Journal of Food Engineering 107 (2011) 366373

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Journal of Food Engineering

journal homepage: www.elsevier.com/locate/jfoodeng

Clarication and concentration of pomegranate juice (Punica granatum L.) using membrane processes
Alfredo Cassano , Carmela Conidi, Enrico Drioli
Institute on Membrane Technology, ITM-CNR, c/o University of Calabria, via P. Bucci, cubo 17/C, I-87030 Rende (Cosenza), Italy

a r t i c l e

i n f o

a b s t r a c t
The production of concentrated pomegranate juice was investigated by using a two-step membrane process based on: (1) a clarication step of the fresh non-depectinized juice performed by hollow-ber ultraltration (UF) membranes; (2) a concentration step of the claried juice by using an osmotic distillation (OD) apparatus. Both processes were performed at ambient temperature (25 2 C) producing a clear juice and a concentrated juice with a total soluble solids (TSS) content of 162 g kg1 and 520 g kg1, respectively. The performance of UF and OD operations was evaluated in terms of productivity (permeate and evaporation uxes) and quality of the processed juice. Suspended solids were completely removed in the clarication step, while soluble solids and organic acids were recovered in the permeate stream of the UF process. Rejections of the UF membrane towards polyphenols and anthocyanins were of 16.5% and 11.7%, respectively. The antioxidant activity of pomegranate aril juice, attributed to a great extent to total phenols and anthocyanins content, was efciently preserved during the concentration step independently on the achieved level of total soluble solids. An integrated membrane process scheme for the production of concentrated pomegranate juice with potential applications for food, pharmaceutical and cosmetic sectors was proposed. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 30 April 2011 Received in revised form 28 June 2011 Accepted 3 July 2011 Available online 13 July 2011 Keywords: Pomegranate juice Ultraltration Osmotic distillation Integrated membrane processes

1. Introduction Signicant progresses have been made over the past 10 years towards a much more comprehensive understanding of some pharmacologic components of pomegranate fruit (Punica granatum). Clinical research studies suggest that some compounds of the pomegranate juice are characterized by anticarcinogenic, antimicrobial, antioxidant and antiviral activities (Malik et al., 2005; Noda et al., 2002; Braga et al., 2005; Vidal et al., 2003). Further, as reported in biological studies, pomegranate juice is enriched in anti-atherosclerotic and anti-atherogenic compounds which have been shown to reduce blood pressure and low density lipoprotein (LDL) oxidation (Aviram and Dornfeld, 2001). These activities have been attributed to its phenolic fraction containing a signicantly high level of hydrolyzable tannins, as well as anthocyanins (delphinidin, cyanidin and pelargonidin 3-glucosides and 3,5-diglucosides), which exhibit high antioxidant activity (Lansky and Newmann, 2007; Visioli and Hagen, 2007). Besides, different studies have shown that pomegranate juice contains much more antiox-

Corresponding author. Tel.: +39 0984 492067; fax: +39 0984 402103.
E-mail address: a.cassano@itm.cnr.it (A. Cassano). 0260-8774/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.jfoodeng.2011.07.002

idant compounds than other fruit juices and beverages (Gil et al., 2000). Due to these characteristics and increasing public awareness about nutritional food, the demand for the pomegranate fruit and its by-products has increased signicantly in the last years. Consequently, many industries producing pomegranate juice, as well as pharmaceutical companies extracting health benecial compounds from the fruit, have been developed (Seeram et al., 2006). Traditional methods of processing fruits limit the possibility to obtain products able to retain as much as possible the peculiarity of the fresh fruit and its high content in health-benecial compounds. For instance, conventional juice clarication processes are based on the use of ning agents (gelatine, bentonite, silica sol, diatomaceous earth, etc.) which create serious problems of environmental impact due to their disposal (Vaillant et al., 1999). Moreover, the concentration of fruit juices, aiming at ensuring a longer storage life and an easier transportation, is performed by thermal evaporation methods resulting in color degradation and reduction of most thermally sensitive compounds, with a consequent remarkable qualitative decline (Jiao et al., 2004). Product quality improvement and energy savings have guided the development of minimal processing techniques. Compared with traditional juice processing methods, membrane processes are low-cost and athermal separation techniques which involve no

