Selective anthocyanins enrichment of cranberry juice by electrodialysis

with ltration membrane: Inuence of membranes characteristics

Eric Husson
a,b,1,2
, Monica Araya-Farias
a,b,2,3
, Audrey Gagn
a,b
, Laurent Bazinet
a,b,n
a
Institute of Nutrition and Functional Foods (INAF), Laval University, Quebec (QC), Canada G1V 0A6
b
Department of Food Sciences and Nutrition, Laval University, Quebec (QC), Canada G1V 0A6
a r t i c l e i n f o
Article history:
Received 13 February 2013
Received in revised form
27 June 2013
Accepted 30 June 2013
Available online 5 July 2013
Keywords:
Cranberry
Polyphenol
Electromembrane process
Zeta potential
Conductivity
Fouling
a b s t r a c t
Enrichment of cranberry juice in anthocyanins by electrodialysis with ltration membrane (EDFM) was
investigated. Six ltration membranes (FM) with distinct constitutive materials and cut-offs were tested.
The higher enrichment yields in anthocyanins (24%) without any signicant depletion of polyphenols
from the raw juice were obtained with 2 ltration membranes: (1) polyvinyldiene uoride (PVDF) with a
cut-off of 150 kDa and (2) polyethersulfone (PES) with a cut-off of 500 kDa. EDFM treatment performed
during 90 min did not affect the pH and conductivity values of the treated juices. The constant degree
Brix obtained after EDFM treatment conrmed that this technology can selectively migrate anthocyanins
without affecting the sugar concentration in the juice. Furthermore, the decrease in titrable acidity of the
enriched juice improved its organoleptic characteristics. It was also demonstrated that the enrichment in
anthocyanins was inuenced by the FM zeta potential (ZP). Indeed, for ltration membranes presenting
positive surface charge (ZP close to 23 mV), repulsions would be established with anthocyanins
positively charged and would avoid their electro-migration through the membrane. On the opposite,
ltration membranes with moderate negative charges (ZP close to 5 mV) seem to facilitate the electro-
transfer of anthocyanins due to the attraction between opposite charges.
& 2013 Elsevier B.V. All rights reserved.
1. Introduction
Cranberry (Vaccinium macrocarpon) from North-America con-
stitutes an excellent agro-resource to combine nutritional proper-
ties and biological activities in a same food [1]. Its biological
activities are mainly due to its high composition in phenolic
compounds such as anthocyanins, proanthocyanidins, avonoids
and phenolic acids [25]. In North America and increasingly in
Europe, cranberry juice is consumed for the prevention of urinary
tract infections due to its antibacterial properties [2,6]. Anthocya-
nins present in the cranberry juice would cause outer membrane
disintegration of Escherichia coli strain [7]. Likewise, another
recent study demonstrated that anthocyanins contained in cran-
berry would be implied in cancer chemo-preventive properties [8].
Furthermore, it was mentioned that the addition of phenolic
phytochemicals in cranberry derivatives such as juice could
increase their health benets [9]. In this context, the production
of a cranberry juice enriched in phenolic antioxidant compounds
constitutes a promising opportunity to enlarge the food industry
market by developing new nutraceutical products [10,11].
Electrodialysis with ltration membranes (EDFM) is an emer-
gent technology which leads to a selective separation of bioactive
compounds from natural sources such as green tea or hydrolysates
[1216]. Recently, the feasibility to enrich specically in antho-
cyanins a cranberry juice fraction from another cranberry juice by
EDFM was demonstrated [1719]. This selective migration in the
enriched juice compartment was due to the positive charge of the
anthocyanins molecules at the cranberry juice pH, leading to 52.9%
increase after 4 h of treatment or 2324% increase after 90 min of
treatment [19]. Furthermore, increases of 18% and 23% in the
antioxidant capacity of the enriched juices were observed, respec-
tively [17,20]. However, to conrm EDFM scaling-up feasibility and
its potential use at an industrial scale, other electrochemical
aspects such as membrane fouling must be understood and
controlled. Indeed, the fouling of anionic/cationic and ltration
membranes (FM) observed may limit the anthocyanin enrichment
efciency of the process [19]. The fouling of FM is probably due to
Contents lists available at ScienceDirect
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Journal of Membrane Science
0376-7388/$- see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2013.06.061
n
Corresponding author at: Department of Food Sciences and Nutrition,
Pavillon Paul-Comtois, 2425 rue de l'Agriculture, Universit Laval, Qubec,
Canada G1V 0A6. Tel.: +1 418 656 2131x7445.
E-mail addresses: eric.husson@u-picardie.fr (E. Husson),
monica.araya-farias@u-psud.fr (M. Araya-Farias),
laurent.bazinet@fsaa.ulaval.ca (L. Bazinet).
1
Present address: Unit de Gnie Enzymatique et Cellulaire,
Universit de Picardie Jules Verne, 33 rue Saint-Leu, FRE CNRS 3580
80039 Amiens Cedex, France. Tel.: +33 3 22 82 74 71.
2
Co-rst authors.
3
Present address: Institut Galien Paris-Sud, UMR CNRS 8612,
Facult de PharmacieUniversit Paris Sud, 5 JB Clment,
92296 Chtenay-Malabry Cedex, France. Tel.: +33 1 46 83 57 86.
Journal of Membrane Science 448 (2013) 114124
polyphenols/UF membrane interactions as pointed out in the
literature [1922]. But, recent studies concerning anthocyanins
concentration by ultraltration processes pointed out the impor-
tance of the cut-off of membrane to allow or to avoid anthocyanins
retention [23,24].
