Food Chemistry 203 (2016) 175182

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Effect of ultrafiltration process on physico-chemical, rheological,

microstructure and thermal properties of syrups from male
and female date palm saps
Ines Makhlouf-Gafsi a,, Samia Baklouti b, Abir Mokni a, Sabine Danthine c, Hamadi Attia a,
Christophe Blecker c, Souhail Besbes a,c,, Manel Masmoudi a
a
University of Sfax/National School of Engineers of Sfax, Dept. of Biology, Laboratory of Analysis Valorisation and Food Safety, Soukra Road, 3038 Sfax, Tunisia
b
University of Sfax/National School of Engineers of Sfax, Research Unit of Industrial Chemistry and Materials, Soukra Road, 3038, Tunisia
c
University of Lige, Gembloux Agro-Biotech, Lab. of Food Science and Formulation, Passage des Dports, 2, 5030 Gembloux, Belgium

a r t i c l e i n f o a b s t r a c t

Article history:
Received 4 November 2015
Received in revised form 12 January 2016
Accepted 9 February 2016
Available online 10 February 2016
Chemical compounds studied in this article:
Sulphuric acid (PubChem CID: 1118)
Boric acid (PubChem CID: 7628)
3 5 dinitrosalicylic acid (PubChem CID:
3663247)
Galacturonic acid (PubChem CID: 439215)
Phenol (PubChem CID: 996)
Zinc acetate (PubChem CID: 11192)
This study investigates the effect of the ultrafiltration process on physicochemical, rheological,
microstructure and thermal properties of syrups from male and female date palm sap. All the studied syr-
ups switched from pseudoplastic rheological behaviour (n = 0.783) to Newtonian behaviour (n
1) from
10 to 50 C respectively and present similar thermal profiles. Results revealed that the ultrafiltration pro-
cess significantly affects the rheological behaviour of the male and female syrups. These differences on
rheological properties are attributed to the variation of chemical composition between sap and sap per-
meate syrups. Furthermore, the effect of temperature on viscosity of the syrups was investigated during
heating and cooling processes at the same shear rate (50 s1). This study provides idea of the stability of
the syrup by evaluating the area between heating and cooling curves. Actually, the syrup prepared from
male sap permeate is the most stable between the four studied syrups.
2016 Elsevier Ltd. All rights reserved.

Keywords:
Ultrafiltration
Date sap syrups
Physicochemical composition
Rheological behaviour
Thermal properties
Microstructure

1. Introduction
Date palm (Phoenix dactylifera L.) is a woody, perennial and
dioecious plant species, with separate male and female trees,
belonging to the Arecaceae family. In Tunisia, the total number of
date palms is around 5.4 million of the 120 million worlds date
palms (Makhlouf et al., 2015). In Tunisia, date palm tapping is a
traditional practice. Its well known that sap extraction for a long
tapping period (higher than three or four months) has always been
marked by a potential risk for date palm tree. In fact, in this case
Corresponding authors at: University of Sfax/National School of Engineers of
Sfax, Dept. of Biology, Laboratory of Analysis Valorization and Food Safety, Soukra
Road, 3038 Sfax, Tunisia (S. Besbes).
E-mail address: besbes_souhail@yahoo.fr (S. Besbes).
three to four years are needed for the tree to bear a full crop of date
again and five years before tapping it again (Barreveld, 1993).
However, date palm groves are preserved when limiting the tap-
ping period to only two or three months or tapping mostly male
palms and aged females respecting the optimal collection period.
Conventionally, the sap collection period lasts in general
34 months (MarchJune) in which the total yield of sap per palm
can easily reach 500 L (Barreveld, 1993). The date palm sap can be
directly consumed as a fresh drink, called Lagmi or used as an alco-
holic beverage after natural fermentation (Makhlouf et al., 2015).
Because of the demand of date palm sap and the difficulty to pre-
serve it from natural fermentation, stabilizing it by producing
syrup through thermal process is a solution to generate added
value to this product. Indeed, a similar process has been applied
by Li and Seeram (2011) to produce syrup by thermal evaporation