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phase change or chemical agents. These features are becoming very important factors in the production of new fruit juices with natural fresh tastes and additive-free. Ultraltration (UF) membranes are commonly used to clarify and stabilize fruit juices and commercial processes have already implemented on industrial scale for juices such as apple and orange (Girard and Fukumoto, 2000). They are able to retain large species such as microorganisms, lipids, proteins and colloids while small solutes such as vitamins, salts, and sugars ow together 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; possibility of avoiding the use of gelatins, adsorbents and other ltration aids; reduction in enzyme utilization; easy cleaning and maintenance of the equipment; elimination of needs for pasteurization; better juice clarity; reduction of ltration times and waste products (Fukumoto et al., 1998). Concentration processes of the claried pomegranate juice by using thermal evaporation have already been proposed. In particular, Chen and Song (1994) developed a fresh-preserving concentrated pomegranate juice producing method adopting a low temperature vacuum process for the concentration of the ltered juice. Pang et al. (2008) patented a method in which the claried juice was concentrated by thermal evaporation and then submitted to pasteurization before the aseptic packaging. The concentrated juice is characterized by a pH value between 2.8 and 3.7, turbidity from 0 to 25 NTU, a transmittance (T625) equal to or greater than 90% and a color ratio (A520nm/A430nm) equal to or greater than 1.0. Membrane concentration processes, such as reverse osmosis (RO), membrane distillation (MD) and osmotic distillation (OD), present some attractive options to overcome limitations associated with vacuum evaporation. In particular, OD is a novel athermal membrane-separation process based on the use of a macroporous hydrophobic membrane separating two aqueous solutions having different solute concentration: a dilute solution on one side and a hypertonic salt solution (concentrated brine stripper) on the opposite side. The driving force of the process is given by a water vapor pressure gradient across the membrane generated by the difference in water activity between the two sides of the membrane. The hydrophobic nature of the membrane prevents penetration of the pores by aqueous solutions, creating air gaps within the membrane. The water vapor pressure gradient across the membrane determines a transfer of vapor across the pores from the high-vapor pressure phase to the low one (Hogan et al., 1998; Nagaraj et al., 2006). This migration of water vapor results in the concentration of the feed and dilution of the osmotic agent solution. Since the OD process is operated at room temperature and atmospheric pressure, products can be concentrated without mechanical and thermal damage. Therefore OD is an attractive process for the concentration of solutions containing thermo-sensitive compounds such as fruit juices and pharmaceuticals. The concentration of claried fruit juices by OD has been investigated by different authors (Cassano and Drioli, 2007; Cassano et al., 2007; Hongvaleerat et al., 2008; Rodrigues et al., 2004; Shaw et al., 2001; Kozk et al., 2006) and its potential for the better preservation of the quality of the raw material has been clearly conrmed. The present study was undertaken to investigate the potentiality of an integrated membrane process in the clarication and concentration of pomegranate juice, as an alternative to conventional processing methods. In particular, the fresh juice, with an initial total soluble solids (TSS) content of 162 g kg1, was preliminarily claried by ultraltration (UF). Then the claried juice was submitted to a concentration step, at room temperature, by using osmotic distillation (OD) up to a nal TSS content of about 520 g kg1. The performance of UF and OD processes was evaluated in terms of

