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Industrial Crops and Products 89 (2016) 195–199

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Industrial Crops and Products


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

Kernel characteristics, oil contents, fatty acid compositions and


biodiesel properties in developing Siberian apricot (Prunus sibirica L.)
seeds
Siqi Fan a,b,1 , Tianyu Liang c,1 , Haiyan Yu a , Quanxin Bi a , Gangtie Li c , Libing Wang a,b,∗
a
Key Laboratory of Tree Breeding and Cultivation, State Forestry Administration, Research Institute of Forestry, Chinese Academy Forestry, Beijing 100091,
China
b
Key Laboratory of Biotechnology and Bioresources Utilization (Dalian Minzu University), State Ethnic Affairs Commission & Ministry of Education, Dalian
116600, Liaoning, China
c
Inner Mongolia Agricultural University, Huhhot 010019, China

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

Article history: Kernel characteristics, oil contents, fatty acid compositions and biodiesel properties were studied in
Received 3 February 2016 developing Siberian apricot (Prunus sibirica L.) seeds, at intervals of 1 week from 3 weeks after anthesis
Received in revised form 25 March 2016 to 10 weeks. Variation of kernel dry biomass, kernel length, kernel breadth and kernel thickness were
Accepted 6 May 2016
significant (P < 0.01). Oil content increased with maturity and reached the highest point at 8 weeks after
anthesis (51.6%). Changes in the content of oleic acid (C18:1) and linoleic acid (C18:2) presented an
Keywords:
opposite trend that oleic acid increased, whereas linoleic acid decreased until 7 weeks after anthesis.
Siberian apricot
Siberian apricot methyl esters meet the specifications better in biodiesel standards when seeds were
Seed development
Kernel characteristics
harvested at 8, 9 and 10 weeks after anthesis. Siberian apricot seeds harvested after 8 weeks after anthesis
Oil contents may be suitable for producing biodiesel.
Fatty acid compositions © 2016 Elsevier B.V. All rights reserved.
Biodiesel properties

1. Introduction tion in oil content and fatty acid composition in developing seeds
for biodiesel production have been focused on Calophyllum inophyl-
Siberian apricot (Prunus sibirica L.) is a fruit species belongs to lum (Hathurusingha et al., 2011), Pongamia pinnata (Pavithra et al.,
the Rosaceae family. The total area of Siberian apricot in China is 2012), and Jatropha curcas (Sinha et al., 2015).
approximately 1.7 million ha, and the annual seeds harvest is nearly Siberian apricot seed oil has been investigated in previous pub-
192,500 tons (Wang, 2011). Siberian apricot is a multipurpose tree lications for producing biodiesel, but they are concerned about the
species with ecological and economic value. It has a strong adapt- biodiesel properties of fully matured seeds (Wang and Yu, 2012;
ability to stress that can be cultivated on marginal land. The trees Wang, 2012; Wang, 2013; Guo et al., 2015). Information of biodiesel
are not only used to sand control and prevention but also cultivated property of Siberian apricot seeds at different stages of develop-
for fruit or oil purpose (Zhang and Zhang, 2003). Moreover, the ment is unavailable. The purpose of this study was to investigate
seed kernel of Siberian apricot was high in oil content (over 50%) the effect of variation in fatty acid composition and oil accumula-
and has been determined to be suitable for biodiesel production tion on biodiesel property in developing Siberian apricot seeds. It
(Wang and Yu, 2012). Fatty acid composition and oil content are may provide a schedule for harvesting Siberian apricot seeds with
considered as prominent attributes in oil crops (Were et al., 2006). the high quality of biodiesel.
It also has an effect on productions and fuel properties of biodiesel
(Ramos et al., 2009; Knothe, 2009). However, oil content and fatty 2. Materials and methods
acid composition change in developing seeds (Slack and Browse,
1984; Cherif et al., 2004; Pavithra et al., 2012). Studies on varia- 2.1. Materials

Twenty trees of Siberian apricot locating in Liao Ning Province in


∗ Corresponding author. China were selected and marked in April 2013 (geographical coor-
E-mail address: wlibing@163.com (L. Wang). dinates approximately 122◦ 22 E; 42◦ 43 N). Seeds were collected at
1
These authors contributed equally to this work. intervals of 1 week from 3 weeks after anthesis to 10 weeks (3, 4,

http://dx.doi.org/10.1016/j.indcrop.2016.05.012
0926-6690/© 2016 Elsevier B.V. All rights reserved.
196 S. Fan et al. / Industrial Crops and Products 89 (2016) 195–199

Fig. 1. Changes of kernel morphological in developing Siberian apricot seeds.

