Journal of Membrane Science 209 (2002) 2737

Inuence of macromolecule adsorption during ltration

of a membrane bioreactor mixed liquor suspension
S. Ognier

, C. Wisniewski, A. Grasmick
Laboratoire de Gnie Des Procds de Montpellier II/GPSA, CC 024Universit Montpellier II,
Place Eugne Bataillon, 34095 Montpellier Cedex 05, France
Received 24 September 2001; received in revised form 25 March 2002; accepted 26 March 2002
Abstract
The aim of this study was to quantify the specic effect of adsorption on membrane fouling during ltration of a mem-
brane bioreactor (MBR) mixed liquor suspension. Adsorption experiments were performed on well-dened protein solutions
(-lactoglobulin solutions) to provide reference results and compare them to those obtained during the ltration of MBR
suspensions (raw suspension and settled suspension). Two different methods were used to quantify the role of adsorption in
membrane fouling: a static methodinwhichmembranes were immersedinthe biological suspensionanda dynamic method
supposing that the resistance due to adsorption is an irreversible phenomenon that remains after ltration and back-washing. It
was shown for the two types of suspensions that (i) due to limited diffusion, the dynamic method appears to be more adapted
than the static method; (ii) adsorption is a rapid fouling phenomenon that induces irreversible resistance and that, in frontal
mode takes place at the beginning of the operation; (iii) the adsorption phenomenon shows specic hydraulic resistance of
the same order of magnitude as the clean membrane resistance; (iv) other phenomena, i.e. progressive pore clogging, can also
take place though subcritical hydrodynamic conditions.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Adsorption; Membrane fouling; Protein solution; Bacterial suspension; Membrane bioreactor
1. Introduction
Subcritical ltration conditions can be dened
to avoid macroscopic deposits from building up on
the membrane surface of the membrane bioreactors
(MBR) used to treat wastewater [1]. These conditions
allow long ltration periods without having to use
chemical cleaning procedures. However, the fouling
of the membrane is not avoided and generally a rapid
membrane permeability decrease occurs at the very be-
ginning of the ltration operation. Then, the decrease

Corresponding author. Tel.: +33-4-67-14-48-54;

fax: +33-4-67-14-48-54.
E-mail address: ognier@univ-montp2.fr (S. Ognier).
is much slower with time and the resistance measured
can be considered constant. Fan et al. [2] showed
that a MBR system for the treatment of raw munic-
ipal wastewater can be run continually for over 70
days with a relatively stable transmembrane pressure
(TMP) corresponding to four times the clean water
TMP. However, it is of utmost importance to under-
stand the causes of resistance variations in subcritical
conditions to optimise the process control and the fre-
quency of chemical cleaning. The fact that the subcrit-
ical fouling do not depend on pressure and shear-rate
suggests that adsorption and/or pore clogging inside
the membrane matrix could cause this fouling [2].
Few studies have looked at the effect of adsorption
during ltration of MBR mixed liquor suspension.
0376-7388/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S0376- 7388( 02) 00123- 0
28 S. Ognier et al. / Journal of Membrane Science 209 (2002) 2737
Nomenclature
C macromolecule concentration
(kg m
3
)
d
-lactoglobulin
protein size (m)
k Kozeny constant
P transmembrane pressure (Pa)
R
ad
membrane resistance after static
adsorption (m
1
)
R
l
membrane resistance after
dynamic adsorption (m
1
)
R
init
initial membrane resistance
(m
1
)
R
m
clean membrane resistance
(m
1
)
R
mono
calculated membrane resistance
after monoadsorption (m
1
)
S
ad
specic surface area of the
adsorbed membrane (m
1
)
S
m
specic surface area (m
1
)
t time (s)
V cumulated volume of ltrate (m
3
)
V
adsorbed protein
total volume of adsorbed
protein (m
3
)
Z membrane thickness (m)
Greek letters
specic resistance (mkg
1
)