both productivity (permeate and evaporation uxes) and quality of the processed juice. 2. Materials and methods 2.1. Juice extraction Pomegranates of Sicilian origin (Punica granatum L. cv Selinunte) were supplied by Citrech Snc (Messina, Italy). Fruits were washed in cold tap water and drained. They were manually cut-up and the outer leathery skin which encloses hundreds of eshy arils was removed. Arils were pressed by using an electric tomato crusher: the extracted juice, having a deep-red color, was preltered with a stainless steel lter. Then it was stored in a refrigerator cell at 17 C and defrosted before use. 2.2. UF equipment and procedures The clarication of the juice was performed by using a laboratory UF bench plant (DSS LabUnit M10) supplied by Danish Separation System AS, Denmark. The equipment consisted of a 5 L feed tank, a cross-ow pump (ECO type GA4-KDT-TTU), two pressure gauges (02.5 bar) located at the inlet (Pin) and outlet (Pout) of the membrane module, a pressure control valve and a multi-tube heat exchanger fed with tap water. The temperature (T) of the feed was controlled by circulating cooling water through the heat exchanger; the axial feed ow-rate (Qf) and the transmembrane pressure (TMP) were controlled by using a needle concentrate valve and by setting the speed of the pump. Modied poly(ether ether ketone) hollow ber (HF) membranes were prepared via the dry-wet spinning technique through the phase inversion process (Tasselli et al., 2007). Their characteristics are reported in Table 1. The UF plant was equipped with a membrane module prepared by embedding ve HF membranes inside a 20 cm long glass tube (effective membrane length 18 cm, effective membrane area 46 cm2) with epoxy resin (Stycast, Emerson and Cuming, Belgium). The juice was claried according to the batch concentration mode (recycling the retentate in the feed tank and collecting separately the permeate stream) in the following operating conditions: TMP, 0.96 bar; T, 25 C; Qf, 1166 mL min1. The hydraulic permeability of the membrane was determined by the slope of the straight lines obtained plotting the water ux values in selected operating conditions (T, 25 C; Qf, 900 mL min1) versus the applied TMP. The value obtained for a new clean membrane is referred to as L0 p. The hydraulic permeability measured after the treatment with pomegranate juice was indicated as L1 p. After the experiments with pomegranate juice the membrane module was cleaned in two steps. The rst cleaning step was performed recirculating distilled water for 20 min through the module at a Qf of 1500 mL min1 and a TMP of 0.4 bar in order to remove the reversible polarized layer. The hydraulic permeability measured afterwards was L2 p . In the second step the membrane module was submitted to a cleaning procedure using a NaClO solution at a

Table 1 Characteristics of UF membranes. Conguration Material Water permeability (L m2 h1 bar1) Dextran 68,800 MW rejection (%) Thickness (mm) Inner diameter (mm) Outer diameter (mm) Hollow-bers Poly(ether ether ketone) 655.6 10.0 0.235 1.64 2.11