http://dx.doi.org/10.1016/j.foodchem.2016.02.055
0308-8146/ 2016 Elsevier Ltd. All rights reserved.
176 I. Makhlouf-Gafsi et al. / Food Chemistry 203 (2016) 175182
of the colourless watery sap collected from maple (Acer) species.
The maple sap has an important socioeconomic impact in the
north-eastern region of North America as evoked (Li & Seeram,
2011), in addition, it is especially considered as a safe alternative
to refined sugar as a sweetener (St-Pierre et al., 2014).
Date palm sap syrups, until now, have not been not produced in
an industrial scale. To our knowledge, this is the first study to val-
orize this natural drink by producing syrups which are marked by a
good nutritional value. In fact, they are characterized by high
amounts of sugars (5875 g/100 g fresh matter basis), minerals
(2.12.6 g/100 g fresh matter basis) and phenolics (147.61
224.55 mg of ferulic acid equivalents/kg fresh weight) (Ben
Thabet et al., 2009). These new syrups can be used as an ingredient
in to many food products such as dessert and cake topping, as is
the case with maple syrup.
Processes leading to obtain stabilized products are, in general,
delicate and depend on various parameters; one of the determinis-
tic factors of the success of such a process in food industry is the
viscosity of the treated fluid. Magerramov, Abdulagatov, Azizov,
and Abdulagatov (2007) showed the importance of the accurate
viscosity data of a fluid used in food technology, such as developing
food processes and processing equipment, control of products, fil-
ters and mixers, quality control and an understanding of the struc-
ture of food and raw agricultural materials.
In addition, viscosity presents the fundamental parameter of
the rheological study of liquids conducted by simple analyses
and is more and more applied to determine the behaviour of trea-
ted solutions, suspensions or mixtures and to characterize the fluid
texture (Rao, 1999).
Liquid viscosity depends essentially on temperature and com-
position. Rao (1999) showed the necessity to document the tem-
perature effect on rheological properties, since a wide range of
temperatures encountered processing and storage problems of liq-
uid foods.
Moreover, the physicochemical properties of the fluid food
could be altered during processing, such as ultrafiltration, which
consist of separate micro scaled particles from the other elements
of the treated matter affecting physicochemical properties and
sensory characteristics of food products.
The ultrafiltration process becomes an essential part in food
technology as a tool for separation and concentration (De
Carvalho, de Castro, & da Silva, 2008). Its importance lies in the
preservation of the natural juice constituents such as sugars, vita-
mins, as well as the volatile aroma profile, improving the microbi-
ological quality of the permeates (Mohammad, Ng, Lim, & Ng,
2012).
Ben Thabet et al. (2009) studied the rheological behaviour of the
syrups prepared from date palm sap. However, neither the effect of
date palm sex nor the effect of the ultrafiltration process on rheo-
logical properties of syrups has been reported. The present work
constitutes, to the best of our knowledge, the first study of the
effect of the ultrafiltration process on physicochemical, rheological,
microstructure and thermal properties of syrups prepared from
male and female date palm saps, pursued by an investigation of
the effect of temperature on viscosity of these syrups during heat-
ing and cooling processes.
2. Materials and methods
2.1. Syrup preparation
Exuding saps were collected by a traditional tapping method
from a palm grove in Tunisia from male and female date palms
(P. dactylifera L.). The trees were subjected to the same sunlight
