMBR significantly lowered the TMP on long-term operational.
The BFR0 system produced 120 mbar after 72 days of operation,
while the systems with BFR produced 73 mbar (after 74 days),
43 mbar (after 68 days) and 68 mbar (after 63 days), respectively.
The BFR addition lowered the concentration of SMPc and SMPp in
the reactor; however, these additions increased both the concentra-
tion of EPSc and EPSp. The addition of BFR1, BFR2 and BFR3, as com-
pared to the ASMBR system without BFR, significantly reducing the
membrane fouling and enhanced the ASMBR systems critical flux
from 20 LMH to 36, 42 and 30 LMH, respectively.
Acknowledgment
The authors wish to thank the Research Management Center (RMC) of
UniversitiTeknologi Malaysia for the financial assistance under VOT no.
79903. Acknowledgment also to InstitutTeknologiSepuluhNopember
(ITS) Surabaya Indonesia for giving generous support to the first author.
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