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The Chemical Composition of Barley Grain (Hordeum Vulgare L.) Landraces From The Canary Islands

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The Chemical Composition of Barley Grain (Hordeum Vulgare L.) Landraces From The Canary Islands

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The chemical composition of barley grain (Hordeum vulgare L.) landraces


from the Canary Islands

Article in Journal of Food Science · June 2020


DOI: 10.1111/1750-3841.15144

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The chemical composition of barley grain
(Hordeum vulgare L.) landraces from the Canary
Islands
Marı́a Panizo-Casado, Pilar Déniz-Expósito, Beatriz Rodrı́guez-Galdón, Desirée Afonso-Morales, Domingo Rı́os-Mesa,
Carlos Dı́az-Romero , and Elena M. Rodrı́guez-Rodrı́guez

Abstract: The proximate composition, total phenolics, antioxidant activity, minerals, and trace elements were determined
in 42 barley landraces in order to highlight their nutritional potential and promote their cultivation. Two-row barley
landraces had a higher average content of starch, protein, total phenolic compounds, and iron, when compared with
six-row ones that presented higher mean ash and fiber concentrations. Additionally, the six-row barley landraces with
strongly pigmented grains had lower zinc and manganese and higher protein mean concentrations than the whitish or
lightly pigmented barley landraces. Factor analysis and linear discriminant analysis were used to correctly differentiate
samples according to type of barley (landrace or commercial) and number of rows. In general, all the parameters varied
considerably among the barley landraces analyzed, but some barley landraces could be emphasized according to fiber,
minerals, and phenolic antioxidants. There were important differences in the mean values in all the chemical parameters
according to the island of origin of the barley grains. The application of linear discriminant analysis was also a useful tool
to differentiate all the barley landraces with six rows according to the island of origin.

Food Chemistry
Keywords: barley, Canary Island, food composition, landraces, mineral and trace elements, NIR

Practical Application: Barley is a versatile cereal that can be used for human and animal feed, brewing, and as biodiesel.
From the nutritional point of view, barley is rich in starch, protein, dietary fiber and minerals, as well as antioxidant
compounds and vitamins. The landraces analyzed in this study have remained intact for the last 900 years, which gives
opportunity to genome of these barley landraces to evolve some very specific traits. The physicochemical characterization
of these local landraces carried out by us could be very useful as a source of new quality in breeding programs.

1. INTRODUCTION in a wide range of food products (Lee et al., 2008). Analogously


Barley (Hordeum vulgare L.) is the most cultivated cereal in Spain to other cereals, the consumption of barley contributes to the in-
with a production of 5,785,944 tons, more than 40% of the total take of starch, protein (deficient in lysine), vitamins B, minerals,
of cereals. It is mainly used to manufacture animal feed (MAPA, and trace elements (Kaur, Gill, & Karwasra, 2017). Consider-
2018), in brewing and in the production of ethanol for biodiesel. able amounts of proteins, vitamins, minerals, and trace elements
The cultivation of two-row barley has increased in Spain and are commonly found in the husk of the grain, which is closely
throughout the world due to the presence of new varieties with linked to the grain. Therefore, the flour produced by milling
better brewing qualities and a higher yield compared to six-row the whole grain has a higher nutritional value and which is com-
barley (Callejo-González, 2002). The chemical composition and monly associated with more brownish colorations (Márquez-Elı́as,
quality of barley grains is influenced by factors such as genetic char- 2007). In fact, barley has been recognized worldwide including
acteristics, specific treatments, environmental conditions, and agri- the European Food Standards Agency as having numerous health
cultural practices (Abdel-Aal & Choo, 2014). This implies that the benefits (EFSA, 2006). This cereal is rich in (1-3) (1-4)-β-D-
grain of the same varieties may differ in their chemical composition glucans that are among the most important soluble fibers in hu-
according to agronomic, climatic, soil conditions, and cultivation man nutrition. These compounds regulate blood glucose levels
techniques (Woźniak, Soroka, Stepniowska, & Makarski, 2014). and reduce the effects of cholesterolemia and blood pressure, and
The first two decades of the 21st century have seen a growing consequently, reduce the risk of cardiovascular diseases. Further-
interest in the investigation and development of the use of barley more, they are considered antioxidant, antibacterial, antitumor,
and anti-inflammatory agents, and play an important role in the
immunomodulation and regulation of the human gut flora (Bai
JFDS-2019-1869 Submitted 11/14/2019, Accepted 3/26/2020. Author Panizo- et al., 2019). In addition, a high content of fiber in food in-
Casado, Rodrı́guez-Galdón, Dı́az-Romero, and Rodrı́guez-Rodrı́guez are with Área creases the intestinal transit lowering the exposure of colonocytes
de Nutrición y Bromatologı́a, Departamento de Ingenierı́a Quı́mica y Tecnologı́a Far- to carcinogens and increasing the satiation from a meal that can
macéutica, Universidad de La Laguna, Tenerife, Spain. Author Déniz-Expósito is with
Cereales Archipiélago S.A., La Laguna, Tenerife, Spain. Authors Afonso-Morales and
be useful in weight control (Abdel-Aal & Choo, 2014). Like the
Rı́os-Mesa are with Centro de Conservación de la Biodiversidad Agrı́cola de Tener- rest of the grains, barley has considerable amounts of phenolic
ife (CCBAT), Servicio de Agricultura, Cabildo de Tenerife, Tenerife, Spain. Direct compounds, particularly in the external parts of the grain (cover,
inquiries to author Rodrı́guez-Rodrı́guez (Email: [email protected]). testa, and aleurone). Flavanols, especially catechin, procyanidins,

C 2020 Institute of Food Technologists


 R

doi: 10.1111/1750-3841.15144 Vol. 00, Iss. 0, 2020 r Journal of Food Science 1


Further reproduction without permission is prohibited
Chemistry barley landrace from Canary Islands . . .

and prodelphinidins, are the main compounds in the free phe- Table 1–Description of barley landraces.
nolic fraction, while phenolic acids, such as ferulic, coumaric, Aleurone Lenght of
and vanillic acids, are major constituents of the bound phenolic N Island Rows Spike density color vegetative cycle
fraction (Abdel-Aal & Choo, 2014).
1 Tenerife 6 Lax Green 159
Geographical isolation allows the genome of traditional and 2 Tenerife 6 Lax Green 143
local barley landraces to develop specific traits that could be use- 3 Tenerife 2 Intermediate White 158
ful as a source of new quality in breeding programs. Barley lan- 4 Gran Canaria 6 Lax Green 159
draces from the Canary Islands have been characterized molecu- 5 Tenerife 2 Intermediate White 145
6 Gran Canaria 6 Lax White 152
larly and morphologically (Hagenblad, Leino, Afonso, & Morales, 7 Lanzarote 6 Lax Green 162
2019); these landraces were characterized as having a covered grain, 8 La Palma 6 Lax Green 153
rough edges, and an absence of pilosity in the basal leaves. The 9 Gran Canaria 6 Lax Green 152
molecular studies carried out using single nucleotide polymor- 10 La Gomera 6 Lax Green 141
phism concluded that their genetics have remained intact for the 11 Tenerife 6 Lax Blue 138
12 Tenerife 6 Lax Green 153
last 900 years (Leino, Hagenblad, Edqvist, & Strese, 2009), which 13 Gran Canaria 6 Lax Green 150
gives an idea of the invaluable legacy that these landraces provide.14 Gran Canaria 6 Lax Green 161
However, the production of this cereal in the Canary archipelago 15 Tenerife 6 Lax Green 138
has markedly decreased in the first two decades of the 21st century,16 Tenerife 6 Lax Green 155
17 Fuerteventura 6 Lax Green 154
which put these ancient landraces at serious risk, not only for the 18 La Palma 6 Lax Green 152
loss of this genetic heritage but also because of the disappearance 19 La Gomera 6 Lax Blue 150
of the landscapes associated with this crop (Hagenblad et al., 2019).
20 Gran Canaria 6 Lax Green 157
Knowledge of the nutritional profile of traditional barley landraces21 Gran Canaria 6 Lax Green 159
of the Canary Islands is a good way to increase the value of this 22 Tenerife 6 Lax Green 161
23 La Gomera 6 Lax Blue 150
Food Chemistry

