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Journal of Stored Products Research 62 (2015) 16e21

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Journal of Stored Products Research


journal homepage: www.elsevier.com/locate/jspr

Effect of storage atmosphere and temperature on the oxidative


stability of almond kernels during long term storage
Marzieh Raisi, Mohammad Ghorbani*, Alireza Sadeghi Mahoonak, Mahdi Kashaninejad,
Hamed Hosseini
Department of Food Science and Technology, Gorgan University of Agricultural Sciences & Natural Resources, Gorgan, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the oxidative stability of almonds (Var. Mamaei) stored for a period of 10 months was
Received 15 December 2014 examined. The influence of temperature (ambient and refrigeration), type of atmosphere (vacuum, CO2
Received in revised form and normal air) and the product physical shape (whole kernels and ground) on the oxidation stability
28 February 2015
were studied under conditions of darkness. Peroxide value (PV) and conjugated trienes (K268) were used
Accepted 13 March 2015
Available online 24 March 2015
as indicators for oxidation progress. Odor and flavor were also used for sensory evaluation. According to
the results, effects of differing temperature, type of atmosphere or physical shape on PV and K268 were
significantly different (P < 0.05). At the end of storage with PV of 3.41 meqO2/kg and K268 of 3.42 mmol/g
Keywords:
Almond
the ground almond sample exposed to air at ambient temperature was the least stable, and the whole
Oxidative stability kernels under vacuum kept in a refrigerator at 4  C with PV of 0.69 meqO2/kg and K268 of 0.63 mmol/g
Modified atmosphere packaging were the most stable form against oxidation. As a result, with regard to PV, unpacked whole kernels and
Peroxide value ground almonds stored at ambient temperature remained fresh for 8e9 and 7 months of storage,
Conjugated triene respectively, while the same samples in refrigeration had shelf lives above 10 months. The use of
modified atmosphere packaging under vacuum and CO2 provided a shelf life of at least 10 months for all
samples irrespective of storage temperature and physical shape of the nuts. Thus modified atmosphere
packaging was a most effective method for protecting the almonds from oxidation.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction as components of many foodstuffs including bakery products and


confectionery as well as in flavoring agents for beverages and ice-
The almond, Prunus dulcis belongs to the subfamily Prunoideae creams (Mexis and Kontominas, 2010). The quality of stored al-
of the family Rosaceae (Ahmad, 2010). Almonds and other tree nuts monds depends mainly on the kernel moisture and fat content,
contain dietary fiber, vitamin E, phytosterols, antioxidants, min- storage temperature, relative humidity (r.h.), oxygen level, type of
erals, numerous bioactive substances and several key micro- packaging, the form of stored nut (in-shell or shelled, peeled,
nutrients that have health benefits and nutrient profile (Dreher roasted, etc.), content of tocopherols and peroxide value. Also the
et al., 1996; Kris-Etherton et al., 2001; Amarowicz et al., 2005; soils and the climates where almonds are grown as well as the
Blomhoff et al., 2006; Chen et al., 2006). Lipid contents with a range almond variety can play an important role in the shelf-life (Garcia-
of 44e61% have been reported for almonds in studies of commer- Pascual et al., 2003; Kazantzis et al., 2003). Lipid oxidation is the
cially or locally important cultivars grown in different zones (Yada main cause of off-flavor development in almonds due to their high
et al., 2011). Healthy fats in nuts contribute to the beneficial effects content of unsaturated fatty acids. Oxygen concentration is one of
of frequent nut intake observed in epidemiological studies as they the most important extrinsic factors affecting nuts lipid oxidation.
can prevent coronary heart disease, diabetes, and sudden death Shelf lives of almonds stored in different conditions have been
(Ros and Mataix, 2006). Almonds are consumed as peeled or un- reported by a few researchers (Guadagni et al., 1978; Senesi et al.,
peeled, raw or roasted, whole or ground kernels, and are also used 1991; Severini et al., 2000; Garcia-Pascual et al., 2003; Mexis
et al., 2009; Mexis and Kontominas, 2010). However the effect of
packaging almonds under CO2 and under vacuum at different
storage temperatures on oxidative stability of the whole kernels
* Corresponding author.
and ground form has not yet been reported.
E-mail address: m.ghorbani@gau.ac.ir (M. Ghorbani).

