Journal of Cereal Science 88 (2019) 132–137

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Journal of Cereal Science

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Comparison of the lipid profile and tocopherol content of four Peruvian T

quinoa (Chenopodium quinoa Willd.) cultivars (‘Amarilla de Maranganí’,
‘Blanca de Juli’, INIA 415 ‘Roja Pasankalla’, INIA 420 ‘Negra Collana’)
during germination
Erika Pachari Veraa,∗, Juan Jose Alcaa, Giuliana Rondón Saraviaa, Nicolás Callejas Campionib,
Iván Jachmanián Alpuyb
a
Department of Food Industry Engineering, Universidad Nacional de San Agustín de Arequipa, Arequipa, Peru
b
Department of Food Science and Technology, Universidad de la República, Montevideo, Uruguay

ARTICLE INFO ABSTRACT

Keywords: Quinoa (Chenopodium quinoa Willd.) is an Andean pseudocereal that has acquired a commercial interest in recent
Quinoa decades, partly due to its nutritional characteristics and lack of gluten. Controlled seed germination has been
Germination used to improve the nutritional value of different species for human consumption, besides reducing anti-nu-
Tocopherol tritional factors. Polyunsaturated fatty acids are important in a balanced diet, particularly ω-3 fatty acids whose
Lipid profile
ratio to ω-6 fatty acids has been reported to be increased by germination. However, the fatty acid profile of the
seeds of each species and variety behaves differently during germination, and few studies have addressed quinoa
and its different cultivars. In this study, four Peruvian quinoa cultivars from Puno and Cusco were germinated in
the dark at 25 °C and analysed for their fatty acid profile after 24 and 48 h by GC-FID. The lipids were extracted
by a mixture of hexane/isopropanol and the determination of tocopherols was performed by HPLC with a
fluorescence detector. The content of lipids and tocopherols was carried out until 72 h. A slight increase in lipid
content was found in three of the cultivars, which may be because of better extractability of quinoa seed lipids
caused by germination. The highest average lipid content was presented by INIA 415 ‘Roja Pasankalla’ (5.89%,
db), which did not vary significantly during germination the first 48 h of germination. The lipid content of the
quinoa seeds tested did not vary between 48 and 72 h. With regard to the fatty acid profile, linoleic, oleic and
palmitic acids were predominant for all cultivars. The INIA 420 ‘Negra Collana’ cultivar had the highest content
of linoleic acid (56.24 ± 2.22%, on average). The PUFAs content increased mostly during germination and the ω-
6/ω-3 ratio improved for all cultivars, even for ‘Roja Pasankalla’ which showed the slightest variations in its fatty
acid profile. The increase of the concentration of ω-3 benefited notably INIA 420 ‘Negra Collana’, although the
cultivar with the best ratio ω-6/ω-3 and α-tocopherol was ‘Amarilla de Maranganí’ after 48 h of germination.
Only the ‘Blanca de Juli’ white seed cultivar show a decrease in total tocopherol content at the end of germi-
nation (from 1354 to 1011 ppm). The germination of quinoa seeds for 48 h has improved the profile of fatty acids
and α-tocopherol content, although it is necessary to investigate the effect of storage on the metabolism of each
fatty acid to understand new ways of optimising this process.

1. Introduction territories of Colombia, Ecuador, Peru, Bolivia, Argentina and Chile,

while its altitudinal distribution varies from sea level to 4000 m above
Quinoa (Chenopodium quinoa Willd.) is an Andean crop originated in sea level (Apaza et al., 2013). This dicotyledonous pseudocereal has a
the area surrounding the Titicaca lake and is currently found in South stem that varies in colour, depending on the variety, from white, yellow
America from 5° North Latitude to 43° South Latitude, covering or light brown to red. Its leaves are goose-foot-shaped and its flowers

Abbreviations: YQ, ‘Amarilla de Maranganí’; WQ, ‘Blanca de Juli’; RQ, INIA 415 ‘Roja Pasankalla’; BQ, INIA 420 ‘Negra Collana’; HSD, honest significant difference;
db, dry basis; wt%, weight percent
∗
Corresponding author. Department of Food Industry Engineering, Universidad Nacional de San Agustín de Arequipa, Independencia Avenue s/n, Arequipa, Peru.
E-mail address: epachari@unsa.edu.pe (E. Pachari Vera).

