Study of the shelf life of ripe olives using an accelerated test approach

P. Garc a-Garc a
*
, A. Lo pez-Lo pez, A. Garrido-Fernandez
Departamento de Biotecnologa de Alimentos, Instituto de la Grasa (CSIC), Apdo. 1078. Avda. Padre Garca Tejero, 4, Sevilla, Spain
Received 19 March 2007; received in revised form 6 June 2007; accepted 7 June 2007
Available online 15 July 2007
Abstract
An Accelerated Shelf Life Test (ASLT) was carried out to estimate the shelf life of ripe olives (Californian style) as a function of rm-
ness, colour and pH. Changes followed an apparent rst-order kinetic. Their rates and activation energies were estimated from the
response surface obtained from one-step non-linear tting of the kinetic model to the experimental data as a function of temperature
and time. There was a similar trend in the evolution of rmness, colour and pH rates with changes in temperature. Graphic represen-
tations of expected shelf lives as a function of temperature and relative degradation for rmness, colour and pH are provided. Based on
them, producers can deduce the appropriate shelf life for each specic storage condition and quality level. The current shelf life on the
label (1080 days) was higher, when assessed for product rmness, than that found for a relative quality change of 0.20 at 30 C in initially
soft ripe olives. Exposure to higher temperatures markedly reduces shelf life.
2007 Elsevier Ltd. All rights reserved.
Keywords: Ripe olives (Californian style); Accelerated shelf life tests; Firmness; Colour; pH
1. Introduction
World table olive production reached around
1,700,000 ton in the 2003/2004 season. Thirty percent of
them were processed as ripe olives (Californian style).
The main producers of this style were the United States
(120,000 ton) and Spain (100,000 ton). According to
the International Olive Oil Council statistics, there is a
trend for the progressive increase in the elaboration of this
style (IOOC, 2005).
The process for ripe olive production consists of succes-
sive treatments of the fruits with a dilute solution of NaOH
(lye) (Sanchez-Gomez, Garc a-Garc a, & Rejano-Navarro,
2006). During the intervals between lye treatments the
fruits are suspended in water through which air is bubbled.
Throughout this operation the fruits darken progressively
(Brenes, Garc a, & Garrido, 1992). The colour formed is
not stable and fades progressively after oxidation. To pre-
vent this deterioration, fruits are immersed in ferrous lac-
tate or gluconate for several hours (Cruess, 1962; Garc a,
Brenes, & Garrido, 1986). The product has a nal pH
above 4.6 and its preservation is only achieved by steriliza-
tion (CODEX/COI, 1990). This treatment is also supposed
to stabilize the product with respect to its quality attri-
butes. Consequently, a shelf life of three years is usually
acceptable for ripe olives. However, there is no published
scientic evidence to support such a supposition.
The UK Institute of Food Science and Technology
(IFST) dened shelf life as the period of time during
which the food product will remain safe, retain its desired
sensory, chemical and microbiological characteristics, and
comply with any label declaration of nutrition data
(IFST, 1993). In The European Union, The Labelling
Directive was adopted in March 2000 (OJ No L 109,
6.5.2000) and it states (Art. 9) the indication of minimum
durability of foodstus. The North American Free Trade
Agreement (NAFTA) encourages the use of specic terms
for durability indications throughout the continent, but
no universal terms exist yet. In Canada, the term durable
life is used for this period and the expression best before
must be printed on the label (Anonymous, 1996). In the
United States there is no federal regulation on the subject
0260-8774/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2007.06.023
*
Corresponding author. Tel.: +34 954 690 850; fax: +34 954 691 262.
E-mail address: pedrog@cica.es (P. Garc a-Garc a).
www.elsevier.com/locate/jfoodeng
Journal of Food Engineering 84 (2008) 569575
of durability indications and a wide range of styles are used
in the dierent States. Thus, there is still certain confusion
about the terminology, determination and legal implica-
tions of shelf life, although requirements are progressively
converging and demanding proper compliance.
