Desalination 212 (2007) 15–27

Clarification of blood orange juice by ultrafiltration: analyses of

operating parameters, membrane fouling and juice quality

A. Cassano*, M. Marchio, E. Drioli

Institute on Membrane Technology, ITM-CNR, c/o University of Calabria,
via P. Bucci, cubo 17/C, I-87030 Rende (CS), Italy
Tel. +39 (0984) 492011; Fax +39 (0984) 402103; email: cassano@itm.cnr.it

Received 3 February 2006; accepted 30 August 2006

Abstract
Blood orange juice was clarified by cross-flow ultrafiltration (UF) using tubular polyvinylidenefluoride (PVDF)
membranes. In experimental tests performed according to the total recycle mode the effect of transmembrane pres-
sure (TMP), axial feed flow-rate and temperature on permeate fluxes was studied. The clarified juice was produced
in experimental tests carried out according to the batch concentration mode working in optimal operating and fluid
dynamic conditions. A theoretical evaluation of the fouling effects on flux performance was performed by using a
modified form of the differential equation used to describe classical dead-end filtration. The fouling mechanism
during cross-flow UF was identified by estimation of the model parameters according to a nonlinear regression
optimization procedure. The theoretical predictions, in terms of permeate flux as a function of time, resulted in a
good agreement with the experimental data. Analysis of the results revealed that, in the fixed operating conditions
of TMP and temperature, the fouling mechanism evolves from a partial to a complete pore blocking condition in
dependence of the axial velocity. The quality of the samples coming from the UF process was evaluated in terms of:
total soluble solids (TSS), suspended solids (SS), total antioxidant activity (TAA), ascorbic acid, flavonones and
anthocyanins content. The resulting clarified orange juice was highly similar to the initial juice except for insoluble
solids which were concentrated in the retentate stream. In the permeate of the process a low reduction of the TAA
(1.5%) was observed with respect to the fresh juice.
Keywords: Blood orange juice; Ultrafiltration; Fouling; Total antioxidant activity

1. Introduction blonde or blood oranges. The latter are commonly

cultivated in the Mediterranean area but Sicilian
Sweet oranges (Citrus sinensis L.) are classi-
ones, that account for around 60% of the Italian
fied according to the colour of the pulp as either
orange harvest, express a better quality due to the
special pedoclimatic characteristics of the area [1].
*Corresponding author.

0011-9164/07/$– See front matter © 2007 Published by Elsevier B.V.

