Food Sci. Technol. Res.

, 10 (3), 350-354, 2004

The Effect of Packaging Materials and Storage Condition on the Oxidative

Stability of Refined Sunflower Oil

R. RAMEZANI

Department of Food Science and Technology, Agricultural School, Shiraz University, Shiraz, 71444, Iran

Received March 29, 2004; Accepted June 22, 2004

In this research, refined sunflower oil was packed at various packaging materials namely: yellow PET
(polyethylene terephtalate) bottles, clear PET bottles, yellow HDPE (high density polyethylene) containers
and metal cans. Randomly selected packaged sunflower oils samples were packed in carton as dark condi-
tion and secondary container. The samples were stored at room temperature (26.9'C) for 365 days. At 45
days intervals, the peroxide values of stored samples were determined. Every 180 days the samples were
analyzed for TBA and anisidine values. In order to determine the effect of storage temperature, some samples
were stored at 38'C under dark condition for a period of 56 days. At 7 days intervals, the peroxide value of
samples was determined. The results indicate that at room temperature, increase in peroxide value, thio-
barbituric acid (TBA), anisidine value and totax value were significantly (p < 0.05) higher in sunflower oil
stored in HDPE containers as compared to PET (yellow, clear) bottles and metal cans. No significant differ-
ences were observed in the capability of PET bottles and metals cans to protect the oil against the deterio-
ration effect of primary and secondary oxidation. At 38'C, significant differences on peroxide value of sun-
flower oil in HDPE containers in comparison to the other packaging materials were observed (p < 0.05). The
results indicate that, the estimated shelf life for sunflower oil in HDPE containers at room temperature were
less than 180 days and decreased to 35 days at 38'C. Where as, the shelf life of sunflower oil in PET (yellow,
clear) bottles and metal cans were estimated to be more than 365 days at room temperature. It seems that
PET bottles and metal cans are suitable containers for sunflower oil that protect oil against oxidative dete-
rioration, where as the HDPE container with the low oxidative stability is unsatisfactory.

Keywords: sunflower oil, oxidative stability, storage condition, polyethylene terephtalate, high density polyethylene, metal
cans.