ad
adsorbed membrane porosity
clean membrane porosity
dynamic viscosity (Pa s)
membrane area (m
2
)
This is partly because it is difcult to characterise
the soluble compounds liable to adsorb on the mem-
brane material present in complex suspensions such
as activated sludges. Conversely, many studies have
been carried out on synthetic protein solutions. These
solutions cannot constitute a model to represent the
soluble fraction of a bacterial suspension which is
composed of a wide variety of microbial polymers of
different nature (polysaccharides, proteins, etc.) and
of various molecular weights. However, a compar-
ative study between a well-dened protein solution
and a bacterial suspension could allow to estimate the
adsorption capacity of the soluble macromolecules
of the bacterial suspension in comparison with the
adsorption capacity of a well-dened protein.
Thus, the aim of this study was to quantify the spe-
cic effect of adsorption on membrane fouling in an
MBR suspension. Adsorption experiments were per-
formed on well-dened protein solutions to provide
reference results that were then compared with those
obtained during the ltration of an MBR suspension
(raw suspension and settled suspension).
2. Materials and methods
2.1. Materials
2.1.1. Experimental design
The experimental set-up, shown in Fig. 1, is a
Sartorius ltration module used with plane organic
membrane, the characteristics of which are given
in Table 1. The module consisted of a pressurised
ltration cell with a working volume of 200 ml.
2.1.2. Protein solutions
The protein solutions were prepared by dissolving a
commercial powder (Protarmor 907, Armor protine)
constituted of over 95% -lactoglobulin (molecular
weight of about 18 000 Da) in a ltered distilled water.
The -lactoglobulin molecule is approximately spher-
ical, with a diameter of 3.6 nm [3]. Its isoelectric point
is 5. At 20

C, the pH of the solution was 7.5.

The choice of this protein was based on two rea-
sons: (i) the -lactoglobulin properties are perfectly
dened in the literature; and (ii) according to the
Table 1
Membrane characteristics
VMWP 04700 Millipore
Type Plane
Membrane material Nitrocellulose
Dimension (mm) 47 (diameter)
Filtration area (cm
2
) 11.3
Pore size (m) 0.05
Filtration layer
Porosity (%) 72
Thickness (m) 105
Water permeability
(20

C, 1 bar) (l h
1
m
2
)
400
Membrane resistance R
m
(m
1
) 0.9 10
12
S. Ognier et al. / Journal of Membrane Science 209 (2002) 2737 29
Fig. 1. Schematic diagram of experimental set-up.
molecular cut off of the ultraltration membrane
(

