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Micropollutants Removal and Operating

Strategies in Ultrafiltration Membrane Systems
for Municipal Wastewater Treatment:
Preliminary Results
ARTICLE in INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH AUGUST 2007
Impact Factor: 2.59 DOI: 10.1021/ie070017r

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6716

Ind. Eng. Chem. Res. 2007, 46, 6716-6723

Micropollutants Removal and Operating Strategies in Ultrafiltration Membrane

Systems for Municipal Wastewater Treatment: Preliminary Results
Paolo Battistoni,*, Emanuela Cola, Francesco Fatone, David Bolzonella, and Anna Laura Eusebi
Institute of Hydraulics and Transportation Infrastructures, Marche Polytechnic UniVersity, Via Brecce Bianche,
60131 Ancona, Italy, and Department of Science and Technology, UniVersity of Verona, Strada Le Grazie 15,
Ca` Vignal 37134 Verona, Italy

Membrane systems are reported to enhance the removal of micropollutants (heavy metals and organic persistent
compounds) from wastewaters. However, with regard to real municipal wastewater, where the micropollutants
are present at very low concentrations, the debate on the real convenience of operating membrane systems is
still ongoing. This paper presents the preliminary results from a pilot study where the removal of several
micropollutants (80 compounds, grouped in the families of metals and metalloids, polynuclear aromatic
hydrocarbons (PAH), volatile organic compounds (VOC), halogenated volatile organic compounds (HVOC))
from real municipal wastewater was studied using an ultrafiltration membrane system. With the purpose to
optimize the removal performances, the prime objective was to determine the best plant configuration, tertiary
filtration, or membrane bioreactor, as well as the best operating parameters, with particular concern to the
activated sludge concentration. To expand the practical interest of the results for application in real plants,
the sludge filterability also was studied according to different activated sludge concentrations and permeate
fluxes. The objective was to estimate operating parameters able to enhance the removal of micropollutants
and optimize the ultrafiltration process. After one year of experimentation, the results that were obtained
gave important indications about the real role of the membrane system. The membrane not only demonstrated
that it could be a simple barrier against the particulate pollutants, but it also demonstrated that it can enhance
the removal of dissolved micropollutants, thanks to the layer effect.
Introduction
The necessity to produce treated wastewaters with highquality standards for discharge or reuse implies the adoption of
very effective processes in the field of wastewater treatment.
Among the best-available techniques (BAT), the membrane
bioreactor (MBR) is supposed to be also the best choice for
enhancing the biochemical process performances.1 Recently,
many researchers have studied different peculiarities of MBRs
and their applications,2 with reference to different topics such
as the filterability of sludge,3 the overall feasibility of the
widespread application of MBRs,4 or parameters linked to the
critical flux.5 Numerous studies have showed that the MBRs
have the capacity to efficiently remove conventional pollutants
(carbon, nutrients, suspended solids, pathogens), as well as heavy
metals6 and organic persistent compounds, to obtain reusable
water and high quality standards.7-9 However, in regard to
treating real municipal wastewater, the actual benefits of
adopting membrane technology are still controversial.6
Besides the performance, the process configuration also
should be considered (i.e., the choice between tertiary filtration
(TF) or MBR processes), because these two schemes involve
almost different capital and operation and maintenance (O&M)
costs.10,11
In light of the scenario just outlined, this paper examines
the treatment of real municipal wastewaters by ultrafiltration
(UF) membranes, operating both as TF and as a filter submerged
in the activated sludge, and it focuses on numerous micropol* To whom correspondence should be addressed. Tel.: +39 071
2204530. Fax: +39 071 2204528. E-mail: p.battistoni@univpm.it.

Institute of Hydraulics and Transportation Infrastructures, Marche

Polytechnic University.