http://dx.doi.org/10.1016/j.jspr.2015.03.004
0022-474X/© 2015 Elsevier Ltd. All rights reserved.
M. Raisi et al. / Journal of Stored Products Research 62 (2015) 16e21 17

2. Material and methods 2.5. Sensory evaluation

2.1. Almonds The sensory panel was selected from a group of 30 untrained
people (university students and staff) with ages between 20 and 40
The almonds used in this study were of the Mamaei variety, years. For sample evaluation the panelists were served a control
collected from local farms of Shahre-kord, Iran in September 2012. reference sample (stored at 18  C). Samples were randomly coded
The nuts were cracked by hand cracker and after shelling, half of with 6-digit numbers and were allowed to equilibrate to tasting
the kernels were kept intact while the other half was ground using room temperature (21 ± 1  C). The panelists rinsed their mouths
a domestic grinder. with water, between each tasting. All samples were supplied in a
white plastic cup, containing 30 g of whole kernels or ground
almond. Sensory attributes evaluated were odor and flavor since
2.2. Packaging and storage these attributes are directly dependent on lipid oxidation. Scoring
was carried out on paper ballots using a 9 point hedonic scale
The shelled and ground almonds were prepared to be stored where: 9 ¼ extremely like and 1 ¼ extremely dislike for evaluation
under three different storage conditions: 30 g of the test samples 1) of the samples' odor and flavor. Analyses were performed at least
exposed to open air in polypropylene (PP) single use trays without twice and a score of 5 was considered as the lower limit of
lids, 2) under 95% vacuum, 3) under 95% CO2 and 5% air. The latter acceptability for odor and flavor. Sensory evaluations were per-
two were carried out using a packaging set with gas injector formed bimonthly during a period of 10 months.
(Henklman, Model Boxer 42) in low-density polyethylene/poly-
amide/low-density polyethylene (LDPE/PA/LDPE) laminated 2.6. Statistical analysis
sheeting. Flexible pouches, with 75 mm thickness, having an oxygen
permeabilitzy of 52.2 cm3 m2 day1 atm1 at 75% r.h., 25  C, a Data were subjected to analysis of variance (ANOVA) using JMP
water vapor permeability of 2.4 g m2 day1 at 100% r.h., 25  C, and 10 software for Windows. Differences were estimated by the
a CO2 permeability of 189 cm3 m2 day1 atm at 25% r.h., 25  C analysis of variance followed by Tukey's ‘‘honest significant differ-
(according to the supplier's data) were employed for the experi- ence’’ test. Differences were considered significant at P < 0.05.
ments. Samples were stored in the dark at two temperature con-
ditions, ambient (c.23  C) and refrigeration (4  C, 78% r.h.) for 10 3. Results and discussion
months. All samples were analyzed regularly (every month) to
study the oxidation progress. In the ambient storage trials the 3.1. Chemical composition
temperature and r.h. were monitored every day using a digital
temperature and moisture meter (Gemini Data Loggers, West Chemical compositions of the nut which were measured on a
Sussex, UK). Duplicate measurements were carried out for chemical wet basis are summarized as follows. Moisture, total oil, protein,
analysis. Moisture content, total oil contents, protein, ash, fiber and ash, fiber and carbohydrate contents of the fresh almond measured
carbohydrate of fresh almond were determined using standard 3.29 ± 0.5, 48.32 ± 2.45, 18.36 ± 1.54, 3.38 ± 0.51, 5.36 ± 0.98 and
AOAC (2005) methods. 21.37 ± 3.01 g/100 g respectively.

