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Agricultural University of Athens, Department of Natural Resources Management & Agricultural Engineering, 75 Iera Odos Str., 11855 Athens, Greece
National Technical University of Athens, School of Chemical Engineering, 9 Heroon Polytechniou Str., 15780 Zografou, Greece
a r t i c l e
i n f o
Article history:
Received 11 August 2011
Received in revised form 2 February 2012
Accepted 7 February 2012
Available online 23 February 2012
Keywords:
Modied atmosphere packaging (MAP)
Strawberries
Mathematical modelling
Finite element method
MaxwellStefan equations
a b s t r a c t
A space-and-time dependent mathematical model was developed to predict O2, CO2, N2 and H2O concentration in perforation-mediated polymeric packages during cold-storage of strawberries. The numerical
solution of the corresponding mathematical model was obtained by applying the nite element method
(FEM). The problem was solved in a domain corresponding to the headspace of a package augmented by
the total void spaces of the contained bulk produce and for realistic boundary conditions. Transport of O2,
CO2, N2 and H2O was modelled based on MaxwellStefan equations for gas transport through packagings
headspace and on Ficks law for diffusion through the micro-perforated packaging. The model predictions
were tested against published experimental data of O2 and CO2 concentrations in modied atmosphere
packaging storage of strawberries and the agreement is satisfactory. As for reaching the recommended
in the literature gases concentrations for strawberry storage, the model predictions revealed that the
tested micro-perforated polypropylene packaging combined with the adopted storage conditions are
marginally adequate. To this end, the theoretical ndings are suggestive of improvements, in terms of
material properties, especially with regard to the permeability of the polymeric packaging lm.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Modied atmosphere packaging (MAP) is a technique for modifying the in-package atmosphere using polymeric lms with or
without perforations to reduce quality deterioration and improve
shelf-life of the packaged produce through water loss, metabolic
and microbial activity reduction. The response of the packaged
produce to the generated atmosphere is affected by controllable
factors, such as packaging permeability, produce respiration, and
storage environment as well as uncontrollable factors, such as specie, cultivar, cultural practices, stage of development, harvest technique, tissue type, and postharvest handling. The permeability of
the commercially used packagings depends on their type, area
and thickness. The mean permselectivity that is the CO2-to-O2 permeability ratio, of the commercial packaging is close to 3.0 which,
according to Exama et al. (1993), Smith et al. (2003) and Guillaume
et al. (2011), is inadequate to achieve the recommended O2 and
CO2 concentrations when used with highly respired produce, unless micro-/macro-perforations are employed. In the design of a
MAP, produce mass/surface ratio, package dimensions and permeability should be considered. Signicant design parameters are also
Corresponding author. Tel.: +30 210 529 4031; fax: +30 210 529 4032.
E-mail address: xanthopoulos@aua.gr (G. Xanthopoulos).
0260-8774/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2012.02.016
327
Nomenclature
Ac
Af
aw
dc
Di/air
Di/eff
Dij
dpac
Dv
EaVmO2 =CO2
ei
hpac
Ka
K f ji
KmO2
KmO2 f
KmuCO2
Ks
lf
mb
Mi
_ total ji
m
_w
m
n
np
P
Pi
P0
Ps
R
Re
respi
RH0
RMSE
RQox
RRi
Sc
Sf
Sh
Sp
St
T
t
Tref
Vb
Vc
Vmi,ref
VPD
xiorj
x0ji
Xm
e
q
qb
qi
xi
328
Table 1
Properties of the packaged produce, package dimensions, and storage conditions used
in the model.