genetic heritage, and thereby encouraging its use and promotion. 24 La Palma 6 Lax Green 147
The proximate composition, total phenolics and antioxidant 25 Gran Canaria 6 Lax Green 161
activity, and minerals and trace elements were determined in tra- 26 Tenerife 6 Lax Green 161
ditional barley landraces from the Canary Islands to establish dif- 27 Tenerife 6 Lax Green 162
28 Gran Canaria 6 Lax Green 155
ferences not only between the landraces but also with respect to 29 Gran Canaria 6 Lax Green 151
commercial varieties. This characterization will allow the selec- 30 Gran Canaria 6 Intermediate Green 162
tion of barley landraces with the best nutritional characteristics and
31 Gran Canaria 6 Lax Green 156
the promotion of their cultivation and use. Multivariate analysis 32 Gran Canaria 6 Lax Green 114
was applied to the differentiation of barley landraces according to 33 Gran Canaria 6 Lax White 157
34 Gran Canaria 6 Lax Blue 155
genetic and agronomic characteristics. 35 Lanzarote 6 Lax Blue 140
36 Tenerife 6 Lax Blue 150
37 Gran Canaria 6 Lax Green 150
2. MATERIALS AND METHODS 38 Tenerife 6 Lax Blue 156
39 Gran Canaria 6 Lax Blue 144
2.1 Description of barley landraces and cultivation 40 Tenerife 6 Lax White 151
Forty five barley samples were analyzed, 42 were ancient lan- 41 Tenerife 6 Lax Green 150
draces from the Canary Islands, and three were commercial ones 42 Tenerife 6 Lax Green 151
used as control. Data about island of origin, spike density, number 43 Control 6 Intermediate White 184
of rows, aleurone layer color, and length of vegetative cycle are 44 Control 2 Intermediate White 147
45 Control 2 Intermediate White 148
shown in Table 1 (Hagenblad et al., 2019). Most of the barley
samples were of six rows, and only four (two landraces and two
commercial samples barley) were of two rows.
All the samples were supplied by the Center for the Conser- chemically controlled following the technical recommendations.
vation of Agricultural Biodiversity of Tenerife. All the landraces Drip irrigation was installed and water was supplied according to
were grown in the same climatic and soil conditions; in the Araya the crop needs. Harvesting was performed manually between May
area (Tenerife Island) (28°21 47 N and 16° 23 38  W) on a farm and June 2013, when physiological maturity was reached.
located at 530 m above sea level. The experimental samples were
planted on December 18, 2012, in a flat outdoor plot. The physic- 2.2 Proximate analysis
ochemical characteristics of the irrigation water and soil used are A 600 g sample of barley grain was collected from each plot
summarized in Table S1. The cultivation soil was classified as for analysis. A 20 g subsample was cleaned with Milli-Q water
saline and the irrigation waters had moderate electrical conduc- and homogenized with an electric grinder (Ika-Werke, Staufen,
tivity. These values were considered adequate for the cultivation Germany) to determine phenolic compounds, antioxidant
of this cereal as barley is considered moderately resistant to salinity. capacity, and mineral and trace elements. Moisture, protein,
Data for accumulated precipitation, temperature, relative mois- starch, crude fiber, and ash were analyzed in the whole grain and
ture, and wind speed and direction were recorded on a monthly in quadruplicate using near-infrared spectroscopy (NIRS) at the
basis by a meteorological station located on the same farm. The “Cereales Archipiélago” (Tenerife, Spain). As quality control of
test cultivation was conducted in a randomized complete block data, moisture, starch, protein, and ash were determined in two
design with three blocks. The sowing density was 350 seeds/m2 , samples of barley in triplicate, using classical methods (AOAC
which was sowed manually in four rows, 4 m long and 20 cm International, 2006) for comparison with the results obtained
apart. The plots were fertilized before planting with 300 kg/ha of by NIRS. No significant differences were found in the three
complex 15-15-15 complex NPK fertilizer. Pest and diseases were analyzed parameters between both methods.

2 Journal of Food Science r Vol. 00, Iss. 0, 2020


Chemistry barley landrace from Canary Islands . . .

2.3 Total phenolic content and antioxidant activity sify the barley samples as homogeneous groups established by the
Total phenolic content was determined by the Folin-Ciocalteu dependent variable.
assay. Briefly, 0.1 g of flour sample was weighed into a polyethylene
tube and 6 to 7 mL of 50% methanol were added. After sonication 3. RESULTS AND DISCUSSION
and centrifugation, the volume was adjusted to 10 mL with 50%
methanol. One milliliter of this acid extract was mixed with 1 mL 3.1 Proximate composition, total phenolic compounds,
50% Folin-Ciocalteu reagent (Sigma-Aldrich Chemical Co., St. and antioxidant activity
Louis, MO, USA). After 5 min, 2 mL 10% Na2 CO3 solution was Results (mean ± standard deviation) of the proximate compo-
added and kept for 10 min in the dark. After centrifugation, the sition, total phenolic compounds, and antioxidant activity of the
absorbance was measured at 750 nm. Gallic acid was used as a 42 landraces and 3 commercial barley samples are shown in Ta-
calibration standard and the results were expressed as mg of gallic ble 2. The moisture concentrations in the barley landraces ranged
acid equivalents (GAEs)/g dry weight (dw). Antioxidant activity between 11.9% and 16.2% and the values were, in general, higher
was determined using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) than the data found in the literature (Abdel-Aal & Choo, 2014).
(Bondet, Brand-Williams, & Berset, 1997). The DPPH solution The moisture in barley grains should be low to prevent the growth
(0.1 mM in methanol) was diluted with methanol to obtain an of microorganisms as well as changes in grain vitreous stability. Six
absorbance of 1.00 ± 0.01 at 517 nm. After which, 1 g of flour of the 42 barley samples studied had moisture values higher than
sample was weighed into a polyethylene tube, and 6 to 7 mL 15%, and therefore, had a considerable risk of microbial alteration.
of 25% methanol was added. After sonication and centrifugation, Whole cereal grains are considered a good source of mineral and
the volume was adjusted to 10 mL with 25% methanol. After trace elements when compared to refined flours. The content of
this, 0.15 mL of the extract was mixed and shaken with 1.85 mL ash oscillated in a relatively narrow range, 2.4% and 2.9% dw. The
of solution of DPPH. The extract was then incubated in the ash values found here fall within the range reported by several
dark for 25 min, and the absorbance was measured at 517 nm. researchers (Åman, Hesselman, & Tilly, 1985; Holopainen et al.,

