Inuence of packaging geometry and material properties

on the oxidation kinetic of bottled virgin olive oil

M.A. Del Nobile
a,
*
, S. Bove
a
, E. La Notte
a
, R. Sacchi
b
a
Istituto di Produzioni e Preparazioni Alimentari, University of Foggia, Via Napoli, 25-71100 Foggia, Italy
b
Dipartimento di Scienza degli Alimenti, University of Naples Federico II, Via Universit aa, 100-80055 Portici, Italy
Received 3 January 2002; accepted 24 June 2002
Abstract
A two-dimensional mathematical model able to predict the time course of hydroperoxides and oxygen concentration prole
inside bottled virgin olive oil during storage is presented. By simulating the behavior of the bottled virgin olive oil it was possible to
assess the inuence of the bottles shape and size on the quality decay kinetics of virgin olive oil bottled in glass and plastic con-
tainers. In particular, ve geometrically dierent containers were used to predict the storage behavior of bottled virgin olive oil. The
obtained results show that the quality decay kinetics of bottled virgin olive oil greatly depends on container geometry. However, the
extent to which the containers geometrical factors aect the quality decay kinetics depends on the material used to make the bottle,
and on the initial value of the oxygen partial pressure in the bottle headspace.
2002 Elsevier Science Ltd. All rights reserved.
Keywords: Modeling; Shelf life; Olive oil; Active packaging
1. Introduction
The shelf life of a bottled vegetable oil is limited by
the auto-oxidation of unsaturated fatty acids with the
formation of hydroperoxides. The decomposition of
hydroperoxides gives rise to dierent compounds, some
of which are volatile and responsible for the sensory
degradation of the oil (Frankel, 1998).
It has been proved that mathematical models able to
predict the shelf life of packed foods are a valuable tool
in designing packaging systems (Del Nobile, Mensitieri,
Nicolais, & Masi, 1997; Labuza & Contreras-Medellin,
1981; Tubert & Iglesias, 1985). In a previous paper, Del
Nobile, Ambrosino, Sacchi, and Masi (in press) pre-
sented a mathematical model able to predict the evolu-
tion of oxygen and hydroperoxide concentrations in
virgin olive oil bottled in plastic and glass containers.
The developed model was used to assess the eect of
the following upon the quality decay kinetics of bottled
olive oil: oxygen diusivity and the thickness of the
plastic container, the presence of an oxygen scavenger in
the container wall and the concentration of oxygen in
the oil prior to bottling. In particular, it was established
that by increasing the barrier properties of the polymer
used to manufacture the bottle it is possible to obtain a
quality decay kinetic as slow as that obtained for olive
oil bottled in glass containers. Oxidation kinetics slower
than that found with glass bottles can be obtained by
bottling olive oil in innovative materials containing an
oxygen scavenger. However, the slowest decay kinetics
were obtained by bottling the oil in poly(ethylene tere-
phthalate) (PET) containers and reducing the oxygen
concentration prior to bottling to 10% of the equilib-
rium value. Even though the above model was advan-
tageously used to demonstrate several advantageous
aspects related to the design of plastic bottles for
packaging of virgin olive oil, it has some limitations. In
fact, it can not be used to predict the quality decay
kinetics of small containers (i.e., only for h
c
=r
b
> 10)
and/or to assess the inuence of the bottles geometrical
factors on the quality decay kinetics of the bottled oil.
The above restrictions are a direct consequence of one of
the hypotheses used to derive the model; i.e., oxygen
diusion takes place only in the radial direction (mono-
dimensional model).
Journal of Food Engineering 57 (2003) 189197
www.elsevier.com/locate/jfoodeng
*
Corresponding author. Tel.: +39-881-589-233; fax: +39-881-740-
211.
E-mail address: ma.delnobile@unifg.it (M.A. Del Nobile).
0260-8774/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S0260- 8774( 02) 00297- 2
In this work the mono-dimensional model was im-
proved by taking into account also oxygen diusion in
the bottles axial direction (two-dimensional model).
The new model was then used to assess the inuence of
some of the bottles geometrical factors on the quality
decay kinetics of virgin olive oil bottled in glass and
plastic containers.
2. Materials and methods
In this study ve geometrically dierent bottles were
investigated. The rst three dier in volumetric capacity
(i.e., 1, 1/2 and 1/4 l), while the latter two contain the
same amount of oil, 1 l, but dier in the capacity of the
bottle headspace. Fig. 1 shows the axial section of
the bottles used to run the simulations, while Table 1
lists the dimensions of the above bottles. The thickness
of the bottles is equal to 350 lm.
2.1. Evaluation of the oil oxidation parameters
The oxidation kinetics simulations were made using
experimental data obtained from shelf-life tests made at
40 C using extra virgin olive oils extracted from olives
(Olea europaea sativa, cv Biancolilla) by the percolation-
centrifugation system (Rapanelli, Foligno, Italy). The
parameters characterizing extra virgin olive oil auto-
oxidation at 40 C were evaluated in a previous pa-
per (Del Nobile et al., in press) and are summarized in
Table 2.
2.2. Evaluation of the oxygen transport parameters
2.2.1. Oxygen/olive oil System
There are no data reported in the literature on the
solubility and diusivity of oxygen in virgin olive oil.
However, considering the chemical nature of virgin olive
oil it is reasonable to assume that S
Oil
O
2
is enclosed in an
Nomenclature
C
Av
ROOH
average hydroperoxide concentration
C
Oil
O
2
oxygen concentration in virgin olive oil
C
Polym
O
2
concentration of the oxygen dissolved in the
container wall
C
Polym
OS
oxygen scavenger concentration in plastic
container
C
ROOH
local hydroperoxide concentration in the
bottled oil expressed as cm
3
(STP)/cm
3
(Oil)
D
Oil
O
2
oxygen diusivity through virgin olive oil
D
Polym
O
2
diusivity of oxygen through the plastic
container wall
D
PET
O
2
oxygen diusivity in PET
J
Cap
O
2