Property
Value
Reference
dc
aw
mb
Af
lf
Kf|H2O
Vc
Kf|O2
Kf|CO2
dp
RHo
EaVm;CO2
EaVm;O2
VmO2 ;ref
VmCO2 ;ref
Tref
RQox
KmO2
KmuCO2
KmO2f
0.03 m
0.27
48.96 106 kg m2 h1 Pa1
600 kg m3
0.99
0.5 kg
0.1 m2
50 lm
4.5 1013 m3 m h1 m2 Pa1
0.0015 m3
8.5 1014 m3 m h1 m2 Pa1
2.8 1013 m3 m h1 m2 Pa1
80 lm
0.6
64 kJ mol1
64 kJ mol1
242 nmol kg1 s1
175 nmol kg1 s1
10 C
0.7
1.2 kPa
51 kPa
0.14 kPa
R
dpac
Kf o jO2
Kf o jCO2
Pauly (1996)
Kf o jH2 O
Ef jO2
Ef jCO2
Ef jH2 O
Pauly (1996)
45.7 kJ mol1
41.145.7 kJ mol1
42.345.7 kJ mol1
Pauly (1996)
Pauly (1996)
Pauly (1996)
e
Ks
qb
Table 2
Binary diffusion coefcients for low pressure (1 atm).
T (C) Dij 106 m2 s1
15
10
O2/CO2
O2/H2O
O2/N2
CO2/H2O
CO2/N2
H2O/N2
H2O/air
O2/air
CO2/air
14.15
19.48
19.10
13.73
14.13
19.13
19.43
19.30
14.25
13.69
18.82
18.52
13.25
13.68
18.48
18.77
18.70
13.80
13.25
18.17
17.94
12.79
13.24
17.84
18.13
18.11
13.35
12.81
17.53
17.36
12.33
12.81
17.22
17.49
17.53
12.91
Table 3
Initial in package mass, volume and molecular gases fractions.
Gases
Molecular fraction
N2
O2
CO2
H2O
76.46a
23.11
0.05
0.38
78.49a
23.11 (28.89/32) = 20.87
0.05 (28.89/44) = 0.033
0.38 (28.89/18) = 0.61
0.78a
0.21
0.00033
0.0061
transport taking place through the headspace and the tested perforation-mediated modied atmosphere packaging.
2.1. Model assumptions
O2 consumption and CO2 production due to respiration depend
on the O2 and CO2 partial pressures through a MichalisMenten
type of model.
CO2 production is a combined oxidative and fermentative process; the oxidative contribution is proportional to the O2 consumption and the fermentative follows a MichalisMenten
type of model.
O2 consumption and CO2 production are temperature dependent following an Arrhenius law.
O2, CO2, H2O and N2 are exchanged between headspace and
packaging surroundings through the packaging lm and its
micro-perforations.
S1
MICRO-PERFORATED FILM
z
x
S3
S4 h pac
S2
d pac
PRODUCE AREA
Fig. 1. Schematic diagram of a perforation-mediated modied atmosphere package (left). The meshed computational domain (X) with 240 elements and boundary
conditions (S1, S2, S3, S4) are depicted on the right diagram.
329
RRCO2 RQ ox RRO2
1
1 PO2 =KmO2 f
"
EaVmCO2
#)
2
Ac 61 eV b =dc
where 1=1=K s 1=K a (kg m2 s1 Pa1) is the transpiration coefcient and Ks (kg m2 s1 Pa1) the skin mass transport coefcient
(ASHRAE, 1997; Diner, 2003)-cf. Table 1. Ka (kg m2 s1 Pa1) is
the air-lm mass transport coefcient, calculated from SherwoodReynoldsSchmidt correlation for a sphere (Becker et al.,
1996):
20
40
60
80
100
120
80
100
120
80
100
120
0.5
O2 / CO2Concentration
0.4
0.3
0.2
0.1
0
0
20
40
60
Time (h)
0.5
0.4
0.3
0.2
0.1
0.0
0
20
40
60
Time (h)
Fig. 2. The average headspace O2 and CO2 concentrations versus time for
experimental (Renault et al., 1994), (points) and predicted data (lines) for 5 (a),
10 (b) and 20 (c) micro-perforations of the PP packaging.
0.1
_ w VPD=1=K s 1=K a
m
0.2
Time (h)
O2 / CO2Concentration
0.3
0.4
where Vb (m3) and e are the volume and porosity of the bulk produce, respectively; dc (m) is the equivalent produce diameter
(Richardson et al., 2002). Porosity values for different bulk agricultural products can be found in literature. The quantities PO2 ,
PCO2 , RRCO2 and RRO2 in Eqs. (1) and (2) are calculated in every
time step (see below) and the rest of the variables are taken from
Table 1.