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concentration of 4 g L1 and at a T of 40 C for 60 min. Then the membrane module was rinsed with tap water for 20 min and the hydraulic permeability, indicated as L3 p was determined. 2.3. OD equipment and procedures The claried juice, with a TSS content of 162 g kg1, was submitted to an OD treatment by using a laboratory plant supplied by Hoechst-Celanese Corporation (Wiesbaden, Germany). The unit featured a Liqui-Cell Extra-Flow 2.5 8-in. membrane contactor (Membrana, Charlotte, USA) containing microporous polypropylene hollow bers (having external and internal diameters of 300 lm and 220 lm, respectively) with an average pore diameter of 0.2 lm and a total membrane surface area of 1.4 m2. The claried juice was pumped through the shell side of the membrane module; a 10.2 mol L1 calcium chloride dehydrate solution, used as stripping solution, was pumped through the ber lumens (tube side). Feed and stripping solution were recirculated through the contactor in a counter-current mode with an average ow-rate of 500 mL min1 and 333 mL min1, respectively. Temperature was maintained almost constant in both compartments at 25 2 C, whereas the TMP was 0.4 bar. The initial weight of the stripper was about 10 kg, four times higher if compared to that of the claried juice, in order to prevent its signicant dilution with a consequent decreasing of the driving force during the process. Evaporation uxes (Jw) were determined gravimetrically measuring the weight of the water extracted from the juice by means of a digital balance placed under the juice container. After each trial, the pilot plant was cleaned rst by rinsing the tube side and shell side with de-ionized water. Then, a KOH solution at 2% (w/w) was circulated for 1 h at 40 C. After a short rinsing with de-ionized water a citric acid solution at 2% (w/w) was circulated for 1 h at 40 C. Finally, the circuit was rinsed with deionized water. 2.4. Analytical measurements Fresh pomegranate juice, claried juice (permeate UF) and concentrated juice (retentate OD) were collected at different stages of the integrated membrane process and analyzed for their chemical and physical properties. The suspended solid content was determined in relation to the 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 determined after removing the supernatant. Total soluble solids (TSS) were measured by an Abbe refractometer Bellingham + Stanley 60/DR (Bellingham + Stanley Ltd., Kent, UK) at 20 C. pH was measured by an Orion Expandable ion analyzer EA 920 pH meter (Allometrics, Inc., LA, USA) with automatic temperature compensation. Total titrable acidity was determined potentiometrically with 0.1 N NaOH to the titration end point of pH 8.2 and expressed as g citric acid L1. Total antioxidant activity (TAA) was determined by using an improved version of the ABTS radical cation decolorization assay (Rice-Evans and Miller, 1994; Re et al., 1999). Results were expressed as Trolox Equivalent Antioxidant Capacity (TEAC). Total phenolic content was evaluated according to the Prussian blue spectrophotometric method (Price and Butler, 1977). Results were expressed as g catechin L1. The viscosity of the juice at 25 C was estimated by using data published in literature on the rheological behavior of pomegranate juice and concentrate (Altan and Maskan, 2005). Anthocyanins were assessed by using an HPLC system (Agilent 1100 Series, USA) equipped with a pump, an UVVis detector and a data acquisition system. Chromatographic separation was per-

formed by using a Luna C 18(2) column (250 4.6 mm, 5 lm Phenomenex, Torrance, CA, USA); the following conditions were used: V = 1 mL min1; T = 25 C; k = 518 nm. The mobile phase was a mixture of H2O/HCOOH (9:1) as solvent A and H2O/HCOOH/CH3CN (4/ 1/5) as solvent B. Anthocyanins separation was achieved by using the following linear gradient: starting condition, 88% A, 12% B; 26 min, 70% A, 30% B; 35 min, 100% B; 43 min, 88% A, 12% B; 46 min 88% A, 12% B. Anthocyanins were identied by matching the retention time and their spectral characteristics against those of standards (cyanidin 3,5-diglucoside, delphinidin 3-glucoside, cyanidin 3-glucoside, pelargonidin 3-glucoside). Quantication was made according to the linear calibration curves of standard compounds (Mondello et al., 2000). The quantitative determination of ascorbic, malic and citric acids was carried out by using the same HPLC system equipped with an Hypersil ODS column (250 4.6 mm, 5 lm) (Alltech Associates, Inc., IL); samples were eluted in isocratic mode by using a 0.025 M KH2PO4 solution at pH 2.5. Operating conditions were as follows: V = 1 mL min1, T = 25 C, pressure = 80 bar. A sample volume of 10 lL was used. Analyses were monitored at 206 nm. Prior to HPLC analysis all samples were ltered by using 0.45 lm cellulose acetate lters. All organic acids were identied by matching the retention time and their spectral characteristics against those of standards. Quantization was made according to the linear calibration curves of standard compounds. Each assay was performed in triplicate. The deviation of each measurement was of 2% from the average value. The rejection (R%) of UF membranes towards specic compounds was determined as:

