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ABSTRACT
The effects of pretreatment solutions and drier types (solar vs sun) were
investigated for grapes (var: sultanas). Pretreatment solutions containing 570
K&O3 plus 1.570 olive oil and 470 K&O3 plus 2% ethyl oleate accelerated
dying rates nearly to the same extent, as compared to untreated grapes. Dying
rates were classified for the tested dying methods: solar dying > sun dying on
concrete ground > sun dying on wooden racks, or on polypropylene canvas
sheets. Increasing K&O3 concentration from 4 to 770 in ethyl oleate (270)
solution increased. dying rates on concrete ground. Treatment with SO, gas
(645 mglkg) in addition to ethyl oleate, further increased the dying rates but the
color of the product was rated to be too light and unacceptable to the market.
The moisture content and color intensities of the sun-dried grapes were found to
be non-uniform. Storage stability of treated, dried grapes was investigated in (I)
modified atmosphere (170 O2 plus 13% CO,), (2) vacuum packed and (3)
ordinay plastic pouch packed storage at 6°C. Untreated grapes had the lowest
Hunter L (lightness), a (redness) and b (yellowness) values compared to treated
grapes. Storage caused color parameters to decline, but this reduction was less
pronounced for SOz gas treated products. Copyright 0 1996 Elsevier Science
Limited
NOMENCLATURE
INTRODUCTION
Grapes (var. sultanas) harvested from Manisa region of Turkey (September, 1993)
were treated with the following solutions (Table 1):
traditional solution: 5% K,CO,+15% olive oil, for grapes coded as SDPOl,
WRPOl, CSPOl and COPOl;
alkaline ethyl oleate solution A: 4% K,CO,+2% ethyl oleate, for grapes coded
as SDAEl, WRAEl, CSAEl, and COAEl.
alkaline ethyl oleate solution B: 5% K,CO,+2% ethyl oleate, for grapes coded
as COAE2, CSAE2, WRAE2, SDAE2 and SDS02. Note that, SDS02 was first
treated with SO* gas then was dipped into alkaline ethyl oleate solution.
alkaline ethyl oleate solution C: 6% K&0,+2% ethyl oleate, for code COAE3;
alkaline ethyl oleate solution D: 7% K,CO,+2% ethyl oleate, for code
COAE4.
Dipping time for treatment with the solutions above is about 20-25 sec. Codes
NATUR (untreated) to COAEl, in Table 1, form the first, COAE2 to COAE4 form
the second and CSAE2 to SDS02 form the third group of the drying experiments
which were started the same day.
TABLE 1
Pretreatment: Methods Applied for Grape Drying and Moisture Diffusion Coefficients
Fans Air
“frqrl
I \ I
\
\, ,j; \\
\
‘1 “, \
0 -
lnrulating Panel Caged Wire Fruits
Black Painted
Radiation Collection
hea
Fig. 1. Solar drier (not to scale): the radiation collection and drying sections are 10 m2
each, and velocity of the air through the drying section is 3 m/s.
Those pretreated grapes were then dried in a solar drier (Fig. 1) which was
developed by Hohenheim University (Stuttgart), or by sun drying on wooden racks,
or on polypropylene canvas sheets, or on concrete ground (Table 1). The maximum
air temperature reached in the solar drier was 50°C and ambient air temperature
was in the range 17-40°C. During drying, dry matter content (AOAC, 1984 method
no. 14.125) and water solubles (Atago hand refractometer) were measured. Among
the dried products representative samples for different pretreatments were chosen
and stored at 6°C to test storage stability. The chosen codes were NATUR
(untreated), SDPOl (treated with 5% K,CO,+l.S% olive oil), SDAE2 (treated with
5% K&0,+2% ethyl oleate) and SDS02 (treated with 5% K,CO,+2% ethyl
oleate after treatment with SO2 gas). The products were divided into 250 g portions
and stored at the conditions as explained and coded below:
l MA: modified atmosphere storage at 1% O2 plus 13% COz, the rest being
nitrogen, and packaged with LDPE film;
l VA: vacuum storage packaged with LDPE film; LDPE (110 pm) film have
permeabilities of 54.77 (20°C) and 15.34 (6°C) for 02, 64.44 (20°C) and 13.53
(6°C) for CO* and 5.11 (37.8”C) for water vapor as ml/m2 day atm.