Table 1
Variation of kernel dry biomass and characteristic in developing Siberian apricot seeds.

Weeks Kernel dry biomass(g) Kernel characteristics


after
anthesis

Kernel Length (mm) Kernel breadth (mm) Kernel thickness (mm)

3 0.05 ± 0.03d 9.62 ± 1.59c 7.66 ± 1.29c 1.37 ± 0.23d


4 0.13 ± 0.03c 10.50 ± 0.51bc 7.70 ± 0.47c 3.23 ± 0.47c
5 0.22 ± 0.06b 10.89 ± 1.02ab 8.40 ± 1.64ab 4.28 ± 0.58b
6 0.24 ± 0.07b 10.95 ± 0.83ab 8.85 ± 1.24bc 5.04 ± 0.72a
7 0.25 ± 0.09b 11.01 ± 1.07ab 9.24 ± 1.52ab 5.05 ± 0.69ab
8 0.27 ± 0.05ab 11.28 ± 0.93ab 9.33 ± 0.88ab 5.07 ± 0.65a
9 0.29 ± 0.08ab 11.55 ± 1.18ab 9.68 ± 1.25ab 5.41 ± 0.47a
10 0.34 ± 0.08a 12.19 ± 1.13a 10.52 ± 1.13a 5.59 ± 0.70a
** ** ** **
P
**
P < 0.01.

hammer by carefully removing the exocarp. And the dry biomass,


length, breadth and thickness were measured using electronic bal-
ance and vernier caliper. The kernel characteristic values across
different development stages were reported as mean ± standard
deviation and compared by Duncan Multiple Test (DMRT) using
the software SPSS 20.0.

2.3. Kernel oil extraction and trans-esterification

The kernels were crushed and extracted by n-hexane double


extraction at 25 ◦ C using a rotary evaporator (LABORTA 4000-
efficient, Heidolph, Germany). Oil content was determined by
comparing the weight of dry kernel before and after extraction. The
Fig. 2. Variation of kernel oil content in developing Siberian apricot seeds.
determination was performed in triplicate, and data are reported
as mean ± standard deviation. Siberian apricot kernel oils were
5, 6, 7, 8, 9, and 10 weeks) in June–August. One hundred fruits from methylated following a trans-esterification method as Wang (2012)
the 20 trees (Random 5 seeds each tree) were selected each time. described.
The fresh seeds were removed from the flesh and stored at room
temperature for 1 week to dry before they were transferred to the 2.4. Fatty acid methyl ester analysis
laboratory.
The obtained fatty acid methyl esters (FAMEs) were analysed
2.2. Kernel characteristic by gas chromatograph, using the Agilent 6890 (California, USA)
equipped with a flame ionization detector (GC–MS). Methyl ester
The 800 seeds (8 × 100) of Siberian apricot were dried to con- solution (1 ␮l) was injected into a HP-INNOWax capillary column
stant weight using a hot air oven which the temperature was (inner diameter 0.32 mm, length 30 m, film thickness 0.5 ␮m, split
maintained at 60 ◦ C for 6–7days. Fig. 1 shows the morphological 1:20). The temperature of injector and detector was 250 and 280 ◦ C.
characteristics of dry kernels at different stages of development. Oven temperatures were programmed from 190 ◦ C for 3 min, with a
The dry kernels of Siberian apricot were obtained using a small rise of 5 ◦ C/min to 240 ◦ C for 10 min. The carrier gas was high-purity
S. Fan et al. / Industrial Crops and Products 89 (2016) 195–199 197

hydrogen. The peaks of FAMEs were identified by comparing their

37.60 ± 2.11b
38.00 ± 2.26b
57.96 ± 3.28a
60.06 ± 3.55a

26.53 ± 2.13c

23.78 ± 2.26c
23.85 ± 2.21c
24.05 ± 2.43c
PUNSAT
retention time with authentic standards. Peak integration was per-
formed by applying HP3398A software. The determination was run
in triplicate. Values are reported as mean ± standard deviation and

**
compared by Duncan Multiple Test (DMRT) using SPSS 20.0.

54.88 ± 3.85b
56.15 ± 3.91b
MUNSAT

68.81 ± 4.19a
71.88 ± 4.93a
72.10 ± 5.06a
71.70 ± 4.02a
33.18 ± 3.18c
29.60 ± 3.03c
2.5. Biodiesel properties


