1 s2.0 S0956713509001959 Main PDF
1 s2.0 S0956713509001959 Main PDF
1 s2.0 S0956713509001959 Main PDF
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414 G. Pristouri et al. / Food Control 21 (2010) 412418
oil packaged in PET + aluminum foil the acidity and PV did not ex-
ceed the limit even after 12 month; K
232
exceeded the limit after
6 months while K
270
exceeded the limit after 9 months of storage.
Color was affected (P < 0.05) in samples of olive oil packaged in
both clear PET and PET + UV bottles after 6 months of storage. A
rst observation to be made is that olive oil exposed intermittently
to light at 22 C will retain its quality characteristics packaged in
clear PET for a period of less than 3 months. Respective shelf lives
of samples packaged in PET + UV blocker and PET + aluminum foil
is 3 and 9 months. It is noteworthy to mention that the UV blocker
used in the PET bottles provided only partial protection to the
product from light while complete protection from light (i.e. using
aluminum foil) provided an adequate retention of olive oil quality
for at least 9 months. The discrepancy between PV and K
232
values
is probably related to the fact that the former measures hydroper-
oxides while the latter measures hydroperoxides plus conjugated
dienes. According to the literature (IOOC, 1996) PV and K
232
corre-
late rather well during the early stages of oxidation, something
that was not shown in this study.
Similar ndings on the effect of light on olive oil quality were
reported by Coutelieris and Kanavouras (2005) and Kanavouras,
Hernandez-Mnoz, and Coutelieres (2004). They are also in agree-
ment with those of Coltro, Padula, Segantini Saron, Borghetti, and
Penteado Buratin (2003) who reported that the addition of 0.08%
of Tinuvin 326
TM
UV absorber is probably enough to provide the
studied PET bottles with the light barrier characteristics necessary
to maintain stability of olive oil for 6 months at 25 C.
3.3. Effect of storage temperature on olive oil quality
Olive oil quality parameter values for PET as a function storage
temperature and time are given in Table 3. Results show that for
olive oil packaged in clear PET, stored in the dark at 13 C the acid-
ity and PV did not exceed the adopted limits of 0.8% and 20 meq
O
2
/kg oil, respectively, even after 12 months of storage; K
232
ex-
ceeded the limit of 2.5 after 6 months while K
270
exceeded the limit
0.22 after 9 months of storage. For olive oil stored at 22 C both the
acidity and PV did not exceed the respective limits even after
12 months of storage; K
232
exceeded the limit after 6 months while
K
270
exceeded the limit after 9 months of storage. Finally for olive
oil stored at 35 C both the acidity and PV exceeded the respective
limits after 9 months while both K
232
and K
270
exceeded the
respective limits for a period less than 3 months of storage. By
plotting the change in PV over time the peroxidation reaction rate
constant (k) was calculated. Then by plotting ln(k) as a function of
1/T the activation energy for peroxidation of EVOO was calculated
to be 8.004 kJ/mol (Fig. 1).
Color was not substantially affected (P > 0.05) by storage tem-
perature given that olive oil was stored in the dark. Thus olive oil
stored in clear PET in the dark will retain its quality characteristics
for a period of 6 months at 13 C and 22 C and for less than
3 months at 35 C.
Similar effect of storage temperature on olive oil quality were
reported by Gambacorta et al. (2004) and Kanavouras and Coute-
lieris (2006) who showed that elevated temperatures caused sub-
stantial deterioration in olive oil quality but less than that caused
by light.
3.4. Effect of container headspace volume on quality of olive oil
Olive oil quality parameter values for clear PET stored in the
dark at 22 C are given in Table 4 as a function of headspace vol-
ume and storage time. The experiment was designed so as to re-
move the rst 200 mL of olive oil after 3 months of storage
(resulting headspace equal to 200 mL), the following 200 mL of
oil after 6 months (resulting headspace equal to 400 mL) and nal- T
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G. Pristouri et al. / Food Control 21 (2010) 412418 415
ly the following 200 mL of oil after 9 months (resulting headspace
volume equal to 600 mL).
Results show that for olive oil packaged in clear PET held in the
dark at 22 C the acidity exceeded the adopted limit of 0.8% after
9 months (headspace 400 mL); PV exceeded the limit of 20 meq
O
2
/kg oil after 6 months (headspace 200 mL); K
232
exceeded the
limit of 2.5 after 3 months (headspace 0 mL) and K
270
exceeded
the limit of 0.22 after 6 months (headspace 200 mL). Color was
not affected (P > 0.05) by headspace volume and storage time un-
der the present experimental conditions. Thus even with no head-
space auto-oxidation proceeded to such an extent that K
232
reached its upper acceptable limit (2.50) for extra virgin olive oil
after 3 months of storage. This most probably may be attributed
to oxygen permeation through the PET bottle walls and possibly
to the action of oxygen dissolved in the oil (Del Nobile et al.,
2003). What should be stressed is the fact that PV increased expo-
nentially after 9 months of storage when the headspace volume
was P400 mL. This has also been reported by Bauer-Plank and
Steenhorst-Slikkerveer (2000).