https://doi.org/10.1016/j.jcs.2019.05.015
Received 4 December 2018; Received in revised form 25 May 2019; Accepted 27 May 2019
Available online 02 June 2019
0733-5210/ © 2019 Elsevier Ltd. All rights reserved.
E. Pachari Vera, et al.
are incomplete, adopting different forms, either amaranthiform or
glomerulate. Its fruit is an achene that produces a circular seed, about
2 mm in diameter (Valencia-Chamorro, 2003).
The composition of quinoa seeds varies significantly depending on
the source. An average protein content of 14.2%, a starch content in the
range of 47.22–59.72% (Diaz-Valencia et al., 2018), and a lipid content
between 5.94 and 10.71% (Apaza et al., 2013) have been reported, all
on dry basis. Quinoa oil has a high concentration of linoleic (C18:2) and
linolenic (C18:3) fatty acids, which represent 52–63% of lipids (Tang
et al., 2016), while oleic acid represents up to 33% (Encina-Zelada
et al., 2018). It has been indicated that quinoa seeds have an ex-
ceptionally high flavonoid content (from 111 to 165 mg 100 g-1)
(Padmashree et al., 2018). The fatty acid profile is important for eval-
uating the nutritional value of the oil, especially the content of poly-
unsaturated fatty acids (PUFAs). The recommended intake of PUFAs
(European Food Safety Authority, 2009) was established as 2 g day-1
alpha-linolenic acid (ALA, ω-3), 250 mg day-1 eicosapentaenoic (EPA)
plus docosahexaenoic (DHA) fatty acids (long-chain ω-3) and 10 g day-1
linoleic acid (LA, ω-6). The tocopherol content of quinoa was reported
to be between 37.88 and 77.73 mg kg-1, containing between 8.70 and
16.02 mg kg-1 of α-tocopherol (Tang et al., 2016). Tocopherols are im-
portant for their biological activity that protects cells from oxidative
damage, with α-tocopherol being the only form that is maintained in
the blood. The Recommended Dietary Allowance (RDA) for α-toco-
pherol is 15 mg day-1 (Food and Drug Administration, 2016).
Germination has been used to improve the nutritional value of
quinoa seeds for human consumption, and to reduce their anti-nutri-
tional factors (Padmashree et al., 2018). Germination also affects the
fatty acid profile of quinoa seeds and their content of bioactive com-
pounds such as tocopherols (Park and Morita, 2004; Carciochi et al.,
2016), so it is important to study the effect of parameters such as the
time of germination on the nutritional traits of the seeds. However, this
effect on the fatty acid profile varies between seed species and even
within the same species, for each variety or cultivar and for different
fatty acids (Megat Rusydi et al., 2011).
In the case of quinoa, few studies have evaluated the effect of ger-
mination on the fatty acid profile, as did Park and Morita (2004),
Morita et al. (2013), and Padmashree et al. (2018). Carciochi et al.
(2016) were the first to study the effect of germination on the toco-
pherol content. None of the works identified the variety or cultivar. The
colour of the seeds was not reported, except for Padmashree et al.
(2018), which used unidentified varieties of red and white quinoa. No
relationship has been found between the colour of quinoa seeds and the
fat content or fatty acid profile (Encina-Zelada et al., 2018), but with
the tocopherol content (Encina-Zelada et al., 2018; Granda et al., 2018).
This study seeks to evaluate the effect of germination on the fatty acid
profile and tocopherol content of quinoa seeds of four cultivars
(‘Amarilla de Maranganí’, ‘Blanca de Juli’, INIA 415 ‘Roja Pasankalla’,
and INIA 420 ‘Negra Collana’), in order to improve these nutritional
traits for human consumption.
2. Experimental
2.1. Samples
Three cultivars of quinoa of different colours were used, cultivated
by the Instituto Nacional de Investigación Agraria (INIA) in Puno, Peru
(‘Blanca de Juli’, INIA 415 ‘Roja Pasankalla’, and INIA 420 ‘Negra
Collana’, coded as WQ, RQ and BQ, respectively) and one cultivated in
Cusco (‘Amarilla de Maranganí’, coded as YQ) also by INIA. The seeds
of BQ, WQ, RQ and YQ were obtained from plants sown in 2012, 2013,
2015 and 2016 respectively, and harvested the following year. All the
samples were stored at 10 °C since the harvest in order to maintain the
germination potential (> 80%, tested by INIA).
133
Journal of Cereal Science 88 (2019) 132–137
2.2. Germination
The germination was carried out using a modification of the pro-
cedure described by Abderrahim et al. (2012). 100 g of seeds of the four
quinoa cultivars were selected, washed with 0.3% of sodium hypo-
chlorite for 15 min and then rinsed with distilled water. The seeds were
then subjected to a conditioning and wetting process at approximately
45% of humidity. This quantity of seeds was prepared for each com-
bination of cultivar and germination time, for each of the analyses.
They were then distributed in previously disinfected stainless steel trays
and covered with a sterile gauze. Germination occurred in the dark, in
an Incucell laboratory incubation chamber (MMM Medcenter Einrich-
tungen GmbH, Germany) at 25 °C for 24, 48 or 72 h. The germinated
seeds were dried in a Binder oven (Tuttlingen, Germany) at a tem-
perature of 40 °C for about 15 h. This procedure was performed for each
experimental unit and repetition.
2.3. Lipid extraction
A modification of the method described by Hara and Radin (1978)
was used. The dried quinoa sprouts were ground in a coffee grinder, a
