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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem
Ministry of Food, Agriculture and Livestock, Directorship of Olive Research Institute, Department of Food Technologies, Bornova, Izmir, Turkey
Adana Science and Technology University, Department of Food Engineering, Seyhan, Adana, Turkey
a r t i c l e
i n f o
Article history:
Received 13 April 2016
Received in revised form 8 June 2016
Accepted 10 June 2016
Available online 11 June 2016
Keywords:
Extra virgin olive oil
Ripening
Quality
Chemical composition
Antioxidant activity
Principal component analysis
a b s t r a c t
The aim of this study was to discriminate the extra virgin olive oils (EVOO) based on quality characteristics, chemical composition and antioxidant activity according to ripening stages of olives. Two different
olive varieties (Memecik and Gemlik) were obtained at different stages of ripening based on skin color
(green, purple and black). Quality properties of olive oils; free fatty acidity, peroxide value, K232 and
K270, purity properties; fatty acid and triacylglycerol (TAG) composition and antioxidant compounds like
total phenol, carotenoid and chlorophyll content and antioxidant activity (oxidative stability, ABTS
radical scavenging activity) analyses were performed. Higher amount of oleic, linoleic and palmitic acids
were observed in olive oils. Oleic acid amount of olive oils decreased, linoleic acid increased with ripening. The most abundant TAG of olive oils were ECN 48, OOO, SLO + POO, ECN 46 and LOO/PLO. Olive oils
were clearly classified by principal component analysis based on fatty acid and TAG composition.
2016 Elsevier Ltd. All rights reserved.
1. Introduction
Extra virgin olive oil (EVOO) consumption has increased due to
the increased attention of consumers for health benefits of food
products (Ortega, 2006). Olive oils extracted from Memecik and
Gemlik olive varieties are economically important olive oils in
_
lu &
Turkey (Sevim, Kseoglu, & ztrk Gngr, 2013b; Ilyasog
zelik, 2011). South Aegean Olive Oils produced from Memecik
cultivar are certified by the Turkish Patent Institute as PDO
(Protected Domination Origin) (TPI, 2004). The health benefits of
olive oil can be related with its chemical composition which has
effect on olive oil oxidative stability and quality (Bendini et al.,
2007). Olive oil chemical composition consists of TAG (99%)
and free fatty acids, mono- and diacylglycerols, and lipids such as
hydrocarbons, sterols, aliphatic alcohols, tocopherols, and
pigments fatty acid composition of olive oil includes palmitic
(C16:0), palmitoleic (C16:1), stearic (C18:0), oleic (C18:1), linoleic
(C18:2), and linolenic (C18:3) acids (Boskou et al., 2006). Phenolic
compounds are the minor compounds in olive oils with high
antioxidant activity providing nutritional and sensorial properties.
Carotenoids exhibit antioxidant effect on virgin olive oils by
quenching singlet oxygen inhibiting photosensitised oxidation
Corresponding author at: Adana Science and Technology University, Department of
Food Engineering, 01180, Seyhan, Adana, Turkey.
E-mail address: pkadiroglu@adanabtu.edu.tr (P. Kadiroglu).
http://dx.doi.org/10.1016/j.foodchem.2016.06.027
0308-8146/ 2016 Elsevier Ltd. All rights reserved.
(Beltran, Aguilera, Del Rio, Sanchez, & Martinez, 2005). The green
colors of the olive fruits and olive oils are provided by chlorophylls
and it is one of the quality parameters for olive oils (Giuliani,
Cerretani, & Cichelli, 2011). Chlorophylls show antioxidant activity
in the dark while they act as pro-oxidant in the light (Gandul-Rojas
& Minguez-Mosquera, 1996). Olive oil extraction using healthy
fruits harvested at the right stage of ripening by using proper
methods have influence on chemical characteristics of olive oils
(Olias, Perez, Rios, & Sanz, 1993). Olive oil is resistant to oxidation
because of its low polyunsaturated fatty acid composition and high
contents of a-tocopherol and phenolic contents (Sevim, Tuncay, &
Kseoglu, 2013a).
