Coupling of adsorption, coagulation, and ultraltration processes for the removal

of emerging contaminants in a secondary efuent

Juan L. Acero

, F. Javier Benitez, Francisco J. Real, Fernando Teva

Departamento de Ingeniera Qumica y Qumica Fsica, Universidad de Extremadura, 06006 Badajoz, Spain
h i g h l i g h t s
" The removal of eleven emerging contaminants by combined treatments was investigated.
" PAC pre-treatment decreased membrane fouling and improved the quality of the permeate.
" Pre-coagulation with Fe(III) was slightly more favorable than with Al(III).
" The combinations PAC/UF and UF/GAC led to a signicant removal of contaminants.
a r t i c l e i n f o
Article history:
Received 2 March 2012
Received in revised form 13 August 2012
Accepted 13 August 2012
Available online 29 August 2012
Keywords:
Emerging contaminants
Municipal secondary efuent
Ultraltration
Permeate ux
Adsorption
Coagulation
a b s t r a c t
The removal of eleven emerging contaminants (acetaminophen, metoprolol, caffeine, antipyrine, sulfa-
methoxazole, umequine, ketorolac, atrazine, isoproturon, 2-hydroxybiphenyl and diclofenac) present
in a WWTP efuent by applying several combined treatments has been investigated. These combinations
were constituted by PAC adsorption and/or coagulation pre-treatments followed by UF, as well as by an
UF treatment followed by GAC adsorption post-treatment. PAC pre-treatment decreased membrane foul-
ing, with the advantage that PAC was separated from the nal efuent in the UF step. Low PAC dose in the
range 1050 mg L
1
in the adsorption pre-treatment was enough in order to remove most of the emerg-
ing contaminants and to partially improve water quality parameters. However, if the goal is to reach a
high improvement of water quality parameters in the pre-treatment step, a PAC dose above 500 mg L
1
was required. Although coagulation pre-treatment did not increase appreciably the permeate ux in the
UF step, the nal quality of the permeate was improved, especially when the combination Fe(III)/UF was
applied. Finally, a signicant positive effect of the GAC post-treatment after the UF treatment was appre-
ciated, which led to an increase in the removal of the water quality parameters and a signicant elimi-
nation of emerging contaminants.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Currently new technologies and procedures for the reuse of
efuents must be developed, because of increasing demands for
water which coincides with the depletion of natural sources.
Among other efuents, municipal wastewater may be suitable for
reuse if after conventional purication processes further treatment
is applied to remove resistant micropollutants [1]. Although at very
low concentrations, there are a large number of chemical com-
pounds involved in this pollution that have been detected in the
outows of the wastewater treatment plants (WWTPs) [2], many
of which may have chronic toxic effects in aquatic organisms and
may pose a risk to human health. Among these organic substances,
a group commonly known as emerging contaminants plays an
important role in the pollution of these waters. This group of con-
taminants includes, among others, pesticides, pharmaceuticals,
personal care products, fuel additives, ame-retardants, plasticiz-
ers and numerous other industrial pollutants.
Separation processes by membranes, such as ultraltration (UF),
are technologies increasingly used in the eld of water and waste-
water treatments, and produce clear water suited for different
applications. However, single UF is sometimes ineffective for the re-
moval of most of these emerging contaminants due to the limited
retention capacity of UF membranes as well as to the membrane
fouling. Then, membrane ltration processes must be combined
with pre-treatments or post-treatments in order to produce a per-
meate that can be reused, such as coagulation and adsorption
stages, which permit additional removals of organic compounds
that play an important role in fouling phenomena. Specically,
powdered activated carbon (PAC) and granular activated carbon
(GAC) in combination with UF are promising technologies for water
1385-8947/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.08.043

Corresponding author. Tel.: +34 924289384; fax: +34 924289385.

E-mail address: jlacero@unex.es (J.L. Acero).
Chemical Engineering Journal 210 (2012) 18
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j our nal homepage: www. el sevi er . com/ l ocat e/ cej
treatment. The benets of the combination PAC/UF are due to the
adsorption capacity of PAC and the UF membrane ability to retain
high molecular weight compounds and particles (including PAC
particles). Therefore, the combination PAC/UF allows the removal
of low molar mass compounds which would not be removed by
the UF membrane alone [3]. However, there are contradictory re-
sults concerning the PAC effect on the membrane fouling: thus,
some authors reported improvements in the permeate uxes [4,5]
while others presented similar uxes [6], or even ux decline
[7,8]. In general, the PAC effect seems to be a function of the mem-
brane characteristics, mainly its hydrophobic or hydrophilic char-
acter, and of the raw water composition [3].