Food Chemistry
The antioxidant capacity was calculated using a calibration curve 2014; Ragaee, Abdel-Aal, & Noaman, 2006), but were higher
prepared with Trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2- than those contents shown by others (Abdel-Aal & Choo, 2014;
carboxylic acid) within a range of 200 to 800 µM, and the results Griffey et al., 2010). Starch is the major carbohydrate in all cereals
were expressed as mg of Trolox equivalents (TE)/g dw. and contributes significantly to energy intake, while the sugars are
found in barley grain at very low concentrations (Gray, Abdel-Alal,
Seetharaman, & Kakuda, 2010). The starch contents obtained in
2.4 Minerals and trace elements
the present study are in the range of 52.2% to 59.2% dw, which was
The previously dried and homogenized barley samples were
below that of most of the published values (Abdel-Aal & Choo,
acid-digested using nitric acid, according to the procedure de-
2014; Åman et al., 1985; Griffey et al., 2010; Holopainen et al.,
scribed by Suárez, Rodrı́guez, and Romero (2007). Therefore,
2014). Some investigators reported starch values similar to the ones
1 g of dried sample was weighed into a digestion tube, and
reported here, such as Ragaee et al. (2006) for naked barley and
6 mL of HNO3 Hiperpur (Panreac, Barcelona, Spain) were added.
by Griffey et al. (2010) for husked barley.
The mixture was heated until 160 °C, and finally, 1 mL of HCl
Whole cereals make a considerable contribution to fiber intake.
Hiperpur (Panreac) was added and the mixture was heated at
In barley, most of the fiber consists of β-glucans and pentoses in
160 °C/5 min. The acid extract obtained was adjusted to 10 mL.
variable proportions. The β-glucans are located in the cell wall and
The mineral and trace element analysis was performed on this
aleurone layer, so their proportion is higher in naked grains than
acid extract in triplicate. The minerals (K, Mg, Ca, Fe, Cu, Zn,
in whole grains (Abdel-Aal & Choo, 2014). The mean concentra-
and Mn) were determined using a Varian SpectraAA 50B (Var-
tions of crude fiber in the 42 barley landraces varied considerably
ian Iberica S. L., Madrid, Spain) atomic absorption spectrometry
(4.2% to 8.1% dw), and were higher than those reported by Åman
with flame air–acetylene, equipped with a D2 lamp background
et al. (1985). The proportion of soluble proteins (albumins and
correction system. Phosphorous was determined by the colori-
globulins) was relatively high (25%) (FEDNA, 2014). The pro-
metric method with Vanadate-Molybdate reagent (BOE, 1995).
tein concentrations for the barley landraces studied here ranged
Briefly, 0.15 mL of the previous acid extract was diluted to 2.5 mL
between 10.8% and 14.0% dw, which was similar to the values
with Milli-Q water. After which 2.5 mL of molybdate-vanadate
reported by many other authors (Abdel-Aal & Choo, 2014; Åman
reagent (Panreac) were added. The mixture was stirred and left for
et al., 1985; FEDNA, 2014; Holopainen et al., 2014; Lahouar
10 min to form the colored yellow complex; the absorbance was
et al., 2017). However, the protein content of the barley landraces
then measured at 400 nm.
studied here was higher than other reported data (Bertholdsson,
1999; Griffey et al., 2010) of barley used to make malt in which
2.5 Statistical analysis the protein content should not exceed 11.5% under any environ-
All the statistical analyses were performed using the SPSS ver- mental condition and all the barley samples analyzed here, except
sion 25.0 for Windows (SPSS Inc., Chicago, IL, USA). Mean for three, had higher contents than this value. High-starch content
values obtained for the variables studied in the different groups is another condition to take into account when using barley in
were compared by one-way analysis of variance (Duncan’s multi- malting. The barley landraces analyzed here presented low starch
ple range), assuming that there were significant differences among values, and therefore, traditional Canary barley landraces do not
them when the statistical comparison gave P < 0.05. A statisti- appear to meet the standards required for producing industrial
cal study of correlation between all the quantitative parameters beer although they could be used in the artisanal beers that do not
determined was carried out. Factor analysis, using principal com- require standardized conditions.
ponents as the method of factor extraction, was used to establish Barley grains contain a wide range of phenolic compounds,
a more simplified view of the relationship among all the analyzed among which are phenolic acids. These compounds may be the
parameters. Linear discriminant analysis (LDA) was applied to clas- main contributors to the antioxidant activity of barley (Abdel-Aal

Vol. 00, Iss. 0, 2020 r Journal of Food Science 3


Chemistry barley landrace from Canary Islands . . .

Table 2–Results (mean ± standard deviation) of the major chemical components, total phenolic compounds, and antioxidant
activity of the barley samples.

Total phenols (mg DPPH (mg


Number Moisture (%) Ash (%) Starch (%) Crude Fiber (%) Protein (%) GAE/100 g) TE/100 g)
b
1 13.9 ± 0.15 2.84 ± 0.04 54.1 ± 0.41 7.44 ± 0.14 12.0 ± 0.13 210 ± 19 0.95 ± 0.02
b
2 13.1 ± 0.16 2.76 ± 0.05 53.8 ± 0.41 7.08 ± 0.13 12.6 ± 0.23 259 ± 19 0.89 ± 0.05
c
3 13.7 ± 0.40 2.43 ± 0.07 59.2 ± 0.68 4.21 ± 0.12 13.3 ± 0.07 202 ± 18 0.86 ± 0.07
b
4 13.5 ± 0.20 2.78 ± 0.08 54.3 ± 0.68 7.66 ± 0.25 11.7 ± 0.15 220 ± 15 0.86 ± 0.09
c
5 13.3 ± 0.09 2.63 ± 0.10 58.3 ± 0.67 4.94 ± 0.28 12.8 ± 0.12 284 ± 15 0.78 ± 0.04
b
6 13.7 ± 0.25 2.74 ± 0.05 54.6 ± 0.66 7.14 ± 0.22 12.8 ± 0.23 206 ± 23 0.75 ± 0.07
b
7 12.5 ± 0.20 2.87 ± 0.05 53.8 ± 0.41 7.86 ± 0.16 11.4 ± 0.18 197 ± 7.3 0.88 ± 0.06
b
8 13.3 ± 0.16 2.72 ± 0.03 54.4 ± 0.14 7.68 ± 0.16 11.4 ± 0.26 163 ± 6.5 0.91 ± 0.06
b
9 12.9 ± 0.18 2.75 ± 0.06 54.6 ± 0.30 7.53 ± 0.23 11.9 ± 0.26 247 ± 17 0.76 ± 0.06
b
10 13.3 ± 0.19 2.82 ± 0.03 52.6 ± 0.42 7.67 ± 0.08 12.5 ± 0.30 181 ± 9.7 0.93 ± 0.05
b
11 12.1 ± 0.14 2.80 ± 0.01 52.4 ± 0.26 7.50 ± 0.16 13.0 ± 0.38 170 ± 15 0.86 ± 0.08
b
12 13.7 ± 0.11 2.80 ± 0.03 53.4 ± 0.15 7.84 ± 0.06 12.0 ± 0.22 168 ± 2.7 0.92 ± 0.02
b
13 13.3 ± 0.29 2.74 ± 0.02 53.4 ± 0.40 7.42 ± 0.23 12.5 ± 0.14 259 ± 16 0.90 ± 0.06
b
14 11.9 ± 0.15 2.81 ± 0.05 53.0 ± 0.26 7.48 ± 0.07 12.7 ± 0.33 147 ± 10 0.88 ± 0.02
b
15 12.1 ± 0.29 2.83 ± 0.04 52.2 ± 0.31 7.34 ± 0.10 13.1 ± 0.24 155 ± 6.4 0.76 ± 0.06
b
16 13.2 ± 0.13 2.80 ± 0.03 53.5 ± 0.27 7.58 ± 0.14 11.6 ± 0.27 167 ± 15 0.90 ± 0.05
b
17 12.9 ± 0.17 2.84 ± 0.03 53.1 ± 0.40 7.99 ± 0.03 11.6 ± 0.19 193 ± 3.8 0.77 ± 0.01
b
18 14.6 ± 0.36 2.76 ± 0.03 54.5 ± 0.34 7.57 ± 0.13 11.6 ± 0.34 221 ± 23 0.96 ± 0.03
Food Chemistry