conditions, mineral nutrition and watering. After filtration through
a fine cloth, male sap was divided into two quantities; the first one
was concentrated with a rotary vacuum evaporator, at 60 C, to
74 Brix. The second sap quantity was clarified by the ultrafiltra-
tion process (as described below in Section 2.2). The obtained per-
meate was after that concentrated with a rotary vacuum
evaporator, at 60 C, to 74 Brix. The same procedure was applied
for female sap. Final concentration value of the sap and permeate
(74 Brix) was chosen according to a previous study (Ben Thabet
et al., 2009). Indeed, these authors found that sap syrups concen-
trated to 74 Brix presents better sugar and phenolic compounds
composition, better antioxidant activity and a better acceptability
by consumers than syrups concentrated at lower values (64 and
68 Brix).
Finally, 4 syrup samples, elaborated from male sap (MSS), male
permeate (MPS), female sap (FSS) and female permeate (FPS), were
obtained. The concentration of the juices was then carried out in
the dark using aluminium foil, allowed to cool and stored at 4 C
before further uses.
2.2. Ultrafiltration process
Male and female date palm saps were clarified using a pilot-
scale UF unit (Rhodi a Orelis, France). The UF pilot consisted of a
screw pump, and two pressure transducers (06 bars) located at
the inlet (Pi) and outlet (Po) of the membrane module. Transmem-
brane pressure TMP was calculated as TMP = (Po + Pi)/2. The feed
temperature was adjusted by passing the date palm saps through
a thermo stated bath fixed at 25 C 2. The feed flow rate was mea-
sured using a magnetic flow meter. Experiments were performed
in a batch mode. Permeate was continuously recollected, and the
flow rate was measured. CARBOSEP membrane with nominal
molecular weight cut-off (MWC O) of 15 kDa (M2) made of zirco-
nium oxide with carbon support, with inner and outer diameters
of 6 and 10 mm, respectively, and 40 cm in length, with a surface
area of 0.0075 m2 was used. The membrane was cleaned after each
run according to the manufacturers recommendations with NaOH
(510 g L1, T = 8085 C; operating time = 30 min; TMP = 2
3 bars) and followed by an acidic treatment with HNO3 (35 mL
L1 at 5560 C for 30 min at a TMP of 23 bars), until the original
water flux was restored.
2.3. Physico-chemical analyses
Water activity was measured by a water activity meter (AW
SPRINT TH-500 Novasina, Swiss). The pH was measured using a
pH-meter (METTLER TOLEDO. MP220). The Brix degree was mea-
sured with an Abbe refractometer (Optech, Germany) at 20 C.
Pectin content was determined as described by Englyst,
Quigley, and Hudson (1994), using galacturonic acid as a standard.
Ash content was estimated by combustion of 2 g of syrup sample in
a Muffle furnace (Nabertherm, Germany) at 550 C for 6 h (AFNOR,
1999). The residue was dissolved in HNO3 (14.44 mol/L) and min-
eral constituents (Ca, K, Mg, Na and Zn) were analysed separately,
using an atomic absorption spectrophotometer (analytik jean, ZEE-
nit, Germany) (Larrauri, Ruprez, Borroto, & Saura-Calixto, 1996).
Total sugars content was determined using the phenol sul-
phuric method (Dubois, Gilles, Hamilton, Rebers, & Smith, 1956).
Reducing sugars were estimated according to Miller (1959).
2.4. Rheological properties
Rheological properties of syrups were measured using a modu-
lar compact rheometer (MCR 302, Anton Paar). Cone/plate geome-
try was used with a plate radius of 40 mm and a cone angle of 4.
The gap between the cone and plate was set at 150 lm. For each
test, the sample was placed on the bottom plate of the rheometer.
 I. Makhlouf-Gafsi et al. / Food Chemistry 203 (2016) 175182 177