Int D
oxygen mass ux at the bottle headspace/
aluminum cap interface
J
Oil
O
2

Int A
oxygen mass ux at the oil/bottle wall in-
terface (in the oil)
J
Oil
O
2

Int B
oxygen mass ux at the bottle headspace/oil
interface (in the oil)
J
Polym
O
2

Int A
oxygen mass ux at the oil/bottle wall
interface (in the container wall)
J
Polym
O
2

Int C
oxygen mass ux at the bottle headspace/
bottle wall interface (in the container wall)
K
i
s constants, they have to be regarded as tting
parameters
n
HS
O
2
number of oxygen moles present in the bottle
headspace
n
Oil
O
2
number of oxygen moles dissolved in the
virgin olive oil prior to bottling.
p
Oil
O
2
oxygen partial pressure in virgin olive oil
p
HS
O
2
oxygen partial pressure in the bottle head-
space at time t
p
HS
O
2
0 oxygen partial pressure in the bottle head-
space at time zero
p
Oil
O
2

Int A
oxygen partial pressure at the oil/bottle wall
interface (in the oil)
p
Oil
O
2

Int B
oxygen partial pressure at the bottle head-
space/oil interface (in the oil)
p
Polym
O
2

Int A
oxygen partial pressure at the oil/bottle
wall interface (in the plastic)
p
Polym
O
2