 cp 100 cf

where Cp and Cf are the concentration of a specic component in the permeate and feed, respectively. In order to quantify loss of valuable compounds during the integrated process UF/OD, retentate samples obtained in the OD process were diluted at the same total soluble solids content of the claried juice. 3. Results and discussion 3.1. Pomegranate juice clarication The evolution of the permeate ux during the UF of pomegranate juice in the selected operating conditions is illustrated in Fig. 1. The initial permeate ux of about 29 L m2 h1 decreased gradually with operating times due to concentration polarization and fouling phenomena to reach a steady-state value of about 20 L m2 h1. After the cleaning with water the hydraulic permeability of the membrane was 97.7 L m2 h1 bar1, about 85% lower than the initial value (655.6 L m2 h1 bar1). The cleaning with a NaClO solution permitted the recovery of about 88% of the initial water permeability of the membrane (Fig. 2). The UF step can be considered a fundamental pre-treatment of the raw juice in order to apply high ow rate and maximize yield during the subsequent OD process (Bailey et al., 2000). 3.2. Concentration of claried juice Fig. 3a shows the time course of evaporation ux and TSS content during the juice concentration by OD. The initial evaporation ux, of about 0.85 kg m2 h1, decreased gradually up to a nal value of 0.38 kg m2 h1 when the TSS content of the concentrated juice was 520 g kg1. In particular, during the rst part of the OD

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35 30

1.50
Jw TSS

600

1.25

500

Permeate flux (L m h )

-2 -1

25
Jw (kg m h )
-2 -1

1.00 400 0.75 300 0.50

20 15 10

0.25

200

5
0.00 0 20 40 60 80 100 120 140 100 160

0 0 25 50 75 100 125 150 175

200

225

250

Operating time (min)

Operating time (min)

Fig. 1. Evolution of the permeate ux during the ultraltration of pomegranate juice (operating conditions: TMP = 0.96 bar; T = 25 C; Qf = 1166 mL min1).

b
CaCl2x2H2O concentration (mol L )
-1

12

11

10

700
before juice treatment after juice treatment after rinsing with water after chemical cleaning

600

Permeate flux (L m h )

-1

Lp0 = 655.6 L m-2 h-1 bar-1 Lp3 = 579.6 L m-2 h-1 bar-1

500

-2

400
6

300

20

40

60

80

100

120

140

160

Operating time (min)

200
Lp2 = 208.9 L m-2 h-1 bar-1

100
Lp1 = 97.7 L m-2 h-1 bar-1

Fig. 3. Concentration of claried pomegranate juice by osmotic distillation. Time course of (a) evaporation ux and total soluble solids; (b) concentration of stripping solution (operating conditions: T = 25 2 C; TMP = 0.4 bar; Qf = 500 mL min1; Qb = 333 mL min1).

0
0.0 0.2 0.4 0.6 0.8 1.0 1.2

TMP (bar)
Fig. 2. Hydraulic permeability of the UF membrane before and after cleaning procedures (T = 25 C; Qf = 900 mL min1).

70

60

50

process (range 080 min), the decline in evaporation ux from 0.85 kg m2 h1 to 0.55 kg m2 h1 (ux decline of 35.3%) could be attributed to the decrease in brine concentration (Fig. 3b) from 10.2 mol L1 at TSS of 160 g kg1 to 8.77 mol L1 when TSS reached 292 g kg1. The dilution of the brine solution leads to the decrease in vapor pressure of the osmotic agent and, consequently, to the decrease of driving force for water transport from the feed through the membrane (Alves et al., 2004). During the second part of the OD process (range 80140 min) evaporation ux declined of 30.2% (from 0.55 kg m2 h1 to 0.38 kg m2 h1) corresponding to a decrease in brine concentration of 7.4% (from 8.77 mol L1 to 7.87 mol L1 when TSS reached 520 g kg1). This result can be attributed to the strong inuence of the concentration level on the evaporation ux considering the slight decrease in brine concentration during the last part of the process. As shown in Fig. 4, the increase in TSS content of the juice results in an exponential increase in juice viscosity (Altan and Maskan, 2005; Magerramov et al., 2007) which may raise resistance to mass transfer in the liquid phase and, consequently, to determine a polarization effect leading to a lower driving force. These results conrm that at low TSS content evaporation uxes seem to be mainly dependent on brine concentration. At concentration values