Several studies have been performed for determination of the
effect of olive ripening stage on quality and chemical composition
of olive oils obtained from Tunisian cultivars (Baccouri et al.,
2008); Hojiblanca cultivars (Beltran et al., 2005); Moroccan Picholine and autochthon cultivars (Boukachabine, Ajana, & El Antari,
2011); Spanish olive cultivars (Gmez-Rico, Fregapane, &
Salvador, 2008); Chilean cultivars (Romero, Saavedra, Tapia,
Seplveda, & Aparicio, 2016) and Oblica and Leccino cultivars
(pika et al., 2015).
According to our knowledge there is no detailed study on the
influence of ripening stage on chemical composition and quality
evaluation of Turkish olive varieties; Memecik and Gemlik. Therefore, the aim of this study is to determine the effect of olive ripening stage on chemical composition, oxidative stability and quality
properties of olive oils obtained from Memecik and Gemlik cultivars in combination with PCA as a multivariate statistical method.
2. Materials and methods
2.1. Olive oil samples
Two different olive varieties; Memecik (M) and Gemlik (G) were
harvested (15 kg) in the Olive Research Institute of Ministry of
Food, Agriculture and Livestock in Izmir/Turkey in 2015 crop season at three stages of ripening according to skin pigmentation
(green, purple, black). Olive oils were extracted by using Abencor
laboratory oil mill (MC2 Ingenieria y Sistemas, Sevilla, Spain)
equipped with fruit crushing, malaxation and centrifuge parts.
The malaxation temperature was 30 C and the duration of malaxation was 30 min. All oil samples were filtered and stored in the
amber glass bottles and at +4 C until they were analyzed. 100 ml
of each oil sample was used for the analyses.
2.2. Maturity index (MI)
The olive maturity index was determined according to the
method given by International Olive Council (IOC, 2011) based
on the evaluation of the olive skin and pulp colors.
2.3. Standard chemical parameters
The free fatty acidity and the peroxide values were determined
according to Turkish Food Codex (Anonymous, 2014) and UV spectrophotometric indices (K232 and K270 measurements) were measured according to the methods given by International Olive
Council (IOC, 2015). All parameters were determined duplicate
for each sample.
629
7.5 g of olive oil sample was dissolved in cyclohexane and completed to 25 ml in a volumetric flask. Carotenoid and chlorophyll
content of the sample was determined by measuring the solution
at 670 nm and 470 nm with a spectrophotometer (UV-1700,
Shimadzu, JAPAN), respectively (Minguez-Mosquera, Rejano,
Gandul, Sanchez, & Garrido, 1991).
630
Fig. 1. MUFA/PUFA and Oleic acid/Linoleic acid ratios of Memecik and Gemlik olive
oils at 3 ripening stages (MG: Memecik (green); MP: Memecik (purple); MB:
Memecik (black); GG: Gemlik (green); GP: Gemlik (purple); GB: Gemlik (black)).
Table 1
Quality properties of olive oil samples.
af
Samples
Alpha
tocopherol
(mg/kg)
K232
K270
Oxidative
stability (h)
ABTS+ RSA
(lmol TE/100g
oil)
Total phenol
(mgCAE/kg)
Total
chlorophyll
(mg/kg)
Total
carotenoid
(mg/kg)
Free fatty
acidity (% oleic
acid)
Peroxide
values
(meqO2/kg)
MG
MP
MB
GG
GP
GB
296.40 0.33e
305.48 0.79d
313.64 0.21c
377.64 4.22a
335.44 2.28b
299.31 0.71e
1.66 0.00a
1.65 0.01a
1.54 0.01b
1.44 0.03c
1.40 0.00d
1.44 0.00c
0.13a
0.13a
0.11b
0.08d
0.08c
0.08c
16.82 0.04a
13.86 2.22c
11.14 0.23d
16.59 2.02a
15.82 0.04b
9.87 3.64e
132.87 1.00a
126.31 0.25b
118.33 0.50c
94.93 3.01d
79.50 0.75e
76.49 0.50e
372.70 10.76b
407.13 14.15a
296.24 18.12c
194.96 9.62e
245.40 9.62d
150.92 5.10f
8.83 0.02a
3.12 0.03c
2.58 0.05d
3.67 0.02b
1.13 0.02e
0.59 0.02f
4.03 0.04a
1.90 0.01c
1.46 0.04d
2.05 0.04b
0.93 0.01e
0.54 0.05f
0.34b
0.46a
0.45a
0.14d
0.25c
0.24c
4.30 0.03c
3.74 0.01d
4.55 0.01b
4.74 0.00a
2.60 0.00e
2.46 0.02f
Different letters in the same column concerning all samples significantly different values (p < 0.05).