Iodine value (IV), cetane number (CN), density (D), kinematic

**
10.34 ± 2.89a viscosity (), oxidative stability (OS) and cold filter plugging point
8.86 ± 2.45ab
(CFPP) of fatty acid methyl esters were calculated according to fol-

4.67 ± 1.12d

4.12 ± 1.17d
4.07 ± 1.11d

4.44 ± 0.83d
7.52 ± 2.65b
5.85 ± 1.23c lowing equations (Wang et al., 2012; Ramírez-Verduzco et al., 2012;
SAT

Phoo et al., 2014):




 560 × A

**
i
SN = (1)
0.16 ± 0.11b
0.29 ± 0.13a
0.23 ± 0.21a

0.10 ± 0.04c
0.09 ± 0.03c

MWi
Eicosenoic

 254 × DB × A
(C20:1)

i
IV = , (2)
acid

MWi
**


CN = 46.3 + 5458/SN − 0.225 × IV (3)


0.14 ± 0.05d
0.09 ± 0.04d
0.45 ± 0.16b
0.86 ± 0.41a

0.24 ± 0.18c
Arachidic


n
(C20:0)

fb = Ai · fi , (4)
acid

**


i=1
0.21 ± 0.17b
0.40 ± 0.27b

0.11 ± 0.08b
1.15 ± 0.74a
0.91 ± 0.62a

OS = −0.0384 × DU + 7.7704 (5)


Linolenic

(C18:3)

CFPP = 1.7556 × LCSF − 14.772 (6)


acid

**


DU = (Cn : 1, wt.%) + 2 × (Cn : 2, wt.%) + 3 × (Cn : 3, wt.%) (7)


37.79 ± 2.73b
37.20 ± 3.21b
58.91 ± 3.61a
57.05 ± 3.84a

26.42 ± 2.62c

23.78 ± 2.31c
23.85 ± 2.25c
24.05 ± 2.37c

LCSF = ˙(MPn × Cn )/100 (8)


Linoleic

(C18:2)

where Ai is the percentage of the ith FAME, DB is the number of


acid

**

double bonds, MWi is the molecular mass of each component, fb


is a function that represents any physical property (D or ), fi is a
Oleic acid (C18:1)

function of the individual ith FAME properties (D or ), Cn is per-


54.16 ± 3.54b
55.63 ± 3.88b
68.27 ± 4.27a
71.36 ± 4.89a
71.61 ± 5.11a
71.24 ± 4.14a
28.45 ± 2.98c
32.27 ± 3.16c

centage of the nth saturated fatty acids and MPn is the melting point
of nth saturated fatty acids methyl esters. All of the biodiesel prop-
erty parameter analyses were replicated three times for each FAME
**

determination, and the value of biodiesel properties parameters


were reported as mean ± standard deviation.
Stearic acid (C18:0)

The biodiesel properties of Siberian apricot were compared


with specifications of ASTM D6751 (ASTM D6751, 2010), EN
1.36 ± 1.21ab

0.91 ± 0.27cd
0.75 ± 0.32d
0.75 ± 0.27d
0.81 ± 0.32d
1.28 ± 0.76b
1.72 ± 1.64a

1.00 ± 0.31c

14214 (UNE-EN 14214, 2008) and GB/T 20828 (GB/T 20828, [GB/T,
2007]2007).
**

3. Results and discussion


Palmitoleic acid (C16:1)
Changes in fatty acid compositions in developing Siberian apricot seeds.

SAT: saturated, MUNSAT: monounsaturated, PUNSAT: polyunsaturated.

3.1. Kernel characteristic


0.56 ± 0.35bc
0.68 ± 0.61b
0.86 ± 0.43a

0.42 ± 0.21c
0.44 ± 0.19c
0.51 ± 0.27c

0.46 ± 0.16c
0.50 ± 0.32c

Statistical data of the kernel characteristics in Siberian apri-


cot are shown in Table 1. Kernel dry biomass increased from
0.05 ± 0.03 g to 0.34 ± 0.08 g and varied significantly (P < 0.01) dur-
Fatty acids composition (%)