b
19 12.5 ± 0.17 2.65 ± 0.02 54.8 ± 0.61 5.83 ± 0.23 13.7 ± 0.19 200 ± 17 0.91 ± 0.03
b
20 12.0 ± 0.09 2.73 ± 0.05 53.7 ± 0.29 6.96 ± 0.22 13.4 ± 0.09 148 ± 12 0.87 ± 0.07
b
21 13.9 ± 0.23 2.91 ± 0.05 52.8 ± 0.23 7.73 ± 0.15 12.9 ± 0.28 153 ± 11 0.84 ± 0.06
b
22 12.8 ± 0.30 2.84 ± 0.06 53.3 ± 0.81 7.69 ± 0.22 12.3 ± 0.07 205 ± 23 0.86 ± 0.02
b
23 14.1 ± 0.09 2.87 ± 0.02 53.2 ± 0.26 7.97 ± 0.16 11.9 ± 0.13 178 ± 4.8 0.90 ± 0.02
b
24 15.9 ± 0.19 2.83 ± 0.05 54.4 ± 0.40 7.87 ± 0.07 11.7 ± 0.22 117 ± 6.4 0.94 ± 0.03
b
25 16.2 ± 0.22 2.76 ± 0.03 55.1 ± 0.12 7.16 ± 0.13 12.2 ± 0.04 134 ± 10 0.85 ± 0.02
b
26 14.3 ± 0.15 2.82 ± 0.04 54.9 ± 0.65 7.67 ± 0.12 11.6 ± 0.08 168 ± 6.3 0.79 ± 0.05
b
27 15.5 ± 0.21 2.82 ± 0.02 55.3 ± 0.21 7.80 ± 0.16 10.8 ± 0.17 145 ± 3.4 0.66 ± 0.01
b
28 12.6 ± 0.13 2.79 ± 0.06 52.2 ± 0.41 7.44 ± 0.19 13.7 ± 0.27 179 ± 17 0.62 ± 0.05
b
29 13.5 ± 0.13 2.75 ± 0.02 53.6 ± 0.34 6.89 ± 0.33 13.2 ± 0.08 194 ± 6.4 0.59 ± 0.02
b
30 14.6 ± 0.23 2.83 ± 0.04 53.5 ± 0.11 8.05 ± 0.10 11.7 ± 0.16 172 ± 11 0.82 ± 0.01
b
31 12.9 ± 0.14 2.74 ± 0.04 54.0 ± 0.30 7.56 ± 0.03 11.5 ± 0.21 181 ± 13 0.75 ± 0.02
b
32 16.0 ± 0.55 2.74 ± 0.03 54.6 ± 0.50 7.03 ± 0.08 12.9 ± 0.24 174 ± 31 0.82 ± 0.02
b
33 13.9 ± 0.37 2.79 ± 0.02 54.1 ± 0.46 7.46 ± 0.27 12.1 ± 0.31 205 ± 5.2 0.82 ± 0.02
b
34 12.4 ± 0.18 2.74 ± 0.07 52.3 ± 0.43 7.35 ± 0.17 13.9 ± 0.11 168 ± 9.0 0.83 ± 0.02
b
35 12.3 ± 0.18 2.79 ± 0.04 53.2 ± 0.50 7.69 ± 0.18 12.0 ± 0.15 175 ± 4.1 0.85 ± 0.06
b
36 13.4 ± 10.18 2.79 ± 0.07 53.6 ± 0.51 7.69 ± 0.21 11.8 ± 0.33 170 ± 15 0.90 ± 0.05
b
37 15.5 ± 0.06 2.73 ± 0.08 54.1 ± 0.69 6.98 ± 0.13 13.5 ± 0.18 193 ± 19 0.85 ± 0.03
b
38 15.3 ± 0.22 2.78 ± 0.07 54.3 ± 0.60 7.22 ± 0.18 12.7 ± 0.33 199 ± 18 0.91 ± 0.04
b
39 13.1 ± 0.23 2.71 ± 0.05 53.3 ± 0.57 7.37 ± 0.25 12.4 ± 0.24 181 ± 1.1 0.84 ± 0.03
b
40 12.8 ± 0.08 2.85 ± 0.05 52.9 ± 0.81 7.37 ± 0.17 12.6 ± 0.27 154 ± 0.6 0.87 ± 0.03
b
41 13.7 ± 0.09 2.79 ± 0.04 53.6 ± 0.42 7.53 ± 0.17 12.1 ± 0.03 166 ± 3.4 0.86 ± 0.05
b
42 13.6 ± 0.12 2.74 ± 0.07 53.8 ± 0.82 6.44 ± 0.44 14.0 ± 0.46 220 ± 9.4 0.88 ± 0.04
Total 13.6 ± 1.11 2.78 ± 0.08 54.0 ± 1.34 7.30 ± 0.75 12.4 ± 0.77 186 ± 35 0.84 ± 0.08
b
43 A, 11.9 ± 0.25 2.70 ± 0.05 57.4 ± 0.40 4.54 ± 0.20 13.4 ± 0.45 204 ± 19 0.90 ± 0.06
a,c
44 12.6 ± 0.18 2.70 ± 0.02 54.8 ± 0.28 6.07 ± 0.23 13.2 ± 0.10 192 ± 11 0.87 ± 0.05
a,c
45 13.4 ± 0.17 2.55 ± 0.09 57.9 ± 0.32 5.01 ± 0.11 12.3 ± 0.16 218 ± 19 0.85 ± 0.05
Data are shown in dry weight.
a
Commercial barley.
b
Six rows.
c
Two rows.

& Choo, 2014). In barley, most of these phenolic compounds are conditions (Abdel-Aal & Choo, 2014). The concentrations of total
bound to other components, and therefore, free phenolics account phenolic compounds and antioxidant activity in the barley sam-
for a small portion of the total phenolic compounds (Abdel-Aal ples varied between 117 to 284 mg GAE/100 g dw and 0.59 and
& Choo, 2014). Besides, some antioxidant compounds of sol- 0.96 mg TE/g dw, respectively. These values are approximately
uble fiber constituents could inhibit the digestive absorption of twice those values found for wheat landraces from the Canary
minerals. In addition, there is great variability in their concen- Islands (Rodrı́guez, Morales, Rodrı́guez-Rodrı́guez, & Romero,
trations due to differences in genotype as well as environmental 2018). The results obtained here for the phenolic compounds were

4 Journal of Food Science r Vol. 00, Iss. 0, 2020


Chemistry barley landrace from Canary Islands . . .

Table 3–Results (mg/kg dw, mean ± standard deviation) of the mineral and trace element concentrations of the landraces and
commercial barley samples.