0.5
O2 / CO2Concentration
330
80
60
40
20
0
0
20
40
60
80
100
120
Time (h)
Fig. 3. The average headspace RH with time at 10 C for 0.5 kg of strawberries.
"
#
n
X
@ xi
rP
0
q
Di j rxj xj xj
r qxi
P
@t
j1
where q (kg m3) is the gas mixture (O2, CO2, N2 and H2O) density:
4
X
P
q
X i Mi
RT 273:15 i1
13
0:62RH0 Ps
X 100
; 18 T 260 C
P0 RH0 Ps
10a
O2 23:20100 X
10b
CO2 0:046100 X
10c
N2 1 O2 CO2 X
10d
In Eqs. (8) and (9), t (h) is the storage time, Dij (m2 h1) the (i, j)
element of the multicomponent Fick diffusivity matrix D, xiorj the
molecular fraction of component i or j = O2, CO2 and H2O and P
(Pa) the total gas mixture pressure. The mass fraction of N2 is
calculated from the balance of the gas components mass fractions,
xN2 1 xO2 xCO2 xH2 O . Renault et al. (1994) and Rennie and
Tavoularis (2009) found that accounting for CO2 solubility in their
models did not affect the nal steady-state gas concentrations. Predictions with and without CO2 solubility accounted for, differ by
respi RRi M i qb Ac
11
less than 2%. Based on the previous ndings, the CO2 solubility
was ignored. Estimation of the Dij coefcients was based on the
where RRi is calculated from Eqs. (1) and (2) and Ac from Eq. (3). The
ChapmanEnskog kinetic theory analysis (Bird et al., 1960) and
top boundary conditions include the gas component i = O2, CO2, H2O
was carried out for four storage temperatures (0, 5, 10 and 15 C)
transport through micro-perforated packaging lm:
covering the cold supply chain-cf. Table 2. Mi (kg mol1) is the
molecular weight of the component i.
_ total ji K f ji =lf qi np Sp Di=air =lf Af R=M i T
m
For the initial (t = 0) in-package conditions, T = 10 C, P0 = 1 atm 12
x0 ji P 0 xi R=M i qi T
and RH0 = 60%, the model is fed with the initial mass fraction valO2
CO2
ues xi-cf. Table 3 and binary diffusivity coefcients Dij-cf. Table 2
35
q
i
for i or j = O2, CO2, H2O and N2.
!
4
X
The initial xi values of O2, CO2 Kai H2O are calculated from Eqs.
30
x
q
M
=
x
M
i
i
i
i
(10a)(10d), considering that gas components mass fractions in
i1
the dry air are H2O < 1%; O2: 23.20%; CO2: 0.046% (ASAE, 1998).
25
20
15
10
5
0
0
20
40
60
80
100
120
Time (h)
Fig. 4. The average headspace O2 and CO2 concentrations when packaging has no
micro-perforations.
331
1.4E-04
1.2E-04
1.0E-04
O2,
O
2 5-perforations
CO2,
CO
2 5-perforations
O
2,
2 10-perforations
CO
CO2,
2 10-perforations
O
2,
2 20-perforations
CO
CO2,
2 20-perforations
O2,
O
2 no-perforations
CO2,
CO
2 no-perforations
8.0E-05
6.0E-05
4.0E-05
2.0E-05
0.0E+00
0
20
40
60
80
100
120
Time (h)
Fig. 6. Contour maps of O2 and CO2 (%) concentrations for different micro-perforations number and diameters for 30 lm (a) and 60 lm lm (b) thicknesses. Storage
temperature 5 C.
were taken from Renault et al. (1994) study for their tested PP lm.
lf (m) is the thickness of the packaging lm-cf. Table 1, qi (kg m3)
the density of the gas component i and x0|i the initial molecular
fraction of i = O2, CO2, N2, H2O in the headspace-cf. in Table 3. Sp
(m2) is the area of a cylindrical micro-perforation of diameter dp
(m2), np the number of packaging micro-perforations and lf (m)
the micro-perforation length taken equal to the thickness of the
packaging lm-cf. Table 1. Di=air (m2 h1) is the diffusion coefcient
of component i in the air (cf. Table 2) taken at 10 C. Di/air can also be
calculated in terms of an effective diffusion coefcient:
332
O2
CO2
22
20
18
16
14
12
10
8
6
4
2
0
0
20
40
60
80
100
120
Time (h)
Fig. 7. Average O2 and CO2 concentration for PP packaging of 30 lm thickness; 6 micro-perforations; 50 lm diameter of micro-perforation. Storage temperature 5 C.