Int C
oxygen partial pressure at the bottle
headspace/bottle wall interface (in the plastic)
r radial coordinate
R universal gas constant
R
D
rate at which hydroperoxides are decom-
posed expressed as cm
3
(STP)/cm
3
(Oil) s
R
F
rate at which hydroperoxides are formed ex-
pressed as cm
3
(STP)/cm
3
(Oil) s
R
OS
rate at which oxygen is consumed by the
oxygen scavenger
S
Bottle
bottle surface
S
Oil
O
2
oxygen solubility in virgin olive oil
S
PET
O
2
oxygen solubility in PET
t time
T absolute temperature
V
HS
volume of the bottle headspace
V
Oil
volume of the bottled virgin olive oil
z axial coordinate
l liquid viscosity
190 M.A. Del Nobile et al. / Journal of Food Engineering 57 (2003) 189197
interval whose upper limit is the oxygen solubility in n-
hepthane (0.4 cm
3
(STP)/cm
3
atm) and the lower limit
is oxygen solubility in polyethylene (0.08 cm
3
(STP)/
cm
3
atm) (Michaels & Bixler, 1961). Taking into account
that the average molecular weight of virgin olive oil is
closer to that of n-hepthane than to that of polyethylene,
S
Oil
O
2
was set at 0.15 cm
3
(STP)/cm
3
atm.
The values of D
Oil
O
2
were determined through the fol-
lowing expression (Schumpe & L uuhring, 1990):
D 2:6 10
11
l
2=3
1
Eq. (1) was originally derived to correlate oxygen dif-
fusivity through organic solvents to their viscosity. The
viscosity of the virgin olive oil used in this investigation
at 40 C is 0.033 Pa s, having been evaluated using a
Rheometrics RFS II viscometer. Substituting the above
viscosity value in Eq. (1), the value obtained for D
Oil
O
2
is
2:72 10
6
cm
2
/s.
2.2.2. Oxygen/PET system
The values of oxygen diusivity (D
PET
O
2
) and solubility
(S
PET
O
2
) in PET were determined from the data reported in
the literature on the diusivity and solubility of oxygen
in PET at 30 C, which are 4:9 10
9
cm
2
/s and 0.092
cm
3
(STP)/cm
3
atm respectively (Toi, 1973). The value
for the diusion activation energy and for the enthalpy
of solubilization used to evaluate diusivity and solu-
bility at 40 C are 11 and )3.1 kcal/mol respectively
(Michaels, Vieth, & Barrie, 1963a,b). The data obtained
for D
PET
O
2
and S
PET
O
2
are 8:8 10
9
cm
2
/s and 0.078
cm
3
(STP)/cm
3
atm respectively.
The oxygen transport parameters for the oxygen/oil
and oxygen/PET systems used in the present investiga-
tion to run the simulations are listed in Table 3.
3. Results and discussions
During the storage of bottled virgin olive oil hy-
droperoxides are formed through the oxidation of
Table 2
Parameters characterizing the lipid oxidation reaction of the investi-
gated virgin olive oil
K
1
cm
3
(STP)/cm
3
s 8:52 10
9
K
2
2:47 10
10
K
3
(atm) 7:32 10
3
K
4
1.02
K
5
(s
1
) 3:28 10
8
Table 3
Transport parameters of the oil/oxygen and PET/oxygen systems
S
Oil
O2
(cm
3
(STP)/cm
3
atm) 0.15
D
Oil
O
2
(cm
2
/s) 2:72 10
6
S
PET
O
2
(cm
3
(STP)/cm
3
atm) 0.078
D
PET
Eff
(cm
2
/s) 8:8 10
9
Fig. 1. Axial section of the bottle.
Table 1
Dimensions of the investigated bottles
Bottle Volume (cm
3
) S
Bottle
=V
Oil
(cm
1
) V
HS
=V
Oil
n
HS
O2
=n
Oil
O2
r
c
(cm) r
b
(cm) h
c
(cm) h
o
(cm) h
b
(cm)
A 1000 6:1 10
1
1:8 10
2
0.11 1.4 4.4 16.2 18.6 21.6
B 480 7:9 10
1
2:5 10
2
0.14 1.2 3.4 13.0 14.8 17.4
C 251 9:8 10
1
2:8 10
2
0.16 1.0 2.8 10.0 11.6 13.8
D 1000 6:2 10
1
3:3 10
2
0.20 1.4 4.4 16.2 18.6 24.0
E 1000 6:3 10
1
4:6 10
2
0.27 1.4 4.4 16.2 18.6 26.0
M.A. Del Nobile et al. / Journal of Food Engineering 57 (2003) 189197 191
unsaturated fatty acids and consumed by hydroperoxide
breakdown reactions. In the rst stage of oxidation,
when the oxygen concentration is close to saturation, the
rate at which hydroperoxides are consumed is lower than
the rate at which they are produced through the auto-
oxidation of unsaturated fatty acids, leading to an in-
crease in hydroperoxide concentration during storage.
As the lipid oxidation reaction proceeds, oxygen is con-
sumed to form hydroperoxides. This causes: (a) the
formation of an oxygen concentration gradient in the
bottled oil, which in turn brings about the permeation of
external oxygen through the wall of the plastic container;
(b) an increase in the rate at which hydroperoxides break
down. As a result of the above phenomena, concentra-
tions of both local oxygen and hydroperoxides decrease.
Given the above scenario during oil storage, to
properly describe the oxidation kinetics of bottled virgin
olive oil a mathematical model was developed to predict
the time course of oxygen and hydroperoxide concen-
trations in bottled oil during storage.
3.1. Two-dimensional mathematical model
The mathematical model was derived by assuming
that: (a) the axial section of the bottle is that showed in
Fig. 1; (b) the diusive mass ux of hydroperoxides
through both the olive oil and the container wall were
considered negligible.
Under the above restrictions the mass balance equa-
tion of the hydroperoxides dissolved in the bottled oil
have the following expression:
oC
ROOH
ot
R
F
R
D
2
Several models have been reported in the literature to
describe the rate at which hydroperoxides are formed
through the oxidation of unsaturated fatty acids (Quast
& Karel, 1972; Quast, Karel, & Rand, 1972); the model
proposed by Quast et al. (1972) to describe lipid oxi-
dation in potato chips was used in the present investi-
gation. Assuming that relative humidity is constant
during storage, the model proposed by Quast et al.
(1972) is further simplied to the following relationship:
R
F
K
1
K
2
C
ROOH