et al. 1992). Some reports on palm oil quality in different

Introduction
One of the most important parts of oil processing is pack-
aging that protects the product from point of manufacture
through usage by consumer. Package affects on shelf life
of the oil in such away that carefully processed oil may be
damaged by improper selection of packaging materials.
Shelf life is a duration period between packing a product
and using it, for which the quality of the product remain
acceptable to the product user. Environmental factors such
as light, gaseous atmosphere, temperature and moisture can
affect the stability of oil (1eo 1983, 1985). The best-known
effect of oxygen on deterioration is the promotion of the
rancidity of fats. Oxidation is a main problem for polyun-
saturated oil. There have been a number of studies on the
oxidative stability of oils in various packaging materials.
Some investigators concluded that, metal cans, amber glass
and green glass bottles gave the greatest oxidative stabili-
ty to refined palm oil kept in dark condition (27 :~: 1'C),
and where as polyethylene film was unsatisfactory (Nkpa
E-mail: rarnezani @ shirazu . ac , ir
film packaging material indicate that the quality deteriora-
tion of palm oils was more pronounced when they stored
under 30-40% relative humidity and 45'C (Narasimhan et
al. 2001). During long-term storage of soybean oil in plastic
bottles (polyvinyl chloride and acrylonitrile) and glass
bottles (clear and amber), it was concluded that the oil in
plastic containers could serve as an alternative to clear
glass bottles (Warner and Mounts 1984). Some studies on
the storage quality of sunflower oil in different packaging
materials indicated that the oil in glass and steel contain-
ers had better qualities than the others (Jaimand and Rezaee
1995). At room temperature, refined sunflower oil remains
stable in high-density polyethylene (HDPE) bottles and
sealed tin for two years (Semwal and Arya 1992). Some
reports indicate that the storage lives of sunflower oil in
polyethylene terephthalate (PET), clear glass and color
glass bottles under 10 w fluorescence lamp were 10.4, 1 1 . 1
and 11.8 mo. at 10'C and 4.8, 5.1 and 6.5 mo. at 20'C,
respectively (Kaya and Tekin 1993). The effect of various
packaging materials (clear PET, yellow PET, HDPE and
metal can) and light condition on storage stability of refined
sunflower oil indicate that yellow PET with the lowest light
The Effect of Packaging Materials and Storage Condition on the Oxidative Stability of Refined Sunflower Oil
transmittance properties (350-800 nm) and peroxide value
(when exposed to four 20 w fluorescent lamp) proved to
be the most suitable container for sunflower oil (Ramezani
and Karbassi 2002). Kinetic study on the autoxidation of
sunflower oil indicate that the autoxidation reaction occurs
faster in sunflower oil in glass than in PET polymer con-
tainer and faster than in the darkness of the metal contain-
er (Topaller et al. 1997). The effect of polyethylene and
polypropylene films on the storage stability of sunflower
and groundnut oil at 37'C indicate that, reduction in rate
of autoxidation was more pronounced in the presence of
antioxidant incorporated film (sharma et al. 1990). Storage
stability of sunflower oil in the presence of oxygen-scav-
enging film that contain polyfuryloxirane was more than
oil stored without the film, or than film stored with 0.02%
BHT (Maloba et al. 1996).
In lran, the plastic containers, such as high density
polyethylene (HDPE), polyethylene terephthalate (PET)
and metal cans are common for packaging of fats and oils.
These containers are packed in carton as a secondary pack-
aging to provide total opacity and light protection. The
increase in use of plastic containers for oil, motivated the
present study to compare the effect of packaging materials
(clear PET, yellow PET, HDPE and metal can) and storage
conditions (at room temperature and 38'C under dark con-
dition) on oxidative stability of refined sunflower oil.
Materials and Methods
Materials
Chemicals Chemicals such as acetic acid, chloroform,
sodium iodide, sodium thiosulfate, 1-butanol, 2-thiobarbi-
turic acid, iso-octane and p-anisidine were obtained from
E. Merck Chemical Co. (Frankfurter Strass 250, 6100
Darmstadt, Germany).
Samples Sunflower oil was extracted, refined and
packaged by Shiraz Nargase Oil Company. Packaging mate-
rials were manufactured by lran Fila and Shiraz Nargase
Oil Co. as follow: yellow PET bottle, clear PET bottle,
yellow HDPE container and metal can. 72 samples for each
packaging materials in totally of 288 samples in various
packaging materials were prepared.
Method s
Storage condition 1-Ninty four samples of randomly
selected packaged sunflower oil (26 samples of each pack-
aging materials) were packed in carton as a secondary con-
Table 1. Peroxide formation is sunflower oil stored in the dark at room temperature (26.9'C).
Packaging
material
o 45 90
Clear PET(2) 1.05 :!: 0.0la 1.41 :!: 0.05a 1.74 i 0.08a 2.13 d: 0.06a
Yellow PET(2) 1.06 :!: 0.02" 1.41 :!: 0.05" 1.56 :~: 0.06" 2.12:!:O.06a
1.06 :!: 0.0la 2.32 :!: 0.22b 3.28 :!: 0.42b 6.28 :!: 0.53b
HDPE(3)
1.06 :!: 0.0la 1.45 :t 0.09a 1.83 :t: 0.25a 2.31 :!: 0.39*
Metal can
(1) Mean :~: SD. Values in each column with the same superscript are not significantly different (p < 0.05, LSD)
(2) PET (polyethylene terephthalate)
(3) HDPE (High density polyethylene).
351
tainer and dark condition. They were stored in room tem-
perature for 365 days. Relative humidity and temperature
of storage condition were recorded instrumentally (thies,
Germany). At 45 days interval, 12 samples were removed
from storage, shaken vigorously and analyzed for peroxide
value (PV) determination in duplicate (A.O.C.S 1990).
Stored samples during storage periods of O, 180 and 365
days were analyzed for thiobarbituric acid (TBA) and ani-
sidine value (AV) (A.O.C.S 1 990). The total oxidation value
(total) was calculated from the relationship (Rossel 1989):
Totax = 2 (PV) + AV
2-Various packaged refined sunflower oil was stored in air
oven (gallenkamp OV-160 Model, England) at 38'C under
dark condition for a period of 56 days. Every 7 days,
peroxide value of stored samples was determined (A.O.C.S
1990).
The thickness of films was determined by measuring 10
thicknesses with micrometer. The density of the films was
determined by weighing a known area of films, and calcu-
lating (Paine & Paine 1992).
Statistical analysis The data were statistically analyzed
by analysis of variance and compare means by LSD test
(SPSS 1 1.5 for windows statistical software package).
Results
Sunflower oil in various packaging materials stored in
environmental condition with the average temperature of
26.9'C and relative humidity of 36.6%. The results of
peroxide value of refined sunflower oil stored at room tem-
perature are shown in Table 1. As it shows, the peroxide
value of sunflower oil in HDPE containers were increased
sharply while in the other containers this value increased
gradually. Peroxide value of sunflower oil in HDPE con-
tainers changed markedly during storage for a period of 45
days and this value was more than 10 meq/kg after 225
days. During 365 days of storage, the mean of peroxide
value of sunflower oil in HDPE in comparison to the other
packaging material was significantly different (p < 0.05),
while the means comparison of peroxide value in clear
PET, yellow PET and metal cans weren't significantly dif-
ferent.
TBA analysis of stored sunflower oil samples is shown
in Fig. 1. At interval of O, 180 and 365 days of storage,
TBA value of refined sunflower oil in various Packaging
Peroxide value (meq 02/kg oil)(1)
Storage period (days)
135 1 80 225 270 315 365
2.90 :!: 0.02a 3. 16 d: 0.07a 3.35 :!: 0.06a 3.67 :!: 0.1la 4.00 :t 0.15a
2.91 :!: 0.02" 3.02 :!: 0.02" 3.22 :~: 0.16" 3.7 :!: 0.10" 3.98 :!: 0.18"
8.57 :!: 0.97b 12.51 :!: 0.37b 17.3 i 0.77b 24.06 i: 0.6lb 30.9 :~: 0.70b
2.80 :!: 0.23* 3.15 :!: 0.08" 3.54 :!: 0.15" 4.01 :!: 0.08* 4.39 :!: 0.1*
352 R. RAMEZANI
0.03 tainers gave the highest increase in anisidine value, while
0.025 no significant differences were found in anisidine value of
sunflower oil in PET and metal containers.
o O 02 The combined effect of the peroxide and anisidine value
J
~(:1> 0.015
of sunflower oil can be evaluated by total oxidation value
<00 O O1 (Totax). The results are shown in Fig. 3. There is a signif-
H icant difference in the total oxidation value for oil packaged
0.005
in HDPE.
O
90
O 1 80 365
Storage periods (days) 80
b
'J~EF:. .,