homogenised sample of 4 g was taken to which 20 mL of a hexane/
isopropanol solution (3:2 v/v) was added and the mixture was stirred at
40 °C for 60 min. The samples were then centrifuged and the super-
natant extracted using a Pasteur pipette. The cake was washed 4 times
with 7 mL of hexane/isopropanol solution. The supernatant liquid was
then filtered with Whatman filter paper #1 (pore size of 11 μm). Im-
mediately afterwards, the filtered liquid was evaporated using an Or-
ganomation nitrogen evaporator (Berlin, USA) with a water bath set at
40 °C. The total lipid content was reported in relation to the dry weight
of the samples, after weighing the evaporated content of the tubes until
constant mass. Analysis were performed twice for each combination of
cultivar and germination time.
2.4. Fatty acid analysis
The fatty acid methyl esters (FAMEs) were prepared according to a
modification of method AOCS Ce 2–66. An aliquot of 80–90 mg of each
sample was saponified with 1.5 mL of sodium hydroxide in methanol
(0.5 N) at 100 °C for 10 min. After cooling for 1 min, 2 μL of boron tri-
fluoride solution in methanol (14% w/v) was added and reheated to
100 °C for 5 min. After cooling for 1 min, 2 mL of n-hexane was added
and stirred in vortex for 30 s, then 5 mL of saturated solution of sodium
chloride was added, stirred in vortex for 30 s and centrifugated for
5 min (2000 rpm). Finally, the organic phase was transferred to a clean
tube and dried by the addition of anhydrous sodium sulfate. Solvent
with oil converted to methyl esters was transferred to a 4 mL vial using
a Pasteur pipette. The analysis of the FAMEs was performed using a gas
chromatograph with flame ionization detector (GC-FID) Shimadzu GC-
14B (Shimadzu, Japan). The samples (1 μL) were injected using a split
ratio 1:80 (at 250 °C). Separation was performed using a Supelco SP
2330 (30 m × 0.25 mm × 0.2 m). Peak identification was performed by
injection of convenient standards. Analyses were carried out twice for
the four cultivars after 24 and 48 h, besides the ungerminated seeds.
2.5. Tocopherol analysis
Samples were taken to dry at 40 °C to a humidity level equal of less
than 14% using an air drying oven (Binder GmbH, Germany) according
to a modification of the method described by Abderrahim et al. (2012).
Tocopherol analysis was performed on a Shimadzu 20-A HPLC equip-
ment (Shimadzu, Japan) equipped with an RF-20AXS fluorescence de-
tector. The methodology was adapted from Andrikopoulos et al. (1991).
Separation was carried out on a Supelcosil LC-18 column (25 cm ×
4.6 mm ×, 5 μm pore). Column oven was maintained at 40 °C and mo-
bile phase was acetonitrile/methanol/isopropanol/water from
E. Pachari Vera, et al.
47.5:42.8:4.7:5 (v%), which was kept isocratically until 6 min, then
programmed to 50:45:5:0 (v%) to 10 min and kept until 30 min, after
column was washed with acetonitrile 100% solvent proportion was
returned to the starting values. A calibration curve was prepared with
standards of α-tocopherol, γ-tocopherol and δ-tocopherol provided by
Sigma Aldrich. Detection was performed using excitation and emission
wavelengths of 290 and 330 nm, respectively. All the analysis were
performed twice, including ungerminated seeds.
2.6. Statistical analysis
The results were expressed as means values, followed by the stan-
dard deviation. None of the experiments was replicated. Analyses of
variance were performed using Tukey's HSD test in the statistical en-
vironment R (RStudio Team, 2015) (version 3.4.4) using the IDE
RStudio (version 1.1.442) and the statistical procedures package agri-
colae version 1.2–8.
3. Results and discussion
3.1. Lipid content
The lipid content on a dry basis (db) is shown in Table 1. In the case
of RQ, lower (5.07 ± 0.06%, Ludena Urquizo et al. (2016)), similar
(6.85 ± 0.10%, Repo-Carrasco-Valencia et al. (2010)) and higher (9.08
± 0.20% by Larico Vera et al. (2014)) lipid contents (db) have been
reported. Likewise, a slightly higher (5.94% by Apaza et al. (2013))
lipid content (db) was reported for BQ. However, a highest lipid content
for this cultivar was reported by Larico Vera et al. (2014) (8.38 ±
0.18%). For WQ, Apaza et al. (2013) reported a lipid content of 5.94%
(db), close to that obtained in this study. In the case of YQ the lipid
content is lower than previously reported (10.71% (db) by Apaza et al.
(2013)). This differs from the findings of Encina-Zelada et al. (2018),
who found no significant difference in the mean lipid content in co-
loured quinoa (white, black and red, that included samples of BQ and
RQ) of different varieties and cultivars (from 6.0 to 6.8 g 100 g-1, db).
It has been suggested as an explanation that different agronomic,
genotypic and climatic factors play a role in the lipid content of seeds of
different species and varieties, even within the same cultivar. For in-
stance, winter sowing dates resulted in a higher concentration of lipids
in quinoa seeds (Curti et al., 2018). For some varieties of oats grown in
the same location in Scotland, the lipid content varied every year,
probably due to climatic variations such as rainfall (Chappell et al.,
2017). In the case of Ludena Urquizo et al. (2016), the seeds were
grown in Junín without indicating the year of sowing or harvest, nor
did Apaza et al. (2013) who used seeds grown in Puno. Repo-Carrasco-