=100 kDa), its penetration throughout the membrane

pores is possible.
2.1.3. Bacterial suspensions
The bacterial suspension was taken from a contin-
uous MBR that was working on organic compound
removal in anoxic conditions (oxygen supply by ni-
trate ions). The bioreaction was ensured by a mixed
culture, taken from the aeration tank at the munic-
ipal WWT-plant (WWTP) in Montpellier (France)
and acclimated to the chosen substrate. This one was
prepared by dissolving ethanol and potassium nitrate
in tap water so that the inuent chemical oxygen
demand (COD) concentration and the COD/N ratio
were 1000 mg l
1
and 4.5, respectively. The system
was maintained in a biological steady-state during
more than 1 month before experiment beginning
and therefore, the composition of the MBR suspen-
sion samples can be considered as stabilised. The
working conditions of the MBR are summarised in
Table 2.
Table 3
Suspension characteristics
COD (mg l
1
) Total suspended solids (g l
1
) Turbidity value NTU Protein concentration (mg l
1
)
Raw suspension 2600 1.8 2200
Supernatant 160 <0.001 20 40
Table 2
Biological conditions
Volumetric loading rate (g
COD
l
1
per day) 3
Hydraulic retention time (h) 8
Sludge retention time (day) 3.5
Specic denitrication rate (g
N
g
VSS
1
per day) 0.4
Conversion yield (g
VSS
g
COD
1
) 0.2
COD/N 4
Biomass concentration (g
VSS
l
1
) 1.8
During the experiments, two kinds of suspension
were tested:
the MBR suspension (raw suspension);
the supernatant of the MBR suspension obtained
after centrifugation (acceleration rate = 2g) used
to eliminate the particles and the largest colloids.
The main characteristics of these two suspensions
are given in Table 3. The total protein content of
the suspension was not measured, facing the relative
complexity of the required techniques and the real
interest of this data. Only supernatant protein content
30 S. Ognier et al. / Journal of Membrane Science 209 (2002) 2737
was determined because only soluble proteins are sup-
posed to be able to penetrate inside the membrane ma-
trix. In the supernatant, the protein concentration was
low (40 mg l
1
), what conrmed other published val-
ues [4].
2.2. Experimental procedure
Two different methods were used to quantify the
role of adsorption in membrane fouling: a static
method in which the membrane was immersed in the
biological suspension [5] and a dynamic method
supposing that the resistance due to adsorption is
the irreversible effect that remains after ltration and
back-washing [6]. The back-washing consisted of l-
tering 50 ml of distilled water at 0.5 bar in the opposite
direction to the direction of ltration. A new mem-
brane was systematically used before each experiment
and the water resistance of this clean membrane, R
m
,
was measured to provide a reference value and to ver-
ify that all the membranes used were similar. At the
end of the experiment, the membrane was discarded.
2.2.1. Static method
The membrane was submerged in the bacterial sus-
pension or in the protein solution [5]. The suspen-
sion was gently stirred for 4 h and then the membrane
was removed, subsequently rinsed and back-washed
to eliminate the water reversible effects of fouling.
Finally, the membrane resistance to a distilled water
permeation, R
water
, was measured and used to quan-
tify the effect of the irreversible resistance due to the
adsorption phenomenon, R
ad
: R
ad
= R
water
R
m
.
2.2.2. Dynamic method
Bacterial suspensions or proteins solution were l-
tered through the pressurised ltration cell (Fig. 1) at
constant TMP (P = 0.15 or 0.5 bar) in frontal mode
for between 20 and 70 min. The volume of permeate
was monitored during the ltration process. The per-
meate ux was quantied by measuring the weight
of the ltered water with an electronic balance con-
nected to a computer. The membrane was then rinsed
and back-washed. Finally, the membrane resistance
to a distilled water permeation, R
water
, was measured
and used to quantify the effect of the irreversible
resistance due to the adsorption phenomenon, R
l
:
R
l
= R
water
R
m
.
3. Results
3.1. Protein solutions
3.1.1. Water permeability of membranes