Table 2
Fatty acid composition (%) of olive oil samples.
Olive oils
MG
MP
MB
GG
GP
GB
a
*
C16:0
C16:1*
C17:0
C17:1
C18:0
C18:1
C18:2
C18:3*
C20:0
C20:1*
C22:0
C24:0
14.93
14.69
14.56
14.70
15.42
15.49
0.85e
0.95de
1.07cd
1.12bc
1.25b
1.60a
0.04
0.04
0.03
0.16
0.13
0.12
0.07
0.07
0.06
0.27
0.25
0.24
2.12
2.00
1.95
3.09
2.81
2.43
72.37
71.23
68.92
73.95
72.03
68.68
8.01
9.42
11.81
5.01
6.46
9.87
0.69e
0.70de
0.74cd
0.75bc
0.76b
0.79a
0.40
0.38
0.37
0.48
0.44
0.38
0.32a
0.33a
0.31a
0.28a
0.27b
0.26b
0.12
0.11
0.12
0.13
0.12
0.10
0.08
0.08
0.07
0.10
0.09
0.07
First letter indicates the olive variety Memecik (M) and Gemlik (G) and second letter indicates the ripening stage of olives G: Green, P: Purple, B: Black.
ae Different letters in the same column concerning all samples significantly different values (p < 0.05).
631
that transforms oleic acid to linoleic acid and catalyse the formation of double bonds (Gutirrez, Jimnez, Ruiz, & Albi, 1999).
PCA was performed to discriminate the olive oil samples based
on fatty acid composition of olive oils according to harvest time
and variety. PCA was constructed with 2 components accounting
for 87.6% of total variance. The results were graphically represented by PCA score and loading plots. As it can be seen from
Fig. 2a, Memecik and Gemlik olive oils were clearly discriminated
according to variety and stage of ripening. Loading plot (Fig. 2b)
of the variables (fatty acids) showed that gadoleic (C20:1) and linoleic (C18:2) acids were responsible for discrimination of Memecik
olive oils.
3.3.2. Triacylglycerol (TAG) composition
TAG composition of olive oils was listed in Table 3. The main
triacylglycerols were OOO (triolein), SLO + POO, LOO + PLnP, SOO,
POP and PLO + SLL. These accounted for 90.0% of the total peak
areas in the chromatogram. The OOO varies between 31.45% and
36.75% for Memecik olive oils while it ranged between 31.55%
and 39.37% for Gemlik olive oils. The OOO level of Memecik olive
oil has been determined lower than the results of Gkebag,
Draman, and zdemir (2013). The presence of OOO at high levels
indicates authenticity of olive oils (Gkebag et al., 2013). In addition, all olive oil samples had low amount of LLL (trilinolein). The
Fig. 2. a) Scores and b) loading plots with PCA according to fatty acid profiles of Memecik and Gemlik olive oils.
632
Table 3
Triacylglycerol (%) composition of olive oil samples.