Basically, the appropriate shelf life depends on the man-
ufacturer who makes the product. A product should retain
an adequate level of its characteristics at least as long as its
stated shelf life. To be condent of its statement, the com-
pany should have done the necessary work in order to
determine the correct shelf life. Shelf life experiments can
take a long time. Accelerated shelf life tests (ASLT) are
often used to circumvent this problem (Labuza & Schmidl,
1985). The kinetic model is the most common method used
for performing ASLT. The basic process involves the fol-
lowing steps: (i) selection of the kinetically active factor,
(ii) running a kinetic study at such levels that the rate of
deterioration is fast enough, (iii) extrapolation of the
kinetic parameters to normal storage conditions, and (iv)
use of the extrapolated kinetic data to calculate the shelf
life under real storage conditions (Mizrahi, 2000). The pro-
cedure is explained in detail by diverse authors (Mizrahi,
2000; Ross, 1998; Singh, 1994; Taoukis, Labuza, & Saguy,
1997; Vanaclocha & Requena, 1999).
Sanchez, Rejano, and Montan o (1991) studied the inu-
ence of heat treatments on green olives, nding that pas-
teurization produced a degradation in colour and
rmness that followed a rst-order kinetic. Sanchez, Mont-
an o, and Rejano (1997) also studied the eect of acidity,
salt content, light, and storage time on packed green olives.
They reported that there was an increase in pH, brines
exposed to light became paler, the fruits colour slowly
darkened, and rmness degraded slowly. Untreated green
olives of Conservolea cultivar packed in vacuum or modi-
ed atmosphere also presented a progressive loss of fruit
rmness and colour with the time; the best quality charac-
teristics were maintained in vacuum-packed olives (Pan-
agou, 2004). However, no information exists on ripe olive
changes after packing.
The aim of this work was the application of an ASLT to
study the changes in colour and rmness (the main quality
attributes), and pH (the key physicochemical characteristic
for low acid foods) of ripe olives by the application of a
kinetic approach and, based on it, to make estimations
about its shelf life as compared with the currently stated
three year duration of this period.
2. Materials and methods
2.1. Samples
Recently processed ripe olives (supplied by local proces-
sors) were from the following cultivars and commercial
characteristics: canned plain Mazanilla cultivar (MPC)
(ACYCO S. Coop. Andaluza, Sevilla); canned and packed
in jars plain Caceren a (CPC and CPG, respectively) (EXO-
LIVA, S.A., Plasencia, Caceres); canned and packed in jars
plain Hojiblanca (HPC, HPG, respectively), and canned
pitted Hojiblanca (HPtC) (AGRO-SEVILLA S.Coop.
Andaluza, La Roda de Andaluc a, Sevilla).
2.2. Physicochemical analysis
Analysis of olive brines for pH was carried out by the
routine method described by Garrido Fernandez, Fernan-
dez D ez, and Adams (1997). Surface olive colour measure-
ments were performed using a BYK-Gadner, Model 9000,
Colour View
TM
spectrophotometer (Silver Spring, MD,
USA). Interference from stray light was minimized by cov-
ering samples with a box with a mat black interior. Colour
was expressed as reectance at 700 nm (R
700
). Lower reec-
tance values indicate darker colours (Fernandez D ez &
Garrido Fernandez, 1971). Firmness was measured using
a Kramer shear compression cell coupled to an Instron
Universal Testing Machine (Canton, MA, USA). The cross
head speed was 200 mm/min. The rmness of the olives,
shear compression force, was expressed as N/100 g pitted
olives and was the mean of 10 measurements, each of which
was performed on four pitted olives.
Calcium and iron in the olive esh and brine was deter-
mined by ame atomic absorption spectrometry (Garc a,
Romero, Brenes, & Garrido, 2002).
2.3. Experimental design
A sucient number of cans or jars from the same elab-
oration batch from Hojiblanca, Manzanilla and Caceren a
cultivars and dierent commercial presentations were
stored at 20, 30, 40, and 50 C in thermostatic chambers
(Selecta, Barcelona, Spain). Periodically, replicate samples
of each treatment were drawn and rmness, colour, and
pH, were analyzed. Cans or jars used in the analyses were
discarded and the following determinations always per-
formed in two new containers. Sampling periods were dis-
tributed according to the trend observed in the rmness,
colour, and pH changes so that the total number of mea-
surements performed at the end of the experiment was
enough to achieve a good non-linear tting of data.