Present data on the effect of headspace volume on the quality of
olive oil are in general agreement with those of Del Nobile et al.
(2003) who showed that by reducing either the bottle volumetric
capacity or the oxygen partial pressure in the bottle headspace
the quality decay kinetics of olive oil slowed down. Cecchi, De Mar-
co, Passamonti, and Pucciarelli (2006) evaluated EVOO quality
packaged in PET bottles by lling up to one third of their volume
and exposing the product to daylight for 2 months at 20 C. They
Fig. 1. ln(k) versus 1/T plot for peroxidation o EVOO packaged in PET bottles.
Table 4
Changes in acidity, PV, absorption coefcients and color of olive oil packaged in clear
PET at 22 C in the dark as a function of headspace volume and storage time.
Months/
headspace
(mL)
Acidity
(% oleic acid)
PV
(meq O
2
/kg)
K
232
K
270
Color
0/0 0.63 0.01 12.92 0.44 2.25 0.05 0.14 0.02 L = 53.04
a = 2.80
b = 36.09
3/0 0.70 0.02 15.60 0.20 2.50 0.20 0.20 0.01 L = 52.36
a = 2.97
b = 35.64
6/200 0.72 0.02 18.48 0.22 3.14 0.10 0.22 0.01 L = 52.35
a = 3.16
b = 35.64
9/400 0.77 0.02 32.20 0.20 3.24 0.10 0.27 0.01 L = 52.14
a = 2.92
b = 35.50
12/600 0.85 0.02 37.19 0.50 3.26 0.10 0.33 0.02 L = 53.39
a = 3.61
b = 36.35
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416 G. Pristouri et al. / Food Control 21 (2010) 412418
reported substantial losses in quality beyond the acceptable level
from both the analytical and sensory points of view.
3.5. Comparison of relative effect of parameter investigated on quality
of olive oil
3.5.1. Acidity
Acidity is used as a criterion for the categorization of olive oil.
Despite this fact acidity is not a good indicator of olive oil quality
since for instance an olive oil with a relatively high acidity may
possess a highly desirable aroma whereas an olive oil with a low
acidity may lack in aroma (Kiritsakis, 1998). The smallest increase
in acidity after 12 months of storage was observed in glass and
clear PET at 13 and 22 C stored in the dark. Alternatively, similarly
low values for acidity were recorded for PET + UV and PET covered
with aluminum foil at 22 C in the presence of light. Increase in
temperature (from 22 to 35 C) in the dark, increase in headspace
(from 0 to 600 mL) in the dark, use of PP containers in the dark
at 22 C, or clear PET under light at 22 C resulted in the highest
acidity values (0.830.85) after 12 months of storage. Results with
regard to high storage temperatures and the presence of headspace
are in agreement with those of Gutirrez and Fernndez (2002).
Plastics (PP and to a lesser degree PET) exhibit a higher tendency
for hydrolysis of triglycerides which can be justied by their higher
oxygen permeability as compared to glass. A high oxygen concen-
tration results in a high rate of hydroperoxide formation and
decomposition leading to the formation of carboxylic acids,
responsible for an increase in acidity (Velasco & Dobarganes,
2002). Of the two plastics PET provided a better protection to olive
oil than PP due to its signicantly lower OTR. These results are in
agreement with those of Tawk and Huyghebaert (1999). Despite
the negligible OTR of glass its permeation to light enhanced
decomposition of triglycerides increasing olive oil acidity as postu-
lated above. This phenomenon was inhibited by storing glass con-
tainers in the dark. A similar effect was reported by Mndez and
Falqu (2007). Olive oil deterioration in the presence of light is en-
hanced by trace constituents such as chlorophyll which are excited
through the absorption of light. Subsequently they transfer this ex-
cess energy to ground state triplet oxygen to form the excited state
singlet oxygen which readily reacts with free fatty acids (Hamilton,
Kalu, Prisk, Padley, & Pierce, 1997).