Sample temperature was ramped between 10 and 50 C, with
incremental step of 10 C. The shear rate range applied was 0
300 s1. The exposed sample perimeter was covered with silice
oil to prevent sample dehydration at higher temperatures.
Flow behaviour was described by the fitting of the experimental
results of shear stress against the shear rate with the power law
model given by Eq. (1).
s K c_ n
where s is the shear stress (Pa), c_ is the shear rate (s1), K is the con-
sistency coefficient (Pa sn) and n is the flow behaviour index.
The apparent viscosity dependence on temperature was evalu-
ated using the Arrhenius relationship (Eq. (2)):
The values of the apparent viscosity parameter g, measured as
function of temperature, were than plotted in curves in the range
of [1050 C]. As shown in Fig. 1, a part of hysteresis were obtained
in all the graphs, where branches corresponding to the cooling
measuring process were higher than those obtained in the heating
process.
The area of hysteresis was determined by subtracting the inte-
gration of the heating function from the integration of cooling one
1
from 10 C to the intersection point of the two curves. The heating
and cooling function were approximated by a 6 degree polynomial,
using Microsoft Excel 2013 software, the intersection points of the
curves and the integrations were calculated using Wolfram
Mathematica 9 software.

g g0 eRT
Ea
where g is the viscosity (Pa s), g0 is a pre-exponential factor (Pa s),
Ea is the activation energy (kJ/mol) for flow, T is the absolute tem-
perature (K) and R is the perfect gas constant (kJ/mol/K).
The effect of temperature on apparent viscosity on both heating
and cooling processes using a modular compact rheometer (MCR
302, Anton Paar) was performed at a shear rate 50 s1. The mea-
surements of the apparent viscosity g were taken between 10
and 50 C in heating process and between 50 and 10 C in cooling
with an incremental step of 1 C/min. A new sample of syrup was
used for each process.
All the rheological measurements were performed in triplicate.
The molar volume V was evaluated using another simplified
equation which is also suitable to determine the viscous flow coef-
ficient g at any temperature in the liquids (Song, Bian, Zhang, &
Zhang, 2009) using Eq. (3):
hN Ea
g eRT
V cell was calibrated for temperature and heat flow using indium
where h is the Planck constant (6.626  1034 J s), N is the Avogadro
number (6.022  1023 mol1) and V (m3/mol) is the molar volume
of liquid. So g0 can be determined by Eq. (4) as:
hN
g0
V a reference. All measurements were made at least in triplicate.
2
2.5. Optical microscopy
Visual observations were carried out using an optical micro-
scope (Nikon Eclipse E400, Kanagawa, Japan) with a 40 objective
magnification. Sample temperature during observation was con-
trolled automatically by the peltier system (Unkam eclipse E
400) at 10, 20, 30, 40 and 50 C. A portion of the sample was placed
on a glass slide and covered with a coverslip. The software
employed for visualization was Lucia (version 4.5) and pictures
were taken using a Basler video camera (Vision technologies,
Ahrensburg, Germany).
2.6. Differential scanning calorimetry
Thermal properties of syrups samples were performed on a
TA2920 Instruments (New Castle, Delaware, USA), attached with
3 a Refrigerated Cooling Accessory and modulated capability. The
(Tonset: 156.6 C, DH: 8.7 J g1) and eicosane (Tonset: 36.8 C, DH:
247.4 J g1). Specific heat capacity (Cp) was calibrated using a sap-
phire. The analysed sample mass was about 5 0.25 mg. The pans
were hermetically sealed and heated in the calorimeter from 50
4 to 100 C at a rate of 5 C/min, with a sealed empty pan used as

20 50
18 45
MSS FSS
16 40
Viscosity (Pa.s)
Viscosity (Pa.s)

14 35
12 30
10 25
8 20
6 15
4 10
2 5
0 0
9.5 29.5 49.5 9.5 29.5 49.5
Temperature ( C) Temperature ( C)

9 25
8 MPS FPS
7 20
Viscosity (Pa.s)
Viscosity (Pa.s)

6
15
5
4 10
3
2 5
1
0 0
9.5 29.5 49.5 9.5 29.5 49.5
Temperature ( C) Temperature ( C)

Fig. 1. Experimental viscosity data (as the continuous points) for date palm sap syrup prepared from male sap (MSS), male permeate (MPS), female sap (FSS) and female
permeate (FPS) and the fitting curves (as the continuous curves) according to Arrhenius law in both heating ( , ) and cooling ( , ) processes.
178 I. Makhlouf-Gafsi et al. / Food Chemistry 203 (2016) 175182

Table 1
Physicochemical characteristics of date palm sap syrups (74 Brix) prepared from male sap (MSS), male permeate (MPS), female sap (FSS) and female permeate (FPS).

Parameter MSS MPS FSS FPS

b d a
pH 7.51 0.05 7.43 0.04 7.53 0.02 7.47 0.04c
aw 0.654 0.004c 0.648 0.005d 0.658 0.002b 0.66 0.006a
Total sugarsa 75.08 1.68b 75.84 1.56a 74.09 1.75c 74.4 0.89d
Reducing sugarsa 14.2 0.49d 35.3 0.85b 32.68 0.66c 56.4 0.28a
Pectina 1.92 0.19b 1.35 0.14d 2.96 0.25a 1.48 0.12c
Asha 2.97 0.37a 2.52 0.54b 0.88 0.04c 0.81 0.09c
Potassiumb 1585.28 13.4a 1361.09 14.5b 426.92 6.81c 400.26 5.74d
Calciumb 107.44 9.7a 87.73 6.34b 72.86 5.42c 65.28 4.83d
Magnesiumb 63.58 4.74a 50.8 3.82b 21.17 2.5c 18.3 2.7d
Zincb 6.05 0.94a 0.53 0.04d 1.78 0.08b 1.62 0.07c
Copperb 3.74 0.04a 0.38 0.02c 0.96 0.07b 0.086 0.05d
Manganeseb 0.74 0.02a 0.19 0.01c 0.23 0.01b 0.184 0.04d
Ironb 1.88 0.04a 1.25 0.05b 1.149 0.02c 0.79 0.02d