In this context, the rst objective of the present work was to
select the more suitable ltration membrane leading to the high-
est enrichment in anthocyanins of cranberry juice by EDFM
treatment. Six ltration membranes distinct by their characteris-
tics (constitutive material and cut-off) were studied. The second
one was to establish a relationship between enrichment effective-
ness and membrane surface charge by measuring the zeta poten-
tial to better understand the anthocyanins electromigration in an
EDFM system.
2. Material and methods
2.1. Material
2.1.1. Cranberry juice
The EDFM treatments were applied on a pasteurized and
claried cranberry juice produced by Fruit d'Or (Notre-Dame-de-
Lourdes, QC, Canada). A claried cranberry juice was privileged in
the present work to minimize the presence of cell wall polysac-
charides as suggested by Bazinet et al. [17]. The juice was stored at
28 1C and thawed out at 4 1C before each experiment.
2.1.2. Electrodialysis cell
The electrodialysis cell was a Microow type cell (ElectroCell
AB, Karlskoga, Sweden) with a CMX-SB cationic membrane
(Tokuyama Soda Ltd., Tokyo, Japan), one ASM anionic membrane
(Tokuyama Soda Ltd., Tokyo, Japan) and 1 ltration memb-
rane (FM).
The CMX-SB and ASM membranes are copolymers of styrene
divinylbenzene functionalized respectively with sulfonic and
ammonium groups, on a PVC frame. Six ltration membranes
distinct by their cut-offs and their constitutive material were
studied (Table 1). The total effective ltration area was of 10 cm
2
.
The cell has three closed loops, and each one was connected to a
separate external reservoir allowing recirculation of the solutions
during the treatments (Fig. 1). The solutions were circulated using
three centrifugal pumps (Iwaki Magnet Pump, Iwaki Co Ltd.,
Tokyo, Japan) and the ow rates were controlled using ow meters
(Aalborg Instruments and Controls, Inc., Orangeburg, USA). The
anode was a dimensionally stable electrode (DSA) and the cathode
was a 316 stainless steel electrode. The anode/cathode voltage
difference was supplied by an electrical power supply (Model HPD
30-10, Xantrex, Burnaby, Canada).
2.2. Protocol
To avoid a signicant impoverishment in anthocyanin of raw
juice, a volume of raw juice of 9 L and a volume of enriched juice of
300 mL was used according to Bazinet et al. recommendations
[17]. The raw cranberry juice was circulated only one time in the
raw juice compartment to simulate a direct integration of an EDFM
cell on a bottling unit as proposed by Bazinet et al. [17]. A 20 g/L
KCl solution (400 mL) was circulated in the electrode rinsing
compartments. Cranberry juice ow rates were 100 mL/min while
the ow rate of the KCl solution was 400 mL/min. Treatments were
performed in batch process at room temperature using an electric
eld strength of 15 V/cm as used in a previous study [18]. The
duration of the treatments was 90 min. According to the distance
between the two electrodes (2 cm) after cell assembly, the applied
voltage was 30 V. As the electric eld was maintained constant all
along EDFM treatment, the current density varied between 25 and
39 mA/cm
2
. The conductivity and the pH of cranberry juices were
monitored throughout the process as well as the global system
resistance. The samples of both raw and enriched juices were
directly withdrawn before and after treatments to characterize the
evolution of anthocyanin concentration, titrable acidity, juice color
and degree Brix. Membranes thicknesses and their electrical
conductivities were measured before and after treatments. Three
replicates of each treatment were performed. In addition, zeta
potential of the ltration membranes was determined before and
after being soaked in cranberry juice.
2.3. Physicochemical parameters of cranberry juices
2.3.1. pH
The pH of both raw and enriched juices during the treatment
was measured using a pH-meter model SP20 (VWR Symphony,
Thermo Orion West Chester, PA, USA).
2.3.2. Conductivity
The conductivity of both raw and enriched juices during the
treatment was measured using a YSI conductivity meter, Model
3100, with a YSI immersion probe (Model 3252, cell constant
K1 cm
1
; Yellow Springs Instruments, Yellow Springs, OH, USA)
[25].
Table 1
Constitutive material and cut-off of the ltration membranes used to enrich
cranberry juice by EDFM treatments.
Characteristics of ltration membranes
Constitutive material Cut-off (kDa) Companies
PES
a
0.1 mm GE Osmonics, Minnetonka, USA
PES
a
500 Millipore Corp., Bedford, USA
PVDF
b
150 Philos Co., Kyunggi-do, South Korea
PVDF
b
100 GE Osmonics, Minnetonka, USA
PES
a
10 GE Osmonics, Minnetonka, USA
PS
c
10 GE Osmonics, Minnetonka, USA
a
Polyethersulfone.
b
Polyvinylidene uoride.
c
Polysulfone.
Fig. 1. Conguration of the EDFM system used to enrich claried cranberry juice.
AEM: anionic membrane, CEM: cationic membrane, FM: ltration membrane.
E. Husson et al. / Journal of Membrane Science 448 (2013) 114124 115
2.3.3. Degree Brix
The soluble solid content (1Brix) of cranberry juices was
determined using a digital refractometer Reichert AR 200 (Reichert
Inc., Depew, NY, USA).
2.3.4. Juice color
Color parameters of control and treated juices were determined
with a chromameter (Model Minolta meter CR-300, Konica Min-
olta Inc., Mississauga, ON, Canada). Results were reported as Ln
(luminescence or lightness), an (intensity of color varying from red
to green) and bn (intensity of color varying from yellow to blue)
[26].