2.4. Model estimation
From tentative adjustments of experimental data to dif-
ferent kinetic models, it was deduced that the changes in
rmness, colour, and pH of ripe olives during storage at
the dierent temperatures followed an apparent rst-order
kinetic. Instead of a separate estimate of the reaction rate
(k) at dierent temperatures and then using Arrhenius to
estimate the other parameters, a one-step multiple linear
regression, which t data (rmness, colour, or pH) versus
time for all tested temperatures was followed. The equation
took the following form (Taoukis et al., 1997):
A A
0
expfk
ref
t expE
A
=R1=T 1=T
ref
g 1
570 P. Garca-Garca et al. / Journal of Food Engineering 84 (2008) 569575
where A was the parameter value at each temperaturetime
cell, A
0
the initial value (which was considered a parameter
and estimated accordingly), E
A
the activation energy, R the
universal gas constant, T the temperature in absolute scale,
and T
ref
the reference temperature (20 C) in absolute scale
(293 K). This equation has both time and temperature as
variables and the non-linear regression gave simultaneous
estimates of A
0
, k
ref
, and E
A
, as well as their condence
limits.
The use of this method, by eliminating the need to esti-
mate a separate A
0
for each experiment, increased the
degree of freedom for the estimation of k. The use and sta-
tistical benets of employing a one-step method were dem-
onstrated for computer simulated food degradation data,
following rst-order kinetics by Haralampu, Saguy, and
Karel (1985).
The inuence of temperature on the reaction rate was
described using the modied Arrhenius relationship (Singh,
1994):
k k
ref
expE
A
=R1=T 1=T
ref
2
The Q
10
, which also relates reaction rate with temperature
and is dened as the relation of the reaction rates at
(T + 10) and T, was dened as
ln Q
10
10b E
A
=R10=TT 10 3
where b is the slope of the shelf life plot (lnk versus
temperature).
The z value, the temperature change that causes a 10-
fold change in the reaction rate constant, was estimated by
z ln 10=b ln 10 T
2
R=E
A
4
Shelf life (t
s
), for a certain relative level of a quality attri-
bute (attribute value at that time, Q
e
, relative to the initial
one, Q
0
) and temperature was dened as
t
s
flnQ
e
=Q
0
=kg 5
or shelf life (t
s
) for a certain nal level of quality as a func-
tion of temperature
t
s
lnQ
e
=Q
0
=fk
ref
expE
A
=R1=T 1=T
ref
g 6
where the quality level is dened by the rate of the fraction
of the value.
2.5. Statistical data analysis
The Non-linear Estimation Module of the Statistica
software, version 6.0, (StatSoft Inc. OK, USA) was used
to adjust the equation to the experimental data. The Basic
Model was also used for plotting the surfaces, carrying out
the corresponding analyses of variance (ANOVA) and
other data processing. Parameter values are given as aver-
age standard error.
3. Results and discussion
Comparison among the initial values of rmness, colour
and pH of the dierent samples showed that the products
were not homogeneous (Table 1), especially with respect
to the fruits consistency and signicant dierences in rm-
ness between samples were observed. Pitted Hojiblanca
(HPtC) and plain Manzanilla (MPC) had the highest rm-
ness with approximately the same value (around 3000 N/
100 g pitted olives) followed by Cacerena samples (CPC
and CPG) and Hojiblanca plain in jars (HPG), which
had similar values among them, and Hojiblanca plain
olives (HPC). Possibly, samples were from lots destined
to dierent markets but the dierences might rather indi-
cate the use of diverse storage conditions and the absence
of a standardized process to produce these olives. Hetero-
geneity in this quality attribute can aect the condence
of consumers and introduce complexity in the shelf life
compliance. Such rmness dierences can hardly be corre-
lated to the calcium content in olive esh (Table 1), which
was similar for the highest (MCP) and lowest (HPC) rm-
ness values. However, rmness values were signicantly
(p < 0.05) related to iron content (Table 1). This correlation
may indicate a yet unexplored eect of iron in ripe table
olives in addition to its currently known colour xation
action (Cruess, 1962; Garc a et al., 1986; Garrido, Brenes,
& Garc a, 1995). No changes in concentration of calcium
and iron in the olive esh during the ASLT study was
found.
Colour was more homogeneous (Table 1), the range for
this attribute was only of one reectance unit (3.504.49),
and there was just one sample slightly lighter (HPG).