Similarly, coagulation alone or combined with PAC adsorption
has been reported as a very attractive option due to several advan-
tages, such as an easy use and low capital investments [9]. The use
of aluminium sulphate and ferric chloride as coagulants combined
with UF have provided notably improvements in the permeate ux,
with considerably reduction at the same time of turbidity and
chemical oxygen demand (COD) [1012].
With these considerations in mind, the present study was de-
signed for the elimination of emerging contaminants that could
be contained in an efuent from a municipal WWTP, as well as
for the removal of the natural organic matter (NOM) also present
in the efuent. For this purpose, the following eleven micropollu-
tants were selected: acetaminophen (ACET), metoprolol (MET), caf-
feine (CAF), antipyrine (ANT), sulfamethoxazole (SUL), umequine
(FLUM), ketorolac (KET), atrazine (ATR), isoproturon (ISOP), 2-
hydroxybiphenyl (HYD) and diclofenac (DIC). Most of these con-
taminants have been found in different aquatic environments at
concentrations in the range of ng L
1
lg L
1
[2].
In a preceding work [13] the elimination of these compounds
was investigated by using single UF and nanoltration (NF) pro-
cesses in batch concentration mode. As a continuation, the present
work focuses on the elimination of these selected eleven emerging
contaminants from a WWTP efuent by applying several combined
treatments. These combinations were constituted by PAC adsorp-
tion and/or coagulation pre-treatments followed by UF, as well as
by an UF treatment followed by GAC adsorption post-treatment.
The main objective of these combined processes was to evaluate
the effect of the adsorption and coagulation pre-treatments/post-
treatments on the single UF process in terms of membrane fouling
and permeate ux, as well as on the elimination of the selected
emerging contaminants and NOM present in the WWTP efuent.
2. Materials and methods
2.1. Emerging contaminants, secondary efuent, adsorbents and
coagulants
The selected emerging contaminants were the same group of
compounds already used in a previous work [13]. Table 1 summa-
rizes their main physico-chemical properties: pK
a
, log K
ow
and
charge at pH = 8. These substances were simultaneously dissolved
(0.5 mg L
1
of each compound) in ultrapure (UP) water or in a sec-
ondary efuent collected from a municipal WWTP located in Ciu-
dad Real (Spain). The main quality parameters of this efuent
were: pH = 7.8; turbidity = 0.71 NTU; COD = 22.4 mg L
1
, total
nitrogen (TN) = 4.23 mg L
1
, total phosphorus (TP) = 0.173 mg L
1
,
and UV absorbance at 254 nm (UVA) = 0.146 cm
1
.
The PAC used in the adsorption pre-treatment was supplied by
Panreac. The particles were soaked overnight in Milli-Q water, later
oven-dried at 105 C for 2 h and stored in a desiccator until use.
Analysis of this PAC provided a mean particle size of 80 lm BET
surface area of 710.4 m
2
g
1
, mesopore surface area of 29 m
2
g
1
,
and micropore surface area of 684.9 m
2
g
1
. The GAC (Panreac)
used in the adsorption post-treatment of the efuent generated
in the UF process presented the following main characteristics:
particle diameter of 3 mm, BET surface area of 987.4 m
2
g
1
, mes-
opore surface area of 6.2 m
2
g
1
, and micropore surface area of
981.2 m
2
g
1
. The coagulants used, FeCl
3
6H
2
O and Al
2
(SO
4
)
3
18H
2-
O, were provided by SigmaAldrich, and were completely water
soluble. They were preserved in a quite hermetic container safe
from moisture at an ambient temperature of 20 C.
2.2. Experimental equipments and membranes
The UF experiments were performed in a laboratory cross-ow
ltration apparatus, model P-28

supplied by CM-CELFA Mem-

brantrenntechnik AG (Seewen, Switzerland), which was described
previously [14]. Basically, it consisted of a 500 mL pressurized stor-
age vessel and a pump which fed the solution to the at-sheet
membrane module at the desired ow rates. The whole equipment
was pressurized with nitrogen. The temperature was controlled by
circulating water from a thermostatic bath, and the cumulative
permeate volume was measured with a Mettler balance. These
experiments were carried out with a at sheet commercial mem-
brane, designated as PT, and provided by GE Osmonics (Florida,
USA). According to the manufacturer, it is a hydrophilic membrane,
made of polyethersulfone, with a molecular weight cut-off
(MWCO) of 5000 Da. The average value of the pure water perme-
ability (PWP) of the PT membrane was 21.6 L h
1
m
2
bar
1
[13].