1=Di=eff
xj =Dij
14
j1
The previous approach is justied when the diffusive component i moves with velocity close to the rest of the diffusive gas
components (Bird et al., 1960). In preliminary computations, the
Di/air and Di/eff formulations yield almost identical values (difference 6 1%) and thus a simpler approach of a constant diffusion
coefcient, Di=air was used in Eq. (12), for the tested cases. The
_ total ji is calculated from Eq. (12) at each time step, since the inm
package partial pressure of component i = O2, CO2, H2O,
Pi = xi R=M i qi T, changes with storage time.
2.6. Computational domain and numerical solution procedure
The computational domain geometry and the applied conditions correspond to a retail package and have been chosen to improve computational efciency and facilitate comparison with
the experimental data of Renault et al. (1994). The chosen computational domain (cf. Fig. 1) corresponds to a rectangular retail plastic container. Due to the uniform ambient conditions applied, a 2-D
formulation of the gas transport in a perforation-mediated MA
packaging is feasible. The set of the governing equations along with
their boundary and initial conditions was discretized numerically
by the FEM using COMSOL Multiphysics 3.4 (Comsol Inc., 2007,
USA). The mesh was unstructured and composed of triangular elements and Langrange quadratic shape functions. The choice for
solving the resulting linearised equation system was the Generalized Minimal Residual Method (GMRES) with the incomplete
LU-factorization as preconditioner (Pashos et al., 2009), due to its
reduced memory requirements and low computational cost.
Mesh-independence of the solutions was tested by solving the
problem for three meshes composed of 60, 240 and 960 elements.
In each case, the maximum time step taken was 3600 s, as dictated
by the solver. From the trials, small differences (>1%) were detected among the calculated concentrations of O2, CO2, and H2O.
Finally, the mesh of 240 elements (cf. Fig. 1) was selected and used
for obtaining the results presented below.
3. Results and discussion
The case studied here was so chosen as to enable comparison of
model predictions with the experimental data in Renault et al.
333
Total Flux
6.0E-05
5.0E-05
O2
80%
4.0E-05
Mass flux %
100%
3.0E-05
2.0E-05
60%
40%
20%
1.0E-05
0%
0.0E+00
20
40
60
80
100
120
20
40
Total flux
60
80
100
0.0E+00
C2
100%
CO2
80%
-2.0E-05
Mass flux %
-1.0E-05
-3.0E-05
-4.0E-05
-5.0E-05
60%
40%
20%
-6.0E-05
0
20
40
60
80
100
0%
120
Time (h)
Total flux
20
40
60
80
100
120
Time (h)
5.0E-07
100%
H2
4.0E-07
H2
3.0E-07
80%
2.0E-07
Mass flux %
Flux(kg/m 2 h)
120
Time (h)
Time (h)
1.0E-07
0.0E+00
-1.0E-07
-2.0E-07
-3.0E-07
60%
40%
20%
-4.0E-07
-5.0E-07
0%
2
0
12
11
96
10
88
72
80
64
140
56
120
48
100
40
80
Time (h)
32
60
24
40
20
16
-6.0E-07
Time (h)
Fig. 8. O2, CO2 and H2O uxes through PP packaging with micro-perforations and lm (left) and the % mass ux (right).
334
In overall, the model can be used for fruits and vegetables of any
shape, whole or fresh-cut. Based on the adopted boundary conditions, the model can easily be adjusted to different types of packaging (permeable or not) given that the appropriate property
values are available. Moreover, calculations can be performed for
different storage temperature regimes, relative humidity and gas
concentrations met in the fresh cold chain, providing, in this
way, useful predictions about the appropriateness of the used
packaging lm and/or the applied storage conditions.
Acknowledgments
The authors would like to thank the reviewers for their insightful and helpful comments.
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