p
Oil
O
2
K
3
K
4
p
Oil
O
2
!
3
Assuming that the solubilization process of oxygen into
oil is governed by Henrys law, p
Oil
O
2
is related to the
oxygen concentration in the oil through the following
relationship: p
Oil
O
2
C
Oil
O
2
=S
Oil
O
2
.
As reported above, hydroperoxides break down,
thereby giving rise to several secondary products
(Labuza, 1971). Many reactions are involved in this
process, each of which is characterized by a particular
mechanism and should be described with a specic
equation. For the sake of simplicity, in the present in-
vestigation we assumed that at a given temperature the
overall rate at which hydroperoxides decompose de-
pends only on their concentration (Koelsch, Downes, &
Labuza, 1991). Hexanal formation via lipid oxidation as
a function of oxygen concentration (Koelsch et al.,
1991) was obtained through the following expression:
R
D
K
5
C
ROOH
4
Substituting Eqs. (3) and (4) in Eq. (2) the following
expression is obtained:
oC
ROOH
ot
K
1
K
2
C
ROOH

p
Oil
O
2
K
3
K
4
p
Oil
O
2
!
K
5
C
ROOH
5
The mass balance of the oxygen dissolved in the
bottled oil was obtained by assuming that Ficks rst
law and Henrys law govern oxygen diusion and solu-
bilization processes respectively. Starting from the
above hypothesis, it can be easily demonstrated that
oxygen mass balance has the following expression:
oC
Oil
O
2
ot
D
Oil
O
2
1
r
o
or
r
oC
Oil
O
2
or
! "

o
2
C
Oil
O
2
oz
2
#
K
1
K
2
C
ROOH

p
Oil
O
2
K
3
K
4
p
Oil
O
2
!
6
The rst term on the right side of the Eq. (6) is related to
the oxygen diusive mass ux, while the second term
denotes the rate of oxygen consumption by the lipid
oxidation reaction.
To evaluate the amount of oxygen permeating
through the container wall, it is necessary to write the
mass balance equation for the oxygen dissolved in the
container wall, which, in the case under investigation,
has the following expression (Del Nobile et al., 1997;
Masi & Paul, 1982; Paul & Koros, 1976):
oC
Polym
O
2
ot
D
Polym
O
2
1
r
o
or
r
oC
Polym
O
2
or
! "

o
2
C
Polym
O
2
oz
2
#
7
In the presence of an oxygen scavenger uniformly
dispersed in the container wall, Eq. (7) became:
oC
Polym
O
2
ot
D
Polym
O
2
1
r
o
or
r
oC
Polym
O
2
or
! "