pre-adsorbed by static immersion
Membranes were immersed in various protein so-
lutions (concentrations of 0.5, 1 and 5 g l
1
) and
then clean water was passed through the membranes
(P = 0.5 bar). The value and the effect of the ir-
reversible resistance due to the adsorption, R
ad
are
shown in Table 4. No noticeable fouling was observed
at low concentrations (<1 g l
1
). R
ad
reached a third
of the initial membrane resistance when the concen-
trations were greater than 1 g l
1
. Although, the value
of R
ad
increased with the protein concentration, this
increase was weak compared to the increase in pro-
tein concentration. Thus, in the working conditions,
the protein concentration affected the adsorption
phenomenon, but the relative increase of the total re-
sistance due to adsorption never exceeds 35% of the
initial membrane resistance.
3.1.2. Water permeability of membranes
pre-adsorbed by the dynamic method
3.1.2.1. Measurement of the hydraulic resistance dur-
ing the ltration procedure. Two protein solutions
were tested (0.1 and 1 g l
1
) and the ltration tests
were carried out with two different TMPs (0.15 and
0.5 bar). Fig. 2 shows how the volume of the permeate
changed during the procedure.
As classically observed, for a given ltration time,
the volume of the permeate increased with pressure
and decreased with protein concentration.
The changes in the ltered volume can be described
by the cake ltration law, in which the ratio t/V is a
linear function of V (Fig. 3):
t
V
=
C
2 P
2
V +
R
init
P
Table 4
R
ad
and R
ad
/R
m
values for the different tested conditions
Protein concentration (g l
1
)
0.1 1 5
R
ad
(m
1
) <0.1 10
12
0.1 10
12
0.3 10
12
R
ad
/R
m
<0.1 0.11 0.33
Fig. 2. Filtered volume vs. time under 0.15 and 0.5 bar with 0.1 and 1 g l
1
protein solution.
Fig. 3. t/V vs. V under 0.15 and 0.5 bar with 0.1 and 1 g l
1
protein solution. The straight lines correspond to the tting of the nal steps
of fouling to the cake ltration model.
32 S. Ognier et al. / Journal of Membrane Science 209 (2002) 2737
The linear plot was used to calculate the specic cake
resistance and the initial membrane resistance, R
init
(Table 5).
Regardless of the concentration of the protein
solution, the experimental results showed that:
The value of is independent of the TMP and is
approximately equal to 2.610
14
mkg
1
. Thus, the
protein layer is not compressible in the experimental
range of the tested TMP values.
The values of R
init
are similar and close to 1.8
10
12
m
1
. These values are double the clean mem-
brane resistance, R
m
, thus (R
init
R
m
)/R
m
= 1.
This result suggests that an initial fouling pheno-
menon occurs at the very beginning of the run,
before the cake has built up, and that it involves a rapid
decrease in the permeate ux. According to the results
of Martinez et al. [7], this step is essentially due to an
adsorption phenomenon. Indeed, these authors showed
that (i) at low concentrations, the fouling is mainly
due to adsorption and that (ii) at high concentrations,
the solutesolute interactions leads to further fouling,
corresponding to a deposition. This seems to conrm
our experimental results and the cake ltration law.
Finally, two different steps were observed during
the ltrations of -lactoglobulin solutions:
an immediate fouling phenomenon involving
doubling the resistance of the system;
Table 5
Values of and R
init
Protein concentration (g l
1
)
0.1 1
TMP (bar) 0.15 0.5 0.15 0.5
(mkg
1
) 2.60 10
14
2.15 10
14
2.75 10
14
3.05 10
14
R
init
(m
1
) 1.56 10
12
1.70 10
12
1.75 10
12
2.22 10
12
Table 6
R
l
and R
l
/R
m
values for the tested conditions
Protein concentration (g l
1
)
0.1 1 5
0.15 bar
R
l
(m
1
) 0.9 10
12
0.9 10
12
0.9 10
12
R
l
/R
m
1 1 1
0.5 bar
R
l
(m
1
) 0.63 10
12
0.63 10
12
0.63 10
12
R
l
/R
m
0.7 0.7 0.7
a progressive decrease in the ux that can be
described by a cake ltration law.
However, although R
init
is caused by pure adsor-
ption, it is different from the value of R
ad
recorded
during the immersion experiments.
3.1.2.2. Measurement of the hydraulic resistance
after membrane cleaning. After the ltration of pro-
tein solutions, the membrane was washed with water