2.3. Experimental procedures and analytical methods
Each experiment was performed with a new membrane, which
was previously soaked in ultrapure water for 24 h in order to elim-
inate preservative products. The UF experiments were conducted
in batch concentration mode, and according to the protocol de-
scribed in detail in a previous publication [13]. This protocol
started with the determination of the PWP of the membrane from
the measurement of the pure water ux (J
wi
), and those mem-
branes that showed signicant deviation from the measured aver-
Table 1
List of compounds and physico-chemical properties.
Name Use MW (g mol
1
) pK
a
Log K
ow
Charge at pH 8
Acetaminophen Analgesic, antipyretic 151.17 10.2 0.23 Neutral
Metoprolol b-blocker 342.41 9.6 1.72 +
Caffeine Psichoactive stimulant 194.19 0.45 Neutral
Antipyrine Analgesic, antipyretic 188.23 1.3 0.54 Neutral
Sulfamethoxazole Antibiotic 253.28 1.8; 5.7 0.86
Flumequine Antibiotic 261.25 1.3; 6.1 1.31
Ketorolac Anti-inammatory 255.27 4.0 2.15
Atrazine Herbicide 215.69 1.7 2.52 Neutral
Isoproturon herbicide 206.29 2.22 Neutral
Hydroxybiphenyl Biocide 170.21 9.8 3.27 Neutral
Diclofenac Analgesic 318.14 4.3 4.29
2 J.L. Acero et al. / Chemical Engineering Journal 210 (2012) 18
age PWP were discarded. Later, the ltration of the selected emerg-
ing contaminants (dissolved in UP water or in the WWTP second-
ary efuent) was performed, by retiring the permeate stream and
measuring the volume collected in order to determine the perme-
ate ux (J
v
). Samples of this permeate stream were withdrawn for
the analysis of the selected pollutants, as well as the global quality
parameters in the WWTP efuent (Turbidity, COD, UVA, TP and
TN). These experiments were performed at pH 8 in the case of
UP water and at the natural pH of the secondary efuent (around
8) with an initial volume of 300 mL. The transmembrane pressure
(TMP) was xed at 4 bar by pressurizing with nitrogen, the tangen-
tial velocity (v) was kept constant at 0.5 m s
1
, and the tempera-
ture (T) was maintained at 20 C. These experiments lasted until
a volume reduction factor (VRF) of 3 was reached, collecting
around 200 and 100 mL of permeate and concentrate, respectively.
Once the ltration of emerging contaminants was nished, at the
third step the feed tank was emptied and the membrane was
rinsed inside the membrane module with UP water in order to
eliminate the cake layer formed on the membrane surface. The -
nal pure water ux (J
wf
) was then measured in order to determine
the irreversible membrane fouling. Experiments were conducted in
duplicate and average values were reported. The ux of duplicate
tests typically agreed within 2% and analysis of water quality
parameters varied less than 3%.
In order to determine adsorption isotherms on PAC, emerging
contaminants solutions (UP water) at pH 8 with initial concentra-
tions of 0.52 mg L
1
were added into series of Erlenmeyer asks,
and afterwards, PAC (10100 mg L
1
) was added. Then, the aks
were transferred to a temperature controlled shaking water bath.
After the equilibrium was reached (24 h), the solutions were l-
tered through 0.45 lm cellulose nitrate lters to separate the
adsorbent, and the concentration of emerging contaminants in
the liquid phase was analyzed by HPLC.
In the combined adsorption/UF process, the pre-treatment stage
was performed by using different concentrations of PAC (in the
range 10600 mg L
1
) as adsorbent. The dose selected for each
run was added to the water containing the micropollutants in bot-
tles leaving some head-space. The bottles were sealed and stirred
during 24 h at 120 rpm and 20 C. Then, the resulting PAC/water
mixture was the feed for the subsequent UF experiment, which
was performed immediately to prevent settling. In the opposite se-
quence, UF/adsorption, the permeate stream from the UF stage was
immediately treated with GAC in packed beds of 1 and 2 cm length,
and with a mean residence time of around 3 min. The nal efuent
from this adsorption stage was analyzed for the determination of
the emerging contaminants concentration and the water quality
parameters.