Means in the same line, with different small letters are significantly different (p < 0.05).
a
In g/100 g sample.
b
In mg/100 g sample.

2.7. Statistical analyses
Data (of 4 samples performed in triplicate) were analysed by
the Statistical Package for the Social Sciences software (SPSS for
windows version 16.0). Duncans test was performed at the level
of p 6 0.05 to determine significant differences between mean val-
ues (Kilincceker, Dogan, & Kucukoner, 2009).
sequently, it can be used as a liquid sugar ingredient adapted to
many food products such as dessert and cake topping. Therefore,
it becomes important to characterize the rheological behaviour of
the newly elaborated syrups.
3.2. Flow behaviour

The parameters of the power law equation describing the vis-

3. Results and discussion
3.1. Physicochemical composition of sap and sap permeates syrups
Proximate composition of the newly prepared syrups is summa-
rized in Table 1. pH varied from 7.43 to 7.54, within the range of
the pH of male date palm sap syrup described previously by Ben
Thabet et al. (2009). Water activity values ranged from 0.648 to
0.66. Consequently, syrups are stable and protected against all bac-
terial and fungal alteration for a definite period. Sugar was the pre-
dominant component in all prepared sap and permeate syrups. In
fact, it presented similar values with more than 74.09 g/100 g fresh
weight for the four syrup samples. However, a significant differ-
ence (p < 0.05) in reducing sugar content was observed between
syrup samples. Indeed, permeate syrups presented higher reducing
sugar contents than sap syrups (35.3% vs. 14.2% fresh weight in
MPS and MSS, respectively and 56.4% vs. 32.68% fresh weight in
FPS and FSS, respectively). This can be attributed to the ultrafiltra-
tion process which caused the retention of sucrose through the
membrane. Consequently, sucrose content decreased in permeates
(De Carvalho et al., 2008), and also in the corresponding syrups. In
addition, as shown on Table 1, the ultrafiltration process on male
and female date palm sap caused a loss in pectin contents in per-
meate syrups (MPS and FPS) compared with sap syrups (MSS and
FSS). In fact, its well known that losses of high molecular weight
constituents, such as pectin and starch, occur in the clarification
processes (De Carvalho et al., 2008).
On the other hand, when comparing between male and female
sap syrups, FSS presents higher reducing sugar content, higher pec-
tin content but lower ash content than the MSS. This could be
related to the sex of the palm which imposed a variation on date
palm sap between the two sexes (Makhlouf et al., 2016).
The mineral composition of sap and permeate syrups was dom-
inated by potassium, as the case of maple syrup, honey (Ben Thabet
et al., 2009) and date syrup (Abbs et al., 2011), followed by cal-
cium, magnesium, zinc and copper.
Date palm sap and permeate syrups could be considered as a
good source of rapid energy, due to their high sugar content. Con-
cositytemperature relationship were determined by linear regres-