2.3.5. Titrable acidity
Titrable acidity of control and treated juices was determined on
4 mL of juice by titration with a solution of NaOH (0.1 M) up to the
end point of phenolphthalein (pH 8.7) [27]. The titrable acidity
(TA) was expressed as mL of NaOH (0.1 M) added.
2.3.6. Anthocyanins concentration
Total anthocyanins concentration was quantied by UVvisible
spectroscopy [28]. Each sample of cranberry juices was diluted in
two distinct aqueous buffers: 0.025 M potassium chloride buffer,
pH 1.0 and 0.4 M sodium acetate buffer, pH 4.5. Diluted solutions
were equilibrated for 15 min before analysis. Absorbance of each
diluted samples was measured at 510 nm and 700 nm using a
UVvisible Agilent 8453 spectrophotometer (Agilent technologies,
Palo Alto, CA, USA). Absorbance due to the contribution of total
anthocyanins was calculated according to the following equation:
A A
510 nm
A
700 nm

pH1:0
A
510 nm
A
700 nm

pH4:5
1
Concentration in total anthocyanins ([Anth]) was expressed as
mg of cyanidin-3-glucoside equivalent per litre of juice (mg/L)
by applying the following equation:
Monomeric cyanidin 3 glucoside pigmentmg=L
A MW
Cyd3glu
Dilution factor 1000
=
Cyd3glu
l 2
where MW
Cyd-3-glu
is the molecular weight of cyanidin-3-
glucoside (449.2 g mol
1
), l, length of light-path through the
solution (1 cm) and , its molar extinction coefcient (26,900
L mol
1
cm
1
) [28].
The respective yields of impoverishment of raw juice and
enrichment of enriched juice were calculated respectively with
the following equations:
Y
impoverishment
% Anth
f r
Anth
i
=Anth
i
100 3
where [Anth]
f
corresponds to the nal anthocyanins concentration
in the raw juice after EDFM treatment and [Anth]
i
the initial
anthocyanins concentration in the control juice (before treat-
ment).
Y
enrichment
% Anth
f r
Anth
i
=Anth
i
100 4
where [Anth]
fe
corresponds to the nal anthocyanins concentra-
tion in the enriched juice after EDFM treatment and [Anth]
i
the
initial anthocyanins concentration in the control juice (before
treatment).
2.4. Electrodialytic parameters and membrane characterization
2.4.1. Global system resistance
The global system resistance was calculated using the Ohm's law
(URI). The value of voltage was read directly from the power
supply indicators and the current passing through the electrodes was
read from a Mastercraft numerical multimeter (Model 52-0060-2,
Mastercraft, Toronto, ON, Canada) as described in a previous study
[12].
2.4.2. Membrane thickness
The thickness of EDFM cell constitutive membranes was
measured as described in previous studies [29,30], using a Mitu-
toyo digimatic indicator (Model ID-110 ME, Mitutoyo Corp., Japan)
and a digimatic mini-processor (Model DP-1HS, Mitutoyo Corp.,
Japan).
2.4.3. Membranes electrical conductivity
As described in previous studies [29,30], the membrane's
electrical conductivity was measured using a specially designed
cell (conductivity clip) furnished by the Laboratoire des Matriaux
Echangeurs d'Ions (Crteil, France) and connected to a YSI con-
ductivity meter (Model 3100, Yellow Springs Instrument Co.,
YellowSprings, OH, USA). The conductance (G) was measured on
cationic, anionic and FM (G
m
) membranes before and after treat-
ment. Prior to the measurement, clip ends were soaked in a 0.5 N
NaCl reference solution (G
s
) with the jaws wide apart for 1 min,
while the platinized electrodes xed on each jaw were submerged.
(1) The conductance of the reference solution, (G) was measured.
(2) The membrane was equilibrated for 60 min in the reference
solution and then introduced between the clip jaws, to measure
the conductance due to the contribution of the reference solution
and the membrane (G
m+s
).
The transverse electrical resistance of the membrane, R
m
(),
was determined from
R
m
R
ms
R
s
1=G
m
1=G
ms
1=G
s
5
where R
m+s
is the total resistance of the membrane and of the
electrolyte solution between the electrodes and R
s
is the resistance
of the electrolyte solution alone. Three measurements of the
reference solution resistance and six measurements at different
points on the membrane were performed, and the differences
were averaged to give the membrane resistance value. As
described in previous studies [31,32], the membrane electrical
conductivity (S cm
1
) was calculated as follows:
l=R
m
A 6
where l is the membrane thickness (cm), R
m
the membrane
resistance (S) and A the electrode area (1 cm
2
).
2.4.4. Zeta potential characterization of ltration membranes
Zeta potential of membrane represents the electrochemical
nature of the membrane material and the adsorption capacity of
ions. The effect of cranberry juice on the surface charge of the
ltration membranes during EDFM treatments was investigated by
characterizing their zeta potential. Filtration membranes were
stored under wet conditions and immersed overnight in cranberry
juice or in a KCl solution prior to the measurement. Filtration
membranes soaked in KCl solution (1 mM at pH2.6) were used
as control. At pH (2.60), the conductivity (2739 mS/cm) of this KCl
solution was quite similar to the one of the cranberry juice. A
SurPASS electrokinetic analyzer (Anton Paar, Graz, Austria)
equipped with a clamping cell was used to measure the zeta
potential. Two pieces of ltration membranes were mounted in
the measuring cell opposite of each other. The membranes were
separated by 2 spacers that introduce a streaming channel with
dimensions of 2550.29 mm
3
. The zeta potential was deter-
mined in a specied pH range (2.57.5) by measuring the stream-
ing current or streaming potential as a function of a differential
pressure created by the circulation of the electrolyte through the
measuring cell. A 1 mM KCl solution was used as electrolyte and
HCl (0.1 M) and NaOH (0.1 M) were used to adjust the electrolyte
pH by automatic titration. Flow was induced in the measuring cell
E. Husson et al. / Journal of Membrane Science 448 (2013) 114124 116
by linearly ramping the differential pressure from 0 to 300 mbar in
both directions. Two cycles of pressure ramps in each direction
were conducted and measured average zeta potential values were
computed using the FairbrotherMastin model [33].