Valencia et al. (2010) used RQ samples harvested in Puno in 2008,
while Diaz-Valencia et al. (2018) and Larico Vera et al. (2014) used RQ
and BQ samples harvested in Puno in 2012. Although these studies
analysed seeds from the same germplasm bank obtained from the same
crop, the lipid content values were very different. While Diaz-Valencia
et al. (2018) reported values of 7.33 ± 0.11 and 6.67 ± 0.10 for RQ and
Table 1
Lipid content (wt%, db) of each quinoa cultivar at different germination per-
iods.
Cultivar Germination time (h)
0 24 48 72
YQ 4.97 ± 0.25c 6.15 ± 0.04b 7.21 ± 0.08a 7.34 ±
WQ 5.52 ± 0.44b 5.64 ± 0.28ab 6.91 ± 0.37a 6.73 ±
RQ 6.46 ± 0.39a 7.14 ± 0.07a 6.79 ± 0.60a 8.03 ±
BQ 5.04 ± 0.02b 6.02 ± 0.08a 5.88 ± 0.11a 6.16 ±
Values followed by the same letter in the row do not differ (Tukey test,
p < 0.05). Each analyses was performed twice.
Journal of Cereal Science 88 (2019) 132–137
BQ respectively, Larico Vera et al. (2014) obtained 9.08 ± 0.20 and
8.38 ± 0.18 for the same cultivars. None of these authors indicated the
year in which they made the determinations but it could be indicated
that seed storage time should be considered even when comparing re-
sults of seeds from the same season and cultivar.
Respect to the germination period, an increase in the lipid content
on a dry basis is observed for the cultivars YQ, WQ and BQ, which is
higher with respect to ungerminated seeds. For RQ, there was no sig-
nificant differences between the ungerminated and germinated seeds.
Valenzuela Antezana et al. (2015) reported a slight decrease (2.49%) in
the fat content (db) of RQ, and a slight increase (0.74%) in the case of
BQ (after germination at 20 °C for 48 h, with respect to scarified, un-
germinated seeds). The fat content reported for BQ after 48 h of ger-
mination (5.46%, db) was similar to the present one, while RQ showed
a lower content (5.49%, db) in relation with this work. Seed lipids
during germination are catabolised through several consecutive path-
ways in different cell compartments, starting with the hydrolysis of
triglycerides by lipases, transport to glyoxysomes, β-oxidation and
glyoxylate cycle (Graham, 2008). By β-oxidation, the free fatty acids are
converted into acetyl-CoA, which can be condensed into four-carbon
sugars by the glyoxylate cycle (Park and Morita, 2004). reported that
the free lipid content (by Soxhlet extraction using n-hexane) decreases
over time, while the bound lipids (nonpolar lipids, glycolipids and
phospholipids) increased during germination up to 72 h. These authors
reported a total lipid content between 7.2 and 8.8%, which is higher
than the values of the present study, because they used a different
variety or cultivar of quinoa. During barley germination, an increase in
lipid content has been observed during the first few days, and it has
been pointed out as the cause that some lipids are retained in fragments
that initially are not easily extractable by the solvent until after ger-
mination has begun (MacLeod and White, 1961). Thus, this increase in
barley lipids would be the result of a better solvent penetrationrather
than metabolic change. In the case of millet (Opoku et al., 1983), it has
been proposed that the increase in lipid content during the first hours of
germination may be because other seed reserves (such as starch and
proteins) were preferentially metabolised during this period, as the
lipid content then decreased markedly. Our results for quinoa could be
due to the extraction method, and that the lipids of some varieties
would improve their extractability with germination since it has not
been possible to find in the previous literature that the synthesis of
lipids surpasses their catabolism during quinoa germination.
3.2. Fatty acid profile
The content of fatty acids of the YQ, WQ, RQ and BQ samples, at the
beginning and during germination, is shown in Table 2. The saturated
palmitic acid (C16:0) was present in higher concentration (from 9.65 to
10.54%) than linolenic acid (from 2.99 to 11.04%) for ungerminated
samples, except for YQ. Palmitic acid is the predominant saturated fatty
acid in quinoa oil (Encina-Zelada et al., 2018) with a concentration
ranging from 9.32 to 21% (Tang et al., 2016; Encina-Zelada et al.,
2018). There was no significant difference in palmitic acid concentra-
tion between the ungerminated seeds of the different cultivars.
The major fatty acid in ungerminated seeds for all samples was li-
noleic (ranging from 46.98 to 58.56%), followed by oleic (from 18.43
to 31.08%). The ungerminated seeds of BQ and RQ had the highest
concentrations of linoleic and oleic acid, respectively. These values are
similar to the ranges reported for linoleic acid (from 27 to 56.64%
(Tang et al., 2016; Encina-Zelada et al., 2018)) and oleic acid (from
15.71 to 28.85% (Tang et al., 2016)). In previous studies, linoleic acid
0.01a was the main fatty acid, followed by oleic and palmitic acids (Encina-
0.01ab Zelada et al., 2018; Padmashree et al., 2018), with no significant dif-
0.34a
0.25a
ference between black, red or white seeds (Encina-Zelada et al., 2018).
However, Padmashree et al. (2018) reported that red quinoa seeds had
a lower content of palmitic, linoleic and linolenic acid than white
quinoa seeds. Among the ungerminated seeds, YQ stood out for its
134
E. Pachari Vera, et al. Journal of Cereal Science 88 (2019) 132–137