doi:10.1016/j.desal.2006.08.013
16 A. Cassano et al. / Desalination 212 (2007) 15–27
The most common varieties, named Tarocco,
Moro and Sanguinello, are characterised by a red
colour, of varying intensity and prevalence, due
to the presence of anthocyanins, found in the fla-
vedo or juice vescicle, mainly consisting of cya-
nidin-3-glucoside [2] and cyanidin-3-(6″-malo-
nyl)-glucoside [3]. These water-soluble pigments
contribute, together with other blood orange com-
ponents (ascorbic acid, flavonoids and hydroxy-
cinnamic acids), to the antioxidant and antiradi-
cal activities [4,5].
Traditional methods of processing orange juice
are based on the use of high temperatures in or-
der to destroy spoilage bacteria, inactivate en-
zymes and produce concentrated juices. Thermally
accelerated short-time evaporators (TASTE) are
used for example in the concentration step. Al-
though the total residence time of the product
during the evaporation is very short (6–8 min) it
is long enough to affect the aroma and flavour
compounds with a consequent qualitative decline.
In addition the evaporation process is charac-
terised by high energy consumptions. Alternative
techniques to the evaporation, as the freeze con-
centration and sublimation concentration, are not
able to substitute far the evaporative concentra-
tion due to their large energy requirements.
Compared with traditional juice processing
methods, membrane processes are low-cost and
athermal separation techniques which involve no
phase change or chemical agents. These features
are becoming very important factors in the pro-
duction of new fruit juices with natural fresh taste
and additive-free [6].
UF membranes have been shown to be of po-
tential interest for clarification of fruit juices and
have become a commercial success. They are able
to retain large species such as microorganisms,
lipids, proteins and colloids while small solutes
as for example vitamins, salts, sugars flow to-
gether with water. Advantages of the UF over
conventional fruit juice processing are in terms
of: increased juice yield; possibility of operating
in a single step reducing working times; possibil-
ity of avoiding the use of gelatines, adsorbents
and other filtration aids; reduction in enzyme uti-
lization; easy cleaning and maintenance of the
equipment; reduction of waste products; elimina-
tion of needs for pasteurization [7].
An important limitation in the performance of
the UF process is represented by the transient
build-up of rejected species at the upstream inter-
face of the membrane which determines a rapid
permeate flux decay during early period of filtra-
tion followed by a long and gradual decline to-
wards a steady-state limit value. This phenom-
enon is known as concentration polarization. The
material accumulated on the membrane surface
can undergo physicochemical interactions with the
membrane: in this case a fouling mechanism, such
as adsorption on the membrane pore walls and
pore plugging, occurs rather than the build-up of
a particle layer at the interface [8,9].
Membrane fouling is a key factor affecting
economic and commercial viability of a membrane
system since it reduces productivity and poten-
tially shortens membrane life [10,11]. Permeate
fluxes in UF processes are a function of time and
depend strongly on the operating and fluid-dy-
namic conditions, the nature of the membrane and
the nature of the feed solutions. Although the
transmembrane pressure (TMP) is the driving
force for permeation, the flux increases with pres-
sure up to a limiting value TMPlim which depends
on physical properties of the feed to be filtered
and cross-flow velocity. This latter affects the
shear stress at the membrane surface and conse-
quently the rate of removal of deposited matter
responsible of flux decay.
In this work a mathematical model based on
the classical constant pressure dead-end filtration
equations [12] was applied in order to describe
the permeate flux decline observed in the UF of
blood orange juice. Furthermore the effect of op-
erating and fluid-dynamic parameters (transmem-
brane pressure, temperature and feed flow rate)
on permeate fluxes was investigated.
The effect of the UF process on the physico-
 A. Cassano et al. / Desalination 212 (2007) 15–27
chemical and nutritional qualities of the blood
orange juice was also evaluated. In particular,
samples from feed, retentate and permeate were
analysed in relation to the total antioxidant acticity
(TAA), total soluble solids (TSS), suspended sol-
ids (SS), flavanones (hesperidin and narirutin),
ascorbic acid and anthocyanins.
2. Materials and methods
2.1. Blood orange juice
Freshly squeezed blood orange juice (mostly
Tarocco variety from Sicily) was supplied by Par-
malat Spa (Parma, Italy). Total soluble solids con-
tent of the raw juice was about 12.0–12.6°Brix
with a pH of 3.5. The juice was stored at –17°C
and was defrosted to room temperature before use.
2.2. UF unit and procedures
Ultrafiltration of blood orange juice was per-
formed by using a laboratory pilot unit supplied
by Verind SpA (Rodano, Milan, Italy). The equip-
ment consists of a 25 l stainless steel feed tank, a
feed pressure pump, a pressure control system, a
feed flow meter, a thermometer, two manometers
for the measure of the inlet and outlet pressures.
A tube and shell heat exchanger, placed after the
feed pump, was used to maintain the temperature
of the feed juice constant. A data acquirement
system, permitting the continuous monitoring of
the TMP and of the axial feed flow rate, was con-
nected to the UF plant. A digital balance, con-
nected to the system, was used to measure the
permeate fluxes. The plant was equipped with a
UF tubular membrane module (PVDF, NMWCO