Department of Science and Technology, University of Verona.

lutants. Furthermore, the filterability of the activated sludge was

also investigated. This 2-fold approach could allow one to
evaluate whether an operating strategy that optimizes the
removal performances can be also industrially sustainable for
the membrane system. Therefore, the final intention of this
study was to draw useful considerations about the design and
operation of the membrane plants for municipal wastewater
treatment.
Materials and Methods
The Municipal Wastewater Treatment Plant (WWTP)
and the Membrane Pilot Plant. The study was conducted
using a large pilot plant hosted in a full-scale municipal
wastewater treatment plant (WWTP) that had a treatment
capacity of 85 000 population equivalent (PE). Its operation units
were fairly conventional, as shown in Figure 1 and detailed in
Table 1. The membrane pilot plant adopted a ZeeWeed (GEZenon) hollow fiber module; the main characteristics of this
pilot plant are reported in Table 2, together with the main
features of the filtration chamber. As shown in Figure 2, the
pilot plant was equipped with several on-line probes and meters
that measured properties such as the following: transmembrane
pressure (TMP), permeated/backwashed flow rates, soluble
chemical oxygen demand (COD), conductivity, turbidity in the
permeate, temperature, and suspended solids in the filtration
chamber.
The pilot plant could operate at fixed permeate fluxes (J),
set by a program line controller (Figure 2) and a frequency
regulator for the process pump. The filtration cycle was
composed of suction (300 s) and backwashing (30 s). At the
end of each test, the original conditions of the membrane were
re-established by submerging the module in hypochlorite

10.1021/ie070017r CCC: $37.00 2007 American Chemical Society

Published on Web 08/04/2007

Ind. Eng. Chem. Res., Vol. 46, No. 21, 2007 6717

Figure 1. Full-scale wastewater treatment plant (WWTP) and location of

the membrane pilot plant.
Table 1. Main Features of a Full-Scale Wastewater Treatment Plant
(WWTP)
parameter

value

primary circular settler

number
volume
biological process
number of lines
total volume, pre-denitrification
total volume, nitrification
air blowers
total power
secondary settler with radial flow
number
volume

2
1325 m3
2
3500 m3
2450 m3
4
240 kW
2
1608 m3

Sampling and Analysis Methodology. Two types of automatic samplers were used to collect composite samples of
wastewaters over a period of 24 h: the first was conventional
and the second was expressly designed for the experimentation
(it was equipped with a ZeeWeed10 membrane module). The
two samplers allowed one to obtain samples, averaged over 24
h, for the determination of the total concentration of pollutants
and their distribution in the liquid and solid phases. The samples
were collected from the main streams of both the full-scale
WWTP and the pilot plant. In particular, daily averaged samples
were taken from the influent sewage, the effluent from the
primary treatment, the waste-activated sludge (WAS), the
effluent from the full-scale secondary clarifier (which was the
influent to the pilot plant), and the membrane permeate. The
first screening for the characterization of the wastewater
considered the determination of some 80 parameters, according
to the United States Environmental Protection Agency (USEPA)
methods.12 Among the compounds, heavy metals, volatile
organic compounds (VOCs), halogen volatile organic compounds (HVOCs), and polynuclear aromatic hydrocarbons
(PAHs) were detected.
Parallel and Contemporary Tests. Two types of parallel
and contemporary tests were performed. The pilot plant that
was operating as a MBR-like reactor at 5 g MLSS/L was used
in parallel to (i) the previously mentioned UF sampling system
in TF modality, in the Type 1 test; and (ii) a laboratory-scale
filtering system that was equipped with a cellulose membrane filter (with nominal pore size of 0.45 m), in the Type 2
test.

Table 2. Main Characteristics of the Membrane Pilot Plant

characteristic

value

membrane model
module dimensions
nominal pore size
filtration type
module configuration
membrane type
membrane area
filtration chamber volume
analysis tank volume
permeate tank volume

ZeeWeed 500
1000 mm 700 mm 200 mm
0.04 m
out to in
submerged
hollow fiber
21.6 m2
1400 L
210 L
145 L

solution (200-600 mg Cl/L) for 4-12 h, always keeping the

scouring aeration switched to on mode.
The membrane pilot plant was located between the secondary
clarifier and the disinfection contact tank (see Figure 1). This
choice allowed one to (a) easily feed the membrane system with
fresh effluents from the secondary clarifier, and (b) use NaClO
from the disinfection section for the chemical cleanings of the
UF membrane.
Membrane Pilot System: Tertiary Filtration (TF) and the
Membrane Bioreactor-Like (MBR-like) Configuration. The
experimental tests were performed by feeding the filtration
chamber with both secondary clarified effluent (to obtain the
TF modality) and activated sludge that was thickened differently
via the addition of secondary effluent, according to the
experimental test (to obtain a form of MBR-like modality). In
regard to the MBR-like configuration, the objective of the
experimentation was to determine the pure effect of the
membrane system, under different concentrations of mixed
liqour suspended solids (MLSS), on the removal of micropollutants. Hence, at the beginning of each test, the filtration
chamber was fed with activated sludge that was taken from the
full-scale plant and the test lasted for 4 days. According to this
approach, the characteristics of the activated sludge in the pilot
plant and the full-scale WWTP were always similar.