Number P K Ca Mg Fe Cu Zn Mn
b
1 4,707 ± 237 3,751 ± 190 396 ± 10.2 1,360 ± 81.0 51.6 ± 3.41 6.76 ± 0.13 52.8 ± 2.41 17.4 ± 0.46
b
2 4,576 ± 199 4,055 ± 161 454 ± 29.6 1,461 ± 38.0 49.3 ± 0.88 7.10 ± 0.12 51.6 ± 0.29 15.9 ± 0.17
c
3 4,054 ± 179 4,014 ± 10.7 384 ± 23.2 1,371 ± 31.4 50.8 ± 2.64 7.81 ± 0.18 50.0 ± 0.25 15.8 ± 0.66
b
4 4,687 ± 209 4,052 ± 169 423 ± 7.41 1,506 ± 37.7 49.0 ± 4.08 7.65 ± 0.15 51.0 ± 1.18 16.8 ± 0.63
c
5 4,611 ± 301 3,854 ± 158 426 ± 14.7 1,385 ± 44.4 62.8 ± 1.79 6.24 ± 0.48 49.4 ± 3.37 17.5 ± 1.07
b
6 4,959 ± 250 4,383 ± 10.0 441 ± 21.0 1,369 ± 64.6 52.1 ± 3.21 7.51 ± 0.30 54.1 ± 1.74 17.3 ± 0.59
b
7 4,295 ± 301 3,592 ± 102 504 ± 17.6 1,422 ± 19.1 54.3 ± 2.83 6.98 ± 0.11 58.1 ± 1.15 17.9 ± 0.32
b
8 4,528 ± 198 3,808 ± 206 447 ± 15.0 1,395 ± 34.7 45.3 ± 1.28 6.26 ± 0.16 50.9 ± 1.91 13.7 ± 0.55
b
9 4,446 ± 303 4,098 ± 43.3 366 ± 15.8 1,356 ± 54.2 51.4 ± 4.64 8.04 ± 0.20 55.2 ± 1.39 17.6 ± 0.56
b
10 3,906 ± 96.0 3,545 ± 199 482 ± 10.0 1,372 ± 26.7 43.6 ± 2.81 4.87 ± 0.15 40.6 ± 1.58 13.6 ± 0.35
b
11 4,510 ± 236 4,157 ± 162 425 ± 10.1 1,381 ± 19.2 47.5 ± 2.20 5.96 ± 0.61 47.5 ± 1.25 14.0 ± 0.43
b
12 3,899 ± 118 3,891 ± 247 444 ± 28.1 1,287 ± 70.5 41.8 ± 1.10 5.85 ± 0.58 43.0 ± 1.22 14.2 ± 0.57
b
13 4,352 ± 147 4,231 ± 148 394 ± 12.7 1,329 ± 45.5 44.1 ± 0.56 6.55 ± 0.04 49.2 ± 0.29 15.6 ± 0.18
b
14 3,941 ± 131 4,305 ± 140 451 ± 28.3 1,376 ± 41.2 49.1 ± 1.02 5.74 ± 0.18 46.5 ± 1.31 14.2 ± 0.37
b
15 4,447 ± 288 4,020 ± 85.7 480 ± 32.3 1,367 ± 69.2 46.0 ± 1.41 6.27 ± 0.10 48.6 ± 0.52 15.1 ± 0.27
b
16 4,144 ± 400 3,862 ± 112 425 ± 3.91 1,306 ± 25.0 42.1 ± 1.96 6.39 ± 0.07 42.2 ± 1.58 14.1 ± 0.32
b
17 4,204 ± 182 3,645 ± 105 498 ± 10.6 1,399 ± 45.3 41.1 ± 0.74 5.60 ± 0.09 42.6 ± 0.77 12.4 ± 0.24
b
18 4,413 ± 271 4,191 ± 77.6 503 ± 46.2 1,414 ± 98.5 43.3 ± 2.90 6.70 ± 0.26 43.3 ± 2.11 15.0 ± 0.62
b
3,556 ± 263 3,620 ± 35.9 519 ± 9.42 1,434 ± 58.8 48.8 ± 3.44 6.02 ± 0.36 47.8 ± 3.61 13.9 ± 0.73

Food Chemistry
19
b
20 2,774 ± 107 4,309 ± 104 483 ± 13.2 1,351 ± 29.3 64.7 ± 5.30 6.31 ± 0.14 47.0 ± 1.25 15.7 ± 0.34
b
21 3,525 ± 256 4,435 ± 17.6 480 ± 31.4 1,351 ± 134 68.4 ± 1.74 6.95 ± 0.26 54.5 ± 1.58 19.2 ± 0.81
b
22 3,666 ± 115 3,376 ± 261 538 ± 18.4 1,296 ± 81.2 53.8 ± 6.05 6.48 ± 0.37 47.3 ± 2.81 18.1 ± 0.56
b
23 3,428 ± 368 3,436 ± 342 363 ± 35.3 1,172 ± 84.0 57.1 ± 4.09 8.44 ± 0.99 54.1 ± 6.82 17.8 ± 2.56
b
24 3,640 ± 333 4,120 ± 256 512 ± 8.15 1,424 ± 31.7 49.6 ± 0.16 8.44 ± 0.22 53.9 ± 0.66 17.9 ± 0.50
b
25 3,421 ± 277 3,786 ± 342 472 ± 2.69 1,273 ± 37.2 60.5 ± 0.61 8.40 ± 0.53 51.8 ± 1.91 17.1 ± 0.67
b
26 3,909 ± 302 3,684 ± 180 453 ± 30.8 1,441 ± 54.7 34.6 ± 2.64 7.11 ± 0.18 46.7 ± 1.57 13.3 ± 0.38
b
27 4,165 ± 319 3,731 ± 119 413 ± 32.9 1,581 ± 133 44.5 ± 2.40 8.27 ± 0.37 55.7 ± 3.20 14.4 ± 0.97
b
28 3,371 ± 120 3,580 ± 20.8 435 ± 23.5 1,162 ± 33.1 59.6 ± 2.66 6.37 ± 0.45 50.3 ± 3.12 17.3 ± 1.26
b
29 3,476 ± 132 3,833 ± 154 454 ± 39.8 1,218 ± 88.9 41.1 ± 2.36 7.78 ± 0.22 51.1 ± 1.59 16.8 ± 0.63
b
30 2,073 ± 60.2 3,000 ± 156 384 ± 22.5 1,107 ± 85.0 48.3 ± 1.24 6.67 ± 0.29 56.5 ± 1.77 19.4 ± 0.70
b
31 4,565 ± 432 3,729 ± 252 367 ± 34.7 1,265 ± 174 40.4 ± 2.78 7.61 ± 0.06 48.6 ± 1.47 13.8 ± 0.55
b
32 4,311 ± 410 3,640 ± 176 421 ± 15.4 1,129 ± 23.0 37.3 ± 1.77 6.89 ± 0.11 48.2 ± 1.84 14.5 ± 0.45
b
33 5,179 ± 29.4 3,624 ± 189 401 ± 19.9 1,169 ± 110 35.6 ± 3.07 6.82 ± 0.15 45.7 ± 0.66 15.6 ± 0.21
b
34 3,151 ± 60.1 3,656 ± 123 456 ± 33.1 1,296 ± 32.3 41.5 ± 3.60 6.60 ± 0.38 44.4 ± 3.10 15.1 ± 0.55
b
35 3,196 ± 110 3,430 ± 307 471 ± 24.0 1,221 ± 80.1 36.8 ± 2.08 5.32 ± 0.19 42.2 ± 2.67 11.5 ± 0.29
b
36 3,057 ± 164 3,435 ± 67.1 364 ± 24.8 1,036 ± 18.2 34.8 ± 0.41 6.04 ± 0.13 42.6 ± 0.72 12.9 ± 0.37
b
37 4,273 ± 107 4,126 ± 138 437 ± 25.7 1,336 ± 137 37.7 ± 2.83 6.40 ± 0.25 46.5 ± 1.70 13.9 ± 0.70
b
38 3,443 ± 34.4 3,815 ± 37.6 523 ± 35.8 1,296 ± 59.7 45.3 ± 1.87 6.19 ± 0.25 41.6 ± 1.36 13.7 ± 0.17
b
39 3,197 ± 305 3,849 ± 65.8 429 ± 20.0 1,251 ± 110 33.7 ± 0.73 5.44 ± 0.08 38.3 ± 0.07 13.2 ± 0.07
b
40 1,829 ± 68.9 3,220 ± 36.6 484 ± 19.9 1,196 ± 83.4 39.0 ± 0.85 6.77 ± 0.13 51.0 ± 1.49 15.9 ± 0.52
b
41 2,233 ± 115 3,667 ± 267 393 ± 4.34 1,101 ± 93.1 60.7 ± 3.18 7.57 ± 0.19 54.3 ± 1.00 18.4 ± 0.46
b
42 3,063 ± 96.1 3,652 ± 269 417 ± 5.15 1,147 ± 8.13 45.5 ± 0.24 5.80 ± 0.22 49.9 ± 3.43 14.5 ± 1.13
Total 3,838 ± 764 3,814 ± 319 443 ± 46.8 1,312 ± 118 47.2 ± 8.63 6.74 ± 0.89 48.7 ± 4.80 15.5 ± 1.95
b
43 A, 4,609 ± 274 4,534 ± 93.5 380 ± 23.7 1,463 ± 40.4 30.7 ± 1.32 6.89 ± 0.25 48.3 ± 1.61 14.7 ± 0.82
a,c
44 4,433 ± 172 4,747 ± 203 435 ± 17.0 1,477 ± 68.6 47.9 ± 2.95 7.06 ± 0.18 51.8 ± 1.94 15.2 ± 0.53
a,c
45 4,718 ± 355 4,449 ± 265 381 ± 26.0 1,446 ± 120 51.0 ± 1.42 5.87 ± 0.27 49.5 ± 1.69 14.8 ± 0.76
a
Commercial barley.
b
Six rows.
c
Two rows.