Viscosity (mPa s)

40

30

20

10

0
100 200 300 400 500 600 700

Total soluble solids (g kg-1)

Fig. 4. Pomegranate juice viscosity vs. TSS at 25 C (adapted from Altan and Maskan, 2005).

higher than 300 g kg1 evaporation uxes are mainly affected by the juice viscosity and, consequently, by the concentration level. Similar results were obtained in the OD concentration of different claried juices (kiwifruit, citrus, carrot, passion fruit, cactus pear etc.) on laboratory and semi-industrial scale (Cassano and Drioli, 2007; Cassano et al., 2003, 2007; Vaillant et al., 2001, 2005).

TSS (g kg )

-1

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3.3. Quality of processed juice In Table 2 chemical and physical properties of fresh, claried and concentrated pomegranate juice are summarized. It was observed that total soluble solids, pH, acidity and organic acids (malic and citric acids) between fresh and claried juice (permeate UF) were not signicantly different. Suspended solids were completely removed from the fresh juice by the UF membrane producing a clear juice. The freshly squeezed pomegranate juice was characterized by a total antioxidant activity (TAA) of 12.9 TEAC: this value is in agreement with the TAA value of pomegranate juice obtained from fresh arils (1214 TEAC) as reported by Gil et al. (2000). The UF membrane showed a rejection towards polyphenols and TAA of 16.5% and 17.8%, respectively. These results are in agreement with ndings of Tzulker et al. (2007) which reported a signicant correlation between the antioxidant activity of pomegranate aril juice and the total phenol content. In the permeate of the process a 30.8% of ascorbic acid was also observed in comparison with the fresh juice. The UF membrane used in this study is a hydrophobic membrane with a rejection of 10% w.r.t. dextran (68,800 MW): this type of membrane permits to limit the adsorption of polyphenols which results more signicant on hydrophilic membranes. Data reported by Mirsaeedghazi et al. (2010), concerning the clarication of pomegranate juice with mixed cellulose esters at-sheet membranes having pore sizes of 0.22, 0.1 and 0.025 lm, indicated rejections towards total phenolic content of 29.5%, 26.0% and 25.0%, respectively. For hydrophilic polyvinylidene uoride (PVDF) atsheet membranes, with pore sizes of 0.22 lm and 0.45 lm, rejections were of 50.5% and 34.9%, respectively. Clarication methods of pomegranate juice by conventional ning (treatment with 0.3 g L1 of gelatin and 0.3 g L1 of bentonite)
Table 2 General composition of claried and concentrated pomegranate juice. Fresh juice Suspended solids, %(w/w) pH Total acidity, g L1 Total soluble solids, g kg1 TAA, TEACa Ascorbic acid, mg L1 Malic acid, g L1 Citric acid, g L1 Total polyphenols, g catechin L1
a