2.5. Statistical analyses
A complete randomized experimental design with three repeti-
tions was applied. An analysis of variance (ANOVA) was performed
on data using Sigma Plot software (Version 11.0 for Windows,
Chicago, IL) to establish or not difference between treatments.
Furthermore, a Least Signicant Difference (LSD) test analysis was
used to determine which treatment was statistically different from
the other at a probability level of p0.05.
3. Results
3.1. Cranberry juices parameters
3.1.1. Effectiveness of enrichment in anthocyanins
The enrichment and impoverishment yields in anthocyanins
for treated juices by EDFM process are presented in Fig. 2. Based
on the statistical results, enrichment yields in anthocyanins of
enriched juices were signicantly different according to the FM
used (P0.037). In opposite, the impoverishment yields of raw
juices were not signicantly different whatever the FM used
(P0.463). The higher enrichment yields in anthocyanins were
obtained with PES500 kDa and PVDF150 kDa membranes, with
respective values of 2277% and 2472%. Similar enrichment
yields were obtained in a previous study using PES500 kDa
[17]. This is in agreement with the light red coloration observed
on PES500 kDa and PVDF150 kDa membranes (Fig. 3c and d)
and suggests that only a moderate amount of anthocyanins was
trapped or adsorbed on the surface of the membrane leading to a
higher enrichment. Concerning the PS0.1 mm membrane, the
enrichment yield in anthocyanins was moderate (1273%) com-
pared to those obtained for membranes with high cut-offs
(PES500 kDa and PVDF150 kDa). An intense red coloration
was observed on PS0.1 mm as illustrated in Fig. 3b. These
anthocyanins adsorption or surface deposition would explain the
low enrichment yield obtained in spite of the high cut-off of the
membrane. On the other hand, the FM with cut-offs lower than
150 kDa (PVDF100 kDa, PES10 kDa and PS10 kDa) led to
enrichment yields lower to 10% (Fig. 2). These weak enrichment
yields obtained would be principally due to the low cut-offs of
membranes. According to these results, the enrichment yields in
anthocyanins would be strongly affected by the cut-off whatever
their constitutive material.
3.1.2. pH
The average pH of non-treated cranberry juice used for this
study was 2.5970.03. The triple interaction duration/juice/mem-
brane did not suggest any signicant effect of EDFM treatment on
pH (P0.3917). Indeed, pH of treated juices was constant during
treatment whatever the FM used (Fig. 4). Thus EDFM treatments
do not affect signicantly the H
+
concentration of both juices. The
type of FM may have no impact on the pH of juices for treatment
duration inferior or equal to 90 min compared to a longer EDFM
treatment [18]. The constant pH conrmed that anthocyanins
(pKacpH
juice
) are always under positively charged form during
all the process, allowing their unidirectional electromigrations
toward the enriched juice compartment. The constant pH in the
enriched juice (300 mL) suggested that the cranberry juice could
exhibit a high buffering capacity as shown for other feed solutions
[16].
3.1.3. Conductivity
The averaged electrical conductivity of the non-treated cran-
berry juice was 2952746 mS/cm. Double interaction duration/
membrane suggested that no signicant variation of conductivity
occurred during the treatment according to the type of FM used
(P0.4713). Furthermore, triple interaction duration/membrane/
juice were not statistically signicant (P0.2548). According to
these statistical results, the electrical conductivity of the treated
juices (raw and enriched) was not affected by the EDFM treat-
ments whatever the FM used as shown in Fig. 5. The constant
conductivities observed for both juices during EDFM treatments
suggested that no important demineralization phenomenon
occurred in contrast to results reported in another study [18]. In
fact, in the present study, the ions migration occurs during the
process through all membranes, but a balance in ion migration
compensates for the departure of an ion from a compartment by
the entrance of another charged species in the same compartment
as mentioned in the literature [17,18,25,34,35].
3.1.4. Degree Brix
Degree Brix is a measure of the soluble sugars present in
cranberry juice. The degree Brix of the non-treated cranberry juice
was 7.970.1. Based on the statistical results, the EDFM treatments
did not have a signicant effect on degree Brix evolution of raw
and enriched juices whatever the FM used (P0.074). As shown in
Table 2, the values of Brix for the treated juices were similar to
those of the control juice. In previous EDFM studies [17,18], lower
-30
-25
-20
-15
-10
-5
0
5
10
15
20
25
30
PS 0.1 m PES 500 kDa PVDF 150 kDa PVDF 100 kDa PES 10 kDa PS 10 kDa
E
n
r
i
c
h
m
e
n
t

y
i
e
l
d

i
n

a
n
t
h
o
c
y
a
n
i
n
s
(
%
)
I
m
p
o
v
e
r
i
s
h
m
e
n
t


y
i
e
l
d

i
n

a
n
t
h
o
c
y
a
n
i
n
s
(
%
)
Fig. 2. Enrichment/impoverishment yields in anthocyanins of treated cranberry juice (polka-dotted bars for enriched juice and hatched bars for raw juice) obtained after
90 min of EDFM treatments with different ltration membranes.