In the coagulation/UF process, ferric chloride or alum (FeCl
3-
6H
2
O or Al
2
(SO
4
)
3
18H
2
O) were used as coagulants in the
pre-treatment stage. The selected dosages were added and mixed
rapidly with the solution of emerging contaminants in a laboratory
Jar Test with an agitation speed of 100 rpm during 1 min, followed
by slow mixing of 30 rpm during 30 min with the aim of favoring
the growth of the ocks, and a nal phase of settling during
45 min. Samples collected from the upper part of the test jars were
analyzed, while the resultant mixture was the feed of the following
UF stage.
The concentrations of the eleven emerging contaminants were
determined by HPLC, according to the procedure detailed else-
where [13], and the analytical methods for the characterization
of the secondary efuent were followed according to the Standard
Methods [15].
2.4. Theoretical background
The equilibrium isotherm data for adsorption of the selected
emerging contaminants onto PAC were tted by Langmuir [16]
and Freundlich [17] models. Langmuir model is the most widely
isotherm equation [18], which is dened as:
Q
e

Q
m
K
L
C
e
1 K
L
C
e
1
where Q
e
(mg g
1
) is the amount of emerging contaminant ad-
sorbed at equilibrium; Q
m
(mg g
1
) is the maximum emerging con-
taminant adsorption capacity; K
L
(L mg
1
) is the Langmuir constant
or the dynamic equilibrium constant between the processes of
adsorption and desorption, and C
e
is the equilibrium aqueous con-
centration of emerging contaminants.
Similarly, Freundlich model is dened as:
Q
e
K
f
C
1=n
e
2
where K
f
(mg/g(L/mg)
1/n
) is the Freundlich constant indicating the
relative adsorption capacity and n is a constant depicting the sorp-
tion intensity.
On the other hand, the rejection coefcients for the emerging
contaminants were determined according to Eq. (3) [19,20]:
R
C
f
C
p
C
f
100 3
In the case of the secondary efuent, the rejection coefcients
for some water quality parameters (Turbidity, COD, UVA, TP and
TN) were also evaluated. These rejection coefcients were deter-
mined by expressions similar to Eq. (3).
3. Results and discussion
3.1. Adsorption isotherms
As-tted Langmuir and Freundlich parameters for adsorption of
several emerging contaminants onto PAC are given in Table 2 (the
remaining contaminants have not been included due to their low
adsorption onto the selected PAC). As deduced from the values of
R
2
listed in Table 2, the Langmuir model correlated the adsorption
isotherms better than the Freundlich model. In addition, Fig. 1 de-
picts the adsorption isotherms by Langmuir model of some emerg-
Table 2
Langmuir and Freundlich isotherm parameters for adsorption of emerging contaminants on PAC (pH = 8).
Compound Langmuir Freundlich
Q
m
(mg g
1
) K
L
(L mg
1
) R
2
K
f
(mg/g(L/mg)
1/n
) 1/n R
2
Metoprolol 32.34 118.2 0.992 31.82 0.039 0.808
Caffeine 12.63 237.1 0.985 14.97 0.094 0.967
Flumequine 33.46 97.4 0.994 38.47 0.115 0.929
Ketorolac 15.36 325.5 0.992 15.8 0.030 0.865
Atrazine 19.16 100.0 0.988 22.20 0.112 0.905
Isoproturon 27.50 168.6 0.989 34.40 0.143 0.913
Hydroxybiphenyl 41.32 75.4 0.996 60.34 0.249 0.936
Diclofenac 25.35 94.9 0.997 31.25 0.149 0.938
J.L. Acero et al. / Chemical Engineering Journal 210 (2012) 18 3
ing contaminants, taken as examples, and an excellent correlation is
appreciated between experimental (symbols) and calculated (solid
lines) values. As a result, the Langmuir model can represent the
equilibria data reasonably well, which indicates that monolayer
adsorption of the selected emerging contaminants on PAC probably
occurred. According to the values of Q
m
listed in Table 2, the PAC
adsorptioncapacity order is hydroxybiphenyl > umequine > meto-
prolol > isoproturon > diclofenac > atrazine > ketorolac > caffeine.
3.2. Elimination of emerging contaminants by the combination of PAC
and UF treatments
Several PAC/UF experiments with the emerging contaminants
dissolved in UP water and in the WWTP efuent were rstly per-
formed in order to investigate the inuence of the PAC dose used
in the adsorption pre-treatment on the permeate ux and the
micropollutants removal efciency in the latter UF treatment.
The initial PAC doses applied in each experiment are detailed in Ta-
ble 3 (Expts. 24 and Expts. 69).
