Phenolic and mineral profile of Balkan indigenous apple and pear cultivars


  
J. Serb. Chem. Soc. 81 (6) 607–621 (2016) UDC 582.734.3:54.004.12:547.56–3+543(497) 
JSCS–4871 Original scientific paper 

607 

Phenolic and mineral profile of Balkan indigenous apple and 
pear cultivars 

JELENA ŽIVKOVIĆ1*, KATARINA ŠAVIKIN1, GORDANA ZDUNIĆ1, 
BILJANA DOJČINOVIĆ2 and NEBOJŠA MENKOVIĆ1 

1Institute for Medicinal Plants Research ‘’Dr. Josif Pančić’’, Tadeuša Košćuška 1, 11000 
Belgrade, Serbia and 2University of Belgrade, Institute of Chemistry, Technology and 

Metallurgy, Njegoševa 12, 11000 Belgrade, Serbia 

(Received 26 October 2015, revised 16 February, accepted 17 February 2016) 

Abstract: The aim of this study was the determination of phenolic compounds, 
and mineral nutrients in the pulp and peel obtained from Balkan indigenous 
apple and pear cultivars. The phenolic composition, assessed by HPLC-DAD 
and spectrophotometric methods varied significantly between the cultivars for 
both peel and pulp. Among the apples, the Mekica cultivar had the highest total 
phenolic content while Šećerlija and Zlatna Parmenka had the lowest. In the 
case of the pear samples, the maximum total phenolic content was found in 
Crna Takiša while the minimum content was recorded for Bela Arapka. In most 
of the investigated samples, chlorogenic acid in apples and arbutin in pears 
were the major detected polyphenolic compounds. With regard to the mineral 
analysis, K was the most abundant followed by P, Mg, Ca and S. Iron was the 
dominant microelement in apple peel and pulp samples, while in pear samples 
the principal microelement was B. The obtained results provide detailed 
information on the chemical composition of the tested apple and pear cultivars 
and thereby, could encourage their wider cultivation and consumption.  

Keywords: cultivar, autochthonous, apple, pear, peel. 

INTRODUCTION 
Due to excessive and widespread agricultural modernization, many auto-

chthonous cultivars have been neglected and substituted with more productive 
and new international cultivars.1 Accordingly, the global diet currently relies on a 
reduced number of species and varieties. It is becoming homogenized and separ-
ated from Serbian cultural food traditions. This not only endangers the preser-
vation of biodiversity, but could also “open the door” to overall epidemics of 
certain pests and pathogens.2  

                                                                                                                    

* Corresponding author. E-mail: jzivkovic@mocbilja.rs 
doi: 10.2298/JSC151026023Z 

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608 ŽIVKOVIĆ et al. 

On the contrary, indigenous cultivars represent the local germplasm culti-
vated mainly in the marginal areas. Generally, they are resilient to the local envi-
ronment and represent a favorable source for crop genetic variability, resistance 
to biotic and abiotic stresses, as well as for phenological and quality character-
istics. Since traditional cultivars mostly do not meet transport and storage dem-
ands, they are not cultivated for large-scale production.3 Therefore, although 
indigenous cultivars could be more nutritious than newer ones, they are eco-
nomically less important.4 

Owing to its geographical location, the Republic of Serbia has advantageous 
natural conditions and areas for planting a large number of fruit species and cul-
tivars.5 Indigenous Malus and Pyrus varieties are found in Serbia mainly on indi-
vidual farms in hilly–mountainous regions. Due to the ageing of orchards and the 
abandonment of agricultural practices, there is a great possibility that certain 
genotypes will disappear in the future.6  

Increased consumption of fruits has been recommended as one of the essen-
tial components of a healthy diet for the prevention of chronic diseases.7 There 
are numerous reports on health-promoting benefits of phenolic compounds pre-
sent in apples and pears,8,9 and as a result of a recent study,10 there is a new 
claim “an apple or pear a day helps keep the stroke at bay”.  