Permeate UF 0 3.78 0.35 162.0 10.6 47.0 1.82 1.45 1.31

Retentate UF 5.3 3.74 0.44 14.1 71.0 2.01 1.24 1.70

Retentate OD 520.0 10.1b 44.0b 1.80b 1.26b 1.22b

4.8 3.75 0.41 162.0 12.9 68.0 1.90 1.47 1.57

without or with the addition of polyvinylpolypyrrolidone (PVPP) (0.2 g L1) produced a total phenol reduction of 20.9% and 31.8%, respectively (Alper et al., 2005). The UF permeate showed a reduction of anthocyanins in comparison with the fresh juice of 11.7% attributable mainly to the removal of delphinidin 3-glucoside, cyanidin 3-glucoside and pelargonidin 3-glucoside. A higher recovery of cyanidin 3,5-diglucoside in the claried juice was observed (Table 3). In Table 4 the mass balance of the UF process for organic acids, anthocyanins and polyphenols is reported. This balance is referred to an UF run in which, starting from 3.65 L of fresh juice, 2.15 L of permeate and 1.5 L of retentate (nal VRF = 2.43, recovery factor = 58.9%) were obtained. It can be noted that citric acid and malic acid were completely recovered in the permeate stream. The 16.4% loss of ascorbic acid was probably due to an oxidation of this compound caused by continual recycling of the juice around the UF pilot plant loop. In general, ascorbic acid is sensitive to conditions such as light exposure and ascorbate oxidase which promote the transformation of L-ascorbic acid to dehydroascorbic acid. In the concentration step organic acids were well preserved independently on the TSS content achieved. The concentrated juice at 520 g kg1 of TSS showed a slight decrease of the TAA (about 4.7%) when compared with the claried juice, conrming the particular mildness of the treatment (Table 2). HPLC proles of anthocyanins referred to the fresh juice, the UF permeate and the OD retentate (sample diluted at 162 g kg1 of TSS) showed at the end of the concentration process a reduction of anthocyanins of about 23% (Fig. 5). These observations conrm results obtained by Galaverna et al. (2008) in the concentration of red orange juice by OD. On the other hand, data reported in literature indicate a strong degradation of anthocyanin pigments during thermal treatment for the concentration of pomegranate juice accomplished by the presence of signicant levels of 5-hydroxymethyl furfural (an indicator of potential browning of the juice) and by the reduction of minerals, such as sodium, iron, lead, copper and zinc between 44% and 69% (Orak, 2009). Further, heating/evaporation processes (microwave heating, rotary vacuum evaporator and evaporation at atmospheric pressure) employed for production of pomegranate juice at 605 g kg1 decreased the color parameters (L, a and b) signicantly and the products turned reddish brown. The extent of color degradation increased with soluble solids content (Maskan, 2006). Sugar and sugar degradation products have been found to be effective on accelerating anthocyanin breakdown and enhance non-enzymatic browning during thermal processing (Suh et al., 2003). 3.4. Integrated membrane process Fig. 6 shows an integrated membrane process scheme suggested for the production of claried and concentrated pomegranate juice.

TEAC is the concentration of Trolox required to give the same antioxidant capacity as 1 mM test substance (Rice-Evans and Miller, 1994). b Value referred to a TSS content of 162 g kg1.

Table 3 Anthocyanin compounds composition of claried and concentrated pomegranate juice. Operation Sample TSS (g kg1) 162.0 162.0 162.0 250.0 336.0 520.0 Cyanidin 3,5-diglucoside (mg L1) 46.95 0.96 44.26 0.95 45.82 1.55 43.2 1.60 39.4 0.84a 39 0.43a 39 0.70a Delphinidin 3-glucoside (mg L1) 20.6 1.64 17.7 2.00 20.28 1.52 12 0.48 12.25 0.40a 12 0.66a 11.5 0.60a Cyanidin 3-glucoside (mg L1) 30.4 1.11 25.81 2.44 28.74 1.02 23.4 1.70 18.7 1.17a 20 0.95a 20.9 0.78a Pelargolidin 3-glucoside (mg L1) 5 0.44 4.2 0.38 5 0.29 4.3 0.43 4.5 0.11a 4.5 0.15a 4.4 0.05a Total anthocyanins (mg L1) 102.8 3.18 90.7 0.71 100.6 3.53 87.7 5.56 74.6 2.34a 75.55 1.87a 75.85 1.74a

UF

Feed Permeate Retentate Feed Retentate t = 55 min Retentate t = 88 min Retentate t = 135 min

OD

Value referred to a TSS content of 162 g kg1.