In the UF step of the resulting PAC/water mixture, the permeate
ux (J
v
) decreased with the increase in VRF until a constant value
was reached (permeate ux at the steady state, J
vss
). Table 3 com-
piles the values of J
vss
/J
wi
for the UF stage in the experiments con-
ducted by using the micropollutants solution with or without pre-
treatment (Expts. 19). This parameter takes into account the ratio
between the steady state permeate ux for the solution containing
the micropollutants and that corresponding to the ltration of UP
water without solutes. The parameter J
vss
also allowed the deter-
mination of the permeate ux decline: FD = 1J
vss
/J
wi
, which at
the same time represents a measurement of the fouling effects
on the membrane, its values being also compiled in Table 3. Finally,
the values of J
wf
/J
wi
were determined in order to evaluate the mem-
brane ux recovery after washing with pure water, thus removing
the external fouling. These values are also reported in Table 3 and
provide an idea of the internal membrane fouling.
Focusing in the experiments with UP water (Expts. 14 in Table
3), on one hand, the low values of FD indicate the existence of low
membrane fouling, as a consequence of water with low concentra-
tion of solutes. On the other hand, the most important effect ob-
served is the increase in J
vss
/J
wi,
and subsequent decrease in FD,
with the use of PAC in the adsorption pre-treatment, which is due
to the removal of pollutants during the previous adsorption stage.
However, almost no effect is observed in J
vss
/J
wi
with the increase
in the PAC dose from 10 mg L
1
up to 20 mg L
1
. Moreover, the
presence of PAC decreases both, internal and external fouling, lead-
ing to a membrane ux recovery after cleaning with water very
close to 100% (see values of J
wf
/J
wi
in Table 3). According to these re-
sults, the presence of PAC does not exert any negative effect on the
permeate ow, so that PAC particles should be large enough to
avoid membrane fouling through pore blocking. PAC should deposit
on the membrane surface, but must forma porous layer that allows
the passage of water without increasing the resistance [3].
A similar positive effect of the increase in the PAC dose on the
permeate ux is observed in the experiments performed with the
secondary efuent (Expts. 59 in Table 3). Thus, the higher doses
of PAC used in this case (up to 600 mg L
1
) led to a moderate in-
crease in J
vss
/J
wi
, and consequently, to a reduction of FD. However,
the values of FD are higher than those obtained with UP water, as
could be expected, due to the higher amount of organic matter
present in the secondary efuent in comparison to UP water.
Regarding to the rejection coefcients of the emerging contami-
nants, a wide set of R values was obtained for the 11 selected com-
pounds, as a consequence of the different solute properties that
affect the retention (such as MW, molecular size, pK
a
, log K
ow
, dipole
moment) and the different retention mechanisms (such as adsorp-
tion, steric hindrance, electrostatic repulsion). The concentration
of emerging contaminants in secondary efuents is lower than that
used in the present research (0.5 mg L
1
). However, all experiments
shared the same concentration of emerging contaminants, thus the
higher concentration would not inuence our conclusions about the
effects of PAC pretreatment on the subsequent UF process.
Fig. 2 shows the micropollutants removal in the adsorption pre-
treatment alone when using UP water (Expts. 24 in Table 3). It is
clearly observed a direct inuence of the initial PAC amount used
on the micropollutants rejection coefcients, with an increase in
Table 3
Experimental conditions applied and permeate ux ratios obtained in the UF treatments of the emerging contaminants.
Expt. Water matrix Treatment Adsorbent and coagulant dose J
vss
/J
wi
F.D. J
wf
/J
wi
1 UP UF 0.84 0.16 0.95
2 UP PAC/UF 10 mg L
1
0.92 0.08 0.97
3 UP PAC/UF 15 mg L
1
0.92 0.08 0.98
4 UP PAC/UF 20 mg L
1
0.93 0.07 0.98
5 WWTP UF 0.67 0.33 0.81
6 WWTP PAC/UF 10 mg L
1
0.74 0.26 0.85
7 WWTP PAC/UF 20 mg L
1
0.77 0.23 0.88
8 WWTP PAC/UF 50 mg L
1
0.84 0.16 0.90
9 WWTP PAC/UF 600 mg L
1
0.91 0.09 0.93
10 WWTP Fe(III)/UF 130 mg L
1
0.71 0.29 0.86
11 WWTP Fe(III)+PAC/UF 130 mg L
1
+ 600 mg L
1
0.81 0.19 0.96
12 WWTP Al(III)/UF 331 mg L
1
0.69 0.31 0.84
13 WWTP Al(III)+PAC/UF 331 mg L
1
+ 600 mg L
1
0.74 0.26 0.94
14 WWTP UF/GAC 1 cm 0.67
a
0.33
a
0.81
a
15 WWTP UF/GAC 2 cm 0.67
a
0.33
a
0.81
a
a
Values corresponding to Expt. 5.