and back-washed to ensure the total elimination of
the reversible fouling. The irreversible resistance, R
l
,
was measured and the R
l
/R
m
ratio was estimated
(Table 6).
The results show that:
TMP has no signicant inuence on the irreversible
fouling resistance;
in the experimental concentration range (0.15 g l
1
),
R
l
is independent of concentration and the R
l
/R
m
ratio is very close to 1.
In summary, the experiments conducted on protein
solutions showed that:
(i) the values measured by the static method depend
slightly on concentration;
(ii) the values measured by the dynamic method do
not depend on pressure and concentration, and
were greater than values measured by the static
method;
S. Ognier et al. / Journal of Membrane Science 209 (2002) 2737 33
Table 7
R
ad
and R
ad
/R
m
values for the different tested conditions
Raw suspension Supernatant
R
ad
(m
1
) <0.1 10
12
0.07 10
12
R
ad
/R
m
<0.1 0.08
(iii) the initial fouling, which occurs at the beginning
of the ltration process, induces a similar fouling
resistance to the irreversible resistance measured
by the dynamic method.
3.2. Bacterial suspensions
3.2.1. Water permeability on membrane
pre-adsorbed by static adsorption
The hydraulic resistance was calculated after mem-
brane immersion in MBR suspensions and water
cleaning (Table 7).
Regardless of the suspension tested, the decrease in
membrane permeability was relatively low (less than
10% of the clean membrane permeability). The ad-
sorption phenomenon induced by the static procedure
seems to be very weak. This is not surprising in view
Fig. 4. Filtered volume vs. time under 0.5 bar with the raw sludge suspension and its supernatant.
of the low concentration of proteins in the soluble part
of MBR suspension (see Table 2). The resistances
obtained after immersing the membrane in weakly
concentrated protein solutions are generally low.
3.2.2. Water ux of membranes pre-adsorbed by
dynamic adsorption
3.2.2.1. Measurement of the hydraulic resistance dur-
ing the ltration procedure. Fig. 4 shows how the
ltered volume changed over time during the frontal
ltration (P = 0.5 bar) of the MBR suspension and
the supernatant.
These results showed that the MBR suspension
induces more fouling than the supernatant. The foul-
ing mechanism is due both to the interaction of solu-
ble compounds with the membrane matrix and more
particularly to phenomena caused by the presence of
particular elements.
A straight line was obtained when plotting t/V
versus V (Fig. 5). This indicates that the changes in
the evolution of the ltered volume can be described
by the cake ltration model. A specic resistance of
3 10
15
mkg
1
was obtained for the raw suspension,
34 S. Ognier et al. / Journal of Membrane Science 209 (2002) 2737
Fig. 5. t/V vs. V under 0.5 bar with the raw sludge suspension and its supernatant. The straight lines correspond to the tting of the nal
steps of fouling to the cake ltration model.
10 times higher than values observed with protein sus-
pension. This is consistent with the resistance reported
by Kim et al. [8]. With the supernatant, the value of
the slope of t/V versus V (2.7610
12
s m
6
) was sim-
ilar to that obtained with the 1 g l
1
protein solution
(2.4 10
12
s m
6
), although, the protein concentra-
tion was far lower in the supernatant (40 mg l
1
).
This conrms that the macromolecular compounds
present in the soluble part of the activated sludge are
not only proteins. Due to the experimental errors at
the beginning of the ltration, R
init
values could not
be measured precisely. However, their values, ranged
from 0 to 3 10
12
m
1
, were of the order of the R
init
values measured with the protein solutions.
3.2.2.2. Measurement of the hydraulic resistance after
membrane cleaning. As described in Section 3.1.2.2,
the remaining resistance after cleaning of the mem-
brane, R
l
, was evaluated (Table 8). The value of R
l
was the same for both kinds of suspension. It was close
to 0.310
12
m
1
, which corresponds to a R
l
/R
m
ratio
equal of 0.3. At the end of the MBR suspension ltra-
tion, the total resistance, R
tot
, was measured and com-
pared with R
m
and R
l
(Table 9). The different values
of R