3.2. Storage temperature and relative humidity


2.3. Oil extraction
Table 1 shows the variations in temperature and r.h. in the
Extraction of oil from the nut samples was carried out using storage room during the 10-month period of storage. The average
hexane, as described by Lo  pez-Duarte and Vidal-Quintanar, 2009.
temperature and r.h. for the entire 10-month period were 23  C and
The powdered almond (30 g) was stirred for 6 h at room temper- 33.5% respectively. Moisture contents of the whole kernels and
ature (25  C) with hexane (200 ml) in the dark. The resulting oil in ground almonds stored in different conditions did not show sig-
hexane mixture was filtered through a Whatman No.4 filter paper nificant differences during the 10-month period of storage (average
via a Buchner funnel. The solvent was removed by rotary evapo- moisture content was determined as 3.25%). The low moisture
ration (Model RV O5 BASIC, IKA, USA) at 35  C and the residue was content of the nut and insignificant fluctuations in the room r.h.
kept in a screw cap bottle until used for chemical analysis. during the storage period caused little change in moisture contents
of the samples. Also, almonds contain high amounts of fats as well
as proteins. Peptides can react with lipids and affect the stability of
2.4. Assessment of oxidation the nut's membrane which in turn prevents water from being lost

Lipid oxidation was evaluated by measuring a) peroxide value


(PV) for primary oxidation products and b) spectrophotometric Table 1
index (K268) in order to evaluate the formation of triple conjugate Mean psychrometric data of the storage room.

double bonds (Trienes) for secondary oxidation products. Since Storage period Mean storage Mean relative
hydroperoxides are the primary products of lipid oxidation, their in months temperature ±0.1 ( C) humidity ± 1 (%)
content is often used as an indicator for the initial stages of 1 20.6 40%
oxidation during storage. Peroxide value (PV) was determined by 2 20.2 39%
the iodometric assay according to IUPAC standard method 2.501 3 19.3 40%
4 20 40%
(IUPAC, 1992). The contents of 2,2,4-trimethylpentane as a measure
5 20.4 38%
of trienes was measured at 268 nm (K268) with a spectrophotom- 6 24 36%
eter (PG Instruments, T80 þ UV/VIS model, UK) using a quartz 7 24.4 37%
cuvette. Conjugated trienes were calculated according to IUPAC 8 26 31%
Official Method 2.205 based on measured absorbance of a solution 9 26.2 30%
10 26.1 34%
containing 0.01e0.03 g of oil in 25 ml of isooctane.
18 M. Raisi et al. / Journal of Stored Products Research 62 (2015) 16e21

Table 2
Changes in peroxide value (meqO2/kg almond oil) of raw unshelled whole kernel and ground almonds as a function of internal packaging atmosphere and storage time at 23  C
and 4  C.

Temperature Physical Type of Storage time (month)


shape atmosphere
0 1 2 3 4 5 6 7 8 9 10

Ambient (23 C) Whole kernel Air 0.23gA fg
0.34 A fg
0.44 A 0.69efgA fg
0.76e AB 0.95 ABdef
1.13 AB de bcd
1.45 B 1.95bcAB a
2.38 AB 2.72aB
Vacuum 0.23bA 0.23bA 0.29abA 0.37abA 0.44abB 0.50abB 0.69abBC 0.73abC 0.75abCD 0.84abCD 0.90aCD
CO2 0.23cA 0.23cA 0.22cA 0.41bcA 0.53abcB 0.59abcB 0.70abcBC 0.72abcC 0.98abCD 1.05abCD 1.11aCD
Ground Air 0.23hA 0.35ghA 0.59ghA 0.94fgA 1.33efA 1.37efA 1.65deA 2.19cdA 2.54bcA 2.96abA 3.41aA
Vacuum 0.23eA 0.25deA 0.34cdeA 0.39bcde
A 0.518bcdeB 0.71abcdeAB 0.79abcdeBC 0.88abcdBC 0.96abcCD 1.05abCD 1.23aCD
CO2 0.23fA 0.35efA 0.39defA 0.45defA 0.54defB 0.76cdefAB 0.91bcdeBC 1.03bcdBC 1.33abcBC 1.46abC 1.55aC
Refrigerator Whole kernel Air 0.23cA 0.23cA 0.23cA c
0.30 A 0.35abcB 0.48abcB 0.39abcC 0.75abcC 0.84abcCD 0.97abCD 1.02aCD
(4  C) Vacuum 0.23aA 0.23aA 0.26aA 0.34aA 0.4aB 0.45aB 0.48aBC 0.50aC 0.53aD 0.65aD 0.69aD
CO2 0.23aA 0.23aA 0.21aA 0.29aA 0.41aB 0.57aB 0.59aBC 0.66aC 0.70aCD 0.724aD 0.75aD
Ground Air 0.23dA 0.33cdA 0.35cdA 0.46cdA 0.53cdB 0.54cdB 0.63bcdBC 0.86bcdBC 0.95bcCD 1.24abCD 1.33aCD
Vacuum 0.23aA 0.25aA 0.31aA 0.35aA 0.40aB 0.46aB 0.59aBC 0.68aC 0.73aCD 0.82aCD 0.85aD
Co2 0.23dA 0.31cdA 0.33cdA 0.45abcdA 0.5abcdB 0.57abcdB 0.62abcdBC 0.83abcdBC 0.98abcCD 1.05abCD 1.07aCD

