4. Results and discussion
4
.
1
. Film permeability The permeability of the LDPE film used in the
packaging experiment to O
2
and CO
2
increased exponentially with increasing temperature Fig. 1.
The estimates for activation energy Ea
O
2
film
, Ea
CO
2
film
and permeability at reference temperature P
O
2
,ref film
, P
CO
2
,ref film
for O
2
and CO
2
are given in Table 1. The two activation energies appeared to be very similar.
The parameter values were consistent with data reported earlier by Donhowe and Fennema 1994
and Exama et al. 1993, although the permeability at the reference temperature was about three times
higher than reported by Beaudry et al. 1992.
4
.
2
. Packaging experiment The time needed to achieve steady-state condi-
tions in the packages was longer at lower storage temperatures. For the packages with the smallest
areas of permeable film, steady state O
2
and CO
2
partial pressures were reached after 11, 14, 27 and 32 days at 30, 20, 12 and 0°C, respectively. This
seems fairly long, but is in agreement with what is expected based on the film permeability, the respi-
ration rate of bell peppers and the dimensions of the packages.
At steady state, the measurements in the packag- ing experiment showed an almost one-to-one rela-
tionship between the gas conditions in the pack p
O
2
pkg
and p
CO
2
pkg
and in the cavity of the fruit p
O
2
cav
and p
CO
2
cav
; data not shown. This was due to the relatively large permeance of the fruit’s stem plate
that, on average, was 0.014 nmol·s
− 1
·Pa
− 1
for both O
2
and CO
2
, comparable to the permeance of a 0.25 m
2
LDPE bag at 20°C. As a consequence of the one-to-one relationship
between the gas conditions in the pack and in the cavity of the fruit, plots of other gas variables as
a function of composition of the cavity atmosphere were a virtual copy of those in terms of composi-
tion of the package atmosphere. As the set of experimental data on package atmospheres was the
most complete, all results are shown in terms of package atmosphere composition.
The soda lime treatment was applied to elucidate the possible effect of CO
2
on gas exchange. How- ever, there was no evidence that the CO
2
levels up to 25 kPa that occurred in the experiments had any
effect on the gas exchange of the capsicums data not shown. As a result, only the straightforward
model formulation for gas exchange without CO
2
inhibition was applied.
Fig. 1. Effect of temperature on the O
2
and CO
2
permeabilities of the low-density polyethylene film used for the packaging
experiment. Symbols are measured values. Lines were calculated using Eq. 10 using the corresponding parameter values from
Table 1.
Table 1 Parameter estimates and their standard errors S.E. resulting
from the non-linear regression analysis of the data on the effect of temperature on permeation of O
2
and CO
2
through the LDPE film used in this study
a
P
i,ref film
S.E.
b
Ea
i film
S.E.
c
Gas i R
2 adj
d
n
e
46 97.1
30450 7.3 1.46 4.6
O
2
4.25 3.4 31751 5.0
98.5 CO
2
46
a
The standard errors S.E. are expressed as a percentage, relative to the estimated values.
b
P
i,ref film
is the permeability 10
− 15
mol·s
− 1
·m·m
− 2
·Pa
− 1
of the film to gas i at reference temperature T
ref
= 15°C.
c
Ea
i film
is the energy of activation J·mol
− 1
of the perme- ability P
i film
.
d
R
2 adj
is the percentage variance accounted for.
e
n is the number of observations.
Fig. 2. Gas exchange rates A – D: r
O
2
; E – H: r
CO
2
of ‘Tasty’
green capsicum Capsicum annuum L. in MAP at different package O
2
levels p
O
2
pkg
at temperatures ranging from 0 to 30°C. Symbols are measured values. Lines were plotted ac-
cording the model fitted using the parameter values from Table 2.
packed fruit Fig. 4. Large areas resulted in almost atmospheric conditions inside the pack-
ages. By reducing the film area, O
2
levels dropped towards 0 kPa while CO
2
levels first increased to about 5 – 7 kPa. This accumulating CO
2
mainly originated from oxidative respiration. At the ex-
tremly small packaging areas 0.0018 and 0.806 m
2
, CO
2
levels increased even more up to 20 – 25 kPa due to the slight fermentation present. Al-
though the absolute fermentation is low as indi- cated by Fig. 2, the fermentation indicated by the
shift in RQ Fig. 3 was enough to generate high CO
2
levels when the product was packed with small permeable film areas. Film areas larger than
0.075 m
2
result in O
2
levels above 10 kPa, not effectively inhibiting the gas exchange of packed
capsicums Fig. 2. The multi-response, multivariate, non-linear re-
gression analysis of the packaging data resulted in the parameter estimates as shown in Table 2 and
the fitted lines from Figs. 2 and 4. During the iterative process of non-linear regression the
parameters on fermentation were not clearly defined due to lack of data on fermentation. As
the packs with the smallest film areas were defin-
Fig. 3. Respiration quotients RQ of MA packed capsicums as a function of the package O
2
level p
O
2
pkg
for temperatures ranging from 0 to 30°C. The dotted line marks the estimated
value for the model parameter RQ
ox
of 0.88 Table 2.