sion (ln s f lnc), and can be found in Table 2.
The coefficients of determination (R2) obtained were higher
than 0.963 confirming suitability of the power law model for
describing the flow behaviour of samples.
Table 2 shows flow behaviour index of elaborated syrups.
Ultrafiltration process seemed to increase flow behaviour index
of syrups for both male and female saps. This effect was more
marked in the case of female saps. An opposite effect of ultrafiltra-
tion treatment was observed on consistency coefficient, which
decreased, especially for female sap syrups. These results could
be explained by retention of pectin in the ultrafiltration membrane
which contributes to lower consistency of permeates and therefore
on syrup permeates (Table 1).
Concerning the date palm sex effect, results (Table 2) shows
that syrups obtained from female sex had lower n values and
higher consistency coefficient k than those of the male sex, except
at the highest temperature (50 C). This indicates that FSS and FPS
were more viscous than MSS and MPS, respectively. In fact, female
sap syrups had higher pectin content than male sap as previously
shown in Table 1.
On the other hand, as it can be seen from Table 2, the flow beha-
viour index tends to increase with the increasing temperature. Par-
ticularly, for FSS sample, flow behaviour clearly switched from
pseudoplastic (n = 0.783) to Newtonian (n
1) one from 10 to
50 C. Similar results were reported by Higgs and Norrington
(1971) for sweetened condensed milk.
Furthermore, the consistency coefficient (K) decreases with
temperature increasing for all syrup samples reflecting a decrease
in apparent viscosity at higher temperatures. This was expected
since there is a general tendency for the viscosity to decrease with
the temperature (Maceiras, lvarez, & Cancela, 2007). Indeed,
according to Constenla, Lozano, and Crapiste (1989), the viscosity
of a solution is a function of the intermolecular forces and water-
solute interactions that restrict the molecular motion. When this
solution is heated, the viscosity decreases because of increase of
both thermal energy of the molecules and intermolecular distances
due to thermal expansion (Constenla et al., 1989).
 I. Makhlouf-Gafsi et al. / Food Chemistry 203 (2016) 175182 179

Table 2
Rheological properties of date palm sap syrup prepared from male sap (MSS), male permeate (MPS), female sap (FSS) and female permeate (FPS).

Temperature (C) MSS MPS FSS FPS

Flow behaviour index n (dimensionless)
10 0.933 0.008b,B 0.974 0.002b,C 0.783 0.001b,A 0.922 0.000a,D
20 0.959 0.002c,B 0.987 0.003c,C 0.821 0.004c,A 0.922 0.001a,D
30 0.987 0.006e,B00 1.027 0.001e,C 0.856 0.002d,A 1.028 0.003c,C
40 0.963 0.004d,B 1.015 0.002d,D 0.877 0.007e,A 0.994 0.008b,C
50 0.818 0.000a,B 0.813 0.001a,A 1.007 0.003a,D 1.005 0.006d,C
Consistency coefficient K (Pa sn)
10 8.19 0.17e,C 3.876 0.21e,A 35.12 1.37e,D 4.18 0.35d,B
20 3.2 0.36d,B 1.49 0.09d,A 14.15 0.84d,C 1.57 0.19c,A
30 1.33 0.01c,C 0.567 0.01b,A 6.33 0.29c,D 0.527 0.05c,A
40 0.876 0.07a,C0 0.37 0.01a,A 3.49 0.21b,D 0.396 0.01b,B
50 1.18 0.02b,D 0.664 0.02c,B 0.979 0.02a,C 0.22 0.01a,A
Arrhenius model parameters
g0 (Pa s) 4.224  108 2.365  108 2.318  108 2.108  1010
Ea (KJ mol1) 44.039 43.823 48.038 55.471
R2 0.94 0.91 0.99 0.98

Data are expressed as means SD (n = 3). Means SD followed by the same letter are not significantly different according to Duncans test (p > 0.05) for each syrup. To
compare the statistical significance for each syrup capital letter should be used for means within a row and small letters for means within a column.