o
2
C
Polym
O
2
oz
2
#
R
OS
8
In principle, R
OS
depends on the following: the concen-
tration of oxygen and the oxygen scavenger in the
plastic, temperature and humidity. Since there are no
data reported in the literature on the relationship be-
tween R
OS
and the above variables, we have proposed
the following equation:
R
OS
K
6
C
Polym
O
2
C
Polym
OS
9
192 M.A. Del Nobile et al. / Journal of Food Engineering 57 (2003) 189197
K
6
depends on the temperature and humidity. The val-
ues for K
6
and for the initial value of C
Polym
OS
, are
1:58 10
5
cm
3
/cm
3
(STP) s and 14 cm
3
(STP)/cm
3
re-
spectively. They were obtained assuming that a lm
50 lm thick containing the oxygen scavenger consumes
oxygen at a rate equal to 112 cm
3
(STP)/m
2
day at 40 C,
and that the maximum amount of oxygen consumed is
equal to 700 cm
3
(STP)/m
2
.
Interfacial conditions were imposed to ensure chem-
ical and physical equilibrium at the interface between oil
and container. Hence, both the mass ow and the oxy-
gen partial pressure of the juxtaposed substances were
required to be equal at the oil/bottle wall interface, i.e.:
J
Polym
O
2

Int A
J
Oil
O
2

Int A
p
Polym
O
2

Int A
p
Oil
O
2

Int A
(
10
At the bottle headspace/oil and bottle headspace/
bottle wall interfaces the following conditions were im-
posed:
p
HS
O
2
p
Oil
O
2

Int B
p
HS
O
2
p
Polym
O
2

Int C
p
HS
O
2

n
HS
O
2
RT
V
HS
dn
HS
O
2
dt
J
Polym
O
2

Int C
J
Oil
O
2

Int B
8
>
>
>
>
>
<
>
>
>
>
>
:
11
At the bottle headspace/aluminum cap interface the
following condition was imposed:
J
Cap
O
2