Results and Discussions

Micropollutants in the Main Stream of the Full-Scale
WWTP. To compare the performances of the membrane system
and the conventional WWTP, the micropollutant concentrations
were determined in the main streams of both processes. Great
variability of the influent concentrations of hazardous compounds was observed, as a consequence of nonidentifiable
reasons. Therefore, Table 3 reports the ranges of concentration
grouped by the family of compounds that may well show the
basic roles of the different operation units. Generally, the
occurrence and removal of metals was consistent with the data
reported for other municipal WWTPs that treat municipal or
municipal/industrial wastewaters.13-15 In regard to the PAHs,
the influent wastewater showed contents that were lower than
those of other cases;16,17 nevertheless, the concentrations were
on the order of micrograms per liter (g/L) and allowed us to
suppose the presence of industrial discharges in the catchments
area.18 The volatile compounds were almost organic solvents
that had been probably discharged from local factories into the
sewer system; their occurrence were very variable but always
<20 g/L.
Organic Persistent and Hazardous Compounds. The
influent raw wastewater originated primarily from a urban area.
The compounds present in the greatest amounts were as
follows: benzene, toluene, and xylenes (BTEX) (1.31-2.15 g/
L) among the VOCs; naphthalene (0.091-0.126 g/L), fluorene
(0.022-0.074 g/L) and phenanthrene (0.033-0.047 g/L)
among the PAHs; and chloroethylenes and methylene chlorides
(0.9-8.95 g/L) among the HVOCs. With specific reference
to this class of compounds, the first significant removal of
VOCs, PAHs, and HVOCs occurred already in the physical
headworks (screening, aerated degritting, and primary sedimentation). The effect of these processes can be more or less
important, depending on the characteristics of those compounds,

6718

Ind. Eng. Chem. Res., Vol. 46, No. 21, 2007

Figure 2. Pilot-plant flow scheme.

Table 3. Micropollutants Ranges in the Main Streams of the Full-Scale WWTPa
Range of Micropollutant (g/L)

samples taken from:

influent raw
wastewater

outflow from the

physical headworks

effluent from
full-scaleWWTP

UF permeate

metalsb
VOC
PAH
HVOC

18.00-265.00
0.65-7.10
0.23-0.67
1.45-12.17

9.00-112.00
0.23-2.98
0.08-0.27
0.92-5.59

7.70-93.60
0.12-0.80
0.07-0.26
0.23-5.08

4.70-56.00
0.01-0.25
0.05-0.16
0.05-0.52

a Data refer to the total concentrations over the entire experimental period; membranes are applied both as tertiary filtration (TF) and as MBR-like.
Includes Cu, Cd, Hg, Cr, Ni, Pb, and As.

Table 4. Organic Micropollutants Partition in the Liquid Phase

micropollutant
volatile organic compounds, VOCs
polyaromatic hydrocarbons, PAHs
log kow < 5.0
log kow > 5.0
halogen volatile organic compounds, HVOCs

percentage of
compounds in
the liquid phase
>99
<50
<6.0
>99

as well as the solid/liquid partition coefficient and their volatility

(see Table 4). In particular, volatile compounds (VOCs and
HVOCs) were almost completely dissolved and were easily
stripped by blowing air and water movements. On the other
hand, PAHs are both dissolved in the liquid phase and associated
with the suspended particulate, according to the octanol-water
partition coefficient (kow). This behavior is consistent with the
fact that PAHs are rather hydrophobic and, therefore, have a
tendency to associate with the particulate matter. Therefore,
PAHs can be removed in the physical/mechanical headworks
both by gravity separation, if linked to the suspended particulate,
and by volatilization, if very volatile (i.e., naphthalene).17,19 On
the other hand, VOCs can be removed in the biological process
tank, as a result of the volatilization in the aerated tank. In
contrast, no remarkable effects were observed for the PAHs,
probably because these compounds are present at very low
concentrations already in the effluent of primary sedimentation.
Unexpectedly, HVOCs remained at the same concentration,
while an additional removal by stripping and biodegradation
was expected. Therefore, it could be reasonably assumed that,
in the municipal WWTPs, the possible volatilization of HVOCs
could be almost completed before the secondary biological
treatments.