Studies dealing with the phenolic composition of apples and pears are often 
restricted to a few cultivars3,11 that are very popular with customers. Little 
attention has been given to autochthonous apple and pear cultivars,12,13 while 
there are only few reports,14 on the chemical profile of those grown in Serbia. 
Besides phytochemicals, an important part of the nutritional information of fruits 
is their mineral content. The significant impact of metal ions on human health is 
demonstrated by the fact that the function of more than one-third of all human 
proteins depend on them.15 As with polyphenols, the cultivar significantly influ-
ences the mineral content of the fruits.16 

The aim of this study was the chemical analysis of phenolic compounds min-
eral nutrients in the pulp and peel obtained from Serbian indigenous apple and 
pear cultivars. This work is important for an understanding of their nutritional 
potential and for a consequential expansion of their cultivation and use. 

EXPERIMENTAL 
Chemicals 

Chlorogenic acid (95 %, titration), rutin hydrate (94 %, HPLC), hyperoside (97 %, 
HPLC), isoquercitrin (90 %, HPLC), phloridzin (99 %, HPLC), gallic acid (97.5 %, titration), 
arbutin (96 %, HPLC) and 4-(dimethylamino)cinnamaldehyde (p-DMACA, ≥98.0%, HPLC) 
were purchased from Sigma Aldrich (St. Louis, MO, USA), and quercitrin (98.5 %, HPLC) 
from Extrasynthese (Genay, France). Acetonitrile (99.8 %) and formic acid (98–100 %) were 
supplied by Sigma–Aldrich (Steinheim, Germany). Water was deionized by using a Milli-Q 
system (Millipore, Bedford, MA, USA). All other reagents were of analytical grade. 

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 CHEMICAL PROFILE OF AUTOCHTHONOUS FRUITS 609 

Plant material 
The apple and pear cultivars investigated in this study were harvested in two regions in 

Serbia: Ljig in central Serbia (apples Kolačara, Streknja, Šećerlija, Zlatna Parmenka and 
Senabija) and on Zlatibor Mountain in the western part of Serbia (apples Masnjača, Mekica, 
Kožara, Kraljica and Šarenka, as well as pear cultivars Bela Arapka, Bronzara, Bela Takiša, 
Crna Takiša). Samples were collected at the full maturity stage during 2014. Ten apples from 
each cultivar were picked randomly, placed in polyethylene bags and transported to the 
Institute for Medicinal Plant Research. In order to obtain uniform sample, damaged fruits 
were removed. After rinsing with water, the seeds and stems were removed, and the peel was 
mechanically separated from the pulp. Peel and pulp were blended in a Philips microblender 
HR2860 to obtain a paste that was further lyophilized. The obtained lyophilized samples (one 
per each cultivar) were stored at 4 °C until further analysis. 
Extraction procedure  

Ultrasound-assisted extraction was carried out at room temperature. Two grams of 
lyophilized pulp and peel samples were extracted with 25 mL of 70 % methanol for 30 min in 
a Bandelon Sonorex RK52 ultrasonic bath (Bandelon Electronic, Munich, Germany) operating 
at room temperature. After filtration, the obtained extracts were used for the determination of 
the total phenolic content, the total proanthocyanidins content and HPLC analysis. 
Total phenolic content 

Determination of total phenolic content (TPC) was conducted according to a previously 
described method.17 An aliquot of sample (20 μL) was mixed with 1580 μL of distilled water, 
100 μL of Folin–Ciocalteu reagent and 300 μL of 20 % Na2CO3, followed by incubation for 2 
h at room temperature. After incubation, the absorbance was recorded at 765 nm. The contents 
of total phenolics were calculated using a standard curve for gallic acid and are expressed as 
milligrams of gallic acid equivalents per 1 g of dry sample (mg GAE g-1 dry weight (dw)).  
Total proanthocyanidin content 

The content of total proanthocyanidin compounds (TPR) in the samples was determined 
spectrophotometrically using p-DMACA method with slight modifications.18 The investigated 
extracts were mixed with 80 μL of p-DMACA reagent (2 mL), methanol (25 mL) and a drop 
of glycerol. After 7 min, the absorbance at 640 nm was measured. The contents of proantho-
cyanidins in the samples are expressed as milligrams of catechin equivalents per 1 g of dry 
sample (mg CE g-1 dw). The p-DMACA reagent was prepared immediately before use, and 
contained 1 % (w/V) p-DMACA in a cold mixture of methanol and HCl (4:1). 
HPLC analysis 