Int D
0 12
Eqs. (5)(7) (or (8) in the case of active bottles),
(10)(12), form a set of dierential equations, which,
using the proper initial and boundary conditions, were
solved simultaneously by numerical methods to predict
the evolution of oxygen and hydroperoxides inside the
bottled virgin olive oil during storage. The average hy-
droperoxide concentration was obtained by averaging
C
ROOH
over the volume of the bottled olive oil.
In the following, the above model is used to assess the
inuence of some of the bottles geometrical factors on
the quality decay kinetics of virgin olive oil bottled in
plastic and glass containers. The rate of hydroperoxide
formation and breakdown was predicted by using the
data listed in Table 2, while the data listed in Table 3
were used to describe the diusion and solubilization
processes of oxygen in olive oil and in PET. Unless
otherwise specied, the oxygen partial pressure in the
bottle headspace was set at 0.2 atm.
3.2. Inuence of headspace and geometry of PET
containers
Fig. 2 shows the predicted C
Av
ROOH
plotted as a func-
tion of storage time for virgin olive oil bottled in con-
tainers A, B and C made of PET. In the above gure,
two set of curves are shown: the rst was obtained by
setting p
HS
O
2
0 equal to 0.2, while the second was ob-
tained by setting p
HS
O
2
0 equal to 0. As shown in Fig. 2,
in the rst stage of oxidation the six quality decay ki-
netics are identical; as the lipid oxidation reaction pro-
ceeds the six curves diverge. In fact, right after bottling
the lipid oxidation reaction rate depends primarily on
the oxygen dissolved in the oil prior to bottling. As the
oxidation reaction proceeds, the oxygen present in the
bottle prior to bottling is consumed and subsequently
replaced by the oxygen permeating through the bottle
wall. Thus, the lipid oxidation reaction rate will gradu-
ally depend less on the oxygen dissolved in the oil prior
to bottling, and more on the oxygen permeating through
the bottle wall, and thus on the bottle geometry. As
shown in Fig. 2, by reducing either the bottles volu-
metric capacity or the oxygen partial pressure in the
bottle headspace, the quality decay kinetics slow down.
In fact, bottles A, B and C dier in both the values of
S
Bottle
=V
Oil
and V
HS
=V
Oil
. To separate the eects that these
two parameters have on the quality decay kinetics of
bottled oil, let us rst consider the curves obtained by
setting p
HS
O
2
0 equal to 0. As would be expected, as the
ratio S
Bottle
=V
Oil
decreases the quality decay kinetics of
the bottled virgin olive oil slow down. In fact, the
amount of oxygen permeating the bottle per unit volume
of the oil decreases as the ratio S
Bottle
=V
Oil
decreases, thus
slowing down the oil quality decay kinetics. The curves
obtained by setting p
HS
O
2
0 equal to 0.2, show a trend
similar to that obtained by removing the oxygen from
the bottle headspace. As shown in Fig. 2, as the ratio
V
HS
=V
Oil
increases, the dierence between the quality
decay kinetics obtained by setting p
HS
O
2
0 equal to 0.2
and that obtained by setting p
HS
O
2
0 equal to 0 increase.
In fact, as the ratio V
HS
=V
Oil
increases, the oxygen pre-
sent in the bottle headspace, which can freely diuse into
the bottled oil, increases, thus accelerating the time
course during storage of the hydroperoxides.
Fig. 2. Predicted average hydroperoxide concentration versus time:
(- -- -) bottle A, p
HS
O
2
0 0:2; ( ) bottle B, p
HS
O
2
0 0:2; () bottle C,
p
HS
O2
0 0:2; ( ) bottle A, p
HS
O2
0 0; (- -) bottle B, p
HS
O2
0 0;
( ) bottle C, p
HS
O2
0 0.
M.A. Del Nobile et al. / Journal of Food Engineering 57 (2003) 189197 193
Fig. 3 shows the predicted average hydroperoxide
concentration plotted as a function of storage time for
virgin olive oil bottled in PET containers A, D and E. As
shown in Fig. 3, the inuence of the ratio V
HS
=V
Oil
on the
oxidation kinetics is negligible. The above result is due
to the fact that the amount of oxygen present in the
bottle headspace does not change markedly during the
investigated period (Fig. 4).
3.3. Inuence of headspace and geometry of glass
containers
Fig. 5 shows the predicted C
Av
ROOH
plotted as a func-
tion of storage time for virgin olive oil bottled in glass
containers A, B and C. Two set of curves are shown: the
rst was obtained by setting p
HS
O
2
0 equal to 0.2, the
other was obtained by setting p
HS
O
2
0 equal to 0. Also in
this case by decreasing the amount of oxygen that freely
diuses from the bottle headspace into the bottled oil
(i.e., by decreasing the ratio V
HS
=V
Oil
) also the quality
decay kinetics slow down. Contrary to what one would
expect, in the case of the curves obtained by setting
p
HS
O
2
0 equal to zero, by decreasing the ratio V
HS
=V
Oil
the
quality decay kinetics accelerate. In fact, in the latter