15 kDa, membrane surface area 0.23 m2, inner di-
ameter of each tube 12.7 mm, average pores diam-
eter 59 Å, pH operating range 2–11, temperature
operating range 0–55°C, pressure operating range
0.8–5.5 bar) supplied by Koch-Glitsch Italia S.r.l.
(Milan, Italy).
17
UF experiments were performed according to
the total recycle and the batch concentration mode.
In the former the experimental trials were devoted
to the investigation of the effect of the operating
conditions on the flux performance of the system.
In this case the permeate was continuously re-
cycled to the feed tank to ensure a steady state in
the volume and composition of the feed. In the
batch concentration mode the UF system was
operated at a TMP of 0.85 bar, at an axial feed
flow rate (Qf) of 800 l/h and at a temperature of
25°C to clarify the juice up to a volume reduction
factor (VRF, defined as the ratio between the ini-
tial feed volume and the volume of the resulting
retentate) of about 6 units.
The membrane module was rinsed with tap
water for 30 min after the treatment of the juice;
then it was submitted to a cleaning process with a
NaOH solution (pH = 10.9, T = 40°C, Qf = 640 l/h,
TMP = 0.3 bar, operating time = 1 h) followed by
a cleaning with the alkaline detergent Ultrasil 10
(Henkel Chemicals Ltd., Dussendorf, Germany)
(1%, pH = 11.8, T = 40°C, Qf = 640 l/h, TMP =
0.3 bar, operating time = 1 h). A final rinse of the
system with tap water for at least 20 min was car-
ried out. After each cleaning procedure the water
flux of the membrane module in fixed conditions
(T = 25°C; Qf = 500 l/h) was measured.
2.3. Juice analyses
Samples of fresh, clarified (permeate) and con-
centrated (retentate) juice coming from the UF
experiments performed according to the batch
concentration mode were collected and stored at
-20°C for further analyses. Before the analyses
the fresh juice and the UF retentate were centri-
fuged at 6000 rpm for 15 min in order to remove
the pulp fraction.
The total antioxidant activity (TAA) was de-
termined by an improved version of the 2,2'-azino-
bis-(3-ethylbenzothiazoline-6-sulfonic acid)
(ABTS) free radical decolourisation assay [13] in
which the ABTS radical cation is generated by
18 A. Cassano et al. / Desalination 212 (2007) 15–27
reaction with potassium persulphate before the
addition of the antioxidant [14]. The
decolourisation of the ABTS is measured as the
percentage inhibition of absorbance at 734 nm.
The concentration of antioxidant giving the same
percentage inhibition of absorbance of the radi-
cal cation at 734 nm as 1 mM 6-hydroxy-2,5,7,8-
tetramethylchroman-2-carboxylic acid (Trolox)
was calculated in terms of Trolox Equivalent An-
tioxidant Capacity (TEAC) at 5 min contact.
Spectrophotometric measurements were per-
formed by a Lambda Bio 20 model spectropho-
tometer (Perkin-Elmer, Norwalk, USA) at 30°C.
Each determination was performed in triplicate
and repeated at least three times. Results are ex-
pressed as mean ± S.D. of three samples.
Ascorbic acid was determined by HPLC-
analyses performed by using a Waters 2690 sepa-
ration module (Water Corporation, Milford Mas-
sachusetts, USA) equipped with an UV-Vis de-
tector.
The analytical column was a 250 × 2.1 mm i.d.,
C18 Spherisorb RP, thermostated at 30°C. The
mobile phase consisted of phosphate buffer 0.2 M,
pH = 3.0 at a flow rate of 0.3 ml/min. Samples to
be detected were filtered before the injection
through 0.45 µm HPLC filters and monitored at
254 nm. The concentration of ascorbic acid was
calculated from the experimental peak area by
analytical interpolation in a standard calibration
curve and was expressed as mg/l of orange juice.
Each assay was performed in triplicate.
Total anthocyanins were determined after elut-
ing 5 ml of juice through Waters Sep-Pack C18
cartridges (500 mg), previously conditioned with
10 ml ethanol and 10 ml bidistilled water. After
washing with water, anthocyanins adsorbed on the
column were eluted with 2 ml 1% HCl MeOH.
HPLC analyses were performed using the same
equipment as described above. A C18 Spherisorb
RP-column was used and the mobile phase sys-
tems were the following: solvent A (water with
2% v/v formic acid) and solvent B (water:formic
acid:acetonitrile = 40:10:50 v/v) at a flow rate of
0.3 ml/min. The following gradient was applied:
0–20 min linear from 15% to 35% B, 20–22 min
linear to 100% B, 22–27 min isocratic 100% B,
27–30 min linear to 15% B, 30–35 min isocratic
15% B for reconditioning the column. The col-
umn temperature was maintained at 35°C and
analyses monitored at 510 nm. A calibration curve
was obtained by injection of different concentra-
tion of cyanidin-3-glucoside standard. This curve
was used to obtain quantitative data for all the
analysed samples [15].
Flavanones (hesperidin and narirutin) were
determined by HPLC using a Phenomenex C18
column (250 × 4.6 mm, 5 µm) and UV detector
(280 nm). The elution conditions were as follows:
flow rate, 1 ml/min; temperature, 30°C. The sol-
vent system used was a gradient of solvent A (wa-
ter with 0.2% v/v formic acid) and solvent B
(water:acetonitrile = 60:40 v/v with 0.2% formic
acid). The following gradient was applied: 0–
30 min linear from 100% A to 100% B, 30–32 min
linear to 100% A, 32–45 min isocratic 100% A
for reconditioning the column.
Suspended solids (SS) were determined in re-
lation to total juice (w/w%) by centrifuging, at
2000 rpm for 20 min, 45 ml of a pre-weighted
sample; the weight of settled solids was deter-
mined after removing the supernatant.
TSS measurements were carried out by using
a hand refractometer (Atago Co., Ltd., Tokyo, Ja-
pan) with scale range of 0–32°Brix.
3. Mathematical model
Membrane fouling in UF is a key factor af-
fecting the commercial viability of the process