Phenolic compounds in the tested extracts were determined by comparing the retention 
times and absorption spectra (200–400 nm) of unknown peaks with those of pure standards 
injected under the same conditions. The standards used were chlorogenic acid, phloretin 2′-O- 
-glucoside (phloridzin), quercetin 3-O-galactoside (hyperoside), quercetin 3-O-rutinoside 
(rutin), quercetin 3-O-rhamnoside (quercitrin) and quercetin 3-O-glucoside (isoquercetine). 
The HPLC-DAD analysis was performed on an Agilent 1200 Series HPLC (Agilent Technol-
ogies, Palo Alto, CA, USA) equipped with Lichrospher® 100 RP 18e column (5 µm, 250 
mm×4 mm). Mobile phase A was formic acid in water (1 %) and mobile phase B was 
acetonitrile. The injection volume was 30 µL, and the flow rate 1 mL min-1 with a gradient 
program as follows: 5–15 % B 0–5 min, 15–20 % B 5–8 min, 20 % B 8–12 min, 20–30 % B 
12–15 min, 30 % B 15–17 min, 30–35 % B 17–20 min, 35 % B 20–22 min, 35–100 % B 22– 

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610 ŽIVKOVIĆ et al. 

–25 min. The stop time of the analysis was 25 min and column temperature was 25 °C. For the 
quantitative analysis of phenolic compounds, a calibration curve was obtained by injection of 
known concentrations (5–400 µg mL-1) of different standard compounds: arbutin (y = 
= 11560.8x – 0.5, R2 = 1), chlorogenic acid (y = 83506.1x–58.1, R2 = 0.998), quercetin 3-O- 
-rutinoside (y = 26573.7x + 70.4, R2 = 0.999), quercetin 3-O-galactoside (y = 64124.3x + 
+ 172.7, R2 = 0.997), quercetin 3-O-glucoside (y = 69710.5x+15.7, R2 = 0.999), quercetin 
3-O-rhamnoside (y = 57551.6x + 46.7, R2 = 0.999) and phloretin 2′-O-glucoside (y = 58862.7x 
+ 51.9, R2 = 0.999). Quantification was performed based on DAD results, using 280 nm for 
chlorogenic acid and phloretin 2′-O-glucoside and 350 nm for the flavonoid compounds. The 
investigated samples were analyzed in triplicate. The acceptable level of method precision 
was shown by the percentage relative standard deviation (RSD%) lower than 5 %. 
 Determination of the mineral elements 

The contents of mineral elements were determined as described previously by Pavlović 
et al.19 Lyophilized peel and pulp samples were subjected to microwave digestion using an 
Ethos 1 microwave system (Advanced microwave digestion system, Milestone, Italy). One 
gram of apple or pear sample, 1.0 mL of 30 % H2O2, and 7.0 mL of concentrated ultrapure 
HNO3 (69.0–70.0 %)were mixed and transferred into the microwave digestion vessel. After 
the effervescence had subsided, the sample was cooled for 5 min, transferred into a clean 
volumetric flask, and diluted to 25 mL with ultrapure H2O. A blank was prepared in the same 
way. All analyses were performed in triplicate on a Thermo Scientific iCAP 6500 Duo ICP 
(Thermo Fisher Scientific, Cambridge, UK). 
Statistical analysis 

The phenolic composition analyses were performed in triplicate and the data are pre-
sented as mean ± standard deviation. Differences between the group means and their signific-
ance were verified using one-way ANOVA. Statistical significance was set at p < 0.05. On the 
other hand, the data for the elemental analysis were obtained from one measurement. 