E. Husson et al. / Journal of Membrane Science 448 (2013) 114124 117
values of Brix were obtained for the enriched juice. This difference
was due to a dilution effect induced by dead volume of water
present in the system hosing. In the present work, we have
overcome this constraint by a pre-washing of the system with
cranberry juice. Constant degree Brix could be explained by the
constant pH maintained through the EDFM treatment. Indeed, at
low pH (see pH of cranberry juice), constitutive hydroxyls groups
of sugar molecules are protonated and thus uncharged. As a result,
these molecules are not sensitive to the driving force induced by
the external electrical eld, whatever the FM used. It was thus
conrmed that EDFM technology allows the selective enrichment
of cranberry juice in anthocyanins without simultaneous enrich-
ment in sugar in contrary to classical industrial processes like
evaporation [36].
3.1.5. Titrable acidity
The titrable acidity (TA) of the control juice and the treated
juices are presented in Table 2. The analysis of variance showed
that TA values of raw and enriched juices were signicantly
different (p0.004). As reported in previous studies, TA is essen-
tially due to the presence of organic acids in cranberry juices i.e.
quinic, malic and citric acids [37]. These molecules exhibit a pKa
close to the pH of juice. A high proportion of these organic acids
are thus negatively charged and susceptible to electromigrate
toward the anode. After EDFM treatments with FM exhibiting
higher cut-offs (100 kDa, 150 kDa, 500 kDa and 0.1 mm), TA of
enriched juice was decreased whatever the constitutive material
of the FM used while TA of raw juice remained similar to that of
control juice. The decrease in TA of enriched juice led to signicant
Fig. 3. Photographs of ltration membranes after treatments of cranberry juices by EDFM system: (a) control membrane, (b) PES0.1 mm, (c) PES500 kDa,
(d) PVDF150 kDa, (e) PVDF100 kDa, (f) PES10 kDa, and (g) PS10 kDa. PES: polyethersulfone, PVDF: polyvinyldiene uoride and PS: polysulfone.
2.30
2.40
2.50
2.60
2.70
2.80
2.90
3.00
0 10 20 30 40 50 60 70 80 90 100
p
H
Time (min)
2.30
2.40
2.50
2.60
2.70
2.80
2.90
3.00
0 10 20 30 40 50 60 70 80 90 100
p
H
Time (min)
2.30
2.40
2.50
2.60
2.70
2.80
2.90
3.00
0 10 20 30 40 50 60 70 80 90 100
p
H
Time (min)
2.30
2.40
2.50
2.60
2.70
2.80
2.90
3.00
0 10 20 30 40 50 60 70 80 90 100
p
H
Time (min)
2.30
2.40
2.50
2.60
2.70
2.80
2.90
3.00
0 10 20 30 40 50 60 70 80 90 100
p
H
Time (min)
2.30
2.40
2.50
2.60
2.70
2.80
2.90
3.00
0 10 20 30 40 50 60 70 80 90 100
p
H
Time (min)
Fig. 4. Evolution of pH in () raw juice and () enriched juice during the EDFM treatments with different ltration membranes: (a) PES0.1 mm, (b) PES500 kDa,
(c) PVDF150 kDa, (d) PVDF100 kDa, (e) PES10 kDa, and (f) PS10 kDa. PES: polyethersulfone, PVDF: polyvinyldiene uoride and PS: polysulfone.
E. Husson et al. / Journal of Membrane Science 448 (2013) 114124 118
improvement of its taste. Indeed, acidity and astringency sensation
were reduced in the enriched juice. This effect was also observed
in previous studies [17,18].
The decrease in TA of enriched juice is due to the migration of
organic acids in the anode direction through the ltration mem-
brane to reach raw juice compartment. However, to maintain the
electroneutrality of the raw juice, for each organic acid received
from enriched juice compartment, an anion/or organic acid have
migrate to the electrolyte compartment. This, in addition to the
use of large volume of raw juice (9 L) explained the fact that the TA
of the raw juice remained constant and similar to that of the
control juice. For membranes with a cut-off of 10 kDa, no sig-
nicant variation of TA for the cranberry juices treated by EDFM
was observed. FM with small cut-off induce a major limitation in
organic acids electromigration compared with FM exhibiting
higher cut-offs. This difference would be related to membrane
fouling (Fig. 3) and to their low conductivities values (close to 1,
Table 4). FM with lower cut-off would be much faster fouled than
FM with larger cut-offs as evidenced by higher values of global
system resistance observed at the beginning of treatment (Fig. 6).
This, in addition to the low electrical conductivity of those
membranes (Table 4), explained that the migration of organic
acids was slowed down leading to maintain a constant TA in the
enriched juice compartment.
3.1.6. Color parameters
Color of control and treated juices as a function of the FM used
are presented in Table 3. The analysis of variance on color data
revealed no signicant differences for the color parameters Ln
(P0.054) and an (P0.119) whatever the juice (raw or enriched)
and the UF membrane used. However, analysis of variance showed
a signicant difference in color parameter bn between enriched
and raw juices after EDFM treatments (Po0.001). In comparison
with the control juice, bn parameter of enriched juices would not
be affected by EDFM treatment while for raw juice an increase was
observed whatever the FM tested. Albeit anthocyanin pigments in
cranberry are responsible for its red color [37], the variations of bn
parameter were too slight to be related to enrichment and/or
impoverishment in anthocyanins. Indeed, the higher enrichment
obtained by EDFM treatment with the PVDF150 kDa membrane
did not change drastically the visual aspect of the product.