3.5.2. Peroxide value (PV)
Reactions contributing to an increase in PV are auto-oxidation
and photo-oxidation the former occurring in the absence of light
while the latter occurs in the presence of light. Initial PV value of
olive oil was 12.92 meq O
2
/kg. During the initial stages of storage
in the dark, oxidation proceeds in the product due to the oxygen
dissolved in the oil (Del Nobile et al., 2003). PV values after
12 months of storage were 18.86 for glass, 20.61 for clear PET
and 22.54 meq/kg for PP in the dark at 22 C. Increase in PV values
is solely due to auto-oxidation. Respective PV values in presence of
light at the same temperature were 21.98 (for clear PET), 19.24 (for
PET + UV) and 18.81 meq O
2
/kg (for PET + aluminum foil). Thus for
PET the effect of light is more pronounced than that of OTR. After
12 months of storage PV values for PET in the dark were 16.81,
20.60 and 23.61 meq O
2
/kg at 13, 22 and 35 C, respectively. That
is, the effect of temperature under specic experimental conditions
was more pronounced than that of both light and oxygen. Finally,
large headspace volumes (i.e. 400600 mL) resulted to a drastic in-
crease of PV values after 12 months of storage (i.e. 32.20 and
37.19 meq O
2
/kg, respectively) and indicate that under extremely
high concentrations of oxygen, olive oil quality drastically deterio-
rates. At such high oxygen headspace concentrations the effect of
this parameter becomes the most critical compared to the other
three parameters.
The above results are in general agreement with those of Min
(1998) who reported higher losses in olive oil quality stored under
light as compared to those stored in the dark. Kiritsakis and Dugan
(1984) also reported that PV values were higher for olive oil pack-
aged in plastic containers as compared to those packaged in glass
bottles in the dark. According to Interesse, Ruggiero, and Vitagliano
(1971) photo-oxidation does not occur in olive oil stored in the
dark at relatively low temperatures (i.e. 1320 C). Under such
conditions natural pigments of olive oil (i.e. chlorophyll) act as
antioxidants along with polyphenols protecting the product from
oxidation.
Contemporary trends in olive oil packaging include dark colored
glass bottles and PET bottles which have incorporated oxygen sca-
vangers (Del Nobile et al., 2003).
3.5.3. Absorption coefcients (K
232
, K
270
)
The initial values for K
232
and K
270
were 2.25 and 0.14, respec-
tively. K
232
increased from 2.25 to 3.22 after 12 months of storage
in the dark at 22 C as a result of auto-oxidation caused primarily
by oxygen transmission through the packaging material and sec-
ondarily by oxygen initially dissolved in the oil. K
232
also increased
to 3.18 in the presence of light, to 3.27 at 35 C and to 3.26 in the
presence to excess oxygen in the headspace (headspace volume
600 mL after 12 months of storage). Thus the most pronounced
changes in K
232
were caused by an excess of oxygen and tempera-
ture followed by container OTR and container light transmittance.
K
270
increasedfrom0.14to0.35after 12 months of storage inPPin
the darkat 22 Cas a result of auto-oxidationdue tooxygentransmis-
sion through the package. It also increased to 0.37 in the presence of
light, to 0.32 at 35 C and to 0.33 in the presence of excess oxygen in
the container headspace (HS = 600 mL) after 12 months of storage.
Thus all four parameters: oxygen transmission, light transmission,
temperature and HS volume resulted in similar changes of K
270
. Pres-
ent results with regard to K
270
are somewhat different than those of
Kanavouras and Coutelieris (2006) who reported that light had a
more pronounced effect on deterioration of olive oil quality (produc-
tion of higher amounts of hexanal) than elevated temperatures.
Lastly with regard to olive oil color there were no statistically signif-
icant (P > 0.05) changes observed under specic experimental condi-
tions of storage with the exception of olive oil exposed to light.
Similar results were reported by Morell, Motilva, Tovar, andRomero
(2004) regarding the color parameter b (yellowness) of olive oil.
Changes in olive oil color are related to the decomposition of chloro-
phylls during photo-oxidation (Kiritsakis, 1998).
4. Conclusions
Based on the above data the following conclusions may be
drawn:
(a) Containers with high OTRs such as PP, PE are not suitable for
the packaging of olive oil.
(b) UV lters in PET bottles do not substantially contribute to
the retention of olive oil quality.
(c) Packaging olive oil in low OTR bottles such as PET does not
effectively protect the product beyond 3 months in the pres-
ence of light.
(d) Large HS volumes should be avoided indicating the need for
consumption of olive oil within a given container as soon as
possible.
(e) The most appropriate material for olive oil packaging is glass
followed by PET and preferably a dark colored container to
be stored in the dark at temperatures less than or equal to
22 C. Under such conditions the shelf life of extra virgin
olive oil is 6 months.
G. Pristouri et al. / Food Control 21 (2010) 412418 417
(f) The relative contribution of parameters studied to the reten-
tion of olive oil quality are: temperature light > container
headspace > packaging material oxygen transmission rate.
This sequence changes when HS volume becomes
P400 mL (headspace volume/total volume P4/5 = 0.8).
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