RESULTS AND DISCUSSION 

Phenolic composition 
The phenolic concentration is commonly linked with nutritional and sensory 

attributes of fruits.20 Apples and pears are one of the rare food types with precise 
data about their phenolic composition. The polyphenolic profiles of all apple 
cultivars are practically the same but concentrations may range from 0.1 to 5 g of 
total polyphenols per kg fresh weight and may be as high as 10 g kg–1 in certain 
varieties of cider apples.21 In the case of pears, the situation is similar, there are 
reports for TPC ranging from 3.02 to 4.58 g per kg fresh weight.22 

In the present investigation, the content of total phenolics (TPC) and total 
proanthocyanidins (TPR) showed significant variation among the tested cultivars 
(Tables I and II). The TPC in apple and pear peel samples determined by the 
Folin–Ciocalteu assay ranged from 2.82 to 12.24 mg GAE g–1 dw and from 3.81 
to 8.11 mg GAE g–1 dw, respectively. In the case of apple and pear pulp, TPC 
varied between 1.55 to 5.95 mg GAE g–1 dw and 1.38 to 3.50 mg GAE g–1 dw, 
respectively. Among the apples, the Mekica cultivar had the highest TPC while 
Šećerlija and Zlatna Parmenka had the lowest. In the case of pear samples the max- 

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 CHEMICAL PROFILE OF AUTOCHTHONOUS FRUITS 613 

imum TPC was found for Bela Arapka while the minimum TPC was recorded for 
Crna Takiša. The present findings are consistent with those of other researchers. 
For example Huber and Rupasinghe,23 reported that TPC for Red Delicious, 
Empire and Royal Gala peel extracts were 3.80, 4.82 and 4.84 mg g–1 dw, 
respectively. Regarding commercial apple cultivars, Alarcon-Flores et al.24 
showed that the Pink Lady variety had the highest concentration of phenolic 
compounds (4.11 mg g–1 dw) followed by Ambrosia (4.01 mg g–1 dw). For peel 
samples of ten Chinese pear cultivars, Li et al.25 showed variations in the TPC 
from 2.64 to 11.21 mg GAE g–1 dw. The results from the present study were also 
comparable with the results obtained for three Pakistan pear varieties, Nakh, 
Nashpati and Bartlett, for which the TPC ranged from 3.81 to 8.11 mg GAE g–1 
dw in peel and from 3.34 to 3.56 mg GAE g–1 dw in pulp.26 In the same 
investigation, the TPC was approximately 6–20 times lower in pulp samples 
compared to peel. In the present study, the TPC was generally 2–3 fold higher in 
peel compared to pulp samples, in both apples and pears.  

As important bioactive constituents, the TPR content was also determined, 
and found to range from 0.71 to 7.62 mg catechins g–1 dw and from 0.77 to 3.84 
mg catechins g–1 dw in apples peel and pulp, respectively, and from 0.40 to 5.17 
mg catechins g–1 dw and from 0.11 to 1.44 mg catechins g–1 dw in pear peel and 
pulp, respectively, (Tables I and II). It could be observed that the TPR content 
was generally lower in pear peel and pulp samples than in the investigated apple 
samples. In addition, in comparison with the pulp samples, the TPR content was 
higher in the peel samples. Although the obtained values for the TPR content were 
high, it was difficult to compare the results with existing literature data since 
different methodologies for quantification were used. For example, the TPR con-
tent in the cultivar Champion determined by HPLC analysis was 1.65 mg g–1 dw.13 

Chemical analysis of the individual phenolic compounds in the investigated 
pear and apple samples was conducted using the HPLC-DAD technique and the 
results are presented in Table I. Based on retention time and spectrum 
information, seven phenolic compounds were identified, i.e., one phenolic acid 
(chlorogenic acid), one phenolic glucoside (arbutin), four flavonols (quercetin 3-
O-rutinoside, quercetin 3-O-galactoside, quercetin 3-O-rhamnoside and quercetin 
3-O-glucoside) and one dihydrochalcone (phloretin 2′-O-glucoside). For each 
individual phenolic compound, ANOVA evaluated significant differences in 
dependence on the variety considered. Among the identified phenolic com-
pounds, in peel and pulp samples obtained from apples collected in Ljig, chloro-
genic acid was the dominant compound (ranging from 93.68 to 601.62 μg g–1 dw 
in peel and from 336.50 to 652.14 μg g–1 dw in pulp). The situation was similar 
with pulp samples of apples collected from Zlatibor mountain (148.42 to 1530.99 
μg g–1 dw) while for the peel samples (with the exception of the cultivar Kra-
ljica) the situation was slightly different. Namely, phloretin 2′-O-glucoside (in 

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614 ŽIVKOVIĆ et al. 