Table 2
Fatty acid composition (wt %) of oil extracted from the cultivars at different germination periods.
Fatty acid Time (h) Cultivar

YQ WQ RQ BQ

a a a
Palmitic 0 9.75 ± 0.47 9.65 ± 0.11 10.54 ± 0.05 9.91 ± 0.21a
24 9.89 ± 0.05a 9.22 ± 0.05c 9.78 ± 0.03a 9.55 ± 0.07b
48 10.41 ± 0.10a 9.58 ± 0.07b 10.26 ± 0.03a 9.83 ± 0.03b
Oleic 0 18.43 ± 0.13c 28.42 ± 0.12b 31.08 ± 0.91a 26.91 ± 0.19b
24 16.55 ± 0.03d 28.03 ± 0.02b 30.26 ± 0.03a 26.06 ± 0.03c
48 16.14 ± 0.05d 25.94 ± 0.08b 28.93 ± 0.21a 24.32 ± 0.04c
Linoleic 0 51.77 ± 0.17ab 49.79 ± 0.32b 46.98 ± 2.70b 58.56 ± 2.75a
24 56.20 ± 0.91a 50.96 ± 0.08b 46.58 ± 0.10c 54.62 ± 0.07a
48 56.09 ± 1.45a 52.50 ± 0.45b 47.94 ± 0.68c 55.53 ± 0.18ab
Linolenic 0 11.06 ± 0.04a 5.35 ± 0.00c 7.73 ± 0.39b 2.99 ± 0.71d
24 12.01 ± 0.03a 5.94 ± 0.06c 8.21 ± 0.03b 4.02 ± 0.00d
48 12.58 ± 0.03a 7.30 ± 0.05c 8.46 ± 0.05b 4.98 ± 0.01d
Eicosenoic 0 1.44 ± 0.01a 1.60 ± 0.02a 0.99 ± 0.64a 0.63 ± 0.60a
24 1.10 ± 0.18b 1.55 ± 0.08a 1.33 ± 0.04ab 1.40 ± 0.01ab
48 1.13 ± 0.36a 1.31 ± 0.11a 1.27 ± 0.15a 1.36 ± 0.00a
Erucic 0 1.38 ± 0.15a 1.50 ± 0.07a 0.91 ± 0.57a NDa
24 1.06 ± 0.09b 1.26 ± 0.01a 1.22 ± 0.02ab 1.34 ± 0.02a
48 0.96 ± 0.15a 1.09 ± 0.11a 1.13 ± 0.09a 1.22 ± 0.01a
ω-6/ω-3 0 4.68 9.31 6.08 19.59
24 4.68 8.58 5.67 13.59
48 4.46 7.19 5.67 11.15