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Fig. 5. Evolution of conductivity in () raw juice and () enriched juice during the EDFM treatments carried out with different ltration membranes: (a) PES0.1 mm,
(b) PES500 kDa, (c) PVDF150 kDa, (d) PVDF100 kDa, (e) PES10 kDa, and (f) PS10 kDa. PES: polyethersulfone, PVDF: polyvinyldiene uoride and PS: polysulfone.
Table 2
Titrable acidity and degree Brix of control and treated cranberry juices with EDFM system.
Titrable acidity: required NaOH (0.1 N) volume Degree Brix
Control juice 16.270.1 7.970.1
Filtration membranes Raw juice Enriched juice Raw juice Enriched juice
Constitutive material Cut-off (kDa)
PES
a
0.1 mm 16.270.4 14.670.8 7.970.3 7.570.4
PES
a
500 16.270.1 14.870.5 7.970.2 7.570.2
PVDF
b
150 15.970.9 14.271.3 7.770.6 7.270.6
PVDF
b
100 16.070.5 15.270.2 7.870.3 7.670.1
PES
a
10 15.970.9 15.770.2 7.770.4 7.770.1
PS
c
10 16.071.0 14.870.9 7.770.4 7.470.4
a
Polyethersulfone.
b
Polyvinylidene uoride.
c
Polysulfone.
E. Husson et al. / Journal of Membrane Science 448 (2013) 114124 119
3.2. Electrodialytic parameters
3.2.1. Global system resistance
The multivariate analysis of variance of the data showed that
time (Po0.0001) and the double interaction time/membrane
(P0.0193) had a signicant effect on the evolution of the global
system resistance during EDFM treatments. As presented in Fig. 6,
for the membranes with high cut-offs (PES0.1 m, PES500 kDa,
PVDF150 kDa and PVDF100 kDa), the average global resistance
increased from 70.678.3 at the beginning, when the current
was applied, to a value of 91.675.2 after 40 min and then
remained constant until the end of treatment. This increase in
global system resistance could be due to signicant adsorption of
anthocyanins on/in the FM as suggested by their red coloration at
the end of the treatments (Fig. 3bd).
As the increase did not occur continuously during the treat-
ment for these FM, it is supposed that their sites of potential
interaction with anthocyanins were totally saturated after 40 min.
As a result the conductivity of these FM may be affected and could
induce an increase of the global system resistance.
For the membranes with low cut-offs (PES10 kDa and
PS10 kDa), the global resistance remained almost constant all
along of treatments. In fact, the mean of global system resistance
was 99.9712.3 at the beginning and 111.375.4 after 90 min
of treatment. However, these values were high compared to those
obtained with membranes with higher cut-offs. As described
earlier, the FM with low cut-offs led to a weak enrichment due
to an important retention of anthocyanins onto the surface of FM
(Fig. 3g). This anthocyanin deposition could have also resulted in a
higher global system resistance from the beginning of the treat-
ment due principally to the prevented or slowed down migration
of anthocyanins through the membrane.
3.2.2. Conductivity and thickness of membranes
3.2.2.1. Filtration membranes. The thickness and the conductivity
of FM before and after EDFM treatment were presented in Table 4.
Student's t-test indicated that the thickness of FM before and after
EDFM treatments were not statistically different for those with
high cut-offs: PES0.1 m (P0.303), PES500 kDa (P0.175),
PVDF100 kDa (P0.185) and PVDF150 kDa (P0.498). On the
other hand, for the membrane with low-cut-offs, the t-test
indicated a statistically signicant difference of thickness for PS
10 kDa (P0.012) but not for the PES10 kDa membrane
(P0.630). Indeed, the membrane thickness of PS10 kDa
membrane increased from 0.16770.003 to 0.17570.001 mm.
0
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Fig. 6. Evolution of the global system resistance during the distinct EDFM treatments carried out with different ltration membranes: (a) PES0.1 mm, (b) PES500 kDa,
(c) PVDF150 kDa, (d) PVDF100 kDa, (e) PES10 kDa, and (f) PS10 kDa. PES: polyethersulfone, PVDF: polyvinyldiene uoride and PS: polysulfone.
Table 3
Color parameters measured for control and treated cranberry juices with EDFM system.
Filtration membranes Color parameters Color parameters of control juice
Constitutive material Cut-off (kDa) Raw juice Enriched juice
L a b L a b L a b
PES
a
0.1 mm 27.470.2 1.370.2 0.0770.01 27.070.2 1.570.2 0.1470.20 27.370.1 1.570.1 0.1170.04
PES
a
500 27.270.1 1.470.2 0.0670.13 27.170.1 1.570.1 0.1670.06
PVDF
b
150 27.470.1 1.470.1 0.0470.05 27.070.1 1.570.1 0.1770.03
PVDF
b
100 27.570.1 1.470.1 0.0470.04 27.170.1 1.570.1 0.1570.04
PES
a
10 27.470.1 1.470.1 0.0870.02 27.170.1 1.570.1 0.1070.05
PS
c
10 27.570.1 1.470.1 0.0770.03 26.071.9 1.670.1 0.1670.05
a
Polyethersulfone.
b
Polyvinyldiene uoride.
c
Polysulfone.
E. Husson et al. / Journal of Membrane Science 448 (2013) 114124 120
Likewise, only the PVDF100 kDa membrane showed a signicant
difference of electrical conductivity (P0.024) according to
Student's t-test. Indeed, its electrical conductivity dropped from
3.5570.60 to 2.4170.89 mS/cm at the end of the treatment.