**

ing 3–10 weeks after anthesis. After 8 weeks, the kernel dry
biomass changed non-significant. It indicates that seeds at 8 weeks
Palmitic acid (C16:0)

could almost be a matured stage. Similarly, significant variations


(P < 0.01) in kernel length (9.62 ± 1.59–12.19 ± 1.13 mm), ker-
3.67 ± 1.21d
3.32 ± 1.05d
3.37 ± 1.02d
3.63 ± 0.93d
6.00 ± 2.12b
7.76 ± 2.64a
7.05 ± 2.85a

4.72 ± 1.10c

nel breadth (7.66 ± 1.29–10.52 ± 1.13 mm), and kernel thickness


(1.37 ± 0.23–5.59 ± 0.70 mm) were observed during seed develop-
ment (Table 1).
**
Weeks after anthesis

3.2. Oil content

Biodiesel plants with high oil content are considered to have


–, Not detected.

a potential for commercial development. Seed kernel oil content


P < 0.01.

increased slightly during 3–4 weeks (Fig. 2). It may be for this rea-
Table 2

son that triglycerides biosynthesis does not initiate at early stages


10
3
4
5
6
7
8
9

**

in developing fruit (Gaydou et al., 1987). Oil content of Siberian


198 S. Fan et al. / Industrial Crops and Products 89 (2016) 195–199

Table 3
Variation of biodiesel properties in developing Siberian apricot seeds.

Biodiesel properties Iodine value Cetane number Density (kg/m3 ; 15 ◦ C) Kinematic Viscosity Oxidative Cold filter
(mm2 s−1 ; 40 ◦ C) stability (h) plugging point
(◦ C)

Weeks after anthesis 3 136.5 ± 2.5a 42.8 ± 1.4c 880.49 ± 1.11a 4.07 ± 0.11d 1.98 ± 0.08c −8.7 ± 0.2a
4 135.7 ± 2.8a 43.0 ± 1.7c 880.53 ± 1.04a 4.11 ± 0.09d 2.01 ± 0.07c −9.7 ± 0.3b
5 117.9 ± 2.0b 47.1 ± 2.1b 878.26 ± 1.21b 4.29 ± 0.14c 2.76 ± 0.06b −10.5 ± 0.4bc
6 119.2 ± 2.3b 46.9 ± 2.2b 875.86 ± 1.36c 4.28 ± 0.12c 2.69 ± 0.06b −11.4 ± 0.5c
7 110.1 ± 2.2c 48.9 ± 2.5a 877.26 ± 0.98b 4.39 ± 0.11b 3.09 ± 0.05a −12.1 ± 0.2d
8 108.2 ± 2.4c 49.3 ± 2.1a 876.96 ± 0.79bc 4.41 ± 0.09a 3.16 ± 0.07a −12.5 ± 0.5d
9 108.0 ± 1.9c 49.4 ± 2.1a 877.09 ± 1.01b 4.41 ± 0.07a 3.18 ± 0.04a −12.4 ± 0.3d
10 107.7 ± 1.9c 49.4 ± 2.2a 876.89 ± 1.42bc 4.41 ± 0.10a 3.18 ± 0.09a −12.3 ± 0.4d
** ** ** ** ** **
P
Standards ASTM D6751-10 –a 47 min –a 1.9–6.0 3.0 min –a
EN 14214-08 120 max 51 min 860–900 3.50–5.00 6.0 min –b
GB/T 20828-07 –a 49 min 820–900 1.9–6.0 6.0 min Report

–a No specified limit.
–b Not specified Variable by location and time of year.
**
P < 0.01.