Table 1
Initial values of rmness, colour, and pH of the dierent cultivars and commercial presentations used in the accelerated shelf life tests
Acronym Mean SE
Firmness (N/100 g esh) Colour (R
700
) pH Calcium in esh mg/kg Iron in esh mg/kg
HPC 1839 8 3.50 0.04 7.24 0.02 937.7 22.8 85.5 3.4
HPtC 2993 33 3.65 0.08 7.43 0.03 995.3 26.0 75.4 1.4
HPG 2346 4 4.49 0.04 6.73 0.01 1126.0 21.1 53.9 0.4
CPC 2410 10 3.79 0.10 6.96 0.01 529.5 15.3 60.8 1.4
CPG 2255 65 3.59 0.07 7.12 0.04 571.5 14.9 69.5 0.4
MPC 3055 60 3.70 0.04 7.09 0.02 980.1 16.2 163.3 6.2
Notes: Values are the average of two replicates, for which data are, in turn, the average of 10 measurements of rmness, and colour, three in the case of
calcium and iron, and two for pH. SE, standard error. Acronyms for commercial presentations and cultivars: canned plain Hojiblanca (HPC), canned
pitted Hojiblanca (HPtC), packed in jars plain Hojiblanca (HPG), canned plain Caceren a (CPC), packed in jars plain Caceren a (CPG), canned plain
Manzanilla (MPC).
P. Garca-Garca et al. / Journal of Food Engineering 84 (2008) 569575 571
Colour was (p < 0.01) related to the iron content. This cor-
relation was expected because higher levels of iron usually
yield better colouration (Garrido et al., 1995). The pH
values were lower in one sample of Hojiblanca (HPG)
and Caceren a (CPC) but dierences were of only about
0.75 units, which can be explained by slight variations in
processing, especially during the neutralization phase.
Firmness, colour and pH data were plotted as a function
of time and according to temperature. Zero and apparent
rst and second-order kinetic models were applied to such
data. The rst-order kinetic model always resulted in a bet-
ter t, although in a few cases (for colour at low tempera-
ture only) the zero order might also be sucient. Then, the
apparent rst-order model was chosen and transformed to
express changes as a function of temperature and time
simultaneously. The application of Eq. (1) to rmness data
from each sample versus temperature (T) and time (t) per-
mitted, according to Taoukis et al. (1997), the simultaneous
estimation of k, A
0
, and E
A
for all of them. Fit was always
fairly good (p < 0.05) and the percentage of adjusted
explained variance high. The lack of t was always insignif-
icant. Thus, the parameters could be estimated with good
precision. As an example, Fig. 1 shows the experimental
data and the surface adjusted by applying Eq. (1) to the
evolution of rmness as a function of T in canned plain
Hojiblanca (HPC sample). Data values were fairly close
to the estimated response surface. Similar results were
obtained with the other samples. These results support
the fact that degradation followed an apparent rst-order
kinetic and the usefulness of the one-step method to deduce
the kinetic parameters. There were signicant dierences in
rmness degradation rates between samples with high ini-
tial rmness (HPtC and MPC) and those with lower consis-
tency rather than between cultivars and presentation
forms. High initial rmness led to lower degradation rates.
Garc a, Brenes, and Garrido (1994) showed that the pres-
ence of calcium, at sterilization temperature (121 C), not
only had the eect of increasing the rmness after packing
but also protected fruits from deterioration by reducing the
degradation kinetic rate. However, in this case, correlation
with the calcium content cannot explain the dierent
behaviours.
Firmness rates without signicant dierences among
them were averaged, giving a k
ref,F
of (0.90 0.10)
10
4
and (1.58 0.15) 10
4
for the samples with high
and low initial rmness, respectively (Table 2). Sanchez
et al. (1997) also found dierences between pasteurized
and non-pasteurized green olives, but whole, pitted and
stued pasteurized olives showed a similar behaviour using
a single pooled rate constant for all three types. Estimates
of A
0
and E
A
were also averaged (Table 2). Estimated A
0
for high and low initial rmness were 3000 27 and
2174 127 N/100 g esh whereas the averages from real
initial values were 3024 44 and 2213 128 N/100 g esh.
Then estimated and real values were very close and no sig-
nicant dierences in estimations could be found regardless
of the A
0
value used in the further calculations. E
A
were
15,109 1625 and 11,283 388 cal/mol, for high and
low initial rmness, respectively. The increase in E
A
due
to the presence of calcium, for rmness changes during
the sterilization of packed ripe olives was previously
observed by Romero, Garc a, Brenes, and Garrido (1995)
HPC
2
0
0
0
1
8
0
0
1
6
0
0
1
4
0
0
1
2
0
0
1
0
0
0
F
i
r
m
n
e
s
s

(
N
/
1
0
0

g
p
.
o
)
2
0
T
e
m
p
e
r
a
t
u
r
e

(
O
C
)
3
0
4
0
5
0
0
1
0
0
2
0
0
3
0
0
4
0
0
5
0
0
6
0
0
7
0
0
T
i
m
e

(
d
a
y
s
)
Fig. 1. Experimental data and tted surface showing the rmness evolution with time at dierent temperatures.