tot
for the supernatant corresponded to different
ltration times. The value of R
tot
/R
m
obtained with
the raw suspension is particularly high (88) due to the
formation of a sludge cake on the membrane surface.
The irreversible part of the fouling is always in-
signicant in comparison with the total resistance and
the major part of the resistance in frontal ltration
mode was the reversible part that could be removed
by back-ushing. These observations conrm the pre-
vious hypothesis that the main fouling mechanism is
a build-up of a non-cohesive cake on the membrane
or a pore blocking phenomenon. The results are com-
parable with the work of Roorda and Van der Graaf
Table 8
R
l
and R
l
/R
m
values for the different tested conditions
Raw suspension Supernatant
R
l
(m
1
) 0.3 10
12
0.2 10
12
R
l
/R
m
0.33 0.22
S. Ognier et al. / Journal of Membrane Science 209 (2002) 2737 35
Table 9
R
tot
, R
l
and R
l
/R
tot
values for the different tested conditions
Raw suspension Supernatant
R
tot
(m
1
) 80 10
12
2 10
12
8 10
12
12 10
12
R
tot
/R
m
88 2.2 8.9 13
R
l
(m
1
) 0.3 10
12
0.2 10
12
0.1 10
12
0.2 10
12
R
l
/R
tot
0.004 0.100 0.012 0.017
[9] where, after WWTP-efuent ltration in frontal
mode, the fouling layer was removed by back ushing
with a reversibility of over 80%.
Finally, the experiments conducted on bacterial
suspensions showed that:
(i) the values measured by the dynamic method were
greater than those values measured by the static
method;
(ii) the irreversible part is due to the soluble fraction of
the suspension and is independent of the ltration
time. This indicates that the irreversible fouling
phenomenon mainly occurs at the beginning of
the process. Roorda and Van der Graaf [9] also
found that the ltration time had no inuence on
the irreversible resistance, except when the ltered
volume was very large, probably due to a cake
consolidation phenomenon with time.
Some similarities were noted with the results car-
ried on protein solutions: the values measured in the
dynamic method were greater than those values mea-
sured by static immersion, there was a rapid initial
fouling phenomenon, and cake build-up. The value of
R
l
for the BRM suspension was three times lower that
of the protein solution. This could be due to the differ-
ent composition of the two suspension types (nature
and/or concentration of macromolecular compounds).
However, in both cases, the observed values show that
the adsorption phenomenon induces a small part of
the total fouling.
4. Discussion
4.1. Comparison between the static and dynamic
adsorption methodsmonolayer adsorption
hypothesis
The experimental results show that the two ad-
sorption methods are not equivalent. The additional
resistance value obtained by the static method is al-
ways lower than that measured in the dynamic method
and it slightly depends on the solution concentra-
tion. In static mode, the proteins penetrate inside the
porous matrix only by diffusion that directly depends
on compound concentration in the bulk. However, at
the pore entrance, an electrical repulsive barrier can
be constituted (actually a 7.5 pH is above the isoelec-
tric point of the protein and therefore, proteins are
negatively charged and tend to repulse each other). If
this electrostatic repulsion is not negligible compared
to the diffusional force, proteins can be prevented
from reaching all the adsorption sites and so the the-
oretical adsorption equilibrium can not be reached.
Therefore, the quantity adsorbed after static adsorp-
tion is below maximal quantity corresponding to the
equilibrium.
Thus, due to the convective ow of the suspen-
sion throughout the membrane material, the dynamic
method should be the best one for determining the
effects of adsorption. This suggests that the absence
of a relationship between R
l
and concentration is
due to a monolayer adsorption. To verify this hypoth-
esis, the ow property of the membrane was analysed
according to Poiseuilles law.
For a membrane with uniform cylindrical pores,
the membrane resistance depends on the membrane
thickness, Z, the voidage fraction, , and the specic
surface area, S
m
, such as,
R
m
= kS
2
m
(1 )
2

