Stability of Carotenoids in Dried Apricots (Prunus

Armeniaca L.) During Storage

Elena Andreea POP1, Andrea BUNEA1, Florina COPACIU1, Carmen SOCACIU1, Adela PINTEA1*

University of Agricultural Sciences and Veterinary Medicine Cluj-Napoca, Mănăștur 3-5, 400372, Cluj-
Napoca, Romania
*corresponding author: apintea@usamvcluj.ro
Bulletin UASVM Food Science and Technology 73(2) / 2016
ISSN-L 2344-2344; Print ISSN 2344-2344; Electronic ISSN 2344-5300
DOI: 10.15835/buasvmcn-fst:12263

Abstract
Apricots are well known for the high content of bioactive compounds such as carotenoids, polyphenols, vitamins
and minerals. Several studies have pointed out the chemical composition or the biological effects of apricots, but
limited information are available regarding the stability of active compounds during storage or processing. The
aim of this study was to determine the stability of major carotenoids in commercial dried apricots during storage.
Carotenoids were extracted monthly from dried apricots kept in a dark environment, at room temperature, for
twelve months. Total carotenoids were determined using the spectrophotometric method while the most relevant
carotenoids were analyzed by high-performance liquid chromatography-photodiode array detection (HPLC-PDA)
on a C30 column and using a gradient elution system.
Initial carotenoid content of dried fruits was 6.72 mg/100g, while after six months of storage it decreased to
2.46 mg/100g. After twelve months of storage the total carotenoid content was 0.82 mg/100g, representing 20.35
% of the initial concentration. The major carotenoids identified in apricots were: all trans β-carotene, its geometrical
isomers (9-cis-β-carotene; 13-cis-β-carotene; 9,13-di-cis β-carotene); β-carotene-5,8-epoxide; β-cryptoxanthin
and β-cryptoxanthin palmitate. Significant decreases were observed for all pigments but all trans β-carotene
appears to be the most sensitive pigment, with 15.7 % residual concentration. Although the concentrations of
β-cryptoxanthin palmitate is small, it has shown significant increased stability compared to carotenes.