l PA: plastic packed in ordinary pouches (thickness 60 pm) with permeabilities of
4528.3 (20°C) and 2832-O (6°C) for 02, 18.076 (20°C) and 12.828 (6°C) for CO;?,
and 13.73 (37*8”C) for water vapor as ml/m* day > atm.
l Some of the products were stored in the unpacked form in plastic cases as a
control.
During storage, dry matter content, water solubles content, pH (WTW-model
532 pH meter), acidity as tartaric acid (titration with NaOH solution), Hunter
color values L, +a and +b (Hunterlab Color D 25 D 2 P model) were measured.
SO2 concentration for the product coded. as SDS02 was measured by the
Reith-Wiliams method (AOAC, 1984). The microstat computer package was used
to make statistical analysis as paired comparisons between means of groups
(Student’s t-test).
Drying and storage stabilityof grapes 293
Mathematical modelling
Liquid or vapor diffusion was assumed to be the primary mass transfer mechanism
in drying of grapes. The most widely investigated theoretical model in the thin layer
drying of various foods is given by the solution of Fick’s second law (Hutchinson &
Otten, 1983):
(1)
with the assumptions: (1) the principal driving force for mass transport is the
internal moisture gradient, (2) temperature within the fruit is constant, (3) either
liquid or vapor diffusion predominates (Hutchinson & Otten, 1983).
Dimensions of the grapes suggested that they can be treated in spherical
coordinates. Solution of eqn (1) for constant diffusion coefficient, after making a
number of simplifying assumptions (constant diffusivity, no shrinkage) and with
suitable boundary conditions, for spherical coordinates gives:
M-M, 6 = 1
_~3+-- Ded (2)
M,-Me =,2 c-, n* exP(
R2
The values of the equlibrum moisture content, M,, are relatively small compared
to M or Mi (Alzamora et al., 1979), SO (M-M,J/(Mi-Me) is simplified to MIM,. For
D&/R* larger than O-1, the first term of the series solution (eqn (2)) can be used.
Consequently, eqn (2) can be further simplified to a straight line equation:
Table 1 gives the resultant ?-values of the Exponential and Page equations as well
as the moisture diffusion coefficients (De& for the corresponding pretreatment-
drier combinations. The effects of pretreatment with solutions A to D (2% ethyl
oleate plus 4-7% K,CO,) were compared to a traditional solution (5% K2C03 plus
1.5% olive oil), and also to various drying methods as on concrete ground, on
wooden racks, on polypropylene canvas sheets or by solar drying.
294 T Mahmutoglu et al.
-..-. NATUR
- SDPOl
---- SDAEl
. cope,
-.-.- COAEl
.. - . . 5u.n dlying
.-.___
.-__
-.._..
-..___
-..-.._.,_
0 I I I
,
1 I I I
I
I
I
I
I I
0 50 100 150 200 250 300 350 400 450
tW
Fig. 2. Moisture content vs drying time: comparison of untreated grapes (NATUR) with
the ones treated with either 5% K&0,+1-5% olive oil (SDPOl, COPOl) or 4%
K,CO,+2% ethyl oleate (SDAEl, COAEl). Only predicted data are shown.
Referring to Fig. 2 and D eff values given in Table 1, it is seen that both treatment
with ‘traditional’ and with ‘solution A’ (codes SDPOl to COAEl), for a particular
drying method, reduces the drying times nearly to the same extent as compared to
untreated grapes coded as NATUR.