0
5
10
15
20
25
30
35
40
45
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Q
e
(
m
g

g
-
1
)
C
e
(mg L
-1
)
caffeine
flumequine
hydroxybiphenyl
diclofenac
Fig. 1. Equilibria adsorption isotherms for some selected emerging contaminants
on PAC by Langmuir model.
4 J.L. Acero et al. / Chemical Engineering Journal 210 (2012) 18
this removal when the PAC dose was increased from 10 mg L
1
to
20 mg L
1
. At the same time, the efciency of the adsorption stage
for each compound agrees reasonable well with the adsorption
capacity order obtained from the adsorption isotherms.
Similarly, Fig. 3 represents the rejection coefcients obtained
for the selected micropollutants in the single UF process without
pre-treatment (Expt. 1), as well as the total removals obtained in
the combined PAC adsorption/UF system with different initial
PAC doses (Expts. 24). Signicant improvements in the global
removals were obtained for all contaminants when the adsorption
pre-treatment was applied in comparison to the single UF process.
Moreover, these removals increased with the increase in the PAC
dose, as a direct consequence of the increasing elimination of the
emerging contaminants in the adsorption pre-treatment. The nal
removals of the selected compounds follow a similar sequence
than in the single adsorption stage: higher removals of hydroxybi-
phenyl, metoprolol and umequine; and lower removals of acet-
aminophen, antipyrine and sulfamethoxazole. These results
conrm that the adsorption stage plays an important role in the
combined process and constitutes the major retention mechanism
in the UF of micropollutants, such as emerging compounds [13],
with minor contribution of the size exclusion mechanism, since
the MWCO of the membrane is much higher than the MW of the
selected pollutants.
Similar trends were obtained in the experiments performed
with the emerging contaminants dissolved in the efuent from
the WWTP (Expts. 59 in Table 3), as can be observed in Fig. 4
which shows the rejections reached in the single UF stage without
pre-treatment and those obtained in the combined PAC adsorp-
tion/UF system with different PAC doses. The global sequence of
removals for the micropollutants was quite similar to that obtained
in the experiments performed with UP water, with higher nal
eliminations of those contaminants that were adsorbed to a greater
extent in the previous PAC adsorption stage.
However, a signicant difference was observed in the secondary
efuent results: the global removals for each compound were gen-
erally lower than those obtained in UP water, as can be observed in
Fig. 5, which represents the removals obtained in the single
adsorption stages for both water types, as well as the removals ob-
tained in the combined processes PAC adsorption/UF with a spe-
cic PAC dose of 10 mg L
1
, taken as example. This decrease in
the removal in the WWTP efuent is a consequence of the presence
of organic matter that competes with the micropollutants for the
active sites of the PAC, and thus, the adsorption of contaminants
is less effective [3]. Due to this negative effect of the presence of
organic matter in the secondary efuent, the PAC doses were in-
creased in these experiments up to 600 mg L
1
, leading to an al-
most complete removal of the selected emerging contaminants in
Fig. 3. Removal of emerging contaminants in the UF stage alone and in the PAC/UF combined process in UP water.
Fig. 2. Removal of emerging contaminants in the PAC adsorption stage in UP water, with different PAC dosages.
J.L. Acero et al. / Chemical Engineering Journal 210 (2012) 18 5
the pre-treatment step with PAC (data not shown). Lower concen-
trations of emerging contaminants in secondary efuents might in-
crease their removal by adsorption onto PAC.
The results obtained for the reduction of water quality parame-
ters reached in the single PAC pre-treatment and in the global pro-
cess (PAC/UF) are summarized in Table 4 (Expts. 59). These
results reveal a clear improvement in the efuent quality when
the pre-treatment step is added, being this improvement more evi-
dent with increasing PAC doses. Higher removals were obtained for
COD, UV absorbance at 254 nm and turbidity, while TN and TP
removals were lower, mainly because they were slightly retained
by the UF stage alone. Moreover, the high reduction of COD and
especially of UV absorbance at 254 nm in the global process is
due to the impact of PAC pre-treatment. This excellent retention
of organic matter is due to the adsorption of hydrophobic and
UV
254nm
absorbing compounds on PAC [3].