Kožara peel) or quercetin 3-O-rhamnoside (Masnjača, Mekica, Kraljica and 
Šarenka peel) were prevalent compounds followed by chlorogenic acid (from 
147.68 to 688.69 μg g–1 dw). In general, the content of chlorogenic acid was 
significantly higher in apple pulp compared to apple peel. The exceptions were 
cultivars Zlatna Parmenka and Streknja, in which the content was approximately 
1.5 fold higher in peel, and Masnjača, in which, chlorogenic acid was equally 
present in peel and pulp. For some cultivars (Streknja, Zlatna Parmenka, Kožara 
and Kraljica), the content of chlorogenic acid was quite high compared with the 
results obtained by other authors for some commercial cultivars. Awad and de 
Jager27 reported values between 160 and 330 μg g–1 dw in peel of Jonagold 
cultivar and Lata et al.11 values 260 and 280 μg g–1 dw for peel samples of the 
cultivars Elstar and Granny Smith, respectively. In addition, the obtained values 
for Streknja, Kožara, Šećerlija and Kraljica peel are much higher than those 
reported in previous studies for peel samples of Fuji, Royal and Pink Lady when 
the content of chlorogenic acid ranged from 280 to 430 μg g–1 dw.24 Among 
apple phenolics, chlorogenic acid is one of the most important substrates for 
polyphenol oxidase (PPO); its oxidation generates pigments that can co-oxidize 
other substances.28 Therefore, apple cultivars with a low concentration of 
chlorogenic acid would be more appropriate for producing apple juice, to 
minimize enzymatic browning, and to control the stability of the final product. 
For this reason, it could be stated that the cultivars Mekica and Kraljica are less 
suitable for producing apple juice. 

Arbutin and chlorogenic acid were detected as the major phenolic com-
pounds in case of pear peel and pulp samples. Such results were consistent with 
previous data.29 In peel and pulp samples of Bela and Crna Takiša, arbutin was 
the main phenolic compound, as well as in pulp samples obtained from the cul-
tivars Bela arapka and Bronzara, while chlorogenic acid prevailed in their peel 
samples. In a study conducted by Li et al.,25 arbutin was the dominant compound 
in 11 Chinese cultivars in peel (ranging from 323.3 to 6982.0 µg g–1 dw) and in 
pulp (ranging from 92.8 to 2077.0 µg g–1 dw).  

Quercetin glycosides were the only flavonols found in analyzed apple and 
pear samples. In some cultivars, they were the most abundant phenolic group 
mainly identified in the peel of the investigated apple and pear cultivars, while 
they were present only in traces in the pulp. Significant differences in the con-
tents of these compounds were found among the tested cultivars. The exception 
was quercetin 3-O-rhamnoside with a content of around 100 µg g-1 dw in cul-
tivars Masnjača, Mekica, Kožara and Šarenka. Among the apple peel samples, 
the highest contents of individual flavonols were detected in Mekica, while in the 
case of the pear samples, Bela arapka was the cultivar with the highest content. 
Senabija among apples and Bronzara and Crna Takiša among pears had the low-
est levels of these compounds. In most of the pear and apple samples, quercetin 

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 CHEMICAL PROFILE OF AUTOCHTHONOUS FRUITS 615 

3-O-rhamnoside was the dominant flavonol, the exception being the apple 
cultivar Kolačara, in which quercetin 3-O-glucoside was dominant. The quercetin 
3-O-rhamnoside contents in apple peel samples of the studied cultivars (from 
traces to 2129 μg g–1 dw) were comparable with previously obtained results for 
cultivars Jonagold (2660 μg g–1 dw) and Elstar (580 μg g–1 dw).8 On the other 
hand, the levels of quercetin 3-O-glucoside (5 to 344 μg g–1 dw) were lower 
compared with those of the commercial cultivars Jonagold and Elstar for which 
values of 530 and 700 μg g–1 dw were found.8 In the case of the apple pulp 
samples, the contents of quercetin 3-O-rhamnoside in Masnjača, Mekica, Kožara 
and Šarenka pulp (≈100 µg g–1 dw) were significantly higher compared to the 
commercial cultivars Royal, Fuji, Golden and Pink Lady that contained from 2.7 
to 28.6 µg g–1 dw.24 In terms of the content of flavonols in pears, the peel of 
Bela Arapka was the richest one, followed by the peel sample of Bela Takiša.  