As a second part of the experiments, the effects of increasing K2C03
concentration in 2% ethyl oleate solution on the drying rates were estimated, so the
grapes were treated with ‘solutions B to D’ as described in Table 1: codes COAE2
to COAE4, which were dried at the same ambient conditions. A slight increase in
the diffusion coefficients, from 1.08 x lo-” (for COAEl) to 1.19 x 10-‘” m”/s (for
COAE4) was seen for drying on concrete ground. But since expert grades for
COAE3 and COAE4 (6-7% K2C03 containing ethyl oleate treated) were
‘unsuitable for marketing’, we further decided to make a third group of experiments
with ‘solution B’ containing 5% K2C03: codes from CSAE2 to SDS02 (Table 1).
From Deff values, it is seen that, increasing K&O3 concentration from 4% (CSAEl,
WRAEl, SDAEl) to 5% (CSAE2, WRAE2, SDAE2) did not increase the drying
rates for drying on canvas sheets, wooden racks and solar drying. Still, SDPOl
(treated with traditional solution) and SDAEl (treated with 4% KzC02-2% ethyl
oleate) had the largest Deff values. The reason for this could be the changing
weather conditions from the first to third group of experiments. Drying curves of
grapes treated with solution B are given in Fig. 3. To see the’ effect of SO,
treatment, the grapes coded as SDS02 (treated with first SOz. gas and then with 5%
Drying and storage stabilityof grapes 295
0.8
. COAEZ (exp)
COAEZ (pre)
. CSAE2 (exp)
---- CSAU(P@
I WRAE2 (exp)
- WRAE2 (pm)
0 SDAE2 (Sxa)
-..-. SDAU(pr@
* SDS02 (ap)
02 - SDS02 (Pre)
0.1
0 ]
I
I
I
I
I
I
0 50 100 150 200 250
t(h)
Fig. 3. Moisture content vs drying time: comparison of solar drying (SDAE2, SDS02) with
sun drying (COAE2, CSAE2, WRAE2) for grapes treated with 5% K&0,+2% ethyl oleate.
SDS02 fist treated with SOz gas.
K2C03-2% ethyl oleate), were solar dried (Table 1). SO2 treatment increased the
drying rate as seen from Fig. 3 (SDAE2 vs SDS02).
The solar drier considerably reduced drying times compared to sun drying on
concrete, wooden racks or canvas sheet, as is seen from Deff values (Table 1) and
drying curves (Figs 2 and 3). The drying rates for the tested drier types were as
follows: solar drier > concrete ground > wooden racks and canvas sheets.
Evaporation of water during drying resulted in concentration of other constituents
such as water solubles and increased acidity, as expected. Compared to fresh grapes,
treatment with alkaline solutions caused pH to increase slightly (Table 2); this
increase is more pronounced for treatment solutions containing larger K&JO3 con-
centrations.
It was found that, the Hunter L (lightness) value correlates well with the color of
the raisins, so that it can be used to express the level of the thermal inactivation of
enzymes responsible for browning (Aguilera et al., 1987). The grapes which are
untreated (NATUR), and the ones treated with traditional solution dried on con-
crete ground (COPOl), had the lowest Hunter color L of about 25 and 24,
respectively (Table 2); for other treatments it was about 28-33. This indicates that
treatment with alkaline ethyl oleate solutions gives a slightly lighter product. Brown-
ing rates of those treated products decreased, probably due to reduced drying times.
Drying on concrete ground had adverse effects on the color, since the concrete may
overheat and cause the darkening of the bottom layers of the grapes. It should be
noted that, although it was not the subject of this research, higher drying tem-
296 T Mahmutoglu et al.
TABLE 2
Quality Parameters of Dried Grapes at the End of Drying (Prior to Storage)
peratures obtained in the solar drier may cause the browning reactions to be
accelerated, which may result in a darker product. Hunter +a (redness) and +b
(yellowness) intensity of the NATUR coded (untreated-sun dried) grapes were the
smallest (3.33 and 4.86) and those of SO2 plus alkaline ethyl oleate treated ones
(SDS02) were the highest (9.77 and 1571) among the codes. Although SO2 treat-
ment resulted in a more red-colored product, it was rated to be too light (high
Hunter L and +b values) and unsuitable for marketing. It is difficult to investigate
the pH dependence of the intensity of the red color from this study, since pH of
differently treated, dried grapes changed in a narrow range of between 3.6 and 4.3
(Table 2).