The effect of the UF membrane was significant for the

removal of the organic micropollutants, because of its barrier
effect. HVOCs underwent the most important removal. This
evidence, when coupled to the low removal observed in the
full-scale conventional biological process, indicates that HVOCs
are partially recalcitrant to biodegradation but can be retained
by the sieving effect of the UF membrane. Unfortunately, the
HVOC contents in the activated sludge (on dry basis) were
always below the limits of quantification and did not allow us
to verify the mass balances.
Metals. Heavy metals and metalloids (Cu, Cd, Hg, Cr, Ni,
Pb, As) observed in the influent raw wastewater are mainly
represented by Cu (13-94 g/L), Cr (7-45 g/L), Ni (4-51
g/L), and Pb (5-15 g/L), whereas As, Hg and Cd usually
showed a minor occurrence (typically <1 g/L). Also, in this
case, the preliminary treatments could have an important role,
both in degritting and in primary sedimentation. This fact was
partially in agreement with the partitioning between the liquid
and solid phases: the maximum soluble fraction (90%) was
observed for Ni and the minimum (<4%) for Hg. Differently
from the fate of organic micropollutants, the activated-sludge
process had a significant effect on the removal of metals, mainly
because of the sorption/precipitation on the biomass and/or the
extracellular polymeric substances (EPS). This behavior has
been widely observed and reported in the literature.20,21 The
resulting concentrations of heavy metals in the activated sludge,
expressed in terms of mg (kg SS)-1, are shown in Table 5.
Because of their concentration in the sludge, a low presence of
suspended solids in the effluent also can result in a significant
concentration of heavy metals in the effluent. With specific
reference to the presence of heavy metals in the effluent, it

Ind. Eng. Chem. Res., Vol. 46, No. 21, 2007 6719
Table 5. Heavy Metals in the Activated Sludge
element

average
(mg/kg SS)

standard deviation
(mg/kg SS)

As
Hg
Cu
Pb
Cd
Ni
Cr

3.6
2.1
347.8
61.1
1.2
106.9
525.1

1.3
1.7
28.6
11.2
0.6
48.3
129.1

Table 6. Removal of Metals from the Dissolved Phase: MBR-like

and TF Modality
Percentage Removal (%)
metal
Cu
Pb
Cd
Ni
Cr

influent concentration
range (g/L)
5.6-75.0
3.5-11.0
0.4-7.7
3.4-90.0
2.8-40.0
TSS range

MBR-like

TF

81
74
64
41
85

50
34
17
33
73

2500-10000 mg/L

5-1500 mg/L

should be noted that the most persistent are Crtot, Ni, and Cu,
while Pb is present in a minor amount.
In regard to the overall effect of the membrane system, a
further removal of 40%-50% was observed. This can be
attributed to the sieving effect, as well as other phenomena that
are better discussed in the following section of the paper.
Optimization of Heavy-Metals Retention: MBR or TF?
After the macroscopic effect of the UF membrane on the
removal of priority pollutants was estimated, the role of the
UF membrane was better investigated. The effect of the MBRlike and TF configurations is described and discussed in this
section. For this purpose, metals that were used in operation of
the plant were monitored according to the configuration shown
later in this paper in Figure 5. However, note that, during TF
tests, the concentration of activated sludge into the membrane
tank led to values of 1.5 g/L, whereas in the MBR-like modality,
the concentrations were in the range of 2.5-10 g/L and were
kept stable at the desired levels by adjusting the influent flow
rates. Furthermore, it is not worth noting again that, according
to the methodology of the test previously described, the MBRlike configuration reproduced only the impact of different
activated-sludge concentrations on the membrane role. In fact,
the characteristics of the activated sludge, both physicochemical
and microbiological, were typical of the conventional activatedsludge process from which the sludge originated.
Twelve experimental tests were performed, always treating
the real liquor effluent from the secondary clarifiers of the
WWTP. Table 6 shows the concentrations of heavy metals
influent to the membrane filtration system and the average
removals obtained in MBR and TF configurations, respectively.
The TF configuration showed satisfactory metals removal
(17%-70%), but the value always was less than that observed
in the MBR-like configuration. This particular observation
suggests that, besides the barrier effect exerted by the membrane,
the fouling and/or cake layer on the membrane area may have
a role on the removal of metals in the liquid phase. Furthermore,
because the hydrodynamic conditions were the same, the higher
removal performances (increases in the range of 8%-47%) of
the MBR configuration indicated that different biomass concentrations enhance the layer effect. This fact suggested that
an equilibrium occurred between the metal ion concentration
in the aqueous phase and the metal in the sludge, probably on
or close to the membrane surface, where a higher concentration