572 P. Garca-Garca et al. / Journal of Food Engineering 84 (2008) 569575
but this study had also shown that a similar increase in the
activation energy can simply be due to higher initial rm-
ness. Softening in ripe olives may be due, as in other fruits
and vegetables, to degradation of the pectin chain from the
cell wall by b-elimination. Results obtained by Garc a et al.
(1994) supported such a hypothesis.
To calculate the kinetic parameters related to colour,
expressed as R
700
, Eq. (1) was tted to all colour data as
a function of T and t. Global adjustment in each sample
was poorer than that obtained in the case of rmness
although there was always a good statistical t (p > 0.05
for lack of t). Only slight improvement of tting was
achieved by using weighted regression. Degradation rates
k
ref,colour
were negative because of the increase in reec-
tance (lighter olives) with time. The poorer tting was
observed in pitted Hojiblanca (HPtC). This result may be
a consequence of the special characteristics of this commer-
cial presentation (the only pitted sample) in which the sur-
rounding solution can reach the esh through the interior
hole even easier than through the exterior surface where
the skin may represent a certain barrier. Thus, changes
may be due to eects not only from the external surface
by also from the interior of the fruit. The other samples
had fairly high adjusted explained (%) variance. The poorer
tting of colour data with respect to that obtained in the
case of rmness led to slightly less precision in the estima-
tion of the equation parameters especially in k
ref,colour
and
E
A
. There were no signicant dierences between the
k
ref,colour
of samples. So, the mean rate was estimated
(Table 2) and used for further extrapolation calculations.
Values of A
0
and E
A
were also averaged (Table 2). The esti-
mated value for A
0
was 4.18 0.21 whereas the real value
obtained averaging colour at time t = 0 was
3.78 0.18R
700
units. Estimated A
0
was slightly higher
than the real value but their condence intervals at
p = 0.05 overlapped. As a result, estimated A
0
was also
used for shelf life calculations as a function of this attri-
bute. The average E
A
was 12,835 2023 cal/mol, which
was of the same order as the average E
A
obtained for rm-
ness. This colour fading was quite dierent from that
described by Sanchez et al. (1991) and Sanchez et al.
(1997) for green olives where the initial yellow colour was
subject to browning with time. In ripe olives, colour
became progressively lighter as time progressed possibly
due to the gradual destruction of the polyphenol polymers,
formed in the alkaline medium from the hydroxytyrosol
and caeic acid during the oxidation stage (Brenes et al.,
1992).
Values of pH decrease with time during storage. Their
changes as a function of T and t were also adjusted by
Eq. (1). In this case, there was a fairly good t in all sam-
ples (p > 0.05 for lack of t) and their adjusted (%)
explained variances were high. There was an overlapping
among the k
ref,pH
condence intervals of the samples with
only signicant dierences between the two extreme values:
0.68 10
4
(HPtC) and 1.49 10
4
(CPC) days
1
. The
pitted olive (HPtC) sample had the highest initial pH but
CPC had a lower initial pH. In addition, initial pHs of sam-
ples were relatively close. Then, segregation among pH
degradation rates based on dierent initial conditions was
not considered justied. The mean of all estimations was
obtained, (1.10 0.22) 10
4
, and this value considered
as the average degradation rate of pH. Values of A
0
and
E
A
were also averaged. The average estimated value for
A
0
was 6.79 0.21 whereas the average real value was
7.01 0.1. So their dierences were also insignicant.
The activation energy estimated for pH degradation was
10.914 542 cal/mol, which was slightly lower than that
found for the average degradation of colour and rmness.
Estimated average values of A
0
and E
A
were later used for
predictions.
The relationship between k and temperature for rm-
ness, colour and pH degradation was obtained by
graphing Eq. (2) as a function of T. We changed the
sign of k for colour to facilitate comparisons among
absolute values because the sign only indicates the direc-
tion of the degradation. This graph showed that the
averaged k
ref
for rmness, colour and pH at the refer-
ence temperature (20 C) were rather similar (Fig. 2).
Their changes with temperature followed a similar trend,
although as temperature was higher dierences between
the eects on the three attributes were increasing. The
highest increase corresponded to the k
ref,F
of fruits with
high initial rmness. This means that at relatively high
temperatures, these samples could become softer more
quickly. For colour, degradation means (due to its
actual negative sign) an increase in reectance values
or lighter olives.