which depends on the permeate fluxes and their
stability with time [16]. For fruit juices foulants
are represented mainly by polysaccharides of cell-
wall such as pectin, cellulose, lignin and hemi-
cellulose.
Although the TMP is the driving force of the
process, the permeate flux increases with the pres-
sure up to a limiting value (TMPlim) which de-
 A. Cassano et al. / Desalination 212 (2007) 15–27
pends on the physical properties of the suspen-
sion and on the axial velocity [17].
The membrane structure and the molecular
weight cut-off have an important role for what
concerns the performance of the process in terms
of permeate fluxes. Large pores can permit the
penetration of particles in the internal structure
of the membrane causing an irreversible fouling.
On the contrary, membranes characterized by
pores with dimensions lower than the size of sus-
pended particles behave as support promoting the
formation of a particle layer during the early fil-
tration period with the formation of a secondary
membrane or cake. The thickness of this layer,
which constitutes an additional resistance to the
mass transport, can be controlled by choosing ap-
propriate fluid-dynamic conditions [18].
Different mathematical models have been pro-
posed in order to describe the flux decline based
on equations applied to dead-end filtration mecha-
nisms at constant pressure [12] and opportunely
modified in order to describe the fouling mecha-
nism involved in cross-flow filtration [19]. In par-
ticular, the Field model describes the permeate
flux decline with time by the following differen-
tial equation:
dJ
− = k ⋅ ( J − J lim ) ⋅ J 2 − n
dt
in which Jlim represents the limit value of the per-
meate flux obtained in steady-state conditions; k
and n are phenomenological coefficient and gen-
eral index, respectively, depending on fouling
mechanism.
The model expressed by Eq. (1) permits, on
the basis of experimental data, to point out the
fouling mechanism involved in the filtration pro-
cess, according to the estimated value for n as
follows:
• Complete pore blocking (n = 2)
This situation corresponds to a condition of
complete pore obstruction by means of sealing
19
(blocking) which occurs when the particles are
larger than pore size.
• Partial pore blocking (n = 1)
In these conditions a dynamic situation of
blocking/unblocking occurs in which particles
may bridge a pore by obstructing the entrance but
not completely blocking it.
• Cake filtration (n = 0)
When solid particles or macromolecules do not
enter the pores they form a cake on the membrane
surface. In this case the overall resistance to the
mass transport is composed by a cake resistance
and a membrane resistance which is assumed to
remain unchanged.
• Internal pore blocking (n = 1.5; Jlim = 0)
Particles enter the pores reducing pore volume.
In this case membrane resistance increases as a
consequence of pore size reduction. In these con-
ditions fouling phenomenon becomes independent
of cross flow velocity and a limit value of the per-
meate flux is not reached, i.e. Jlim = 0.
A schematic representation of different situa-
tions above mentioned is reported in Fig. 1 [20].
(1)
(a)
(b)
(c)
(d)
Fig. 1. Scheme of fouling mechanism: complete pore
blocking (a); partial pore blocking (b); cake filtration (c);
internal pore blocking (d) [20].
20
4. Results and discussion
4.1. Effect of operating parameters on the per-
meate flux
UF experiments, carried out according to the
total recycle mode, were performed in order to
study the effect of TMP, temperature and axial
feed flow rate on the permeate fluxes.
Fig. 2 shows permeate flux values at steady
state versus the applied TMP. For small pressures
the solvent flux is proportional to the applied pres-
sure. As the pressure is increased flux shows a
deviation from a linear flux-pressure behavior and
it becomes independent of pressure. In these con-
ditions a limiting flux is reached at a TMP value
of about 0.8 bar and any further pressure increase
determines no significant increase of the perme-
ate flux. The existence of a limiting flux can be
related to the concentration polarization phenom-
enon that arises as the feed solution is convected
towards the membrane where the separation of
suspended and soluble solids from bulk solution
takes place. A concentration profile from bulk
solution to membrane surface is generated by the
20
15
Permeate flux (l/m2h)
10
0
0.0
Fig. 2. Effect of the TMP on the permeate flux (T = 21°C; Qf = 800 l/h).
A. Cassano et al. / Desalination 212 (2007) 15–27
rejected material accumulated on the membrane.
The formation of a viscous and gelatinous-type
layer is responsible for an additional resistance to
the permeate flux in addition to that of the mem-
brane.
The TMP limiting value (TMPlim) depends on
physical properties of the suspension and feed
flow rate. The cross-flow velocity affects the shear
stress at the membrane surface and, consequently,
the rate of removal of deposited particles respon-
sible of flux decay. Fig. 3 shows the influence of
the axial feed flow rate on the permeate flux at a
temperature of 21°C and at a TMP of 0.85 bar: as
expected, an increase in the flow rate led to higher
permeate fluxes.
Fig. 4 shows the influence of the temperature
on the permeate fluxes: when the operating tem-
perature is raised the feed viscosity is reduced and
the diffusion coefficient of macromolecules in-
creases. The effect of these two factors is to en-
hance mass transfer and to increase the perme-
ation rate. At the steady state an increasing of the
temperature from 21 to 25°C determines a 12%
increasing of the permeate flux.
0.2 0.4 0.6 0.8 1.0 1.2 1.4
TMP (bar)
 A. Cassano et al. / Desalination 212 (2007) 15–27 21