of heavy metals is observed as an effect of concentrationpolarization phenomena and fouling and/or cake layer formation.
To confirm the previous results and to better investigate the
sieving and the layer effects, contemporary and parallel
investigations were performed, according to the method described in the previous section.
The comparison between the different configurations of the
membrane systems is reported as proportional values and,
therefore, can be simply calculated, according to eq 1:

modality )

C e - Cp
100
Ce

(1)

where Ce is the concentration of metal in the effluent from the

TF and Cp is the concentration of metal in the effluent from
the MBR-like configuration.
Results reported in Table 7 confirm that the MBR modality
is more effective than the TF filtration. Furthermore, although
considerations are possible only for Cu and Ni, which were
always over the detection limits, the benefits of the MBR-like
modality, with respect to the TF configuration, are comparable
in test types 1 and 2. This experimental evidence may indicate
the major effect of the layer on the role of the membrane system,
which seems to be dependent on neither the membrane material
nor the pore size.
Consideration on the TMP Decline: TF and MBR. To
generalize the results also for a possible industrial application
of the system, the results about micropollutants removal must
be coupled with considerations about the fouling of the
membranes in TF and MBR configuration. Therefore, a detailed
campaign of filtration tests was conducted to study the
membrane fouling rates, which are defined as the decline of
TMPs over time (or increase as TMPs absolute value). The
final objective of this activity was to study the conditions that
both optimize the membrane life and operation and, at the same
time, enhance the removal of the micropollutants.
To evaluate the long-term performances, each filtration test
lasted four days or more (except for test 1). This approach
allowed the steady-state fouling rates to be taken into consideration, avoiding the need to consider the initial conditioning
fouling11 in the calculations. At the end of each test, the initial
conditions of the membrane surface were re-established by
chemical cleaning, according to the protocol described in the
Materials and Methods section of this paper.
The TMPs of the TF operation are reported in Figure 3,
whereas Table 8 reports the steady-state fouling rates. Considering that the critical flux for this type of membrane was reported
to be in the range of 17-30 LMH5 (where the term LMH
means liters per square meter per hour), tests 1, 2 and 3 clearly
were conducted under stressed conditions, whereas tests 4 and
5 were performed under conditions of subcritical flux, where
low or null fouling rates are generally observed. Here, the
conditioning fouling lasted the first day, when the TMP decline
was less severe, whereas the steady-state fouling rate was
observed from the second day onward. As expected, the higher
the permeate flux, the faster the membrane fouling; however,
unexpectedly, the net flux (34 LMH) involved a lower TMP
decline (0.028 bar/d).
Operating the direct filtration of the activated sludge (MBRlike), the membrane permeability was studied by applying
different permeate fluxes, in the range of 7-20 LMH, according
to different suspended solids concentrations (in the range of
0.5-10 g MLSS/L. According to the scale of the experimentation, also in this case, the objective was to study the macroscopic

6720

Ind. Eng. Chem. Res., Vol. 46, No. 21, 2007

Figure 3. Behavior of the membranes working in tertiary filtration (TF) modality. Table 5 reports the fouling rates.