Degradation of rmness, colour and pH were compared
in terms of their respective Q
10
and z values at the reference
Table 2
Kinetic parameters (k
ref
, A
0
, and E
A
) for rmness, colour and pH degradation versus time and temperature
Attribute (k
ref
SE) 10
4
(days
1
) A
0
SE (N/100 g esh) E
A
SE (cal/mol) Range of variance explained
a
(%)
Firmness (high initial values) 0.90 0.10 3000 27 15,109 1625 93.1795.46
Firmness (low initial values) 1.58 0.15 2174 127 11,283 388 96.6697.26
Colour (R
700 nm
) 0.99 0.15 4.18 0.21 12,835 2023 69.3090.57
pH 1.10 0.22 6.79 0.12 10,914 542 84.3689.70
Average values were obtained from the non-linear t of the surface equation to the particular experimental data from the dierent cultivars and
commercial presentations.
Notes: SE, standard error; total data points for each attribute, 54; degrees of freedom for error, 51.
a
Expressed as R
2
adjusted.
P. Garca-Garca et al. / Journal of Food Engineering 84 (2008) 569575 573
temperature, 20 C. An increment of 10 C increases the
degradation rate of ripe olives with high and low initial
rmness by 2.35 or 1.90-fold, respectively. The increase in
temperature required to multiply these rmness degrada-
tion rates by 10, z, were about 26.88 and 36.02 C. Q
10
for colour and pH were 2.07 and 1.86, respectively. Tem-
perature increase for a 10-fold increase in degradation rates
for colour and pH were 31.2 and 37.2.
The values obtained in the accelerated experiment were
used to calculate the shelf life as a function of the relative
degradation of rmness, colour, and pH (Fig. 3), using
the averaged A
0
, k
ref
, and E
A
values for each characteristic.
The use of the estimated values for A
0
instead of the real
initial values in these calculi is justied because no signi-
cant dierences between either were found for any attribute
(rmness, colour and pH). This shelf life estimation is only
an approximation since, usually, ripe olives (or any other
food) are not stored under constant temperature but infor-
mation on temperature changes through time can hardly be
obtained and there is not a certainty that temperature pro-
le would always be the same. So, an approach considering
a reasonable average storage temperature could give good
practical shelf life estimations.
Shelf life, as assessed by the relative rmness degrada-
tion (Fig. 3a), was always higher for olives with initial high
rmness. At 30 C, which is a fairly moderate high average
temperature for storage, and for reduction of 15% in the
original rmness (relative degradation = 0.85), the shelf life
for high and low initial rmness canned olives would be
766 and 542 days, respectively. Thus, soft olives had a
shorter shelf life than initially harder fruits. Desirable rm-
ness level possibly depends on markets and consumer hab-
its but shelf life studies for markets demanding high
rmness products will not be appropriate for those accus-
tomed to low rmness. These markets would require their
own shelf life, which will be shorter. However, at the
moment, no such dierentiation was observed because all
cans or jars were given 1080 days (3 years) shelf life.
After being on the shelves, at 30 C, for 1080 days high
and low rmness olives would have suered 20% and 30%
rmness degradation, respectively. Thus, the current xed
shelf life could be appropriate for high rmness olives, con-
sidering that a 0.2 relative degradation is acceptable, but
the period should be reduced if the same quality criterion
is applied to initially softer olives. These shelf lives are
markedly higher than those found by Sanchez et al.
(1997) for pasteurized green olives (3150 days). Dier-
ences may be explained by the relative low pH of the green
olives that could degrade rmness at a faster rate (Brenes,
Garc a, & Garrido, 1994). Storage at temperatures above
30 C should be prevented because, in these conditions,
rmness degradation rates increase markedly (Fig. 2) and
shelf life diminishes dramatically (Fig. 3a). Results from
this study question the validity of 1080 days as an appro-
priate shelf life period for canned ripe olives of low initial
rmness, if only a reasonable loss (<20%) in this quality
attribute is to be guaranteed.
Shelf life, assessed by colour changes, as a function of
relative degradation and temperature (Fig. 3b) followed a
similar trend as rmness. Shelf life at 30 C, for a 15%
increase in colour, would be 793 days. This value is close
but still lower than the 1080 days currently used. At the
end of this period, the relative colour degradation would
be 20%. Thus, the current established shelf life, as assessed
by colour, would also be appropriate if a 20% loss is
accepted as the maximum degradation limit.