3.3. Elimination of emerging contaminants by the combination of
coagulation and UF treatments
In a following stage, a combined treatment constituted by a
coagulation pre-treatment, alone or combined with PAC adsorp-
tion, followed by an UF step was tested for the elimination of
emerging contaminants, as well as the organic and inorganic mat-
ter present in the WWTP efuent. In the coagulation pre-treat-
ment, FeCl
3
6H
2
O or Al(SO
4
)
3
18H
2
O were used with the initial
concentrations listed in Table 3 (Expts. 1013), concentrations that
were reported to be optimal for the removal of NOM present in a
municipal wastewater [1].
The inuence of the pre-treatment on the permeate ux ob-
tained in the UF step is given by the values of J
vss
/J
wi
, FD and J
wf
/
J
wi
that are summarized in Table 3. Firstly, it was observed that
Table 4
Global removals obtained for the main water quality parameters in the sequential
treatments of the WWTP efuent. Values in parentheses correspond to the removals
reached in the pre-treatment step (PAC and/or coagulation).
Expt. R
COD
(%) R
UVA
(%) R
Turbidity
(%) R
TP
(%) R
TN
(%)
5 24.1 34.1 30.0 8.5 9.7
6 33.9 (15.3) 39.2 (22.7) 33.3 (20.0) 12.5 (2.3) 29.2 (16.5)
7 37.0 (19.9) 45.3 (29.5) 57.1 (35.7) 17.9 (11.4) 28.2 (16.8)
8 52.3 (37.5) 60.3 (48.7) 62.5 (37.5) 29.5 (13.5) 28.8 (16.9)
9 81.3 (80.5) 95.1 (94.0) 66.7 (58.3) 40.1 (21.4) 31.7 (20.5)
10 44.6 (30.4) 90.9 (50.8) 45.0 (0) 86.2 (85.5) 10.0 (6.4)
11 88.3 (83.4) 96.5 (95.1) 66.0 (0) 87.9 (83.4) 15.9 (9.8)
12 34.6 (21.6) 85.5 (45.2) 33.4 (0) 34.0 (28.7) 14.3 (8.7)
13 83.9 (82.8) 96.2 (95.6) 61.1 (0) 34.0 (29.3) 32.9 (21.6)
14 67.0 91.3 nd nd 35.0
15 86.0 96.8 nd nd 49.0
nd: Values not determined.
Fig. 4. Removal of emerging contaminants in the UF stage alone and in the PAC/UF combined process in the WWTP efuent.
Fig. 5. Inuence of the water matrix on the removal of emerging contaminants in the PAC adsorption stage alone and combined with UF. PAC dose of 10 mg L
1
.
6 J.L. Acero et al. / Chemical Engineering Journal 210 (2012) 18
the permeate ux was only slightly improved by the introduction
of the single coagulation stage (comparison of J
vss
/J
wi
values of
Expts. 5 and 10 or 12), which is due to the removal of the colloidal
fraction of the secondary efuent that plays an important role in
membrane fouling [21]. This increase was also mainly due to the
decrease of internal membrane fouling, demonstrated by the ux
recovery, which was slightly higher for the combined coagula-
tion/UF treatment than for single UF. In addition, a slightly greater
fouling phenomena occurred with the use of Al(III) than with
Fe(III).
However, a more pronounce permeability increase was ob-
served when using the combinations Fe(III) + PAC and Al(III) + PAC
(Expts. 11 and 13), which led to values of J
vss
/J
wi
of 0.81 and 0.74,
respectively. Compared to the single coagulation pre-treatment,
the additional presence of PAC reduced both, internal and external
fouling due to the removal of NOM adsorbed onto the PAC. Never-
theless, the values of J
vss
/J
wi
were lower than that of 0.91 obtained
with the single PAC pre-treatment at the same initial concentration
(Expt. 9), although the nal ux recoveries were similar in both
cases. Therefore, the coagulation pre-treatment does not improve
considerably the permeate ux obtained in the subsequent UF step
with the PT membrane, which implies that the coagulation step
probably increases external membrane fouling and decreases
internal fouling, especially when Al(III) is used.
Regarding to the removal of emerging contaminants, the values
obtained for the single coagulation pre-treatment with both coag-
ulants were low in all cases (typically below 3%) and the nal
retentions of emerging compounds in the combined process (coag-
ulation/UF) were very similar to those reached in the single UF.