Table 7. Metals Removal: Comparison between MBR and TT Modality

Test Type 1

metal

concentration
range (g/L)

As
Hg
Cu
Pb
Cd
Ni
Cr

<2
<2
16-52
5-7
<0.25
20-29
9-11

Test Type 2

[(Ce - Cp)/Ce] 100 (%)

nda
nda
69
20
nda
18
32

concentration
range (g/L)

[(Ce - Cp)/Ce] 100 (%)

<2
<2
5.6-10.6
<2.5
<0.25
3.4-9.5
<2.5

nda
nda
60
nda
nda
24
nda

Not detected.

Table 8. Filtration Tests in TT Configuration

test

permeate flux
(LMH)

TMP decline
(bar/d)

MLSS concentration
(g/L)

5
4
3
2
1

7
14
20
27
34

-0.001
-0.001
-0.055
-0.063
-0.028

0.014
0.017
0.013
0.025
0.055

phenomena. Figure 4 shows the TMP trends during the test at

0.5, 2, 5, and 10 g MLSS/L, and Table 9 reports the main results
obtained. As a general and most-evident remark, the higher the
permeate flux, the more evident the impact of the MLSS
concentration on the fouling phenomena.
Although no relevant changes were observed when the
permeate flux was much lower than the critical value (7 LMH
(see Figure 4a)) and approaching the critical flux (e.g., 14 LMH
(see Figure 4b)), the membrane was more sensitive to the MLSS
concentration. As a result, passing from 2 g MLSS/L to 5 g
MLSS/L, the TMP decline increased from -0.006 bar/d to
-0.03 bar/d.
However, no further decrease of the TMP decline was
obtained when passing from 5 g MLSS/L to 10 g MLSS/L (see
curves C and D in Figure 4b). Therefore, among the MLSS
contents typically applied for municipal wastewaters treatment,
certain values in the range of 2-5 g MLSS/L were supposed
to mark the borderline between weak and severe fouling
phenomena. Furthermore, when the permeate flux was supposed
to be close to the critical flux (e.g., 20 LMH (see Figure 4c)),
the TMP decline was not remarkably influenced by the MLSS
concentration. However, its effect was clearly visible in the
starting TMP (that is, the initial pressure) soon after the
triggering of the filtration.
All experimental results can be simply summarized by
plotting the membrane permeability (Js) versus the net flux (J),

where Js is calculated considering the average TMP over days

2-4:

Js (permeability @ 20 C) )

J (net flux)
/
TMPaveragesdays 2-4

(2)

Therefore, the pure effect of the MLSS concentration on the

sludge filterability is visible from Figure 5, where the curves at
2, 5, and 10 g MLSS/L are plotted.
Figure 5 confirms that the filterability of the sludge is affected
by the MLSS content if the concentrations pass from 2 g/L to
5 g/L, whereas a MLSS concentration from 5 g/L to 10 g/L has
similar impacts on the UF process. In light of the results just
described, the correct compromise between the activated-sludge
concentration and the permeate flux must be pursued, to achieve
the industrial and economical sustainability of the process. As
a result, from one side, biomass concentrations up to 2 g
MLSS/L can increase the membrane permeability, so this
strategy can reduce the capital and O&M costs; from the other
side, higher concentrations might enhance the removal of
micropollutants. However, in this last case, overcritical conditions are observed and more-frequent chemical cleanings of the
membranes are required, which deteriorates the membrane life.
As a general preliminary consideration, the application of
higher fluxes seems to be convenient, but further investigations
are needed to better evaluate the membrane life and real impact
on micropollutants removal.
Conclusions
The main remarks of this study can be summerized as follows:
(1) The physical/mechanical headworks (screening, sieving,
degritting, and primary sedimentation) have an important role
in the volatilization and/or gravity separation of numerous
hazardous compounds present in raw municipal wastewater.

Ind. Eng. Chem. Res., Vol. 46, No. 21, 2007 6721

Figure 4. Membrane bioreactor (MBR) modality, shown using transmembrane pressure (TMP) profiles versus time at different fluxes ((a) 7, (b) 14, and
(c) 20 LMH) and concentrations of mixed liquor suspended solids (MLSS).