A. Cassano et al. / Journal of Food Engineering 107 (2011) 366373 Table 4 Mass balance of the UF process.a Feed Volume Malic acid Ascorbic acid Citric acid Anthocyanins Total polyphenols
a

371

Permeate 2.150 L 3.913 g 0.101 g 3.117 g 0.195 g 2.816 g 59% 56.4% 40.7% 58.1% 52.0% 49.1%

Retentate 1.5 L 2.015 g 0.106 g 1.860 g 0.151 g 2.55 g 41% 43.4% 42.9% 34.7% 40.2% 44.5%

Balance (permeate + retentate) 100% 99.8% 83.6% 92.8% 92.2% 93.6%

3.650 L 6.935 g 0.248 g 5.365 g 0.375 g 5.730 g

At a nal volume reduction factor (VRF) of 2.43.

a
mAU 35 30 25 20 15 10 5 0 -5 0 5 10 15 20 25 30

b
mAU 35 30 25 20 15 10 5 0 -5 0 5 10 15 20 25 30

min

min

c
mAU 35 30 25 20 15 10 5 0 -5
0

10

15

20

25

30

min

Fig. 5. HPLC chromatograms of anthocyanins in (a) UF feed (TSS content: 162 g kg1); (b) UF permeate (TSS content: 162 g kg1); and (c) OD retentate (sample diluted at 162 g kg1). 1: Cyanidin 3,5-di-O-glucoside; 2: delphinidin 3-O-glucoside; 3: cyanidin 3-O-glucoside; 4: pelargonidin-3-O-glucoside.

The UF process provides two fractions of pomegranate juice: the retentate and the permeate. The permeate is considered to be claried and sterilized juice while most microorganisms are separated

and concentrated in the retentate. This fraction, corresponding to a small volume of the juice, can be sterilized for the elimination of microbes, while most of the avor and nutritional compounds are

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Fig. 6. Proposed scheme for the production of claried and concentrated pomegranate juice by integrated membrane process.

preserved in the claried juice. Consequently, a large amount of the juice can be processed by UF avoiding the loss of phytochemical compounds due to high temperatures (Torregrosa et al., 2006). The concentrated juice is a stable product from a microbiological point of view and represents a product with peculiar characteristics which can be exploited for the formulation of new marketable products. The aspect of the concentrated juice is similar to that of fruit syrups, sugar products which are normally stored and marketed at ambient temperatures. It can be added to the water and to the pasteurized UF retentate (UF membranes retains microorganisms which have to be inactivated) to obtain a juice with sensorial, organoleptic and nutritional properties similar to those of the fresh juice. Alternatively, the concentrated product can be used as avoring for alcoholic or zzy beverages, baked goods, sweets and other food products. It can be also exploited as food color additive as an alternative to synthetic pigments: it satises the desired functional characteristics of a natural colorant such as high dyeing efciency, good stability and attractive color. The development of formulations for pharmaceutical applications (anticholesterolemic, antiviral, antimicrobial, anti-inammatory, antihypertensive products) is also of great interest. Within the nutraceutical sector the OD retentate can be added as functional supplement in food and beverages. Finally, the preparation of products with whitening and moisturizing function, could be a successful application in cosmetic eld. The industrial feasibility of the UF/OD integrated process requires a detailed economic study in order to evaluate the impact of these technologies on the cost of the nal products. Performances of the UF process, in terms of productivity, could be improved by optimizing the operating and uid-dynamic conditions to limit concentration polarization and fouling. Large scale applications of the OD are limited by low uxes in comparison with thermal evaporations. In order to improve the competitiveness of membrane contactors vis a vis conventional technologies, efforts must be dedicated to improve process engineering, especially module and process design. 4. Conclusions The integrated membrane process involving the clarication of the juice by UF and the concentration of the claried juice by OD

was observed to be an attractive process for the production of a concentrated juice with high antioxidant activity which can be employed for the formulation of pharmaceuticals, cosmetics and food products (avoring for beverages, juice blendings, alcoholic beverages, food colorants, sweets, baked products, etc.). Clarication by UF essentially enables the removal of suspended solids which remained totally concentrated in the retentate stream producing a claried juice with physic-chemical and nutritional properties similar to those of the fresh juice. The concentration process performed by OD allowed claried juice to be concentrated without modifying the main physic chemical parameters of the product. A 3.2-fold concentration of total soluble solids was achieved by using OD without any back diffusion of solute and burned off avor due to the hydrophobic nature of the membrane. References
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