The same observations were previously reported in date palm
syrups (Abbs et al., 2014), in orange juice (Ibarz, Gonzalez, &
Esplugas, 1994) and in clarified apple juice (Constenla et al., 1989).
3.3. Activation energy
In order to assess further the temperature dependence of the
viscosity of syrups, Arrhenius-type model was applied, and the cor-
responding parameters were determined by linear regression (ln
g = f (1/T)) and are summarized in Table 2. The correlation coeffi-
cients (R2) for all samples were greater than 0.911. The Arrhenius
model has been successfully applied to describe the viscosity tem-
perature dependence of various food products such as honey,
maple syrup and juice concentrates (Ben Thabet et al., 2009). Acti-
vation energy reflects the sensitivity of apparent viscosity to tem-
perature variations (Abbs et al., 2014). According to Holdsworth
(1971), the higher the value of activation energy, the larger is the
effect of temperature on the considered property.
The activation energy Ea describes the energy needed for the
molecules to exceed the liquid-specific energy barrier (potential
barrier). Using this energy, the molecules are able to move against
the internal flow resistance which is caused by the friction
between the neighbouring molecules (Mezger, 2006).
The syrup elaborated from permeates showed higher values of
Ea compared to the syrups elaborated from native date palm sap
in the case of female sex, due to the immobilization of pectin
through tubular membranes. Similar observations have been made
by Abbs et al. (2014), which reported that activation energy val-
ues increased for enzyme-treated date syrups (pectinase and
cellulose).
In addition, the palm sex affects significantly the activation
energy. In fact, the female date palm syrups exhibits the higher
Ea compared to male date palm syrups (48,038 vs. 43,823 kJ/mol
for the syrups from native saps and 55,471 vs. 44,039 kJ/mol for
the syrups from permeates). These results are in accordance with
many studies which reported that the change of activation energy
depends on the chemical structure and origin of samples (Karaman
& Kayacier, 2011)
The pre-exponential factor values in the Arrhenius equation,
which represents apparent viscosity (g0) at a temperature
approaching infinity, were slightly lower to those found in the case
of date palm syrup at the same Brix degree (Ben Thabet et al.,
2009).
3.4. Effect of heating and cooling processes on rheological behaviour of
date palm sap syrups
The effect of temperature on the apparent viscosity at a shear
rate of (50 s1) of each sample was plotted on Fig. 1. The values
of the fitting parameters, EH and R2H, EC and R2C for heating and cool-
ing processes are listed in Table 3. The continuous viscosity data for
heating and cooling processes were fitted by Eq. (2), respectively.
From Fig. 1, it can be clearly seen that these data fit the Arrhenius
equation well.
On heating, as the temperature increases, the viscosity falls sig-
nificantly due to less molecular friction and reduced hydrodynamic
forces (Mossel, Bhandari, DArcy, & Caffin, 2000).
However, in the same syrup sample, viscosity varies differently
during heating and cooling processes. In fact, higher values of vis-
cosity have been recorded during cooling than those relative to the
heating process. In addition, activation energy EC and molar vol-
ume V during cooling were significantly higher than that during
heating process. The same observation was previously reported
by Ren, Bian, Lin, Bai, and Wang (2010) which diluted honey with
water mixtures. They ascribed these differences to the amount and
the state of water molecules in each honey sample: some water
molecules were at free state and evaporate during the measuring
process. However, this cannot explain differences observed in this
study, since silice oil was used during all the measurement to limit
the evaporation of water. In order to better explain this behaviour,
variation of activation energy, molar volumes and viscosity during
heating and cooling process were studied. Indeed, as previously
reported by Song et al. (2009), these parameters manifest the
microstructure change which has taken place in each syrup
sample.
During heating process, the sample was subjected to a high
temperature for a relatively long time. This leads to a deterioration
of the product the intensity of which depends strongly on the ini-
tial composition of the syrup. However, during the cooling process,
the sample was subjected to a high temperature only for a short
time. So, this led to a less marked deterioration than that in the
heating process. Consequently, this section provided ideas about
the stability of each syrup sample. In fact, more stability of syrups
corresponded to a lower variation of viscosity, lower activation
energy and lower molar volume and thus to a smaller area
between heating and cooling curves (Table 3 and Fig. 1).
These areas were determined and results are plotted in
Table 3. This table shows significant differences between the 4
180 I. Makhlouf-Gafsi et al. / Food Chemistry 203 (2016) 175182

Table 3
gH0 , EH, gC0, EC are fitting parameters for the heating and cooling processes according to Eq. (2), V is the molar volume calculated according to Eqs. (3) and (4) and A is the area of
hysteresis.

Samples gH0 (Pa s) EH (KJ mol1) R2H V (m3/ml) gC0 (Pa s) EC (KJ mol1) R2C V (m3/ml) A
10 13
MMS 7.813  10 53.7 0.981 0.51 8.44  10 72.29 0.981 472.76 86.061
MPS 3.021  1010 54.53 0.984 1.32 2.955  1013 72.89 0.997 1.352  103 33.282
FSS 4  108 46.35 0.992 9.97  103 1.92  1010 61.69 0.987 2.078 287.326
FPS 5.803  1011 58.65 0.982 6.87 3.56  1016 91.11 0.982 1.119  106 118.916