Macro and microelement analysis 
Besides phytochemicals, an important part of nutritional information is the 

concentration of essential elements. Minerals play a key role in different physio-
logical functions of the body, especially in regulation processes. Numerous 
factors, such as soil type and conditions as well as the variety, may cause vari-
ations in mineral contents of fruits. In this study, the content of most of the inves-
tigated elements was significantly different depending on the species, cultivar, 
and part of the fruit examined (Tables III and IV). Generally, peel samples 
showed a higher mineral content compared to pulp. These results are in accord-
ance with previous results.30,31 The most common mineral in the tested apple 
and pear samples was potassium with contents ranging from 4.12 to 8.86 and 
from 6.27 to 8.36 mg g–1 dw in apple and pear peel, respectively. In pulp, the 
potassium content was lower varying from 3.86 to 7.49 and from 4.59 to 6.59 in 
apple and pear samples, respectively. The concentration of K was the highest in 
the cultivar Šećerlija among the apples and regarding the pears, the cultivar Bela 
Takiša was the richest in this element. Remarkable contents were also observed 
for P, Mg, Ca and S. These data are consistent with the results obtained by other 
authors.31,32 The highest content of P and S in peel and pulp was obtained for the 
cultivar Šećerlija, while the concentration of Ca was highest in Zlatna Parmenka. 
The present results for macroelements were in agreement with those reported by 
Manzoor et al.31 for cultivars Golden Delicious and Red Delicious. On the other 
hand, the contents of Mg and Ca determined in the present investigation were 
lower than those reported by Ekholm et al.16 for apple peel (0.7 and 0.5 mg g–1 
dw, respectively) and pulp (0.5 and 0.4 mg g–1 dw, respectively). Considering the 
pear samples, the highest contents of Ca, Mg and P were recorded in Crna Takiša 
cultivar, while Bela Arapka was the one richest in P. The contents of Ca in the 

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616 ŽIVKOVIĆ et al. 

pear peel samples were remarkably higher compared to those found in the apple 
peel samples. 

TABLE III. The concentration of macroelements (expressed as mg g-1 dw) in the apple and 
pear samples (n = 1); * samples from Ljig, ** samples from Zlatibor 

Sample 
Mineral 

Ca K Mg P S 
Apple cultivar 

Kolačara* peel 0.28 7.42 0.39 0.68 0.29 
Kolačara* pulp 0.17 6.09 0.24 0.44 0.17 
Streknja* peel 0.29 7.32 0.46 0.82 0.33 
Streknja* pulp 0.17 6.05 0.21 0.39 0.16 
Šećerlija* peel 0.36 8.86 0.50 1.09 0.43 
Šećerlija* pulp 0.28 7.49 0.31 0.58 0.22 
Zlatna Parmenka* peel 0.69 4.87 0.48 0.56 0.24 
Zlatna Parmenka* pulp 0.36 5.69 0.25 0.54 0.17 
Senabija* peel 0.33 7.43 0.45 0.69 0.30 
Senabija* pulp 0.27 6.71 0.30 0.41 0.16 
Masnjača** peel 0.37 6.68 0.65 0.99 0.36 
Masnjača** pulp 0.13 5.03 0.23 0.50 0.24 
Mekica** peel 0.59 6.24 0.60 0.79 0.38 
Mekica** pulp 0.28 3.86 0.18 0.38 0.13 
Kožara** peel 0.28 4.12 0.90 0.31 0.24 
Kožara** pulp 0.07 5.46 0.30 0.22 0.11 
Kraljica** peel 0.28 7.19 0.62 0.78 0.36 
Kraljica** pulp 0.09 5.40 0.22 0.63 0.24 
Šarenka** peel 0.49 7.28 0.42 0.74 0.29 
Šarenka** pulp 0.22 5.45 0.17 0.33 0.10 