These changes might be explained by a fouling of the membranes
by positively charged anthocyanins of cranberry juice. In fact, the
surface of these membranes exhibited the reddest coloration
(Fig. 3e) at the pH of cranberry juice.
3.2.2.2. Ion-exchange membranes. For all the six EDFM treatments,
student's t-test indicated a statistically signicant difference in
electrical conductivity and thickness of anion-exchange memb-
ranes (AEM) before and after treatments (Po0.0001) but these
differences were similar whatever the FM used during the
treatment. In fact, the membrane thickness increased from
0.16670.001 to 0.17170.002 mm and the electrical conductivity
from 14.2170.23 to 24.972.0 mS/cm respectively (Table 4).
However, despite the difference in membrane thickness no
visible fouling was observed on the membrane surface
(photographs not shown). The high electrical conductivity of
AEM membrane after treatment could be due to a variation of
membrane charge surface caused by negatively charged molecules
such as organic acids of cranberry juice. In fact, since organic acids
are negatively charged at pH of juice, it would be expected that
organics acids could be electrostatically attracted by the
membranes AEM surface, which is a polymeric membrane with
xed functional groups of a positive charge. Moreover, as
previously discussed, the decrease of TA in enriched juice
suggested that a high proportion of these organic acids were
susceptible to electromigrate toward anode from enriched juice to
raw juice compartment. Organic acids were in contact with AEM
membrane (Fig. 1) and this would have resulted in a higher
electrical conductivity of the AEM membrane.
According to Student's t-test, there is no signicant difference in
the thickness (P0.307) and the electrical conductivity (P0.033) of
cation-exchange membranes. In fact, thickness and electrical con-
ductivity of membrane were very similar before and after all
treatments (Table 4). The mean of membrane thickness was
0.16970.001 mm after treatment and 0.17170.002 mm before
treatment. The electrical conductivity varied from 11.671.3 to
16.073.4 mS/cm at the end of treatment. Moreover, following each
treatment, a red coloration (photograph not shown) was observed at
the surface of the membrane in contact with the enriched juice
compartment. Anthocyanins can interact with the negatively charged
functional groups of cationic membranes but the non-porous struc-
ture would avoid their migration. This phenomenon was reported in
recent studies for anthocyanins and peptides [17,20,38].
3.2.3. Zeta potential of ltration membranes
According to Student's t-test, the zeta potential of FM before
and after incubation in cranberry juice was statistically different
(Po0.0001).
Except for the membranes PVDF100 kDa and PS10 kDa at
pH of juice (2.6), the UF control membranes displayed a negative
zeta potential (from 1.51 to 24.96 mV) within the pH range
2.67.0 (Fig. 7) which is close to data obtained in the literature for
similar membrane material [39,40]. Prole of the curve and
magnitude of zeta potential values of control FM indicate that
the membranes PES0.1 m, PES500 kDa, PVDF150 kDa,
PES10 kDa contain weakly acidic groups in their nature. This is
a characteristic of polyethersulfone, polysulfone, polyvinylidene
uoride membranes as reported in the literature [39,41]. These
membranes contain no ionic groups and the initial negative charge
can be attributed to the adsorption of Cl

ions or OH

from the
electrolyte solution onto the membrane surface [39]. In all the
cases, it can be expected that surface charge of membranes takes
positive values at low pH and get more negative with increasing
pH. Data presented in Fig. 7 do not exhibit any distinct relationship
between pore size and the values of zeta potential among the
membranes made of the same material which is not surprising as
the membranes were obtained from different manufacturers
(Table 1). However, similar behavior was obtained for membranes
PES10 kDa and PES0.1 m which were manufactured from the
same manufacturer (GE Osmonics). Kim et al. [39] observed an
increase of zeta potential values with an increase of pore size for
the membranes in polysulfone obtained from the same manufac-
turer. However, a study has reported a non-uniform variation of
zeta potential with pore size for microporous membranes of the
same structure treated with different types of electrolytes and
concentrations [42]. After incubation in cranberry juice, mem-
branes generally show positive zeta potentials which indicate an
adsorption of anthocyanins or positively charged molecules on FM
(Fig. 7). The magnitude of positive zeta potential values of
membranes varied from +0.78 to +5.15 mV. The zeta potential
modication after incubation in cranberry juice was higher for
membrane PES0.1 m (10.40 to 5.15 mV). These positively
charged molecules may be adsorbed by simple diffusion through
the UF membrane and could exhibit their charge at the surface of
the membrane [19].
3.3. Overall discussion
To explain the different obtained results, a tentative model
describing the evolution of FM zeta potential during EDUF treat-
ment due to the contact with anthocyanins-containing cranberry
juice is proposed (Fig. 8). In fact, based on the respective
Table 4
Thickness and electrical conductivity of ltration membranes before and after treatments by EDFM.
Filtration membranes Thickness (mm) Membranes conductivity (mS/cm)
Constitutive material Cut-off (kDa) Before After Before After
PES
a
0.1 mm 0.2170.03 0.2370.01 5.0370.76 4.471.6
PES
a
500 0.3270.01 0.32370.010 10.9270.53 30.478.7
PVDF
b
150 0.10870.003 0.11070.003 8.873.0 5.6470.90
PVDF
b
100 0.2370.01 0.23170.004 3.670.6 2.4170.89
PES
a
10 0.1570.01 0.1570.01 1.2370.05 1.2070.04
PS
c
10 0.16770.003 0.17570.001 1.3570.13 1.4970.07
Anionic membranes 0.16670.001 0.17170.002 14.2170.23 24.972.0
Cationic membranes 0.16970.001 0.17170.002 11.671.3 16.073.4
a
Polyethersulfone.
b
Polyvinyldiene uoride.
c
Polysulfone.