Concrete ground and canvas sheet dried grapes did not have a uniform color and
moisture content. Moreover it was necessary to turn them periodically, which in turn
increased labor requirements.
Due to exposure to heat and O2 for prolonged times during solar drying, SO2
concentration was seen to decrease from about 645 to 297 mg/kg (Fig. 4).
All of the unpacked stored products (controls) were discarded after about 3 months
of storage due to excess moisture absorption, dark color (Hunter L: 23-25; a:
3.4-3.7; b: 4.2-7.1) and excess mould growth. Gas composition of MA packaged
products (initially 1% O2 and 13% CO*) changed to 14.3% O2 with no CO2 left at
Drying and storage stability of grapes 297
O-l I
0 20 40 60 80 100 120 140
drying time (h)
Fig. 4. Change of SO2 concentration with drying time for SDS02 (SO2 gas plus alkaline
ethyl oleate treated).
the end of sixth months of storage. O2 concentration was further found to increase
to 17.9% at the end of the 12 months storage period. This means that O2
permeability of the packaging material should be chosen to be lower than the one
employed in this study. Thus, the reduced availability of O2 would not promote
some reactions, such as browning and loss of SO,.
Table 3 gives Means+SE of the measurements of some quality attributes
throughout a storage period of 12 months. It was seen that, all of the changes were
independent of the storage condition (MA, VA or PA) employed in this study. It
indicates that, those changes depend on the initial value at the start (Table 2) and
the storage time. Figure 5 gives the change in dry matter content with the storage
time for MA stored raisins. Similar results were obtained for VA and PA stored
raisins. Comparing the values given in Tables 2 and 3 and referring to Fig. 5, it is
seen that, the overall change of dry matter content, hence of the moisture content,
was dependent on the initial values at the start of the storage: NATUR, SDPOl and
SDS02 desorbed while SDAE2 absorbed to reach equilibrium with the surrounding
atmosphere. It was expected that application of a pretreatment solution to increase
the drying rates (NATUR vs others) should also increase the desorption or
absorption of moisture during storage. However, it is difficult to validate this
assumption in this study because we could not achieve exactly the same moisture
content for all the treatments at the end of drying to exclude the effect of the initial
moisture content and to see the effects of the pretreatment during storage. One
consequence of water absorption or desorption is the slight decrease (for SDAE2)
or increase (for NATUR, SDPOl and SDS02) in water solutes content.
Comparing the initial values (Table 2) and means during storage (Table 3), it is
seen that acidity increased more for NATUR coded products than for alkaline
treated ones. The lowest acidity, and hence the highest pH, were seen for SDAE2.
The color darkened, which is recognized from a decreasing Hunter L value. Except
for NATUR, the intensity of the red color (Hunter +a) was seen to decrease during