25

20
Permeate flux (l/m2h)

15

10

5
400 500 600 700 800 900

Axial feed flow rate (l/h)

Fig. 3. Effect of the axial feed flow rate on the permeate flux (T = 21°C; TMP = 0.85 bar).

28

26 15°C
21°C
24 25°C

22
Jp (l/m2h)

20

18

16

14

12
0 20 40 60 80 100 120 140 160 180 200

Time (min)

Fig. 4. Time course of permeate flux at different temperatures (TMP = 0.85 bar; Qf = 800 l/h).

4.2. Batch concentration configuration perature of 25°C was chosen in experimental tri-
als performed according to a batch concentration
Although an increasing of temperature pro- mode in order to preserve the organoleptic and
duces higher permeate fluxes, an operating tem- nutritional properties of the fresh juice. TMP and
22 A. Cassano et al. / Desalination 212 (2007) 15–27

axial feed flow rate were fixed at 0.85 bar and The initial permeate flux of 19.00 l/m2h decreased
800 l/h, respectively. to about 11 l/m2h when the VRF value reached
Results showed that the permeate flux de- 5.95. The Jp vs. VRF curve (Fig. 6) could be di-
creased gradually with the operating times by in- vided in three periods. An initial period in which
creasing the volume reduction factor (Fig. 5) due a rapid decrease of permeate flux occurs; a sec-
to concentration polarization and gel formation. ond period, up to VRF 3, corresponding to a

20 7

15
5
Permeate flux (l/m2h)

4
10

VRF
3

2
5

Jp
1
VRF

0 0
0 20 40 60 80 100 120 140 160 180

time (min)

Fig.5. Time course of permeate flux and VRF (TMP = 0.85 bar; T = 25°C; Qf = 800 l/h).

20

18
Permeate flux (l/m2h)

16

14

12

10
0 1 2 3 4 5 6 7

VRF

Fig. 6. Effect of the VRF on the permeate flux (TMP = 0.85 bar; T = 25°C; Qf = 800 l/h).
 A. Cassano et al. / Desalination 212 (2007) 15–27 23