[] Clear PET I Yellow PET 70

E~] HDPE ~ Metal can o 60
::
75
> 50
Fig. 1. Thiobarbituric acid value in refined sunflower oil stored at room ~a:l

temperature (26.9'C) and dark condition. In each storage period, means ~ 40

Fo b
of values with similar letters are not significantly different (p < 0.05, LSD). 30 }:1.i: i:iii a
Abbreviations as in Table I . a *
ai
materials were increased. Any significant differences weren't
20
10 aa aa I B 5-
~.-...-
I :~i~~~i
observed in TBA of sunflower oil in PET (yellow, clear) O
and metal containers where as the TBA value of sunflow-
er oil in HDPE containers as a compared to the other pack- O 1 80 365
Storage Periods (days)
aging materials, were significantly different (p < 0.05). [] Clear PET I Yellow PET
Anisidine values of stored refined sunflower oil in various E~I HDPE ~ Metal can
packaging materials are shown in Fig. 2. During storage Fig. 3. Total oxidation value in refined sunflower oil stored at room tem-
periods, anisidine values of packaged sunflower oils were perature (26.9'C) and dark condition. In each storage period, means of
values with similar letters are not significantly different (p < 0.05, LSD).
increased. At 365 days, refined sunflower oil in HDPE con-
Abbreviations as in Table I .

16
The peroxide value of sunflower oil stored at 38'C (Table
14
2) indicate that peroxide value of refined sunflower oil
12 samples in various packaging materials were increased
~o 10
c:f
steadily during 56 days of storage. The limiting peroxide
> value specified by lran standard (1993) was used to deter-
o 8
c mine the keeping quality of sunflower oil. The shelf life
I'co 6 estimated in this way to be less than 35 days for sunflow-
<Z 4 er oil in HDPE containers and less than 56 days for PET
2 (yellow, clear) and metal cans. Significant differences in
O peroxide value of sunflower oil in HDPE containers in
O 1 80 365
Storage periods (days)
comparison to the other packaging materials were observed
(p < 0.05). Where as the means comparison of the peroxide
[] Clear PET I Yellow PET value of sunflower oil in PET (yellow, clear) and metal cans
E~ HDPE ~ Metal can weren't significantly different.

Fig. 2. Anisidine value in refined sunflower oil stored at room temper-

ature (26.9'C) and dark condition. In each storage period, means of values
with similar letters are not significantly different (p < 0.05, LSD).
Abbreviations as in Table 1.
The tests carried out on plastic packaging materials must
be chosen to examine those properties which are relevant
to the application. Table 3 Iists the properties of plastic pack-
aging films.

Table 2. Peroxide formation is sunflower oil stored in the dark at 38'C.