similar to those obtained by Abdel-Aal and Choo (2014) and La- are several environmental factors affecting the mineral content of
houar et al. (2017) and higher than those reported by Ragaee et al. the barley grains including cultivation soils, water, and fertilizers
(2006). (chemical, organic, and biofertilizers) (Farahani, Caichi, Mazaheri,
Afshari, & Savaghebi, 2011). The same environmental conditions
3.2 Minerals and trace elements were maintained during this study, so the differences were due to
Table 3 shows the results regarding minerals and trace elements genetic characteristics of the barley samples.
in all the barley samples. Differences were found among barley Although barley contains appreciable amounts of minerals,
samples in the concentrations of most of the minerals. There its bioavailabilities are low due to the formation of insoluble

Vol. 00, Iss. 0, 2020 r Journal of Food Science 5


Chemistry barley landrace from Canary Islands . . .

Table 4–Contents of the major chemical compounds, total phenolic compounds, and antioxidant activity in six-row landrace
barleys according to spike density, aleurone layer color, and precedence island.

Total phenols (mg DPPH (mg


Moisture (%) Ash (%) Starch (%) Crude Fiber (%) Protein (%) GAE/100 g) TE/100 g)
Spike density
Intermediate 14.6 ± 0.2 b 2.83 ± 0.04 a 53.5 ± 0.1 a 8.05 ± 0.1 b 11.7 ± 0.2 a 172 ± 11 a 0.82 ± 0.01 a
Lax 13.5 ± 1.1 a 2.79 ± 0.07 a 53.7 ± 0.9 a 7.43 ± 0.4 a 12.4 ± 0.8 a 184 ± 34 a 0.84 ± 0.09 a
Aleurone layer color
White 13.4 ± 0.5 bc 2.79 ± 0.06 a 53.9 ± 1.0 a 7.32 ± 0.3 a 12.5 ± 0.4 a 188 ± 29 a 0.81 ± 0.06 a
Green 13.7 ± 1.2 c 2.79 ± 0.06 a 53.8 ± 0.9 a 7.49 ± 0.4 a 12.3 ± 0.8 a 184 ± 37 a 0.84 ± 0.09 a
Blue 13.2 ± 1.0 ab 2.77 ± 0.08 a 53.4 ± 0.9 a 7.35 ± 0.6 a 12.6 ± 0.8 a 180 ± 16 a 0.88 ± 0.05 a
Island
Tenerife 13.6 ± 0.9 b 2.81 ± 0.05 ab 53.7 ± 0.9 ab 7.44 ± 0.4 ab 12.4 ± 0.8 ab 183 ± 34 a 0.86 ± 0.08 bc
La Palma 14.6 ± 1.1 c 2.77 ± 0.06 a 54.5 ± 0.3 b 7.71 ± 0.2 bc 11.6 ± 0.3 ª 167 ± 47 a 0.94 ± 0.04 c
Gran Canaria 13.6 ± 1.3 b 2.77 ± 0.07 a 53.7 ± 0.9 ab 7.38 ± 0.4 ab 12.6 ± 0.7 b 186 ± 36 a 0.80 ± 0.09 ab
Lanzarote 12.4 ± 0.2 a 2.83 ± 0.06 b 53.5 ± 0.5 a 7.77 ± 0.2 bc 11.7 ± 0.3 a 186 ± 13 a 0.87 ± 0.06 bc
La Gomera 13.1 ± 0.8 ab 2.79 ± 0.09 ab 53.3 ± 1.1 a 7.29 ± 0.9 a 12.7 ± 0.7 b 182 ± 16 a 0.90 ± 0.05 c
Fuerteventura 12.9 ± 0.2 ab 2.84 ± 0.03 b 53.1 ± 0.4 a 7.99 ± 0.1 c 11.6 ± 0.2 a 193 ± 3.8 a 0.77 ± 0.01 a
Data are shown in dry weight. Results in the same vertical column with the same superscript were not significantly different.

Table 5–Contents (mg/kg dw) of the mineral and trace elements in six-row landrace barleys according to spike density, aleurone
layer color, and precedence island.
Food Chemistry