case the bottle headspace acts as a empty reservoir that
removes oxygen from the bottled oil. Therefore, the
higher is the ratio V
HS
=V
Oil
, the higher is the amount of
oxygen that diuses from the bottled oil into the bottle
headspace. As an example, in Fig. 6 the time course
during storage of the oxygen partial pressure in the
bottle headspace is plotted.
Similar to what was reported in Fig. 3, Fig. 7 shows
the predicted average hydroperoxide concentration
plotted as a function of storage time for virgin olive oil
bottled in glass containers A, D and E. As in the case of
PET bottles (Fig. 3), the inuence of the ratio V
HS
=V
Oil
on the oxidation kinetics is negligible. Also in this case
the observed behavior is due to the fact that the amount
of oxygen present in the bottle headspace does not
change markedly during the investigated period (Fig. 8).
Fig. 3. Predicted average hydroperoxide concentration versus time:
() bottle A; ( ) bottle D; (- -- -) bottle E.
Fig. 4. Predicted p
HS
O2
plotted as a function of storage time: () bottle
A; ( ) bottle D; (- -- -) bottle E.
Fig. 5. Predicted average hydroperoxide concentration plotted as a
function of storage time: (- -- -) bottle A, p
HS
O2
0 0:2; ( ) bottle B,
p
HS
O2
0 0:2; () bottle C, p
HS
O2
0 0:2; ( ) bottle A, p
HS
O2
0 0;
(- -) bottle B, p
HS
O
2
0 0; ( ) bottle C, p
HS
O
2
0 0.
Fig. 6. Predicted p
HS
O2
plotted as a function of storage time: (- -- -) bottle
A; ( ) bottle B; () bottle C.
194 M.A. Del Nobile et al. / Journal of Food Engineering 57 (2003) 189197
3.4. Inuence of the containers properties
Fig. 9 shows the predicted average hydroperoxide
concentration plotted as a function of storage time for
virgin olive oil bottled in plastic containers A, B and C.
The gure shows three set of curves that refer to virgin
olive oil bottled in plastic containers made of polymers
diering in the value of the oxygen diusion coecient.
As would be expected, regardless of the type of bottle
used to pack the virgin olive oil, as D
Polym
O
2
decreases, the
bottled oil quality decay kinetics slow down. Interest-
ingly, for D
Polym
O
2
higher and lower than that of PET, the
dependence of the quality decay kinetics on the bottle
type is not as marked as that found for PET bottles. The
above results suggest that, at least for the investigated
bottles, the amount of oxygen permeating through the
bottle wall per unit volume of bottled oil strongly de-
pends on the shape and size of the bottle only for values
of D
Polym
O
2
close to that of PET. For D
Polym
O
2
much higher or
much lower than that of PET the oxygen permeating
through the bottle wall depends only slightly on the type
of bottle, either because the oxygen mass ux is too high
or too low.
3.5. Eect of an oxygen scavenger
It has been often reported in the literature (Vermeiren,
Devlieghere, van Beest, de Kruijf, & Debevere, 1999)
that oxygen scavengers can be successfully used to pro-
long the shelf life of foods whose quality decay kinetics
depend on the oxygen concentration in the package. In
the present paper, the two-dimensional model is used to
assess the inuence of the bottle geometrical factors on
the quality decay kinetics of virgin olive oil bottled in an
innovative PET container, the oxygen scavenger being
uniformly dispersed in the container wall.
Fig. 10 shows the predicted average hydroperoxide
concentration plotted as a function of storage time for
virgin olive oil bottled in plastic containers A, B and C.
The rst refers to PET bottles, the second refers to
the innovative PET containers mentioned above. As
expected, by dispersing the oxygen scavenger into the
container wall it is possible to slow down the oxidation
kinetics of the bottled oil. Unlike what was observed in
the case of virgin olive oil bottled in PET containers, the
larger the bottle size, the slower is the quality decay rate
of the bottled oil. In fact, the oxygen scavenger slows
down the oxidation kinetics in part by reducing the
amount of oxygen permeating into the bottle and in part
by removing the oxygen dissolved in the oil prior to
bottling. In fact, by reducing the size of the bottle, and
consequently by increasing the ratio S
Bottle
=V
Oil
and the
ratio V
HS
=V
Oil
, both the amount of oxygen permeating
into the bottle and that removed by the scavenger from
the oil increase. The results obtained suggest that the
eects related to the presence of an oxygen scavenger far
Fig. 7. Predicted average hydroperoxide concentration versus time:
() bottle A; ( ) bottle D; (- -- -) bottle E.
Fig. 8. Predicted p
HS
O2
plotted as a function of storage time: () bottle
A; ( ) bottle D; (- -- -) bottle E.
Fig. 9. Predicted average hydroperoxide concentration versus time:
( ) bottle A, D
Polym
O2
8:8 10
10
; (- -) bottle B, D
Polym
O2
8:8
10
10
; ( ) bottle C, D
Polym
O2
8:8 10
10
; (- -- -) bottle A, D
Polym
O2