Both O
2
uptake and CO
2
production decreased in response to decreasing temperature and de-
creasing steady state p
O
2
pkg
Fig. 2. Increasing tem- perature from 0 to 30°C resulted in a threefold
increase in respiration. This was due to the tem- perature effect on r
O
2
max
and r
CO
2
max
as there was no evidence for a change in Km
O
2
with increasing temperature. From Fig. 2, there is no clear indica-
tion that capsicum exhibits substantial fermenta- tion at low O
2
levels as there was no visible Pasteur effect. However, looking at the RQ for
the different temperatures Fig. 3 shows an in- crease in RQ at O
2
levels below 2 kPa revealing a substantial fermentation relative to the aerobic
respiration. The different O
2
and CO
2
levels measured in the package atmospheres, resulted from the differ-
ent film areas applied coupled with the natural variation in the gas exchange characteristics of the
Fig. 4. Steady-state gas conditions A – D: p
O
2
pkg
; E – H: p
CO
2
pkg
inside MA packages of individually packed capsicums using different film areas. Packs were held at temperatures ranging
from 0 to 30°C. Symbols are measured values. Lines were plotted according the model fitted using the parameter values
from Table 2.
film permeabilities to the respiratory gases Table 1. As a result, capsicums packed in the LDPE
film tested in these experiments would be stable and reliable in terms of gas conditions, irrespec-
tive of any temperature changes. This situation is in marked contrast to that described for blueber-
ries Beaudry et al., 1992; Cameron et al., 1994 in which package atmosphere composition was
highly sensitive to temperature as a result of the very different energies of activation for respiration
and film permeability.
One can argue whether the temperature-inde- pendent atmosphere inside the package is impor-
tant in its own right. The aim of MAP is to retain quality. With constant gas conditions at increas-
ing temperatures, respiration rate and the rate of quality decay will still increase due to the increas-
ing temperature. What we really need is a package design that counteracts this temperature effect by
generating lower O
2
and higher CO
2
levels with higher temperatures, further reducing respiration
rate and the rate of respiration-related quality breakdown processes, without driving the product
anaerobic. However, if the package conditions are already close to the fermentation threshold
Yearsley et al., 1997 there is no space to further decrease O
2
levels. In fact, you would need to provide a greater margin for error at higher tem-
peratures. Depending on the temperature depen- dence of the fermentation threshold Yearsley et
al., 1997, O
2
levels should increase with increas- ing temperature to prevent fermentation Beaudry
et al. 1992.
4
.
3
. Additional respiration measurements Respiration measurements at different tempera-
tures in air on a second lot of green capsicums showed quite a different response to temperature
Fig. 5 from the fruits used in the packaging experiment. This was reflected in the activation
energy Ea
r
O 2
,
which was estimated at 61180 9 2948 J·mol
− 1
, twice the value found for the fruit used in the packaging experiment Table 2. As-
suming the same RQ Table 2, r
O
2
,ref
was esti- mated at 0.098 9 0.005 mmol·kg
− 1
·s
− 1
. This was less than the value previously found Table 2.
itely accumulating CO
2
due to fermentation, it was decided to fix the value of Km
O
2
f
by hand. The parameter Km
O
2
f
represents the O
2
level at which the fermentative CO
2
production reaches half its maximum value. As fermentation is only
occuring below about 2 kPa, Km
O
2
f
has to be fixed at such a level that the inhibition of fermen-
tation above 2 kPa O
2
is complete. The Km
O
2
f
was fixed at the plausible value of 0.1 kPa, en- abling a more accurate estimation of the other
fermentation-related model parameters. In spite of the clear temperature effect on film
permeability Fig. 1 and gas exchange Fig. 2, the gas conditions inside the package Fig. 4 were
almost insensitive to temperature between 0 and 30°C. This is explained by the fact that the energy
of activation for capsicum respiration Table 2 was very close to the energies of activation for
Table 2 Parameter estimates and their standard errors S.E. resulting from the non-linear regression analysis of respiration and cavity
atmosphere data coming from the packaging experiment
a
Parameter Estimate S.E.
Estimate S.E. Parameter
Parameters describing respiration
:
b
Parameters describing fermentation
:
c
r
O
2
,ref max
RQ
ox
0.145 3.7 0.88 1.8
r
CO
2
,ref max
30947 2.6 0.0067 7.5
Ea
r
O2 max
3.4 14 Km
O
2
Ea
r
CO2 max
39869 15 Km
O
2
f
0.1 −
d
n
f
840 96.1
R
2 adj
e a
The standard errors S.E. are expressed as a percentage, relative to the estimated values.
b
r
O
2
,ref max
is the maximum O
2
consumption rate mmol kg
− 1
s
− 1
at reference temperature T
ref
= 15°C; Ea
r
O2 max
is the energy of activation J·mol
− 1
of the maximum O
2
consumption rate r
O
2
max
; Km
O
2
is the Michaelis constant for O
2
consumption kPa.
c
RQ
ox
is the respiration quotient ratio of CO
2
production to O
2
consumption for oxidative respiration; r
CO
2
,ref max
is the maximum CO
2
production rate mol kg
− 1
s
− 1
at reference temperature T
ref
= 15°C; Ea
r
CO2 max
is the energy of activation J·mol
− 1
of the maximum CO
2
production rate r
CO
2
max
; Km
O
2
f
is the Michaelis constant for the inhibition of fermentative CO
2
production by O
2
kPa.
d
Fixed value; no standard error.
e
R
2 adj
is the percentage variance accounted for.
f
n is the number of observations.
Differences between the two batches can be due to differences in fruit maturity related to the
different harvest dates. This raises the interesting possibility of a strong maturity effect on the acti-
vation energy of respiration. If this were shown to be consistent across crop types, this would
provide an interesting interaction effect in MAP. Climacteric fruits, by analogy, could have a very
different activation energy for their climacteric respiration than that of the basal pre-climacteric
process upon which it builds.
5. Conclusions