3
Z (1)
According to the experimental results, the charac-
teristics of the membrane (Table 1) and k equal to 4.5
(Kozeny Karman law), the specic surface area, S
m
,
can be calculated by using Eq. (1), i.e. 9 10
7
m
1
.
To quantify the additional resistance caused by
monolayer adsorption, R
mono
, the porosity,
ad
, and
the specic surface area, S
ad
, of the adsorbed mem-
brane have to be estimated.
36 S. Ognier et al. / Journal of Membrane Science 209 (2002) 2737
Two hypothesis were suggested:
(i) the specic surface area, S
ad
, of the adsorbed
membrane is almost the same as the specic
surface area of the clean membrane [4] and so,
R
mono
R
m
=
(1
ad
)
2

3
(1 )
2

3
ad
1 (2)
(ii)
ad
can be determined by the following equation:

ad
=
V
adsorbed proteins
Z
(3)
If we suppose that the spherical -lactoglobulin
molecules are closely packed on the available mem-
brane surface,
V
adsorbed proteins
=
4
6
d
lactoglobulin
S
m
Z(1 ) (4)
The value of
ad
thus obtained is 0.66, approxi-
mately 15% lower than the porosity of the clean mem-
brane ( = 0.72). According to Eq. (3), the R
mono
/R
m
ratio was 0.92.
It is noteworthy noticed that R
mono
/R
m
is close to the
experimental value R
l
/R
m
which is equal to 1. This
supports the hypothesis of a close packed monolayer
of -lactoglobulin adsorbed on the membrane surface,
which in turn suggests that the dynamic method is a
valuable method for measuring adsorption.
4.2. Role of adsorption in membrane fouling in the
case of a MBR
In subcritical conditions, the formation of a macro-
scopic deposit on the membrane should be avoided.
Therefore, the fouling increase is extremely slow and
the membrane resistance can be considered as constant
with time: a stable ltration regime is obtained. How-
ever, the membrane resistance differs from the clean
one, indicating that a fouling phenomenon takes place.
In subcritical conditions, it was reported that this con-
stant fouling resistance did not depend on hydrody-
namic conditions. Considering these results, one can
ask about the role of internal fouling. Let us consider
some of the results published in the literature:
Tardieu et al. [1] and Fan et al. [2] used activated
sludge ultraltration on tubular ceramic membranes
with a pore size of 0.02 m. They show that the ini-
tial fouling resistance values were below 30% that
of the clean membrane. Then, a very slow increase
in fouling resistance with time was observed in sub-
critical conditions.
Defrance and Jaffrin [10] measured, in short term
experiments with subcritical conditions, a foul-
ing resistance equal to 2.3 10
12
m
1
. This was
approximately 10 times higher than the clean mem-
brane resistance (ceramic membrane with 0.1 m
pores, R
m
= 0.24 10
12
m
1
).
Beaubien et al. [11] studied membrane fouling
in the low pressure zone of an anaerobic MBR
with ceramic membranes of 0.2 m pore diame-
ter. The membrane resistance was independent of
pressure and shear stress and the fouling resistance
values ranged from 1 10
12
to 5 10
12
m
1
when the suspended solids concentration var-
ied from 0.5 to 20 g l
1
, which corresponded to
220 times the resistance of the clean membrane
(0.25 10
12
m
1
).
These results show that in subcritical conditions,
the fouling resistance values range from 20 to 2000%
of the clean membrane resistance R
m
. When the pore
diameter is small (0.02 m), the subcritical fouling re-
sistance values are comparable to those obtained in
the present study, below 100% of the clean membrane
resistance. However, they increase dramatically when
pore size increases (microltration range) with foul-
ing resistance values from 400 to 2000% of the clean
membrane resistance.
If the fouling compounds liable to adsorb on the
membrane material adsorption were only small macro-
molecules, the adsorption phenomenon would induce
a more signicant fouling for small pore diameters.
Therefore, it means that the greater sensitivity of mi-
croltration membranes to fouling is caused by high
molecular weight compounds unable to penetrate in
the membrane matrix when the pore diameter is in
the ultraltration range. For large enough pore diam-
eter, these compounds can adsorb or be physically
blocked in the membrane pores. Thus, the choice of
pore size is a critical point as are the hydrodynamic
conditions. In the case of a MBR used for wastewa-
ter treatment, the results show that the ultraltration
range is more efcient than the microltration one to
prevent the irreversible fouling: in this case, the resis-
tance increase is only due to adsorption and remains
relatively low.
S. Ognier et al. / Journal of Membrane Science 209 (2002) 2737 37
5. Conclusion
Adsorption experiments on synthetic protein so-
lutions and MBR suspensions allowed us to charac-
terise and to quantify the inuence of adsorption on
membrane fouling. It was shown for the two types of
suspensions that:
1. due to limited diffusion, the dynamic method
(irreversible fouling remaining after ltration)
appears to be more adapted than the static method
(membrane immersion);
2. adsorption is a rapid fouling phenomenon that in-
duces irreversible resistance; adsorption takes place
at the beginning of the ltration process before the
deposition mechanism;
3. the adsorption phenomenon shows specic hy-
draulic resistance of the same order of magnitude
as the clean membrane resistance;
4. in the ultraltration range, the membrane resistance
increase obtained in a MBR in subcritical condi-
tions can be explained by an adsorption pheno-
menon. In the microltration range however, higher
size compounds seems to be involved in the fouling.
However, during long-term treatment operation in
a MBR, sudden malfunctions can be observed even
in subcritical conditions [12] and further research is
needed to elucidate the phenomena at the origin of
these sudden resistance increases.
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