Pear cultivar 
Bela Takiša** peel 0.52 8.36 0.42 0.72 0.23 
Bela Takiša** pulp 0.21 6.59 0.30 0.75 0.18 
Bela Arapka** peel 1.29 8.11 0.58 0.85 0.42 
Bela Arapka** pulp 0.24 6.34 0.31 0.72 0.26 
Bronzara** peel 0.50 6.27 0.44 0.59 0.35 
Bronzara** pulp 0.17 4.59 0.25 0.56 0.19 
Crna Takiša** peel 1.43 7.39 0.56 0.95 0.27 
Crna Takiša** pulp 0.36 5.66 0.33 0.84 0.23 

Trace elements with contents higher than 1 µg g–1 dw were Al, B, Ba, Cu, Fe, 
Mn, Na and Zn, while the other microelements were lower in the investigated 
samples. According to the obtained data, Fe was the dominant microelement in 
the apple peel and pulp samples, while B was the principal microelement in the 
pear samples. Appreciable amounts of Fe were recorded in the peel samples of 
Kolačara and Šećerlija. The iron values in the investigated apple samples were 
lower compared to some commercial ones.31 On the other hand, they were com-
parable with the values obtained for Romanian autochthonous cultivars when the  

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 CHEMICAL PROFILE OF AUTOCHTHONOUS FRUITS 619 

Fe content ranged from 2.45 to 3.64 μg g–1 dw.33 The content of B was highest 
in apple cultivars Šećerlija and Kraljica, while the cultivar Crna Takiša exhi-
bited the highest B content (11.50 and 8.15 µg g–1 dw in peel and pulp samples, 
respectively) among the pears.  

According to the obtained data, the Al content was higher in the fruit 
samples from Ljig compared to that in the samples collected on Zlatibor Mount-
ain. While the lowest Al content in apple peel was observed for the cultivar 
Šarenka, the cultivar Zlatna Parmenka was statistically superior as a source of Al. 
For Zn and Cu, the data showed that pear samples were a better source compared 
to apples.  

The investigated non-nutritive toxic elements that are known to have delete-
rious effects even in small quantities (below 100 ppm) were As, Sb, Cd, Pb and 
Se.34 Se was below the limit of detection in all the investigated samples, as were 
Sb in the pear samples and Cd in the apple samples. The content of the remaining 
elements was generally higher in the peel of the fruits than in the pulp for both 
apples and pears. 

The shown variability in the mineral contents could be ascribed to differ-
ences in cultivation conditions, such as soil fertility, pH, climate and seasonal 
variations. However, the differential capacity of the cultivars to absorb metal ions 
from soils and/or the specific capacity of redistribution within the overall plant 
could be other reasons for the exhibited variability. 

CONCLUSIONS 

The results of the present study provide valuable data regarding the phenolic 
and mineral contents of Balkan apple and pear cultivars. The concentrations of 
the identified polyphenols and minerals were significantly different depending on 
the apple or pear cultivar for both peel and pulp. Although it is difficult to 
directly compare the content of apple phenolics between different studies due to 
variations caused by different growth periods, geographic locations, genetic div-
ersity, methodology and many other factors,11 the cultivars Mekica, Šarenka 
(among the apples) and Bela Arapka (among the pears) could be considered as 
rich sources of phenolics according to the results of this study. Based on these 
data, mentioned cultivars show high potential for juice production while the 
cultivars Senabija and Šećerlija, due to their lower phenolic content, are recom-
mended for direct consumption. Balkan autochthonous apple and pear varieties 
could be considered as a good source of dietary minerals.  

Acknowledgements. The authors acknowledge their gratitude to the Ministry of Edu-
cation, Science and Technological Development of the Republic of Serbia for financial sup-
port, project No. 46013. 

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Available on line at www.shd.org.rs/JSCS/



620 ŽIVKOVIĆ et al. 