Similar eects on shelf life as those observed for rmness
and colour were also detected when it was assessed by pH
decrease (Fig. 3c). This is not as critical a quality attribute
15 20 25 30 35 40 45 50 55 60 65
Temperature (C)
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
0.0012
0.0014
0.0016
0.0018
0.0020
0.0022
k

v
a
l
u
e
s

(
d
a
y
s
-
1
)
High Firmness
Low Fimness
Color (R
700
)
pH
Fig. 2. Changes in the degradation rates for rmness, colour and pH as a
function of temperature. To facilitate comparison, k values for colour
were plotted as positive (in this case degradation means reectance
increase or lighter olives).
0.75 0.80 0.85 0.90 0.95 1.00
0
500
1000
1500
2000
2500
a) Firmness
h, 20 C
l, 30 C
h, 40 C
l, 40 C
h, 30 C
l, 20 C
0.75 0.80 0.85 0.90 0.95 1.00
0
500
1000
1500
2000
2500
b) Colour
20 C
25 C
30 C
35 C
40 C
45 C
50 C
0.75 0.80 0.85 0.90 0.95 1.00
0
500
1000
1500
2000
2500
c) pH
20 C
30 C
50 C
45 C
40 C
35 C
25 C
Relative degradation
S
h
e
l
f

l
i
f
e

(
d
a
y
s
)
Fig. 3. Shelf life of ripe olives as function of their relative rmness (h, high
initial rmness; l, low initial rmness), colour and pH degradation.
Dierent lines mean changes at the indicated temperature.
574 P. Garca-Garca et al. / Journal of Food Engineering 84 (2008) 569575
as rmness or colour because its changes are less perceived
by the consumer. Furthermore, a certain decrease with
respect to the initial ones may be favourable for some mar-
kets. The shelf life values estimated from this attribute were
slightly lower than those from colour and similar to that
calculated from low initial rmness. Estimation of shelf life
at 30 C and 0.15 degradation gave a value of 713 days.
The deterioration degree of pH after 1080 days would be
22% (relative deterioration 0.78). Assuming a 20% decrease
in pH, the declared shelf life would only be slightly lower
than the results deduced from this study.
The ASLT has proved to be appropriate for the simulta-
neous estimation of the degradation rate (k
ref
), A
0
, and E
A
of ripe olive rmness, colour, and pH as well as the estima-
tion of the respective shelf lives as a function of them. There
is not any scale on the acceptable levels of the quality attri-
butes of ripe olives; however, current ripe olive shelf life on
the label would be only slightly above the appropriate per-
iod if it is assumed that a 20%, or a limit above this gure,
degradation proportion in rmness, colour and pH were
acceptable. If the admissible degradation criteria were stric-
ter, the limit currently declared should be revised and short-
ened. This study supplies information for an appropriate
selection of such periods as a function of the acceptable rel-
ative degradation of the quality attributes or pH. Due to
their similar behaviour, changes in only rmness or colour
could be sucient for shelf life establishment in ripe olives
because the slightly higher pH changes may be of less con-
cern for consumers than softening or decolouration.
A lack of homogeneity, especially in rmness, among
factories in the canned products was detected and such dif-
ferences could signicantly aect shelf life. Softer products
could markedly reduce shelf life as judged by rmness dete-
rioration. Then some olives in the market may comply with
the shelf life period provided on the label with respect to
colour or pH but not as assessed by rmness. As far as
we know, the industry is not aware of the importance of
temperature on this attribute, or on colour degradation
and pH changes, because no special attention is paid to
obtaining a specic level. Homogeneous high rmness in
nal products and adequate protection from high tempera-
ture during storage seems necessary to comply with the cur-
rently declared shelf life duration on labels.
Acknowledgements
This work was supported by the Spanish Government
(AGL-2003-00779 and AGL-2006-03540/ALI), European
Union (TDC-Olive) and Junta de Andaluc a (throughout
nancial support to group AGR-125).
References
Anonymous (1996). Guide to food labeling and advertising. Section 2.10.
Canada: Canadian Food Inspection Agency.
Brenes, M., Garc a, P., & Garrido, A. (1992). Phenolic compounds related
to the black colour formed during the elaboration of ripe olives.
Journal of Agricultural and Food Chemistry, 40, 11921196.
Brenes, M., Garc a, P., & Garrido, A. (1994). Inuence of salt and pH on
the rmness of olives in acidic conditions. Journal of Food Quality, 17,
335346.