Mean values followed by the same letter in the row do not differ (Tukey test, p < 0.05). Each analyses was performed twice.
a
Not detected.

concentration of linolenic acid. This fatty acid has been reported in
concentrations ranging from 4.77 to 9.57% (Tang et al., 2016) although
it was the main glycolipid (Morita et al., 2013). Glycolipids represented
up to 25% of the lipids of the ungerminated quinoa seeds (Park and
Morita, 2004). Eicosenoic fatty acid (from 0.63 to 1.60%) and erucic
fatty acid (from 0.91 to 1.50%) were in lower concentration in all un-
germinated samples, and their concentration did not vary between the
different cultivars. The previously reported concentration ranges (from
0.30 to 1.48% for eicosenoic acid and from 1.02 to 1.21% for erucic
acid (Tang et al., 2016)) are in agreement with those found in the
present study.
The concentration of palmitic acid did not present any significant
variation (p < 0.05) for YQ and BQ samples during germination time.
The mean concentration of this fatty acid for these two cultivars was
10.02 ± 0.38 and 9.76 ± 0.20%, respectively. On the other hand, the
concentration of the same fatty acid for the WQ and RQ cultivars fol-
lowed a similar trend with that already reported by Park and Morita
(2004) for the non polar lipids of quinoa, it initially decreased and then
increased with germination time. Among the phospholipids of germi-
nated quinoa, palmitic acid has been reported in some cases as the
highest (Morita et al., 2013) or third (Park and Morita, 2004) in con-
centration. The increase in saturated fatty acids has also been observed
in several legumes and rice varieties after germination for 48 h, while in
others it decreased (Megat Rusydi et al., 2011). Oleic acid concentra-
tion did not change during germination for RQ samples (30.09 ± 1.06%
on average), while for the other cultivars the concentration of this fatty
acid decreased. Park and Morita (2004) reported that the oleic acid
concentration was stable after 48 h of germination in the phospholipid
and glycolipid fraction of quinoa oil, but it increased in the non polar
fraction from 22 to 40.7%. Oleic acid was the main glycolipid of the
germinated quinoa (Morita et al., 2013) and its concentration increased
slightly with germination (48 h, 30 °C). This slight increase in the
concentration of oleic acid was also observed for white (from 19.16 to
19.87%) and red (from 20.14 to 21.26%) quinoa seeds after 48 h of
germination at room temperature (Padmashree et al., 2018).
The concentration of linoleic acid did not change during germina-
tion for RQ and BQ (p < 0.05), which had average concentrations of
47.16 ± 1.40% and 56.24 ± 2.22%, respectively. For YQ and WQ, the
concentration increased after 24 and 48 h, respectively. A similar
behaviour was reported by Park and Morita (2004), which showed that
linolenic acid remains stable until 48 h (42.1–49.2%), although then the
concentration decreases significantly after 72 h (26.9%) in the non
polar and phospholipid fraction, while it increased after 48 h in the
glycolipids fraction and then decreased markedly after 72 h. Linoleic
acid was the main fatty acid in all the cultivars tested, as Padmashree
et al. (2018) reported for the germinated red and white quinoa seeds
after 48 h, although its concentration decreased slightly. It was also the
main non-polar lipid in quinoa seeds germinated for 48 h and its con-
centration increased while that of oleic acid decreased (Morita et al.,
2013).
The concentration of linolenic acid increased during the germina-
tion period for all cultivars, except for RQ, which did not vary from its
initial value and had an average concentration of 8.14 ± 0.38%. On the
other hand, Park and Morita (2004) pointed out that during germina-
tion the concentration of this fatty acid decreases with time for the non
polar, glycolipid and phospholipid fraction but returns to the initial
level at 72 h in the non polar lipids fraction. Padmashree et al. (2018)
reported that the concentration of this fatty acid decreased slightly for
the red (from 5.95 to 5.81%) and white (from 6.43 to 6.21%) quinoa
seeds after 48 h of germination. With respect to the concentration of
eicosenoic acid, it did not vary for any of the quinoa cultivars. The
average concentration for YQ, WQ, RQ and BQ was 1.22 ± 0.24, 1.48 ±
0.15, 1.20 ± 0.34 and 1.13 ± 0.47%, respectively. The concentration of
erucic acid remained without significant variation for RQ and YQ
during the experiment (average concentration of 1.08 ± 0.30 and 1.14
± 0.22%, respectively). In the case of WQ, the concentration of this
fatty acid decreased with germination time, while for BQ, it could only
be detected after 24 h of germination, and then it decreased after 48 h.
During the germination of quinoa no drastic changes were expected
in the fatty acid profile after 48 h (Padmashree et al., 2018), except the
improvement of the ratio of ω-6/ω-3 (Park and Morita, 2004) and a
slight decrease of PUFAs (Padmashree et al., 2018). When longer ger-
mination times (72 h) were used, the concentration of ω-3 and ω-6 fatty
acids decreased significantly, while the concentration of oleic acid in-
creased (Park and Morita, 2004). The decrease in the concentration of
PUFAs and increase in MUFAs have been reported for different varieties
of legumes and rice during their germination (Megat Rusydi et al.,
2011). The metabolism of fatty acids is initiated by lipases and is part of