Peroxide value (meq 02/kg oil)(1)

Packaging Storage period (days)

material
o 7 14 21 28 35 42 49 56
Clear PET(2) 1.04 :!: 0.01* 1.67 :!: 0.05' 2.5 :!: 0.12" 3.98 :!: 0.37* 4.84 :!: 0.12* 5.23 :!: 0.21" 6.02 :!: 0.34* 7.05 :!: 0.58" 8.00 :~: 0.19"
Yellow PET(2) 1.08 :t 0.06* 1.68 :!: O.03* 2.69 :!: 0.10" 4.21 :!: 0.12* 4.93 :!: 0.lO' 5.49 :!: 0.21" 6.12 :!: 0.15* 7.13 :!: 0.16* 8.28 :!: 0.33*
HDPE(3) I . 10 :!: 0.09* 2.77 :!:0.1lb 3.94:!:0.3lb 6.71 :!: 0.43b 7.93 :!: 0.14b 8.72 :!: 0.28b 9.64 :!: 0.94b 10.57 :!: 0.67b ll.35 :!: 0.53b

Metal can 1.09 :!: 0.07* 1.63 :!:0.01* 2.58 :!:0.13" 4.25 :!: 0.48* 5.25 :!: 0.24" 5.91 :!: 0.34* 6.39 :!: 0.65" 7.38 :!: 0.73" 8.08 :!: 0.28"