P K Ca Mg Fe Cu Zn Mn
Spike density
Intermediate 2,072 ± 60 a 2,998 ± 156 a 384 ± 23 a 1,107 ± 85 a 48.2 ± 1.2 a 6.67 ± 0.3 a 56.4 ± 1.8 b 19.4 ± 0.7 b
Lax 3,857 ± 747 b 3,829 ± 332 b 447 ± 50 b 1,314 ± 131 b 46.7 ± 8.8 a 6.72 ± 0.9 a 48.5 ± 5.1 a 15.4 ± 2.0 a
Aleurone layer color
White 3,988 ± 1,627 b 3,741 ± 519 a 442 ± 40 a 1,244 ± 121 a 42.2 ± 7.9 a 7.03 ± 0.4 b 50.2 ± 3.8 b 16.3 ± 0.9 b
Green 3,897 ± 711 b 3,852 ± 343 a 446 ± 48 a 1,329 ± 132 a 48.2 ± 8.6 b 6.82 ± 0.9 ab 49.6 ± 4.8 b 15.8 ± 2.0 b
Blue 3,442 ± 480 a 3,674 ± 287 a 444 ± 62 a 1,261 ± 130 a 43.2 ± 8.0 a 6.25 ± 1.0 a 44.8 ± 5.4 a 14.0 ± 1.9 a
Island
Tenerife 3,626 ± 876 a 3,705 ± 280 ab 445 ± 53 ab 1,298 ± 159 a 45.3 ± 7.5 a 6.66 ± 0.7 b 48.3 ± 5.0 a 15.2 ± 1.8 b
La Palma 4,194 ± 481 a 4,040 ± 244 b 488 ± 39 bc 1,411 ± 56 a 46.1 ± 3.2 a 7.13 ± 1.0 b 49.4 ± 5.0 a 15.5 ± 1.9 b
Gran Canaria 3,864 ± 837 a 3,919 ± 388 ab 429 ± 41 a 1,285 ± 124 a 47.9 ± 11 a 6.93 ± 0.8 b 49.3 ± 4.7 a 16.0 ± 1.9 b
Lanzarote 3,747 ± 636 a 3,512 ± 223 a 488 ± 26 bc 1,322 ± 122 a 45.5 ± 9.9 a 6.15 ± 0.9 ab 50.1 ± 8.9 a 14.7 ± 3.5 b
La Gomera 3,850 ± 490 a 3,690 ± 342 ab 447 ± 64 ab 1,340 ± 114 a 49.3 ± 5.9 a 6.32 ± 1.5 ab 47.5 ± 6.1 a 14.8 ± 2.1 b
Fuerteventura 4,203 ± 182 a 3,644 ± 105 ab 498 ± 11 c 1,399 ± 45 a 41.1 ± 0.7 a 5.60 ± 0.1 a 42.6 ± 0.8 a 12.4 ± 0.2 a
Results in the same vertical column with the same superscript were not significantly different.

complexes with phytates, because they reduce the intestinal ab- in the barley grain is influenced by genetic characteristics more
sorption of minerals in humans (Sandberg et al., 1999). The phos- than by the environmental effects. The iron concentrations of the
phorus contents (1,829 to 5,179 mg/kg) in the barley landraces barley landraces were similar to those reported by other authors
varied greatly among the samples analyzed. Most of the phospho- (El-Haramein & Grando, 2008; Farahani et al., 2011; Kandemir
rus in cereal grains is in phytate form; a lower bioavailability of et al., 2005), but lower than those found by Ragaee et al. (2006)
minerals such as calcium, iron, or zinc could be observed when and Woźniak et al. (2014). Our results concerning iron ranged
the phosphorous content in barley is higher. The values found between 33.7 and 68.3 mg/kg dw; only six landraces had concen-
here were within the range described by other authors (Farahani trations near the 60 mg/kg observed by El-Haramein and Grando
et al., 2011; Woźniak et al., 2014) and lower than those published (2008) in Moroccan barley varieties. High concentrations of zinc
by Ragaee et al. (2006) and Lahouar et al. (2017). Potassium were found in barley grains when the crop is under conditions
and magnesium contents were similar to phosphorous, which is of water stress, so this mineral may be mobilized to the grain
within the range described by Woźniak et al. (2014) and lower (Farahani et al., 2011). These investigators found a significant in-
than those results reported by others (Ragaee et al., 2006). The crease in the zinc, nitrogen, and manganese contents in the grain
calcium concentrations were lower than the other three major of 27%, 12%, and 7%, respectively, in drought stressed barleys.
minerals, similar to the mean concentrations found in trace ele- Zinc concentrations varied within a relatively narrow range (38.3
ments with relatively high contents, such as iron and zinc. Ragaee to 58.1 mg/kg). The mean zinc concentration found by us was
et al. (2006) found calcium concentrations above the data found lower than that reported by Ragaee et al. (2006) and Farahani
here; however, Kandemir, Tuzen, Sari, and Mendel (2005) found et al. (2011) although it resembles the data on covered varieties
lower calcium concentrations than those in this study. Coated bar- (El-Haramein & Grando, 2008) and is greater than other published
ley has more calcium than naked barley, which could explain some values (Kandemir et al., 2005). The barley samples had manganese
of the differences detected in the literature (Kandemir et al., 2005). concentrations ranging between 11.5 and 19.4 mg/kg dw, which
As regards the trace elements, the iron content was the highest. were similar to most of the published data (Kandemir et al., 2005;
Farahani et al. (2011) suggested that the iron concentration present Ragaee et al., 2006; Woźniak et al., 2014), but lower than those

6 Journal of Food Science r Vol. 00, Iss. 0, 2020


Chemistry barley landrace from Canary Islands . . .

Food Chemistry
Figure 1–Scores of the barley samples on axes representing the first and third factors differentiating the samples according to the commercial and
landrace barleys and number row.

found by Farahani et al. (2011), Copper had the lowest concentra- the lowest mean fiber concentrations (4.2% and 4.5%, respectively)
tions of all the studied trace elements that were within the range and the highest starch concentrations (59.2% and 57.4%, respec-
reported by other authors (Kandemir et al., 2005; Ragaee et al., tively). Some investigators (Åman et al., 1985) found that the starch
2006; Woźniak et al., 2014). content of the six-row varieties was higher than that in two-row
varieties, which coincides with the results here obtained; however,
3.3 Comparison of chemical composition between type of Holopainen et al. (2014) found the opposite. Therefore, the num-
barleys and number of rows ber of rows and spike density, genetically determined, influenced
The analyzed barley landraces had higher mean ash and fiber the proximate chemical composition of the barley landraces. No
concentrations than commercial barley and lower mean starch, significant differences in mineral and trace element contents were
protein, and total phenolic compounds concentrations than com- detected except for iron. The two-row barley landraces had higher
mercial barley. No significant differences were observed in an- mean iron content than the six-row barley landraces.
tioxidant activity. Major minerals (phosphorous, potassium, and
magnesium) in commercial barley varieties had higher mean con-
centrations than the analyzed barley landraces; however, no sig- 3.4 Comparison of chemical composition according to
nificant differences in all mean trace element concentrations were spike density, aleurone layer color, and island of
observed between both types of barley samples. origin
Most (95%) of barley landraces analyzed in the present study As regards the six-row barley landraces that were selected for
had six rows. Considerable differences were found between the this study, those with a lax spike density had lower mean moisture
two- and six-row barley landraces. Raw fiber, Fe, Ca, Mg, Mn, and fiber concentrations that those with an intermediate spike
and phenolic compounds were the nutritional parameters used to density (Table 4). No significant differences were found for the
nutritionally evaluate the barley landraces because the consump- rest of the parameters considered. The aleurone layer color did
tion of barley can contribute to their daily intake. Therefore, some not have a significant influence on ash, protein, starch, crude
landraces (n° 4, 6, 7, 9, 22) could be emphasized since they had rel- fiber, total phenolic compounds, and antioxidant activity. The
atively high levels of these nutrients. The six-row barley landraces mean moisture content in slightly pigmented barley landraces was
had higher mean ash and fiber concentrations and lower starch, higher than in those with a whitish or strongly pigmented aleurone
protein, and total phenolic compounds than the two-row barley layer, and significant differences were found with respect to the
landraces. Furthermore, the fiber data obtained in the commercial latter. Legzdina and Mezaka (2008) found a significant correlation
barleys, both six rows and two row, were closer to those of the local between the β-glucan contents of the crude fiber and the color of
two-row barley. The two-row barley landraces (n° 3 and n° 5) had the grain, and therefore, naked barley, which has a high content

Vol. 00, Iss. 0, 2020 r Journal of Food Science 7


Food Chemistry Chemistry barley landrace from Canary Islands . . .