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the metabolic activity to generate energy and synthesise new molecules (78.98 mg kg-1 db), followed by RQ (67.86 mg kg-1 db) and above YQ
during germination. Two strategies have evolved in the core group of β- (40.13 mg kg-1 db) (Granda et al., 2018). δ-tocopherol showed similar
oxidation enzymes: either multiple isoforms with different chain length levels among black, white or red quinoa seeds (Encina-Zelada et al.,
specificities or enzymes with broad specificity/low selectivity by the 2018). However, Granda et al. (2018) reported that RQ and a variety of
carbon chain length Graham (2008). This metabolic activity helps meet black quinoa had the highest levels of delta-tocopherol (2.31 and
the needs of the seedling until photosynthesis begins and it can nourish 4.59 mg kg -1 db, respectively) compared to YQ (0.91 mg kg-1 db), while
itself from the medium. No specific metabolism has been reported for no beta-tocopherol was detected in either variety. The concentration of
each fatty acid in the case of quinoa. tocopherols, estimated as the sum of alpha-tocopherol and gamma-to-
In general terms, RQ samples showed the least variation in the copherol, reported by Kozioł (1992) showed a range from 1480 to
concentration of the fatty acids analysed. In a previous study 1670 ppm, while based on data from Repo-Carrasco et al. (2003) it
(Valenzuela Antezana et al., 2015) it had already been pointed out that would be estimated to be around 1518 ppm. The WQ, RQ and BQ
RQ did not present significant variations in its nutritional content as samples showed tocopherol concentrations similar to the reported in-
opposed to BQ, which is the variety with the most benefited from formation, while YQ differs in having a higher concentration than the
germination (increase in the concentration of ashes and proteins, after others at the beginning and during germination. In all cases, quinoa oil
48 h at 20 °C). In the present study, BQ benefited more from germina- would have a higher tocopherol concentration than crude corn oil
tion to improve its ω-6/ω-3 ratio (reduction of 43.08%), which reached (1006.3 ppm), crude sunflower oil (737.0 ppm) and crude rapeseed oil
after 48 h a value of 11.15. However, the lowest ω-6/ω-3 ratio was (822.8 ppm) (Ergönül and Köseolu, 2014).
found in YQ, although germination only reduced it by 4.70% after 48 h. In the case of YQ, RQ and BQ, the content of total tocopherol did not
In brief, YQ was the cultivar with the best profile of fatty acids mainly change significantly with germination. It has been reported (Encina-
by the higher content of ω-3, while the germination time of 48 h im- Zelada et al., 2018) that the total tocopherol content of seeds of dif-
proved its ratio of ω-6/ω-3, as well as for the other cultivars. The ratio ferent varieties and cultivars of red and black quinoa (including BQ and
of ω-6/ω-3 of about 4 is associated with a reduction in mortality from RQ) was similar (from 1388 to 1764 μg 100 g-1), which differed sig-
cardiovascular disease (Simopoulos, 2008). This ratio is close to the nificantly from that of white seeds (971 μg 100 g-1). The α-tocopherol
value obtained in YQ after 48 h of germination. content of YQ was stable during germination, although the concentra-
tion of , , and tocopherol decreased. α-tocopherol was the
major tocopherol for YQ during germination. For the seeds of RQ and
3.3. Tocopherol content BQ, the levels of α-tocopherol increased after germination for 24 and
48 h, albeit for WQ the concentration dropped after 72 h. Carciochi
The content of tocopherols of the oils extracted from quinoa samples et al. (2016) also observed an increase in the concentration of α-toco-
at different germination periods is shown in Table 3. The principal pherol with germination up to 72 h, while δ- and γ-tocopherol initially
tocopherols in quinoa seeds are γ-tocopherol (from 26.23 to 55.32 μg g- decreased their concentration and then increased to 72 h. In the present
1
) and α-tocopherol (from 8.70 to 16.02 μg g-1) (Tang et al., 2016). YQ study the total tocopherol content of WQ decreases slightly after 24 h of