И З В О Д  
ФЕНОЛНИ И МИНЕРАЛНИ ПРОФИЛ АУТОХТОНИХ ВАРИЈЕТЕТА ЈАБУКА И 

КРУШАКА СА БАЛКАНА 

ЈЕЛЕНА ЖИВКОВИЋ1, КАТАРИНА ШАВИКИН1, ГОРДАНА ЗДУНИЋ1, БИЉАНА ДОЈЧИНОВИЋ2 

и НЕБОЈША МЕНКОВИЋ1 

1Институт за проучавање лековитог биља „Др. Јосиф Панчић“, Тадеуша Кошћушка 1, 
11000 Београд и 2Универзитет у Београду, Институт за хемију, технологију и 

металургију, Његошева 12, 11000 Београд 

Циљ ове студије била је хемијска анализа фенолних једињења, као и минералних 
састојака присутних у узорцима коре и меса балканских аутохтоних сорти јабука и 
крушака. Фенолне компоненте одређене применом HPLC-DAD и спектрофотометриј-
ских техника значајно су варирале у зависности од варијетета у узорцима коре и меса. 
Међу јабукама варијетет Мекица имао је највећи садржај укупних фенола, док је у вари-
јететима Шећерлија и Златна парменка он био најнижи. У случају крушака Црна такиша 
је била богат извор ове групе једињења, док је у варијетету Бела арапка забележена 
најнижа концентрација. У већини испитиваних варијетета хлорогенска киселина (код 
јабука) и арбутин (код крушака) била су доминантна фенолна једињења. Анализом 
елемената показано је да је K најзаступљенији, следе P, Mg, Ca и S. Гвожђе је доминан-
тан микроелемент у кори и месу јабука, док је у узорцима крушака то B. Добијени резул-
тати дају детљну информацију о хемијском саставу испитиваних варијетета и на тај 
начин стимулишу њихово шире гајење и примену у исхрани. 

(Примљено 26. октобра 2015, ревидирано 16. фебруара, прихваћено 17. фебруара 2016) 

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    /HRV (Za stvaranje Adobe PDF dokumenata najpogodnijih za visokokvalitetni ispis prije tiskanja koristite ove postavke.  Stvoreni PDF dokumenti mogu se otvoriti Acrobat i Adobe Reader 5.0 i kasnijim verzijama.)
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    /NLD (Gebruik deze instellingen om Adobe PDF-documenten te maken die zijn geoptimaliseerd voor prepress-afdrukken van hoge kwaliteit. De gemaakte PDF-documenten kunnen worden geopend met Acrobat en Adobe Reader 5.0 en hoger.)
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    /ENU (Use these settings to create Adobe PDF documents best suited for high-quality prepress printing.  Created PDF documents can be opened with Acrobat and Adobe Reader 5.0 and later.)
  >>
  /Namespace [
    (Adobe)
    (Common)
    (1.0)
  ]
  /OtherNamespaces [
    <<
      /AsReaderSpreads false
      /CropImagesToFrames true
      /ErrorControl /WarnAndContinue
      /FlattenerIgnoreSpreadOverrides false
      /IncludeGuidesGrids false
      /IncludeNonPrinting false
      /IncludeSlug false
      /Namespace [
        (Adobe)
        (InDesign)
        (4.0)
      ]
      /OmitPlacedBitmaps false
      /OmitPlacedEPS false
      /OmitPlacedPDF false
      /SimulateOverprint /Legacy
    >>
    <<
      /AddBleedMarks false
      /AddColorBars false
      /AddCropMarks false
      /AddPageInfo false
      /AddRegMarks false
      /ConvertColors /ConvertToCMYK
      /DestinationProfileName ()
      /DestinationProfileSelector /DocumentCMYK
      /Downsample16BitImages true
      /FlattenerPreset <<
        /PresetSelector /MediumResolution
      >>
      /FormElements false
      /GenerateStructure false
      /IncludeBookmarks false
      /IncludeHyperlinks false
      /IncludeInteractive false
      /IncludeLayers false
      /IncludeProfiles false
      /MultimediaHandling /UseObjectSettings
      /Namespace [
        (Adobe)
        (CreativeSuite)
        (2.0)
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      /PDFXOutputIntentProfileSelector /DocumentCMYK
      /PreserveEditing true
      /UntaggedCMYKHandling /LeaveUntagged
      /UntaggedRGBHandling /UseDocumentProfile
      /UseDocumentBleed false
    >>
  ]
>> setdistillerparams
<<
  /HWResolution [2400 2400]
  /PageSize [612.000 792.000]
>> setpagedevice