Samples
Codes
MG
MP
MB
GG
GP
GB
LLL
LOLn + POLL
PLLn
OLL
OLnO
PLL
POLn
LOO + PLnP
PoOO
PLO + SLL
PoOP
PLP
OOO
SLO + POO
POP
PPP
SOO
POS
ECN 42
ECN 44
ECN 46
ECN 48
ECN 50
PLO/OOO
LLL/ECN42
PLL/OLL
ECN48/ECN46
LOO/PLO
OOO/POO
L1
L2
P1
O1
O2
P2
P3
L3
P4
P5
P6
P7
O4
S1
P8
P9
S2
P10
E1
E2
E3
E4
E5
P11
L4
P12
E6
L5
O5
0.05
0.23
0.07
1.42
1.26
0.40
0.65
12.38
0.64
6.58
0.57
0.77
36.75
27.46
4.55
0.49
3.63
1.23
0.35
3.73
20.93
69.24
4.86
0.18
0.14
0.28
3.31
31.03
1.34
0.09
0.29
0.09
2.06
1.38
0.54
0.64
14.88
0.55
7.67
0.46
0.85
36.58
24.41
3.66
0.50
3.46
1.06
0.47
4.62
24.40
65.14
4.52
0.21
0.19
0.26
2.67
27.56
1.50
0.18
0.38
0.11
3.08
1.44
0.90
0.70
16.70
0.60
8.89
0.66
1.02
31.45
24.47
4.09
0.43
3.11
1.11
0.67
6.10
27.86
60.42
4.22
0.28
0.27
0.29
2.17
18.67
1.29
0.00
0.24
0.06
0.63
1.41
0.26
0.64
7.87
1.09
4.09
0.37
0.52
39.37
29.81
4.41
0.60
5.54
1.82
0.30
2.94
13.93
74.19
7.36
0.10
0.01
0.41
5.33
30.30
1.32
0.00
0.32
0.08
1.03
1.53
0.40
0.71
9.82
1.40
5.66
0.75
0.94
36.66
28.51
4.28
0.53
4.79
1.57
0.40
3.66
18.56
69.96
6.36
0.15
0.00
0.39
3.77
24.90
1.29
0.14
0.43
0.11
2.35
1.78
0.76
0.76
12.92
1.64
7.78
1.01
1.26
31.55
26.62
4.53
0.42
3.71
1.38
0.68
5.65
24.60
63.12
5.09
0.25
0.20
0.32
2.57
17.11
1.19
ECN
ECN
ECN
ECN
ECN
42
44
46
48
50
results of five equivalent carbon number analysis (ECN 42, ECN 44,
ECN 46, ECN 48 and ECN 50) revealed that ECN 48 fraction was the
determined between 60.42% and 94.96% as the highest values in
the both varieties of olive oil samples at all stages of ripening. This
value was followed by ECN 46 (between 13.93% and 27.86%)
values. These TAG values and other parameters (ECN 42-ECN 50)
were comparable with other studies (Baccouri et al., 2008;
Boukachabine et al., 2011; Gkebag et al., 2013).
TAG composition of olive oils was used to discriminate olive oil
samples obtained from different ripening stages of olives. PCA was
performed with 3 principal components which account for 92.0% of
the variability in the data (Fig. 3a). According to loading plot
(Fig. 3b) of TAG data, Memecik cultivar of olive oil was characterized by OOO/POO (O5) at green and black stages of ripening.
LOO + PLnP, LLL/ECN 42, OLL, PLO/OOO, ECN 46, PLO + SLL were
responsible for discrimination of M olive oils obtained from oils
at black ripening stage. POP played role in characterization of
Gemlik (purple) oils while ECN 48/ECN 46 and SOO were effective
for characterizing Gemlik (green) oils. Also, Gemlik (black) olive oil
was characterized by POLn and PoOP.
3.4. Minor compounds of olive oils
In olive oil, vitamin E is represented by tocopherol. Tocopherols
have inhibitory effect on LDL oxidation and they have several
nutritional benefits (Beltran et al., 2005). Tocopherols play a key
role in preserving oil from rancidity during storage <alpha> tocopherol content of the olive oil samples ranged from 296.40 to
377.64 mg/kg. In our research, a-tocopherol content decreased
during fruit ripening for Gemlik olive oil, but in the Memecik olive
oil it increased with ripening. Gutirrez et al. (1999) reported that
the tocopherol content of olive oil decreased during fruit ripening.
633
Fig. 3. a) Scores and b) loading plots with PCA according to TAG composition of Memecik and Gemlik olive oils.
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