CODEX/COI (1990). Norma del Codex para las aceitunas de mesa (Norma
mundial) CODEX STAN 66-1881, as admended 1990. Roma: FAO.
Cruess, W. V. (1962). Experiments on color xation with iron salts. I. In
41st Annual technical report of California Olive Association (pp. 113).
Sacramento, CA, USA: California Olive Association.
Fernandez D ez, M. J., & Garrido Fernandez, A. (1971). Black olives by
alkaline oxidation. I. Colour as a criterion for maturity in fresh fruits
and quality in nal product. Grasas y Aceites, 22, 193199.
Garc a, P., Brenes, M., & Garrido, A. (1986). Use of ferrous lactate in the
elaboration of ripe olives. Grasas y Aceites, 37, 3338.
Garc a, P., Brenes, M., & Garrido, A. (1994). Eects of pH and salts on
the rmness of canned ripe olives. Sciences des Aliments, 14,
159172.
Garc a, P., Romero, C., Brenes, M., & Garrido, A. (2002). Validation of a
method for the analysis of iron and manganese in table olives by ame
atomic absorption spectrometry. Journal of Agricultural and Food
Chemistry, 50, 36543659.
Garrido, A., Brenes, M., & Garc a, A. (1995). Iron content and colour of
ripe olives. Die Nahrung, 39, 6776.
Garrido Fernandez, A., Fernandez D ez, M. J., & Adams, R. M. (1997).
Table olive. Production and processing. London: Chapman & Hall, pp.
207282.
Haralampu, S. G., Saguy, I., & Karel, M. (1985). Estimation of Arrhenius
model parameters using three least square methods. Journal of Food
Processing and Preservation, 9, 129143.
IFST (1993). Shelf life of foods Guidelines for its determination and
prediction. London: Institute of Food Science and Technology.
IOOC (International Olive Oil Council) (2005). Key gures on the world
market for table olives. In 93rd Session of the IOOC (pp. 1818).
Madrid (Spain).
Labuza, T. P., & Schmidl, M. K. (1985). Accelerated shelf-life testing of
food. Food Technology, 5764.
Mizrahi, S. (2000). Accelerated shelf-life tests. In D. Kilcast & P.
Subramaniam (Eds.), The stability and shelf life of food (pp. 107125).
Boca Raton, FL, USA: CRC Press.
Panagou, E. Z. (2004). Eect of dierent packing treatments on the
microbiological and physicochemical characteristics of untreated green
olives of the Conservolea cultivar. Journal of the Science of Food and
Agriculture, 84, 757764.
Romero, C., Garc a, P., Brenes, M., & Garrido, A. (1995). Colour and
texture changes during sterilization of packed ripe olives. International
Journal of Food Science and Technology, 30, 3136.
Ross, E. W. (1998). Mathematical modeling of quality loss. In I. A. Taub
& R. P. Singh (Eds.), Food storage stability (pp. 331352). Boca Rato n,
FL, USA: CRC Press.
Sanchez-Gomez, A. H., Garc a-Garc a, P., & Rejano-Navarro, L. (2006).
Elaboration of table olives. Grasas y Aceites, 57, 8694.
Sanchez, A. H., Montan o, A., & Rejano, L. (1997). Eect of preservation
treatment, light, and storage time on quality parameters of Spanish
style green olives. Journal of Agricultural and Food Chemistry, 45,
38813886.
Sanchez, A. H., Rejano, L., & Montan o, A. (1991). Kinetic of the
destruction by heat of colour and texture of pickled green olives.
Journal Science of Food and Agriculture, 54, 376385.
Singh, R. P. (1994). Scientic principles of shelf life evaluation. In C. M.
D. Man & A. A. Jones (Eds.), Shelf life evaluation of foods (pp. 324).
Glasgow, UK: Blackie Academic & Professional.
Taoukis, P. S., Labuza, T. P., & Saguy, I. S. (1997). Kinetic of food
deterioration and shelf life prediction. In K. J. Valentas, E. Rotstein, &
R. P. Singh (Eds.), Hanbook of food engineering practice (pp. 361404).
Boca Rato n, FL, USA: CRC Press.
Vanaclocha, A. C., & Requena, J. A. (1999). Bases de la conservacio n de
alimentos. In Procesos de conservacio n de alimentos (pp. 5471).
Madrid (Spain): A. Madrid Vicente Ediciones y Ediciones Mundi-
Prensa.
P. Garca-Garca et al. / Journal of Food Engineering 84 (2008) 569575 575