(1) Mean :!: SD. Values in each column with the same superscript are not significantly different (p < 0.05, LSD)
(2) PET (polyethylene terephthalate)
(3) HDPE (High density polyethylene)
The Effect of Packaging Materials and Storage Condition on the Oxidative Stability of Refined Sunflower Oil
Table 3. Some properties of plastic packaging materials(1).
Packaging materials Density (kg/m3)
Clear PET(2) 1376 i 14
Yellow PET(2) 1359 ~ 19
HDPE(3) 952 ~ 12
(1) Mean t SD
(2) Polyethylene terephthalate
(3) High density polyethy lene
(4)
(5) Light
Oxygentransmissions is percenta
transmission e of light
rate = cm~/25
um2/d./atm./at
Discussion
Deterioration of lipid foods as a result of oxidation is a
particulate problem for polyunsaturated oils, such as sun-
flower oil. Peroxide is considered to be the first product
formed in oils by the oxidation process. Peroxide value is
a good guide to judge about the quality of oil (Rossel 1989).
Peroxide value of refined sunflower oil stored in dark con-
dition at room temperature (Table 1) and 38'C (Table 2)
indicate that the packaging containers such as, yellow and
clear PET bottles and metal cans gave the greatest protec-
tion of sunflower oil against oxidative deterioration. Where
as the highest peroxide value was recorded for the sunflower
oil packaged in HDPE containers. The limiting peroxide
value specified by FAOIWHO (Codex standard 1992) and
lran standard ( 1993) for refined sunflower oil is 10 meq/kg
and 7 meq/kg, respectively. According to the lran standard,
the estimated shelf life of sunflower oil in HDPE contain-
ers at room temperature was less than 180 days, while for
the other packaging containers were more than 365 days
(Table 1). At 38'C, the shelf life decreased to less than 35
days for sunflower oil in HDPE containers and less than
49 days in PET (yellow, clear) and metal cans (Table 2).
This would indicate that the HDPE containers gave the least
protection of sunflower oil against oxidation deterioration.
Although the peroxide value doesn't give information
about secondary oxidative products, they can be used as an
indicator for oil quality. The TBA test is another empirical
method frequently used for the detection of lipid oxidation,
it relates to the level of aldehyde present in the oil by the
reaction of malonaldehyde with TBA (Guillen-sans and
Guzman-chozas 1998) and a representative parameter for
the secondary oxidation step (Angelo 1996). Anisidine
value determine the level of aldehyde, principally, 2-alkenals
(Rossel 1989). This research clearly shows that TBA (Fig.
1), anisidine value (Fig. 2) and totax value (Fig. 3) of sun-
flower oil in HDPE containers were increase significantly
(p < 0.05). It is evident that PET (yellow, clear) and metal
containers gave the greatest protection to the sunflower oil
against secondary oxidative deterioration. No significant dif-
ferences were found in the capability of PET bottles and
metal cans to protect the sunflower oil against the delete-
rious effects of secondary oxidation (Figs. 1-3).
Based on all these determination of peroxide value, TBA,
anisidine value and totax value some trends have clearly
emerged. Firstly, the packaging material enhances the rate
of deterioration of the oil. The deteriorative parameters
353
O (5)
Thickness (mm) Light(4) (350-800 nm) 2
0.44 d: 0.02 86.8 :!: 5.12
}
0.42 d: 0.04 7.79 :t 7.14 47-92
1.46 :!: 0.13 1.95 ~ 1.56 2 1 O0-2900
passing through
wall thickness
23125'C, 50% RH.(Ramezani & Karbassi
(Paine & Paine 1992)2002)
responsible for the low shelf life of sunflower oil in HDPE
containers may be considered to be high oxygen perme-
ability (Table 3). Actually, one of the criteria to choose the
packaging materials is the knowledge of the permeability
of the polymeric material to the gases and vapors of the
environment. Some of the structural parameters of the
polymer play a major role in their effect on permeability
(Jasse et al. 1994). Oxygen is the most critical factors
affecting the quality of oils. It may access the oil by per-
meation of the wall of the container. The quantity of gas
transmitted is, inversely proportional to the thickness of the
film (Paine and Paine 1992). Although, the wall thickness
of HDPE container is more than PET, but PET barrier prop-
erties are also superior to HDPE (Table 3). The rate at which
a gas will pass through a permeable membrane is controlled
by several factors, some governed by the properties of
membrane. Different plastic resins block oxygen at differ-
ent rates (Leo 1983, 1985). PET has a good gas barrier but
oxygen transmission rate in HDPE is relatively high
(Johansoon and Leufven 1994 Table 3). Therefore, PET is
a suitable plastic container for contact with edible oil and
provides an adequate oxygen barrier. The technological
progress has provided PET material with properties of
complete barrier for gas exchange (Robichon and Savina
1996). The prospects for developing PET resin for bottles
in a world are good and should increase over the next years
at a rate which is detrimental to glass and metal container
(Chretien 1996). Also, oxidative deterioration can often be
prevented or minimized by limiting the access of the product
to oxygen through the selection of the packaging materials
(Caudill 1996).
Secondly, other deteriorative parameters responsible to
predict shelf life are storage temperature. The storage sta-
bility of sunflower oil decreases as the storage temperature
increased from 26.9'C to 38'C. The peroxide value of sun-
flower oil in HDPE containers at room temperature (Table
1) and 38'C (Table 2) were increased significantly. As a
result of type of polymer in HDPE containers and high
oxygen permeability, shelf life of sunflower oil in HDPE
containers at 38'C was less than 35 days. Temperature may
have double effect; it affects the rate of oxidation of fats
and modifies the barrier properties of plastic container
(Hine 1987). Temperature and relative humidity as envi-
ronmental factors may affect the barrier characteristics of
the packaging materials (Johansoon and Leufven 1 995). The
influence of temperature on their diffusion behavior may
354
lead to the variation of permeation through polymeric pack-
aging (Jasse 1994). Diffusion and permeability increase with
temperature (Leo 1985).
Light transmittance characteristics of packaging materi-
als (Table 3) indicate that, HDPE container exclude light
at wavelengths of 350-800. But permeability of HDPE to
oxygen is fairly high so where oxidation is likely to be a
problem, they are not suitable. Edible oil often will be
filled into primary containers such as plastic bottles which
are then packaged within protective cartons. In this case
the secondary container provided by the carton, minimize
the light transmittance requirements that must be met by
the primary container and provides total opacity and light
protection for the period of time in which the shipper used.
Conclusion
It is undisputedly clear that PET bottles and metal cans
are suitable containers for packaging of sunflower oil. PET
bottles clearly exhibited their superiority as packaging mate-
rials for sunflower oil. In order to minimize oxidative dete-
rioration of sunflower oil after production and distribution,
it is most preferable that the sunflower oil be packaged in
PET and stored under dark condition. The leakage of air
through poor seals in metal cans and HDPE containers, make
superiority of PET bottles as a seamless container. The
highest oxidative deterioration was recorded for the sun-
flower oil packaged in HDPE containers.
Any packaging material that is used for edible oil must
have provided a barrier compatible with the oil product.
Shelf life and stability are directly related to the oxygen
permeability of packaging material. It is important to deter-
mine the desired shelf life of the edible oils and then select
the packaging material, for institutional trade, it may be
preferable to use a low cost material with a low oxygen
barrier property. The same edible oil packaged in high
oxygen barrier material would allow a retail shelf life of
longer.
Acknowledgments The authors thank the research council of Shiraz
University for the grant supporting of this project (No. 75-AG-972-
557), Shiraz Nargase Oil Company for providing the packaged refined
sunflower oil, and also H. Essfandiyari for chemical analysis.
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