Figure 2–Scatter diagram on the axes representing the two discriminant functions differentiating the landrace barley of six rows according to the origin
island.
of β-glucans, tends to have an association with a light color of the ues in the barley landraces from Gran Canaria and Fuerteventura
grain. were lower than those obtained in barley landraces from La Palma
The island of origin of the landrace grains influenced the pro- and La Gomera.
duction and chemical composition parameters. Significant dif- The results of the mineral and trace element contents in six-row
ferences were found according to the island of origin for all the barley landraces according to spike density, aleurone layer color,
chemical parameters (except total phenolic compounds). The bar- and origin island are shown in Table 5. Barley landraces with a lax
ley landraces from La Palma had the highest moisture levels; and density of spike had higher mean major mineral contents (P, K, Mg,
the landraces from the island of Lanzarote had the lowest moisture and Ca) and lower mean zinc and manganese concentrations than
values. Significant differences were found between barley landraces the six-row landraces with an intermediate spike density. Major
from the islands of La Palma, Gran Canaria, and Tenerife. Bar- mineral concentrations (except phosphorous) were not influenced
ley landraces from La Palma and Gran Canaria Islands presented by the aleurone layer color; however, all the trace elements were
lower mean ash concentrations than those barley samples from affected. Barley landraces with a strongly pigmented aleurone layer
Lanzarote and Fuerteventura. The mean starch content in the lan- presented lower mean phosphorous, iron, copper, zinc, and man-
draces from La Palma was higher than those mean contents found ganese concentrations than those observed in the barley landraces
in the landraces from Fuerteventura, La Gomera and Lanzarote. with whitish (except iron) or slightly pigmented aleurone. The
The mean fiber content in the barley landraces from Fuerteven- island of origin of the landrace grains influenced certain minerals
tura was higher than the mean fiber content observed in barley and trace elements such as potassium, calcium, copper, and man-
landraces from Tenerife, Gran Canaria, and La Gomera. Variance ganese. Barley landraces from Fuerteventura had the lowest mean
analysis was used to classify the barley landraces into three groups manganese and copper concentrations, and significant differences
as a function of protein content. The barley landraces from Gran were found with the corresponding landraces from other islands,
Canaria and La Gomera had a higher mean protein concentration and for copper in those landraces from Tenerife, La Palma, and
than those from La Palma, Lanzarote, and Fuerteventura. Barley Gran Canaria. Besides, the landraces from Fuerteventura had the
landraces from Tenerife were not statistically different from those highest mean calcium concentration, and significant differences
from the other islands. The mean antioxidant activity (DPPH) val- were found in the barley landraces from Tenerife, Gran Canaria,

8 Journal of Food Science r Vol. 00, Iss. 0, 2020


Chemistry barley landrace from Canary Islands . . .

and La Gomera; barley landraces from La Palma had a higher from La Palma, La Gomera, Lanzarote, and Fuerteventura were
mean potassium concentration than the mean value found in the correctly classified. Only three of the barley samples of Tenerife
landraces from Lanzarote. Island were erroneously classified as being from La Gomera (1)
and Gran Canaria (2); and one from Gran Canaria was included as
3.5 Correlational study being from Tenerife. Figure 2 shows the representation of all the
A statistical study of correlation between all the quantitative six-row barley landraces of the LDA results according to the island
parameters analyzed in the barley landraces showed a number of of origin. One can see that the six groups of barley landraces asso-
significant correlations. Ash presented inverse correlations with ciated with the considered islands were reasonably differentiated.
starch (r = −0.727), protein (r = −0.373), and phenolic com-
pounds (r = −0.361), and a positive correlation with fiber (r = 4. CONCLUSION
0.861). It is noteworthy that no positive correlations were found From a technological point of view, the barley landraces ana-
between ash and major minerals such as phosphorous, potassium, lyzed here are not suitable for malting because of their high protein
and magnesium. In addition to ash, fiber showed a strong in- and fiber contents. Notable differences in the proximate compo-
verse correlation (P < 0.001) with starch (r = −0.743) and pro- sition, TP and antioxidant activity, and mineral and trace element
teins (r = −0.555), and a moderate correlation (P < 0.01) with contents were observed among the analyzed barley landraces. Ca-
phenolic compounds. Besides, the starch was weakly correlated nary barley landraces are a good source of phytonutrients and other
(P < 0.05) with phenols and copper. The starch–crude fiber bioactive compounds such as proteins, soluble fibers, antioxidants
correlation suggests that both food components may be synthe- such as phenolic compounds, minerals, and trace elements. The
sized one from the other. Phenolic compounds only correlated six-row barley landraces n° 7 and 22 could be selected as possi-
(r = 0.438) with phosphorus and antioxidant activity did not show ble candidates in biofortification programs to increase the nutrient
significant correlations. The fact that phenolic compounds were density in barleys due to their high levels of raw fiber, iron, cal-
not correlated with antioxidant activity suggests that it must have cium, and phenolic compounds. Many differences were found

Food Chemistry
other antioxidant food components with no phenolic chemical in the chemical composition among the barley samples accord-
structure contributing significantly to the antioxidant activity of ing to the type of barley (commercial and landrace), the number
barley. All the trace elements were correlated (P < 0.001) with of rows, and island of origin of the barley grains. No phenolic
each other except for iron with copper. Besides, the major min- chemical compounds significantly contribute to the antioxidant
erals phosphorous, potassium, and magnesium were correlated (P activity of landrace barleys, which is deduced due to the lack of
< 0.001) with each other; however, the behavior of calcium was correlation between phenolic compounds and antioxidant activ-
different. The common and complex metal interactions occurring ity. Many correlations between trace elements and major minerals
in soils, water, and plants could influence the correlations observed were observed, which could be associated with the metal interac-
here. tions occurring in the soils, water, and plants. The application of
multivariate analysis on the chemical composition is a useful tool
3.6 Multivariate analysis to differentiate and characterize landrace barleys. Thus, factor and
Factor analysis was applied to all the samples to establish a more discriminant analyses can be applied to differentiate the analyzed
simplified view of the relationship among the analyzed variables. barley samples according to the type of barley (commercial and
The first five factors, accounting for 76.0% of the total variance, landrace), number of rows, and island of origin.
were chosen because their eigenvalues were higher than 1, and
therefore, they explain more variance than the original variables. ACKNOWLEDGMENTS
A Varimax rotation was carried out to minimize the number of We gratefully acknowledge the help of Patrick Dennis for re-
variables influencing each factor. The first factor that explains the vising and checking the English in this paper.
higher percentage of variance (25.0%) is strongly and inversely as-
sociated with fiber and ash and is positively associated with starch. AUTHOR CONTRIBUTIONS
The second factor (19.4% of variance) is related with manganese D.A.M. and D.R.M. supplied the barley samples and character-
and zinc and, to a lesser extent, with iron. The third factor (12.7% ized them morphologically. M.P.C. performed the research and
of variance) is associated with magnesium and phosphorus and P.D.E. helped with NIRS data. M.P.C., B.R.G., CD.R., and
the fourth and fifth factors with moisture and antioxidant capacity E.M.R.R. designed the research, analyzed the data, and wrote
(DPPH), respectively. The score plots of all the barley samples for the paper.
the first and third factors (Figure 1) show that the barley landraces
were well separated from the commercial varieties. Besides, com- CONFLICTS OF INTEREST
mercial barley and barley landraces were differentiated according The authors declare no conflict of interest.
to the number of rows. Stepwise LDA was applied on quantita-
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