E. Husson et al. / Journal of Membrane Science 448 (2013) 114124 121
surface charges of PES0.1 m, PES500 kDa and PVDF
150 kDa membranes at the pH of cranberry juice (respective ZP
of 10.476.2 mV, 4.771.9 mV and ZP 5.970.5 mV), elec-
trostatic interactions would be established between positively
charged anthocyanins and the membrane surface negatively
charged (Fig. 8a). Hence, during the EDUF treatment, part of the
anthocyanins would interact with the membrane to neutralize it
and then to allow their further electromigration through the
membrane. This mechanism would be close to the one of cations
migrating through a cation-exchange membrane containing xed
negatively charged groups, rmly attached to its skeleton. So that,
under the inuence of electric eld, the anthocyanins would
migrate through the membrane by exchanging with other
anthocyanins on the xed membrane charged groups (Fig. 8a).
When the electric eld application is stopped, part of the antho-
cyanins neutralizing the charged groups of the membrane would
remain entrapped in the membrane as observed by Bazinet et al.
[20] who tested an electrical desorption treatment. This would
explain the light coloration of these membranes after treatment.
Thus ltration membranes with moderate negative charges (ZP
close to 5 mV) seem to facilitate and to initiate the electro-
transfer of anthocyanins through the membrane due to the force
attraction between opposite charges. However, for ltration mem-
branes presenting positive surface charge, repulsions would be
established with positively charged anthocyanins and would avoid
their electro-migration through the membrane (Fig. 8b). Indeed, in
Anthocyanins electromigration through FM
mediated by electroattractions
Electroattraction between
anthocyanins and FM surface
Electrorepulsions between anthocyanins
and FM surface
Anthocyanins Electromigration through FM
prevented by electrorepulsions
X
+
-
Positively charged anthocyanins
Negative surface charges of FM
+
Positive surface charges of FM
Start of process
During the process
Fig. 8. Schematic representation of anthocyanins electromigration during enrichment of cranberry juice by EDFM: (a) with ltration membrane exhibiting a negative surface
charge and (b) with ltration membrane exhibiting a positive surface charge.
-30
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pH
Fig. 7. Evolution of zeta potential of UF membranes as a function of pH before () and after incubation () in cranberry juice: (a) PES0.1 mm, (b) PES500 kDa,
(c) PVDF150 kDa, (d) PVDF100 kDa, (e) PES10 kDa, and (f) PS10 kDa. PES: polyethersulfone, PVDF: polyvinyldiene uoride and PS: polysulfone.
E. Husson et al. / Journal of Membrane Science 448 (2013) 114124 122
contact with the cranberry juice (natural pH of 2.5970.03), the
surface charge of membrane remains positive all along the EDUF
treatment leading to a permanent repulsion of anthocyanins from
the surface of the membrane. So, these electrostatic repulsions
may contribute to a weak enrichment yield and may also lead to
an accumulation of anthocyanins at the surface of FM (Fig. 3e and
g). The electrostatic repulsive force is dependent on the magnitude
of zeta potential. In the case of PES10 kDa membrane, its surface
is weakly charged and can be considered as close to isoelectric
point (ZP 1.170.7 mV). Consequently few interactions
between the membrane and the anthocyanins are established.
This combined to a low molecular weight cut-off of the mem-
brane, slows the potential migration of anthocyanins. This would
explain the absence of a red coloration at its surface (Fig. 3f).
4. Conclusion
Selective enrichment of a cranberry juice in anthocyanins from
another cranberry juice by EDFM was investigated according to FM
characteristics (cut-off, material and zeta potential). Effectiveness
of EDFM treatment for enriching cranberry juice in anthocyanins
was demonstrated to be under control of both cut-off and surface
zeta potential of membrane whatever its constitutive material.
Higher enrichment yields in anthocyanins (around 24%) without
any signicant depletion in polyphenols from the raw juice were
obtained for PVDF150 kDa and PES500 kDa membranes exhi-
biting respective zeta potentials close to 5 mV. This negatively
charged surface would initiate the electro-transfer of anthocyanins
through the membrane in establishing electrostatic attractive
interactions with anthocyanins. For FM with a cut-off lower or
equal to 100 kDa, the enrichment yields were signicantly lower
whatever the constitutive material. In addition to the inuence of
cut-off, the weak enrichments in anthocyanins obtained with
these membranes would be explained by the positively charged
surface which may induce repulsive interactions with anthocya-
nins and may limit drastically their transfer rates through the UF
membrane. For strongly negatively charged surface, despite high
cut-off, signicant anthocyanins amount would be entrapped on
and in the UF membrane leading to a weak enrichment yield for
the enriched juice.
EDUF treatment for 90 min did not affect the pH, the con-
ductivity and the soluble sugars in juices. The decrease in the
titrable acidity of enriched juice, led to an improvement of its
organoleptic characteristics. Color parameters L, a, and b obtained
in treated juices were similar to those of control juice. These
results constitute thus a promising way toward the technologic
transfer of EDFM treatment to produce and commercialize cran-
berry juice enriched in anthocyanins as new neutraceutical
product.
Acknowledgments
The support of Pascal Dub (M.Sc, Institute of Nutrition and
Functional Foods, Quebec City, QC, Canada) for his technical help in
analyses is gratefully acknowledged. The authors thank the NSERC
for its nancial supports.
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