presented a significantly higher content of α-tocopherol. Granda et al. germination and then recovers to a value similar to the initial one at
(2018) found that YQ had a significantly higher α-tocopherol content 48 h and decreases significantly at 72 h. An inverse trend was identified
(82.87 mg kg-1 db) than RQ (37.66 mg kg-1 db) and an unidentified by Carciochi et al. (2016) which indicated that content of total toco-
black variety (35.55 mg kg-1 db). On the other hand, Encina-Zelada pherols increased significantly after 72 h of germination.
et al. (2018) reported that there was no difference in α-tocopherol
content between different varieties and cultivars of black, white and red 4. Conclusions
quinoa (where BQ and RQ were included), ranging from 125 to 169 μg
100 g-1. γ-tocopherol had higher levels in black seeds, followed by red The present study evaluated the lipid content, fatty acid profile and
and white seeds (Encina-Zelada et al., 2018). Another variety of uni- total tocopherol content of four quinoa cultivars during germination.
dentified black quinoa had the highest γ-tocopherol content The lipid content (ranging from 4.97 to 6.46%, dry basis) was in the
range previously reported for some of the cultivars, except for ‘Amarilla
Table 3 de Maranganí’, which had a lower value. The germination produced an
Content of tocopherol (ppm) in oils extracted from the four quinoa cultivars at increase in the concentration of lipids for the cultivars ‘Amarilla de
different germination time. Maranganí’ and ‘Negra Collana’, contrary to the other two cultivars.
Tocopherol Time (h) Cultivar This increase could be because of a better extractability of the lipids of
the seeds of these varieties, and by the extraction method. The most
YQ WQ RQ BQ important unsaturated fatty acid in the ungerminated quinoa samples
α 0 1444 ± 31 a
639 ± 108 b
608 ± 125b
463 ± 146b was the linoleic acid (46.98–58.56%), followed by oleic acid
24 1522 ± 81a 892 ± 92b 985 ± 109b 832 ± 107b (18.43–31.08%). Palmitic acid was the main saturated fatty acid
48 1803 ± 1114 ± 1214 ± 1011 ± (9.65–10.54%). Germination produced different results depending on
145a 105b 138b 119b the cultivar. Generally, the samples of the cultivar ‘Roja Pasankalla’
72 1538 ± 724 ± 29b 1086 ± 1025 ±
256a 46ab 27ab
showed less variation in its fatty acid profile. Germination improved the
+ + 0 831 ± 17b 715 ± 13b 841 ± 53b 1048 ± 74a omega-6/omega-3 ratio of all varieties, mainly benefiting ‘Negra
24 394 ± 29b 399 ± 48b 542 ± 52b 793 ± 70a Collana’. However, ‘Amarilla de Maranganí’ obtained the best ratio
48 276 ± 23b 299 ± 20b 269 ± 44b 499 ± 60a after 48 h compared to the other cultivars. As for the total tocopherol
72 209 ± 35b 287 ± 9b 239 ± 8b 438 ± 15a
content, only the cultivar ‘Blanca de Juli’ showed a decrease with re-
+ + + 0 2275 ± 14a 1354 ± 95b 1450 ± 72b 1512 ± 72b
24 1917 ± 1291 ± 44c 1528 ± 1625 ± 37b spect to the initial value (from 1354 to 1011 ppm). In all cases, the total
110a 57bc tocopherol content of the samples was above several commercial oils
48 2079 ± 1413 ± 85b 1483 ± 93b 1511 ± 59b (sunflower oil, rapeseed oil, corn oil) and α-tocopherol was prevalent
166a during germination for all the cultivars. These results indicate that
72 1747 ± 1011 ± 39b 1326 ± 1463 ±
291a 53ab 42ab
quinoa could be an oleaginous crop of interest and that the germination
of the cultivars studied does not adversely affect the fatty acid profile of
Mean values followed by the same letter in the row do not differ (Tukey test, quinoa oil. However, due to the fact that the samples came from har-
p < 0.05). Each analyses was performed twice. vests of different years, it is necessary to study the effect that the

136
E. Pachari Vera, et al.
storage and metabolism of each cultivar would have on the lipid con-
tent and their fatty acids after controlled germination. Further tech-
nological research is needed to take advantage of germination for nu-
tritional improvement of different quinoa cultivars.
Declarations of interest
This research received financial support from the Santander
Foundation for a visit and academic stay in Uruguay.
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