apricot kernels increased from 3.7% to 51.6% during 3–8 weeks and varied significantly (P < 0.01) across different development stages
achieved the highest point at 8 weeks (51.6%). Although the oil con- (Table 3).
tent had fallen from 51.6% to 45.4% during 8–10 weeks, the absolute Iodine value is a parameter indicating the degrees of unsatura-
oil content increased continuously. The observation was similar tion in biodiesel. A certain amount of unsaturated fatty acid can
to Camelina sativa which seeds oil content increased continuously prevent deposit formation in engine injectors, but the high content
and steadily during fruit development (Rodríguez-Rodríguez et al., of unsaturated fatty acid is not conducive to the engine lubrication.
2013). Iodine value ranged from 136.5 ± 2.5 to 107.7 ± 1.9 during 3–10
weeks after anthesis (Table 3). The iodine values were less than the
3.3. Fatty acid composition specified EN 14214-2008 maximum limit (120) after 5 weeks after
anthesis.
Physicochemical properties of biodiesel are determined by the Cetane number as an important index for measuring the fuel
fatty acid compositions (Knothe et al., 2005; Knothe, 2008; Moser combustion performance in the engine should be preferentially
and Vaughn, 2012). Oleic acid (C18:1), linoleic acid (C18:2), and considered when selecting methyl esters for biodiesel production.
palmitic acid (C16:0) were the predominant fatty acids during seeds Biodiesel standards of ASTM D6751-2010, EN 14214-2008 and GB/T
development (Table 2). The observation of the main fatty acids is 20828-2007 set the value of cetane number as 47, 51 and 49, respec-
similar to the previous study Wang and Yu (2012) on Siberian apri- tively. The cetane number ranged from 42.8 ± 1.4 to 49.4 ± 2.2
cot. The content of oleic acid and linoleic acid varied significantly during seeds development (Table 3). None of the cetane number
(P < 0.01) and presented an opposite trend in developing seeds. studied satisfied the standard EN 14214-2008 during seeds devel-
Oleic acid increased from 28.45 ± 2.98% to 71.61 ± 5.11%, whereas opment. Cetane number satisfied the ASTM D6751-2010 standard
linoleic acid decreased from 58.91 ± 3.61% to 23.78 ± 2.31% dur- when seeds were harvested at 5, 7, 8, 9, and 10 weeks after anthesis.
ing seeds development. A sharp increase in oleic acid content Seeds were harvested after 8 weeks were in accordance with GB/T
(32.27 ± 3.16%–54.16 ± 3.54%) was observed from 4 to 5 weeks 20828-2007.
after anthesis, whereas linoleic acid (57.05 ± 3.84%–37.2 ± 3.21%) Oxidative stability is one of the important technical issues affect-
decreased sharply. Palmitic acid decreased from 7.76 ± 2.64% to ing the application of biodiesel also can determine the requirement
3.32 ± 1.05% and varied significantly (P < 0.01) during seeds devel- to add antioxidants (Wang, 2013). The oxidative stability of eight
opment. After 7 weeks, the content of oleic acid, linoleic acid, development stages of Siberian apricot biodiesel was derived from
and palmitic acid changed non-significant and tended to be stable. empirical equations, giving values increased among 1.98 ± 0.08 h
Palmitoleic acid (C16:1) and stearic acid (C18:0) changed more sta- to 3.18 ± 0.09 h (Table 3). They did not reach the minimum values
ble than oleic acid and linoleic acid. Linolenic acid (C18:3), arachidic prescribed in the EN 14214-08(6 h) and GB/T 20828-07(6 h) stan-
acid (C20:0), and eicosenoic acid (C20:1) disappeared after 8 weeks dards. Seeds were harvested at 7, 8, 9, and 10 weeks after anthesis
after anthesis. can meet the ASTM D6751-2010(3 h) standard.
The ideal vegetable oil for biodiesel production should include a The poor cold flow properties of biodiesel fuel have been a rea-
high percentage of monounsaturated fatty acids, a low proportion son for impairing its widespread utilization (Wang et al., 2012). And
of polyunsaturated fatty acids, and a controlled amount of saturated the cold filter plugging point (CFPP) is an important parameter for
fatty acids (Ramos et al., 2009). The content of monounsaturated fuels applied in low-temperature. The CFPP is the temperature at
fatty acids in Siberian apricot reached the maximum at 9 weeks which a fuel jams a filter due to the formation of agglomerates crys-
(Table 2). The change of polyunsaturated fatty acids was opposite tals, which indicate whether the biodiesel produced can be used in
to monounsaturated fatty acids and varied non-significant after 7 low-temperate regions. The EN 14214 standard did not mention a
weeks after anthesis. The content of saturated fatty acids was less low-temperature parameter in its list of specifications. However,
than 11% during seeds development. each country using EN 14214 can specify certain temperature lim-
its for different times of year depending on climate conditions
(Zhang et al., 2010). As shown in Table 3, biodiesel obtained at
3.4. Biodiesel properties
eight different development stages displayed a satisfactory CFPP
(−12.5 ± 0.5 ◦ C to −8.7 ± 0.2 ◦ C), especially at 8 weeks after anthe-
The empirical values of fuel properties of Siberian apricot
sis (−12.5 ± 0.5 ◦ C). This value was particularly good because of the
methyl esters like iodine value, cetane number, density, kine-
matic viscosity, oxidative stability, and cold filter plugging point
S. Fan et al. / Industrial Crops and Products 89 (2016) 195–199 199

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