298 T. Mahmutoglu et al.
TABLE 3
Clldlrge of Quality Parameters During Storage of 12 Months, for the Same Pretreatment-
Drying Combination, Under Different Storage Conditions’
NATUR MA’ 85.8-tO.3 83.3 f 0.1 3.9 f 0.05 1.7kO.12 22.1 f 0.8 3.7 + 0.4 3.4kO.4
VA4 85.6 + 0,3 83.2 + 0.3 3.9 + 0.07 1.5 + 0.04 21.1 kO.9 3.2kO.l 2.9 f 0.5
PA5 85.6 f 0.3 83.3 f 0.2 3.8 f 0.06 1.6kO.07 22.5 f 0.5 3.5 f 0.1 3.3 + 0.4
SDPOl MA3 86.8 + 0.8 84.1+ 0.6 4.0+0.08 1.4kO.06 25.8 + 0.7 5.6kO.3 lo,2 kO.8
VA4 86.7 f 0.8 84.8 f 0.7 3.9 f 0.06 1.4+0.06 25.0 f 1.0 5.250.3 9.6 *0.9
PA’ 86.4 f 0.7 84.2 + 0.6 3.9 f 0.07 1.5 f 0.06 24.0 f 1.3 53kO.3 9.5 f 0.9
SDAE2 MA’ 850&0.4 83.2 f 0.3 4.4kO.07 1.2kO.03 23.7 f 1.1 5.OkO.6 8.6 *0.9
VA4 g50*0.2 83.3 +_0.2 4.4 f 0.07 1.2+0.03 23.7* 1.1 4.8kO.6 8.3 f 1.0
PA’ 85.1 f0.3 83.4kO.2 4.4 f 0.06 1.2kO.02 23.7 f 1.2 5.1 f0.6 8.8kO.9
SDS02 MA” 85.8 f 0.5 83.6kO.5 4.1 f 0.04 1.5 f 0.03 29.5 f 1.3 6.6+ 1.6 12.7 + 1.0
VA4 85.3 f 0.3 83.2 f 0.3 4.1 kO.04 1.5 f 0.01 30.5 f 1.1 6.7+ 1.6 12.8 f 1.3
PA-5 84.8 + 0.3 83.0 f 0.5 4.1 kO.03 1.5 kO.01 31.2 k 1.3 6.9k1.4 13.2 f 1.1
‘Means* SE, for a particular treatment-drying type (code), was not significantly different for the
studied storage conditions.
‘Codes are explained in Table 1.
“MA: modified atmosphere packaged, 4VA: vacuum packaged, “PA: plastic pouch packaged (tightly
closed).
8
8 87.5 - NATUR
5 a7
- - - SLIP01
5 86.5
---.*-e SDAE2
g
E 86
g 85.5 --~-~SDSOZ
a5
84.5
, ..
a4 4
0 2 4 6 a 10 12
storage time (months)
04 1
0 2 h 6 8 10 12
storagetime (months)
Fig. 6. Change of SO2 concentration with storage time for SDS02 (SO* gas plus alkaline
ethyl oleate treated).
CONCLUSIONS
Treatment with K2C03 (4%)-ethyl oleate (2%) or with &CO, (5%)-olive oil
(15%) solutions accelerated the drying rates to the same extent. Solar drying
reduced drying times of grapes to about half of that of sun ” _ drying on concrete
ground. Color of the treated grapes were lighter than that ot the untreated grapes.
Drying on polypropylene canvas sheets or on wooden racks or by solar drying gave
a relatively lighter product compared to drying on concrete ground. SO, gas
treatment, in addition to alkaline ethyl oleate, further increased the drying rates, but
the color was too light to be acceptable in the market. Moisture content and color
intensities of the solar dried grapes were more uniform compared to sun dried ones.
Modified atmosphere (1% 0,+13% CO*), or vacuum or ordinary plastic pouch
packaging did not differ when changes in quality parameters (dry matter, water
solubles, pH, acidity and color intensities) are considered during storage. The initial
values of those parameters at the start of storage were seen to be of primary
importance for changes observed throughout the storage. However, further studies
300 T Mahmutoglu et al.
remain to be made to find the optimum gas composition and packaging material of
having appropriate permeabilities for modified atmosphere. The water activities,
microbial load and sensory analysis during storage remain to be studied.
ACKNOWLEDGEMENTS
The authors appreciate Prof. Dr M.ehmet Pala, Caj Langer, Peter Oechsle, Hasan
Yolcular, Yilmaz Girgin, Sedat Unal and Selahattin Nas for their technical
assistance, and Deutsche Gesellschaft fur Technische Zusammenarbeit (GTZ)
GmbH for their financial support.
REFFERENCES
Riva, M. ‘& Peri, C. (1986). Kinetics of sun and air drying of different varieties of seedless
grapes. J. Fd Technol., 21, 199-208.
Saguy, I. & Karel, M. (1980) Modelling of quality deterioration during food processing and
storage. Food Technology, Feb., 78-84.
Saravacos, G. D., Marousis, S. M. & Raouzeos, G. S. (1988). Effect of ethyl oleate on the
rate of air-drying of foods. J. Food Eng., 7, 263-70.