(2) The biological process of a conventional activated sludge

wastewater treatment plant (WWTP) has a major role in the
removal of the heavy metals, even operating at SRT of 10-15
days, which are time periods that are commonly applied in
conventional plants. Also, an effect on the volatile organic
compounds (VOCs) was observed in the full-scale bioreactor.
In contrast, the polyaromatic hydrocarbons (PAHs) were already
present at very low concentrations in the effluent of the primary
sedimentation and the biological process did not perform further
macroscopic removals. Unexpectedly, the halogen volatile
organic compounds (HVOCs) did not undergo significant
removal, probably because of their recalcitrance to biodegrada-

Figure 5. Plots of membrane permeability (Js) versus permeate flux (J) at

different MLSS contents.

6722

Ind. Eng. Chem. Res., Vol. 46, No. 21, 2007

Table 9. Filtration Tests in MBR Configuration

permeate flux
(LMH)

TMP decline
(bar/d)

MLSS concentration
(g/L)

7
7
7
7
7

-0.0047
-0.0077
-0.0056
-0.0076
-0.0066

0.4
0.8
1.5
2.2
8.8

VI
VII
VIII
IX

14
14
14
14

-0.0074
-0.0061
-0.0269
-0.0134

0.8
1.6
5.4
12.5

X
XI
XII
XII

20
20
20
20

-0.0449
-0.0210
-0.0533
-0.0328

0.6
1.7
4.2
9.1

test
I
II
III
IV
V

tion within a time period of 10-15 d, and they are present in

the form of small molecules that are not prone to biosorption.
(3) The sieving effect of the UF membrane system led to a
virtually complete removal of the HVOCs. As for the heavy
metals, the fouling and/or cake layer had a major role and led
to further removal in the range of 40%-50%. This effect is
different depending on whether the membrane system is
filtrating the secondary effluent or the activated sludge directly.
In particular, the presence of activated sludge with MLSS in a
concentration of 5-10 g/L can enhance the layer effect and
increase the removal performances proportionally (18%-69%).
Currently, further reasonable considerations about the removal
mechanisms are not possible, because the concentration of
metals in the liquors are close to the limits of quantification;
(4) Fouling phenomena are more sensitive to MLSS concentrations when the flux is similar to or higher than the critical
value. In particular, either the transmembrane pressure (TMP)
declines or the starting values are influenced. Among the typical
MLSS concentrations applied for the treatment of municipal
wastewaters (3-10 g/L), values in the range of 2-5 g MLSS/L
mark the borderline between weak and severe fouling phenomena;
(5) Higher MLSS concentrations seem to enhance the removal
of micropollutants, but also worsen the fouling phenomena.
Moreover, the application of higher permeate fluxes seems to
be convenient, but, as a consequence, the membrane life can
be severely reduced. As a matter of fact, currently, using MLSS
in a concentration of 5-10 g/L and a permeate flux of 1520 LMH seems to be a good choice to enhance the layer effect
and have a sustainable operation of the membrane system.
However, also in this case, further investigations are still needed.
Nomenclature
AbbreViations
BAT ) best-available techniques
BOD ) biological oxygen demand
COD ) chemical oxygen demand
EPS ) extracellular polymeric substances
HVOC ) halogen volatile organic compounds
LMH ) liter per square meter per hour (measure of flux)
MBR ) membrane biological reactor
MLSS ) mixed liquor suspended solids
O&M ) operation and maintenance
P&Id ) piping and instrumentation diagram
PAH ) polynuclear aromatic hydrocarbons
PE ) population equivalent
TF ) tertiary filtration
UF ) ultrafiltration

VOC ) volatile organic compounds

WAS ) waste-activated sludge
WWTP ) wastewater treatment plant
Variables
J ) permeate flux
Js ) membrane permeability
kow ) octanol-water partition coefficient
SRT ) sludge retention time
TMP ) transmembrane pressure
TSSout ) total suspended solids in the retentate flow rate
Acknowledgment
The authors thank the Italian Ministry of the University and
Research for the financial support of this research through the
projects PRIN 2003 and PRIN 2005. Multiservizi SpA is
also kindly acknowledged to have hosted the pilot plant in the
Falconara-Vallechiara WWTP.
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ReceiVed for reView January 5, 2007

ReVised manuscript receiVed June 22, 2007
Accepted June 23, 2007
IE070017R