Values in the same row with different lowercase letters were significantly different at P < 0.05. Values in the same column with different capital letters were significantly
different at P < 0.05.

from the nut (Epand, 1998). It can be concluded, therefore, that the temperature.
moisture contents of the samples during the experimental storage These results indicate that lower temperatures along with the
period are unlikely to have significantly affected the oxidation presence of vacuum effectively protected the nuts from oxidation,
progress. and are in good agreement with those of Martin et al. (2001). Sig-
nificant differences were not detected between the packaged
3.3. Peroxide values samples during 10 months storage irrespective of temperature and
physical shape. The results also showed that ground almond suf-
Changes in PV of the whole kernels and ground almonds under fered a greater degree from oxidation than whole kernels under all
different conditions are shown in Table 2. The initial PV of fresh conditions (P < 0.05). The whole kernels and ground almond after 7
almonds was very low (0.23 meqO2/kg of almond oil), which in- months showed significant differences in PV at ambient tempera-
dicates that the almonds did not show initial oxidative rancidity. ture, while refrigerated samples did not show significant differ-
According to the results, the PV of the packed and unpacked whole ences in PV.
kernels showed significant differences after 7 months storage at It can be concluded that storage temperature had a more pro-
ambient temperature. The PV of whole kernels when packed under nounced effect on almond oxidation than physical shape. Despite
vacuum and CO2 conditions at the same temperature did not show our results, Garcia-Pascual et al. (2003) reported that the packaging
significant differences at 10 months of storage. Significant differ- atmosphere (air and N2) at 8 and 36  C during 9 months of storage
ence was detected between the PV of packed and unpacked raw did not affect the peroxide value of raw, roasted, shelled and in-shell
ground almonds stored at ambient temperature after 6 months. almonds for four varieties. Sanchez-Bel et al. (2011) also studied the
Also at low temperature conditions the PV of all samples either effect of packaging in nitrogen (N2) atmosphere or in air on the
whole kernel or raw ground almond (packed and unpacked) did not quality of peeled and roasted almond var. Guara during storage for
show significant differences after 10 months of storage. The 20 weeks at 20 ± 1  C and 65e70% r.h. They reported that an effect of
vacuum-packed samples showed the lowest peroxide values. packaging atmosphere on the development of oxidation in the
Samples stored under CO2 showed higher oxidation than vacuum- peeled or roasted almonds was not apparent. The difference be-
packed samples but had lower PV than samples exposed to open air tween the results of different studies and our results can be attrib-
during storage in both temperature conditions. Maximum oxidative uted to a different r.h. in storage, type of product (peeled and roasted
stability was found in the whole kernels packaged under vacuum almonds showing more oxidation than unpeeled almonds under
and CO2, and ground almond under vacuum at refrigeration modified atmosphere), difference in almond variety, type of

Table 3
Changes in conjugated trienes (mmol/g) of raw unshelled whole kernel and ground almonds as a function of internal packaging atmosphere and storage time at 23  C and 4  C.