smaller decrease of permeate flux; a third period
characterised by a small decrease of permeate flux
up to a steady-state.
4.3. Analyses of fouling mechanism
To identify the mechanism of fouling during
the UF of blood orange juice, estimation of the
model parameters, k and n, in Eq. (1) was carried
out according to the nonlinear regression optimi-
zation procedure ROK, based on Powell’s method
of conjugate directions [21].
For each set of J–t experimental data, a series
of four optimization runs were performed sequen-
tially by assigning n (n = 0, 1, 1.5 and 2) and the
corresponding steady state value Jlim already ob-
served experimentally. The procedure for estima-
tion of parameter k consisted essentially of an it-
erative process of numerical solution of Eq. (1)
by an adaptative-step-size Runge-Kutta algorithm.
The process is repeated until the minimum for the
sum of squares deviation (SSD) between numeri-
cal predictions and experimental data is found.
The minimum value of the SSD was the criterion
to identify the optimum value of n and establish
the fouling mechanism. In Table 1 the estimation
of the model parameters k and n for different axial
feed flow rates is reported. For a Reynolds num-
ber of 5800 the model with n = 1 is more adequate
to point out the experimental data; for Reynolds
numbers of 7000, 8100 and 9300 the model with
n = 2 resulted more efficient. Values of the corre-
lation coefficient r showed a good agreement be-
tween the computed values of the permeate flux
and the experimental data.
The estimates of parameters k and n were used
to solve Eq. (1) and to obtain the prediction model
in terms of permeate flux decay. In Fig. 7 the com-
parison between numerical predictions and the
experimental data, at a TMP value of 0.85 bar, is
shown. It can be seen that for a moderate feed
flow rate (Re = 5800) the flux decays within the
first 10 min followed by a gradual decline towards
a limit value, Jlim, of about 14 l/m2h. In these fluid-
dynamic conditions, as established by the esti-
mated value of n = 1, the cross-flow filtration is
governed by a partial pore blocking fouling
mechanism in which a dynamic situation of block-
ing/unblocking occurs. Increasing the Reynolds
number from 5000 to 7000, complete pore block-
ing becomes the predominant fouling mechanism
(n = 2). In this case, higher shear stress prevents
cake formation so that higher permeate fluxes can
be achieved. These effects are more evident as
cross-flow velocity is increased at 8100 and 9300
Reynolds. The optimum estimated value of n = 2
confirms that in a turbulent fluid-dynamic regime
complete pore blocking is the predominant foul-
ing mechanism. The higher feed velocity deter-
mines an increase of the initial and limit values of
the permeate flux: the flux becomes approximately
invariant with respect to time and a negligible
decay is observed. A good agreement is observed
in Fig. 7 between experimental and theoretical data.
On the basis of the obtained results it can be
establish that in the fixed operating conditions of
TMP and temperature the fouling mechanism in-
volved in the UF of blood orange juice evolves
from a partial to a complete pore blocking condi-
tion in dependence of the axial velocity.

Table 1
Estimates of the model parameters k ed n at different axial feed flow rates

Qf (l/h) Re n k·(103) SSD·(103) r

500 5800 1 0.008 0.0512 0.9984
600 7000 2 0.113 0.0313 0.9967
700 8100 2 0.064 0.0245 0.9976
800 9300 2 0.107 0.0609 0.9974
24
22
20
Permeate flux (l/m2h)
18
16
14
12
0 10
Fig. 7. Flux decay in the UF of blood orange juice. Comparison between numerical predictions and experimental data
(T = 25°C; TMP = 0.85 bar).
Fig. 8 shows the pure water permeate flux of
the membrane before and after cleaning treat-
ments.
After the cleaning with water the hydraulic
permeability of the membrane is 35% lower than
the initial value (168 l/m2h bar). The cleaning with
a NaOH solution at pH 10.9 permitted the recov-
ery of about 88% of the initial water permeability
of the membrane. A complete regeneration of the
initial water flux rates was obtained by using the
Ultrasil 10 solution.
4.4. Analytical evaluations
In Table 2 analytical measurements carried out
on samples from the feed, retentate and permeate
of the UF process are reported.
Total soluble solids content appeared to be
higher in the retentate than in the recovered per-
meate: this phenomenon can be attributed to the
presence of a high suspended solids content in
the pulpy products that can interfere with the
measurement of the refractive index. These ob-
A. Cassano et al. / Desalination 212 (2007) 15–27
theoretical data
5800 Re, n=1
7000 Re, n=2
8100 Re, n=2
9300 Re, n=2
20 30 40 50
Time (min)
servations corroborate the results obtained by
Vaillant et al. [22] in the clarification of melon
juice.
Suspended solids in freshly squeezed blood
orange juice were completely removed by UF: the
resulting serum was a transparent liquid of amber
appearance.
In the clarified juice an 8.41% reduction of
the ascorbic acid was observed with respect the
fresh juice, while for the TAA a reduction of about
1.5% was measured. The rejection of the UF mem-
brane towards total anthocyanins and flavanones
was of 9.4 and 0%, respectively.
In Table 3 the mass balance of the UF process
for ascorbic acid, TAA, total anthocyanins and
flavanones is reported. This balance is referred to
an UF run in which, starting from 9.33 l of fresh
juice, 7.76 l of permeate and 1.57 l of retentate
(final VRF = 5.92, recovery factor = 83.1%) were
obtained. It can be noted that 76% and 82% of
the initial content of ascorbic acid and TAA, re-
spectively, were maintained in the permeate of the
UF process. The 8.4% loss of ascorbic acid, as
 A. Cassano et al. / Desalination 212 (2007) 15–27 25