Keywords: apricots, carotenoids, HPLC, stability

INTRODUCTION tissues exposes carotenoids to light, oxygen and

Food which provide high carotenoid intake
are considered very important to maintain health
and to reduce the risks of severe diseases (Krinsky
and Johnson, 2005). The carotenoid content
in plant derived food is influenced by several
factors such as: genetic origin, environmental
conditions, cultivation practice and post-harvest
treatment. Post-harvest treatment is a key step in
preserving the nutritional value of plant food. Due
to the polyenic system (conjugated double bonds),
carotenoids are susceptible to degradation under
high temperature, light, acidic pH and presence
of reactive oxygen species. It was proved that
carotenoids are more stable in vegetables and
fruit than in isolated form and disruption of the
oxidizing enzymes like lipoxygenase (Britton
et al., 1995a; Mercadante, 2008; Caris-Veyrat,
2008). The mechanisms involved in carotenoids
degradation in food are similar with the degrada­
tion of pure compounds and occur mainly through
oxidation, geometrical isomerisation, but also by
rearrangement of 5,6-epoxides and dehydration
(Mercadante, 2008; Rodriguez-Amaya, 2016).
Enzymic oxidation is due to the contact of caro­
te­noids with lipoxygenase which leads to the
bleaching of pigments, while non-enzymic oxida­
tion results in the formation of different epoxides
and apocarotenals. High temperature, light and
presence of acids determine the geometrical
isomerisation of carotenoids (Mercadante, 2008).
94
Apricots are largely consumed worldwide as
fresh, canned or dried fruits. The total world fresh
apricot production was 4,038,520 tons in 2012,
with Turkey as main producer of both fresh and
dried fruits (FAOSTAT). Due to the short shelf life
of fresh apricots, these are subjected to different
preservation methods, the most common being
canning or drying (open air sun drying, hot air
drying, microwave drying or combined methods)
(Garcia-Martinez et al., 2012). Beside their
pleasant taste, apricots are associated with health
benefits such as anti-inflammatory, antioxidant or
antimicrobial effects (Erdogan-Orhan and Kartal,
2013). Carotenoids, polyphenols, vitamin C,
mono- and polysaccharides, volatiles and minerals
are among the most important constituents of
apricot fruits (Ruiz et al., 2005; Sass-Kiss et al.,
2005; Dragovic-Uzelac et al., 2007; Aubert and
Chanforan, 2007; Kurtz et al., 2008; Erdogan-
Orhan and Kartal, 2013). Even if several studies
investigated the effect of drying method on the
total and individual content of carotenoids in
apricots (Ihns et al., 2011; Garcia-Martinez et
al., 2012; Turkyilmaz et al., 2013; Fratianni et
al., 2013) there are no reported data regarding
the stability of individual carotenoids in dried
apricots during storage. Our aim was to monitor
the carotenoid content and profile during one year
storage period of commercially available dried
apricots using an HPLC-PDA method.
MATERIAL AND METHODS
2.1 Plant material
Dried apricots (Prunus armeniaca L.) were
purchased from a local organic product store. The
fruits were divided and kept in individual sealed
polyethylene bags, at room temperature (25ºC), in
dark for twelve months. Samples were taken each
month for carotenoid extraction.
2.2 Carotenoid extraction and quantification
The dried fruits (20 g) were extracted with
a mixture of methanol/ethyl acetate/ petroleum
ether (1: 1: 1, v/v/v) as described previously
(Pop et al., 2015). Total carotenoids content
was determined using the spectrophotometric
method with an UV-VIS Spectrophotometer (Jasco
V-530) (Britton et al., 1995a). The concentration
of total carotenoids was expressed as mg
carotenoids/100 g dried fruits. All experiments
were performed under subdued light.
Bulletin UASVM Food Science and Technology 73(1) / 2016
POP et al
2.3 Separation of carotenoids by RP-HPLC
HPLC analysis of carotenoids was performed
on Shimadzu LC20 AT high performance liquid
chromatograph with a SPDM20A diode array
detector. An YMC C30 column (250x4.6 mm; 5
μm) was used and the mobile phases consisted
in: solvents A: methanol/tert-butyl methyl ether/
water (81:15:4) and solvent B: tert-butyl methyl
ether/methanol/water (90: 7:3). The gradient
was: 0 min 0 % solvent B, 20 min 0 % B; 130 min –
82 % B; 132 min 0 % B, followed by equilibration
of column for 10 min. The flow rate was fixed at 0.8
ml/min and the DAD detector was set at 450 nm.
Standard compounds β-cryptoxanthin, β-carotene
and lycopene were provided by ChromaDex, USA;
β-cryptoxanthin palmitate was obtained by semi
synthesis and purified by HPLC in our laboratory
(Pintea et al., 2013). The chromatographic data and
UV-VIS spectra were compared using Shimadzu
LC software. Calibration curves were made
for β-cryptoxanthin, β-carotene and β-crypto­
xanthin palmitate by plotting peak area against
concentration. The identification of cis isomers
was based on the specific absorption maxima
which appears in the UV region of the absorption
spectra of carotenoids (Britton et al., 1995b).
Statistical analysis. The results are presented
as the mean ± SD. Significant differences between
samples were analysed with one-way ANOVA post
hoc tests, and pairwise multiple comparisons
were onducted using Tukey’s test. Significant
differences were reported based on P ≤ 0.05.
Statistical analyses were performed using the
SPSS programme (SPSS Inc., Chicago, IL, USA).
RESULTS AND DISCUSSIONS
The total carotenoid content, estimated by
the spectrophotometric method in dried apricots
at the beginning of the experiment was 6.72
mg/100 g. This value is relatively low compared
to fresh fruits, where a total carotenoid content
ranging between 1.5-16 mg/100 g fresh weight
was reported for various cultivars (Ruiz et al.,
2005; Sass-Kiss et al., 2005; Dragovic-Uzelac et
al., 2007; Kurtz et al., 2008). Taking into account
that β-carotene is the major compound in
apricots, the carotenoid concentration is close to
values found by Alagoz et al. (2015), 4.1- 6.7 mg
β-carotene/100 g in dried apricots from Turkey.
Higher concentrations of β-carotene (10.4-12.8
mg/100 g d.w), were found in dried apricots (with
Stability of Carotenoids in Dried Apricots (Prunus armeniaca L.) During Storage 95

0.6 0.5
0.4
0.4

0.2
Abs 0.2 Abs

0 0
-0.1 -0.1
300 400 500 550 300 400 500 550
Wavelength [nm] Wavelength [nm]
(a) (b)
0.4 0.3

0.3
0.2
0.2
0.1
Abs Abs
0.1
0
0

-0.1 -0.1
300 400 500 550 300 400 500 550

(c) Wavelength [nm]

(d) Wavelength [nm]

Figura 1. Absorption spectra of total carotenoid extract in dried apricots

(a) December 2014; (b) April 2015; (c) September 2015; (d) November 2015.

Fig 2. Variation of total carotenoids in dried apricots during storage

~25 % water content) obtained from a Spanish
cultivar by different drying methods (Garcia-
Martinez et al., 2012). Also, Türkyilmaz and
coworkers (2013) found concentrations ranging
between 26.6 and 36.2 mg/ 100 g d.w. depending
on SO2 content in one cultivar of dried Turkish
Malatya apricots. As it can be observed in Figure
1, significant changes occurred in the absorption
spectra of total carotenoid extract, with a marked
decrease of absorption at λmax 448 nm and an in­
crease of absorption in the UV region (300-400
nm). These changes are associated with a decrease
of carotenoid concentration and with changes in
the profile of carotenoids, mainly with the cis-
trans isomerization and appearance of “cis-peak”
(Britton et al., 1995b).
A significant decrease of total carotenoid
during storage can be observed (Figure 2), from