Temperature Physical shape Type of atmosphere Storage time (months)

0 1 2 3 4 5 6 7 8 9 10

Ambient (23  C) Whole kernel Air 0.346fA 0.492efA 0.61efA 0.765defAB 0.851defB 0.941cdefB 1.09bcdeBC 1.29abcdBC 1.534abcBCD 1.685abBC 1.832aC
Vacuum 0.346bA 0.355bA 0.397abA 0.415abB 0.478abB 0.483abB 0.514abCD 0.554abD 0.65abE 0.805abDE 1.001aDE
CO2 0.346cA 0.371cA 0.396cA 0.423cB 0.455cB 0.493bcB 0.544bcCD 0.631bcD 0.735bcE 1.113abCDE 1.52aCD
Ground Air 0.346hA 0.346hA 0.595hA 1.342efgA 1.653defA 1.755deA 2.021cdA 2.625abcA 2.885abA 3.292aA 3.42aA
Vacuum 0.346cA 0.382cA 0.439cA 0.475cB 0.502cB 0.613cB 0.724bcCD 0.834bcBCD 0.96abcDE 1.263abBCD 1.566aCD
CO2 0.346fA 0.375fA 0.398fA 0.495defB 0.519defB 0.886defB 1.089deBC 1.101dBCD 1.843abB 2.126bcB 2.599aB

Refrigerator (4 C) Whole kernel Air 0.346aA 0.42aA 0.457aA 0.479aB 0.546aB 0.616aB 0.656aCD 0.714aCD 0.772aE 0.813aDE 0.854aE
Vacuum 0.346aA 0.346aA 0.353aA 0.402aB 0.419aB 0.436aB 0.465aD 0.495aD 0.535aE 0.603aE 0.63aE
CO2 0.346aA 0.349aA 0.353aA 0.391aB 0.402aB 0.467aB 0.522aCD 0.592aD 0.625aE 0.685aDE 0.74aE
Ground Air 0.346gA 0.478fgA 0.598efgA 0.776defgAB 0.886defgB 0.986defB 1.13bcde B 1.346bcdB 1.62abcCB 1.75abB 1.854aC
Vacuum 0.376aA 0.38aA 0.387aA 0.461aB 0.497aB 0.507aB 0.523aCD 0.564aD 0.615aE 0.643aDE 0.956aDE
CO2 0.346bA 0.349bA 0.35bA 0.478bB 0.495bB 0.643bB 0.669abCD 0.715abCD 0.825abE 0.932abDE 1.12aDE

Values in the same row with different lowercase letters were significantly different at P < 0.05. Values in the same column with different capital letters were significantly
different at P < 0.05.
M. Raisi et al. / Journal of Stored Products Research 62 (2015) 16e21 19

Fig. 1. Changes in odor: a) whole almond kernels b) raw ground almonds as a function of internal packaging atmosphere, storage time at ambient temperature and refrigeration.

packaging materials and type of atmosphere in which the nuts were value of fresh almond was 0.346 mmol/g while the highest and
packed. According to Buransompob et al. (2003), peroxide values lowest K268 values at the end of the storage period were recorded
less than 2.0 meqO2/kg in almond oils can be considered as an in- for ground almond exposed to the air at ambient temperature
dicator of fresh almonds, so according our results, whole kernel and (3.42 mmol/g) and for whole kernels under vacuum at refrigeration
ground almonds packaged (under vacuum and CO2) at ambient and (0.63 mmol/g). K268 values of packed (vacuum and CO2) whole
refrigeration temperature had at least 10 months of shelf life kernels and unpacked ones (exposed to air) showed significant
considered as fresh. The whole kernels and ground almond at differences at ambient temperature after 7 months of storage. At
ambient temperature exposed to air remained fresh for 8e9 and 7 low temperature all samples of the whole kernels (packed and
months, respectively, while, the samples stored at the refrigeration unpacked) did not show significant differences during 10 months of
temperature remained fresh for more than 10 months. In a similar storage. Sanchez-Bel et al. (2011) observed that the ultraviolet (UV;
study, Mexis et al. (2009) reported that the PVs of raw ground K268) index increased more slowly in the roasted almonds packaged
almond packaged in LDPE/EVOH/LDPE with the oxygen absorber in N2 during 5 months storage, while in peeled samples the index
after 12 months of storage at 20 and 4  C in darkness were 1.62 and reached the same levels at the end of storage regardless of the
0.99e1.15 meqO2/kg, respectively. Their results were similar to the packaging atmosphere. As can be seen from Table 3, there were
PV of ground almond under CO2 in our study after 10 months at significant differences between K268 values of packed and unpacked
ambient and refrigeration temperatures. raw ground almonds at ambient temperature after 3 months stor-
age. However similar results were obtained after 6 months storage
3.4. Conjugated trienes when the temperature was lowered to 4  C by refrigeration. The
K268 value was increased with storage time (P < 0.05) in all samples,
Table 3 shows the average K268 value obtained for the whole findings in agreement with the results of Senesi et al. (1991).
kernel and ground almond in different storage conditions. The K268 Likewise, Zacheo et al. (2000), Mexis et al. (2009) and Mexis and
20 M. Raisi et al. / Journal of Stored Products Research 62 (2015) 16e21