MSS, MPS, FSS and FPS: syrups of sap from male date palm, sap permeate from male date palm, sap from female date palm and sap permeate from female date palm
respectively.

samples which can be attributed to natural variation in compo- 3.5. Microscopy

sition (Individual sugars, pectin content, etc). In addition, the
male sex of the palms and the ultrafiltration procedure
decreased significantly the evaluated area and then ensured a
better stabilization of syrup. In fact, syrup prepared from the
male permeate presented the lowest hysteresis area (33,282)
and then the best stabilization.
The microscopic observation with polar light of the female sap
syrup at 10, 20, 30, 40 and 50 C elucidates microstructural
changes which took place in the syrup as a function of tempera-
ture. In fact, a clear decrease in crystal sizes was observed, indicat-
ing their melting when temperature increased (Fig. 2). The same

10 C 20 C

30 C 40 C

50 C

Fig. 2. Microscopic observation of female date palm sap syrup (FSS) at 10, 20, 30, 40 and 50 C.
 I. Makhlouf-Gafsi et al. / Food Chemistry 203 (2016) 175182
Fig. 3. DSC thermal scans of date palm sap syrup prepared from male sap (MSS), male permeate (MPS), female sap (FSS) and female permeate (FPS).
observation was detected for all the studied syrups (data not
shown). Thus, microscopic results confirm the rheological aspects
described previously.
Furthermore, syrups elaborated from male and female perme-
ates presented less abundant crystals compared to the syrups elab-
orated from male and female saps. This could be attributed to the
ultrafiltration process, which led to a reduction in sucrose content
and richness in reducing sugars in permeate syrups (MPS and FPS)
(Table 1). Consequently, ultrafiltration contributed to a reduction
of the syrup crystallization phenomenon.
3.6. Thermal profile
The differential scanning calorimetry (DSC) curves of sap and
sap permeate syrups are presented in Fig. 3. Thermal profiles of
all syrups were similar: no glass transition or crystallization was
observed. These results are in accordance with those obtained by
Ben Thabet et al. (2009) on sap syrup concentrated at 74 Brix.
Probably, glass transition temperatures of syrup samples were
below 50 C, which was the limiting temperature of the apparatus
used. Thus, Ahmed, Prabhu, Raghavan, and Ngadi (2007) reported
that glass transition temperatures of Indian honey samples were
equal to 51.14 and 47.18 C. Regarding their thermal profiles, the
elaborated syrups from date palm sap and date palm permeate
were stable products.
4. Conclusion
In this work, the effect of the ultrafiltration process on physic-
ochemical, rheological, microstructure and thermal properties of
date palm sap syrup. Overall, the results of the present study
revealed that the ultrafiltration process affects significantly the
sap syrup composition. In fact, the retention of sucrose through
tubular membranes caused a decrease in its content in sap perme-
ate and also in the corresponding syrups, and a richness in reduc-
ing sugars. This contributes to a reduction of the syrup
crystallization phenomenon observed in syrups prepared from
sap permeates, compared to those prepared from date palm sap,
as previously revealed from the microscopic observation with
polar light.
181
On the other hand, the ultrafiltration process caused retention
of pectin which affects significantly the rheological properties of
sap syrups. In fact, samples prepared from sap permeates showed
lower consistency coefficient K, higher flow behaviour index n and
higher values of activation energy Ea than those prepared from
date palm saps. In addition, the ultrafiltration process decreased
significantly the evaluated area between heating and cooling
curves and then ensured a better stabilization of syrup prepared
from sap permeates compared to those prepared from date palm
sap.
Furthermore, the syrups composition was significantly affected
the date palm sap sex. Indeed, the female syrups present higher
reducing sugar, higher pectin and lower ash contents than the male
syrups. The high pectin content in female syrups involves a lower n
values, higher consistency coefficient, K, and higher activation
energy, Ea, than those of male syrups.
These results might contribute to the current understanding of
the effect of the ultrafiltration process and on chemical, rheologi-
cal, microstructure and thermal properties of date sap syrups.
Accordingly, further studies, some of which are currently under-
way in our laboratories are needed to evaluate the effect of the
ultrafiltration process on some bioactive compounds and the
antioxidant activities of date palm saps.
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