after cleaning with

Ultrasil 10

after cleaning with

NaOH

after cleaning with water

before the treatment

with juice

0 20 40 60 80 100 120 140 160 180

2 -1 -1
Hydraulic permeability (l m h bar )

Fig. 8. Hydraulic permeability of the UF membrane before and after cleaning procedures (T = 25°C; Qf = 500 l/h).

Table 2
Analytical measurements on samples of blood orange juice clarified by UF

Parameters Samples
Feed Permeate Retentate
TSS (°Brix) 12.0 11.2 13.5
Suspended solids (w/w%) 10 0 >50
TAA (mM Trolox) 8.61±0.15 8.48±0.17 8.52±0.09
Ascorbic acid (mg/l) 701±1.7 642±2.3 640±1.6
Total anthocyanins (mg/l) 60.4±0.2 54.7±0.22 60.6±0.16
Narirutin (mg/l) 46.74±0.1 46.79±0.1 46.76±0.1
Hesperidin (mg/l) 33.33±0.1 33.67±0.1 31.14±0.1

Table 3
Mass balance of the UF process

Feed Total permeate Final retentate Balance

Volume (l) 9.33 7.76 83.2% 1.57 16.8% 100.0%
Ascorbic acid (g) 6.54 4.98 76.2% 1.00 15.4% 91.6%
TAA (mmol Trolox) 80.33 65.80 81.9% 13.3 16.6% 98.5%
Total anthocyanins (mg) 564.00 424.00 75.2% 95.0 16.8% 92.0%
Narirutin (mg) 436.08 363.09 83.2% 73.41 16.8% 100.0%
Hesperidin (mg) 310.96 261.27 84.0% 48.88 15.7% 99.7%
26 A. Cassano et al. / Desalination 212 (2007) 15–27
quantified by the mass balance, was probably due
to an oxidation of this component caused by con-
tinual recycling of the juice around the UF pilot
plant loop.
The obtained results show that the clarified
juice presents physico-chemical and nutritional
properties very similar to those of the fresh or-
ange juice, except for the absence of suspended
solids which are totally concentrated in the
retentate of the UF process. Thus, the flux de-
cline during UF could be ascribed to fouling lay-
ers formed by a combination of suspended par-
ticles and adsorbed macromolecular impurities.
5. Conclusions
Blood orange juice was clarified by cross-flow
ultrafiltration (UF) using a tubular polyvinyliden-
fluoride (PVDF) membrane with a molecular
weight cut-off of 15 kDa. The effect of transmem-
brane pressure (TMP), axial feed flow-rate and
temperature on the permeate flux was investigated
and optimal operating conditions guaranteeing
maximum permeation flux, minimum fouling and
preservation of heat-sensitive compounds were
selected. In these conditions an average perme-
ation flux of 15 l/m2h was obtained.
The mathematical analyses of the flux decline
revealed that in the fixed operating conditions of
TMP and temperature the fouling mechanism
evolves from a partial pore blocking (n = 1) to a
complete pore blocking (n = 2) condition in de-
pendence of the axial velocity. The theoretical
predictions in terms of permeate flux as a func-
tion of time agreed well with experimental data.
The clarified orange juice presented physico-
chemical and nutritional properties comparable
with fresh orange juice except for insoluble sol-
ids which were totally concentrated in the retentate
stream. Thus, the flux decline during UF could
be ascribed to fouling layers formed by a combi-
nation of suspended particles and adsorbed mac-
romolecular impurities.
The health-related properties of polyphenols
contained in orange juice were well preserved in
the clarified juice as showed by the low reduction
of the total antioxidant activity (TAA) in the per-
meate in comparison with the fresh juice. This is
a very interesting result considering the positive
therapeutic and protective effect of antioxidant
compounds in the treatment of various microcir-
culation diseases or as antineoplastic, anti-inflam-
matory and hepatoprotective agents.
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