Fig. 2. Changes in flavor: a) whole almond kernels b) raw ground almonds as a function of internal packaging atmosphere, storage time at ambient temperature and refrigeration.

Kontominas (2010) in their studies reported that the secondary pressure, while it was proportional to oxygen concentration at low
oxidation products in almond (malondialdehyde, hexanal content) oxygen partial pressure. The K268 value for ground almond was
increased with storage time. In a similar study, Kazantzis et al. higher than that for the whole kernels, indicating that ground
(2003) compared in-shell almonds versus shelled almonds stored almond was more susceptible to oxidation, due to the higher con-
at either 5  C (80% r.h.) or 23  C (60% r.h.) inside PE bags aerated tact surface to oxygen as compared to whole almonds. The results
with a few 3 mm diameter holes for 6 months. They found that after also show that K268 values of all samples stored in vacuum pack-
6 months of storage, shelled almonds retained a stable K268 value aging were lower than that for CO2-filled and air atmosphere for
which is in contrast to our results of storing almonds at ambient whole kernels and ground almonds at both storage temperatures.
temperature where K268 values for whole almond kernels exposed Kader (1996) stated that O2 is the most important atmospheric
to air, under vacuum and CO2 showed significant differences after 6, component in almond storage, and that high O2 concentrations
10 and 9 months of storage, respectively. However K268 values of resulted in an increase in rancidity and mold growth. These results
the whole kernels under vacuum, CO2 and exposed to air and that also showed that the changes in the K268 of the samples occurred
of ground almond under vacuum at refrigeration temperature did faster as storage time increased. This can be justified by the fact that
not show significant differences after 10 months of storage. No with increase in storage time, i.e. after five months, the amount of
significant differences were found in the K268 value of all samples naturally occurring antioxidant including tocopherols in almonds
with different packagings regardless of storage temperature and has diminished and oxidative stability has been reduced conse-
physical shape of almond. quently. According to Garcia-Pascual et al. (2003), Chun et al. (2005)
According to Labuza and Dugan (1971), the rate of oxidation was and Fourie and Basson (1989), the tocopherol content decreased
independent of oxygen concentration at very high oxygen partial throughout storage in almonds, possibly as a result of its antioxidant
M. Raisi et al. / Journal of Stored Products Research 62 (2015) 16e21 21

function against lipid oxidation. temperature. The rate of oxidation and the generation of odor and
flavor in ground almonds were higher than those for whole kernels.
3.5. Sensory evaluation Thus, to store almonds for longer periods, it is recommended to
store the kernels as whole rather than ground nuts, otherwise for
Flavor and odor changes in the whole kernels and ground al- an extended shelf life a combination of modified atmosphere
monds during storage time are shown in Figs. 1 and 2. As shown in packaging and low temperature is essential to maintain the quality
Fig. 1, after 10 months of storage, odor changes were the least in the of the product.
samples packaged under vacuum and refrigerated for both whole
kernels and ground almonds (scores were 8.23 and 7.94, respec-
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