8:8 10
9
; ( ) bottle B, D
Polym
O
2
8:8 10
9
; () bottle C,
D
Polym
O2
8:8 10
9
; (- - -) bottle A, D
Polym
O2
8:8 10
8
; (- -) bottle B,
D
Polym
O
2
8:8 10
8
; (- -) bottle C, D
Polym
O
2
8:8 10
8
.
M.A. Del Nobile et al. / Journal of Food Engineering 57 (2003) 189197 195
outweigh those deriving from an increase in the
permeated oxygen.
3.6. Predictive ability of mono- and two-dimensional
models
Fig. 11 shows the predicted average hydroperoxide
concentration plotted as a function of storage time
for virgin olive oil bottled in PET containers. The
three curves reported in the above gure refer to the
quality decay kinetics predicted by the mono- and two-
dimensional model. A diusive mono-dimensional
model can be used in place of the more accurate diusive
two-dimensional model if the following relation is sat-
ised: h
c
=r
b
> 10. In the specic case of bottle A, the
above ratio is equal to 3.7. However, as shown in Fig. 11
the dierence between the quality decay kinetics pre-
dicted by the two models is not as marked as expected.
In fact, in the rst stage of storage the oxidation reaction
rate does not depend much on the oxygen permeating
through the bottle wall, thus accounting for the results
shown in Fig. 11. The dierences between the quality
decay kinetics predicted by the two models have to be
ascribed to the fact that the two-dimensional model
takes into account the axial mass ux coming from the
top and the bottom of the bottle as well as the presence
of the oxygen in the bottle headspace. Referring to the
latter point, it is worth noting that, as expected, if p
HS
O
2
0
is equal to 0, the quality decay kinetics predicted by the
two models are closer.
Fig. 12 shows the predicted average hydroperoxide
concentration plotted as a function of storage time for
virgin olive oil bottled in glass containers. The three
curves reported in the above gure refer to the quality
decay kinetics predicted by the mono- and two-dimen-
sional model. In this case the dierence between the
predictions of the two models is less marked than that
that observed in the case of the PET bottle. In fact, for
glass bottles there is no mass ux from the bottom of the
bottle as in the case of PET bottles.
4. Conclusions
By means of the two-dimensional mathematical
model presented it was possible to assess the inuence of
some of the bottle geometrical factor (V
HS
=V
Oil
and
S
Bottle
=V
Oil
) on the quality decay kinetics of virgin olive
oil bottled in polymer containers.
The predictive ability of the mono- and two-dimen-
sional models were also compared. In particular, it was
observed that in the case of the bottle with a volumetric
capacity of 1 l, the prediction of the mono-dimensional
model is close to that of the more accurate two-dimen-
sional model. This could be related to the fact that
during the rst stage of storage the oxidation reaction
rate depends primarily on the oxygen dissolved into the
oil prior to bottling.
Fig. 10. Predicted average hydroperoxide concentration versus time:
(- -- -) bottle A, PET; ( ) bottle B, PET; () bottle C, PET; (- -)
bottle A, PET oxygen scavenger; (- -) bottle B, PET oxygen
scavenger; ( ) bottle C, PET oxygen scavenger.
Fig. 11. Predicted average hydroperoxide concentration versus time:
() mono-dimensional model; ( ) bottle A, p
HS
O2
0 0; (- -- -) bottle
A, p
HS
O
2
0:2.
Fig. 12. Predicted average hydroperoxide concentration versus time:
() mono-dimensional model; ( ) bottle A, p
HS
O2
0 0; (- -- -) bottle
A, p
HS
O2
0 0:2.
196 M.A. Del Nobile et al. / Journal of Food Engineering 57 (2003) 189197
The results obtained in the case of PET bottles
showed that when the ratio S
Bottle
=V
Oil
decreases, then
the amount of oxygen permeating through the bottle
wall decreases, thus slowing down the quality decay
kinetics of the bottled oil. In the case of PET bottles
with an oxygen scavenger uniformly dispersed in the
bottle wall, the opposite is true. This is due to the fact
that the oxygen scavenger consumes part of the oxygen
dissolved in the oil prior to bottling.
The ratio V
HS
=V
Oil
also inuences the evolution of the
hydroperoxides during storage. In particular, it was
observed that if p
HS
O
2
0 is equal to 0.2 the quality decay
kinetics slow down as the ratio V
HS
=V
Oil
decreases. On
the other hand, if p
HS
O
2
0 is equal to 0, the quality decay
kinetics slow down if V
HS
=V
Oil
increases.
These results suggest that, to control the oxidation
kinetics during the storage of bottled oil, it may be
useful to use well-designed plastic bottles, innovative
plastic materials containing an oxygen scavenger and to
perform the bottling operations under a nitrogen at-
mosphere (to reduce the oxygen pressure in the bottle
headspace). These practices are often underestimated by
the oil industry which denes empirically the period of
shelf-life (date of recommended consumption) of bottled
extra virgin olive oil, without carefully considering oil
characteristics, packaging properties and the tempera-
ture conditions during product distribution.
Acknowledgements
The work was funded under the MURST Piani di
Potenziamento della Ricerca Scientica e Tecnologica
and MURST-DIT3 Program grants.
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