However, a great improvement was obtained for the removal of
water quality parameters in the combined coagulation/UF treat-
ment compared to UF alone (Table 4, Expt. 5 vs. Expts. 1013). In
general terms, Fe(III) coagulation led to higher removals of COD,
UVA, and TP than Al(III). Although the turbidity of the coagulated
samples was higher than that of the secondary efuent, the UF
membrane retained similar level of turbidity than without pre-
treatment. After the subsequent UF step, the nal quality of the
permeate was better with the combination Fe(III)/UF than with
Al(III)/UF. As previously reported [12], alum treatment removes
partially compounds of low molecular weight and almost com-
pletely high molecular weight compounds. Similarly, iron chloride
coagulant preferentially removes hydrophobic, charged and high
molecular weight compounds [22].
The removal of NOM was improved with the additional pres-
ence of PAC, and thus the combination Fe(III)/PAC/UF produced a
permeate with lower COD, absorbance at 254 nm and total phos-
phorus than the permeate obtained from the combined PAC/UF
treatment. Most of the hydrophobic compounds are either ad-
sorbed on PAC or trapped in iron chloride ocks, which leads to
an excellent removal of NOM, including emerging contaminants,
in the subsequent UF process.
3.4. Elimination of emerging contaminants by the combination of UF
and GAC treatments
Finally, a combined process including a UF step followed by GAC
adsorption of the permeate stream was investigated. Thus, the per-
meate stream obtained in the Expt. 5 (Table 3) was subjected to a
continuous adsorption process in a GAC bed, with two different
heights, 1 and 2 cm, (Expts. 14 and 15). Values of the water quality
parameters measured in this sequential process (only COD, UVA
and TN, data in Table 4) reveal a signicant positive effect of this
GAC post-treatment, with an additional increase in the removal
of the water quality parameters with the increase in the height
of the bed. These results demonstrate the great adsorption capacity
of GAC, especially for aromatic compounds.
Nevertheless, the most important effect or GAC post-treatment
was the elimination of the emerging contaminants individually
considered. Thus, Fig. 6 shows the removals for the 11 selected
contaminants in the single UF stage and in the combined UF/GAC
adsorption processes. As observed, a signicant improvement
was obtained in the global removals, with almost total elimination
for most of the compounds with the 2 cm GAC packed bed. There-
fore, granular activated carbon can be extremely effective for the
removal of emerging contaminants, especially hydrophobic com-
pounds. However, the efcacy of GAC is greatly reduced by the
presence of natural organic matter, which competes for binding
sites and can block pores within the GAC structure [23,24]. An op-
tion to reduce NOM is a previous UF step, which retains macromo-
lecular and colloidal organic matter, and generates a permeate that
can prolong considerably the GAC lifetime.
4. Conclusions
The present study, focused in the contribution of PAC adsorp-
tion and coagulation pre-treatments on the efciency (ux decline,
membrane fouling, and removal of NOM and emerging contami-
nants) of the subsequent membrane UF process, provided the fol-
lowing conclusions:
0
10
20
30
40
50
60
70
80
90
100
R
e
m
o
v
a
l
,

%
UF/GAC 0 cm bed
UF/GAC 1 cm bed
UF/GAC 2 cm bed
Fig. 6. Inuence of GAC bed height on the removal of emerging contaminants in the combined process UF/GAC.
J.L. Acero et al. / Chemical Engineering Journal 210 (2012) 18 7
The combination PAC adsorption/UF constitutes a promising
option for the treatment of secondary efuents from municipal
WWTP, because it enhanced the quality of the nal efuent.
Increasing doses of PAC signicantly improved the removal of
emerging contaminants, being 600 mg L
1
of PAC enough to
completely eliminate the selected contaminants from the sec-
ondary efuent.
An increment of the permeate ux and the reduction of mem-
brane fouling compared to UF alone was also obtained with this
PAC pre-treatment.
A coagulation pre-treatment with Fe(III) was slightly more
favorable than with Al(III) in order to improve the membrane
permeability and the quality of the efuent obtained after the
UF step. However, coagulation pre-treatment did not lead to
an appreciable reduction of emerging contaminants.
The additional presence of PAC in the coagulation step
improved slightly the global results obtained when single PAC
pre-treatment was applied.
The application to the permeate stream generated in the UF
stage of a post-treatment adsorption stage by GAC was an excel-
lent technology for the elimination of individual emerging con-
taminants present in WWTP efuents.
The combination of UF and activated carbon adsorption gener-
ates a nal efuent which could be reused in several applica-
tions such as irrigation, aquifer recharges.
Acknowledgements
This research was supported by the Ministerio de Ciencia e
Innovacin of Spain through the Projects CONSOLIDER CSD2006-
00044 and CTQ 2010-14823 and by the Gobierno de Extremadura
through the Project RNM021.
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