Bulletin UASVM Food Science and Technology 73(1) / 2016

96 POP et al

the initial value of 6.72 mg/100 g to 0.82 mg/100 The variation of major carotenoids in dried
g after twelve months of storage. Considering apricots is shown in Table 1, where data are
these data, only 20 % of the initial amount of expressed as % residual carotenoid compared
carotenoids can be found after one year of storage to intitial concentration (considered as 100 %).
at room temperature. The degradation rate seems During the storage of fruits, loss of all carotenoids
to be more intense in first seven months (1.96 could be observed but the extent of degradation
mg/100 g) and slower in the last period of storage. depends on the nature of the carotenoid. After
The profile of carotenoids in dried apricots is twelve months of storage, the highest degradation
similar with that found in fresh fruits (Pop et al., was recorded for all trans β-carotene, followed
2015). As previously reported, all trans β-carotene by its cis isomers. A possible explanation could be
is the major carotenoid in fresh or dried apricots, that all trans β-carotene was partially converted
followed by its geometric isomers (13-cis-β- into cis-isomers which represents one of the
carotene; 9,13-di-cis β-carotene; 9-cis-β-carotene). mechanism of carotenoid degradation in food.
In lower amounts, β-carotene-5,8-epoxide, β-cryp­ The ester of β-cryptoxanthin with palmitic acid
to­xan­thin, β-cryptoxanthin esters and lutein was less affected than the corresponding free
are present. A similar profile of carotenoids was xanthophyll (β-cryptoxanthin) and significantly
reported by Kurtz et al. (2008). more stable than β-carotene and its isomers.

5
200
6

150
Intensity (mAU)

3
100

4
50 2
1
7
0

0 20 40 60 80 100 120 140

(a) Retention time (min)

5
200

150
Intensity (mAU)

100 6
3

50
4
12 7
0

20 40 60 80 100 120 140

(b) Retention time (min)

Fig. 3. HPLC/PDA chromatograms of carotenoids from dried apricots (a) – Month 1; (b) – Month 7.
(1) β-cryptoxanthin, (2) β-carotene-5,8-epoxide ; (3) 13-cis-β-carotene; (4) 9,13-di-cis β-carotene (5) all trans
β-carotene; (6) 9-cis-β-carotene; (7) β-cryptoxanthin palmitate

Bulletin UASVM Food Science and Technology 73(1) / 2016

Stability of Carotenoids in Dried Apricots (Prunus armeniaca L.) During Storage
Tab. 1. Variation of residual concentration of major carotenoids (mean ± S.E) in dried apricots during
storage
Compound Month 1
β-cryptoxanthin 97.2 ± 5.7a
13-cis β-carotene 97.1 ± 3.8a
all trans β-carotene 95.5 ± 3.8a
9-cis β-carotene 98.3 ± 3.7a
β-cryptoxanthin palmitate 98.4 ± 4.3a
Note: Different letters within a column denote significant differences (P < 0.05).
A study performed on different fruits and
vegetables monitored the changes induced by
thermal treatment (heating at 98ºC) or freezing
(-20ºC) on the content of anthocyanins, carotenoids
and ascorbic acid. In the case of apricots, the
concentration of individual carotenoids was
estimated spectrophotometrically based on the
wavelength of maximum absorption and on
their molar absorptivity coefficients, without a
chromatographic separation. Using this method
the authors have shown that the highest decrease
was produced by lyophilization, for all carotenoids
the final concentration being approximately 50% of
the initial one. Heating at 98ºC resulted in a greater
reduction of hydrocarbon carotenoid (β-caro­
tene, α-carotene and lycopene) and a mode­rate
fall in the case of xanthophylls (β-crypto­xanthin
and lutein) (Leon et al., 2012). In the case of sun
dried Malatya apricots preserved with potassium
sorbate, it has been observed that the decrease
in the content of β-carotene is dependent on the
storage temperature. Thus, for fruits stored at 4ºC,
10ºC and 20ºC, a significant decrease (up to 64 % )
of β-carotene after 10 months was recorded, while
for fruits stored at 30°C there was no significant
change (Alagöz et al., 2015). The same authors have
previously reported that the duration of storage
and no the storage temperature had a greater
influence on the degradation rate of β-carotene in
the case of apricots treated with sulphur dioxide
(SO2). The concentration of β-carotene decreased
with 24-28 % after 351 days of storage, depending
on the condition (temperature, concentration
of SO2). Also, the degradation of β-carotene was
prevented by using higher concentrations of SO2
(Türkyilmaz et al., 2013). There are no literature
data on the stability of cis isomers β-carotene or
of β-cryptoxanthin esters in apricots. However,
97
Month 4 Month 8 Month 12
75.2 ± 4.2b 45.0± 2.3c 37.2 ± 2.3c
71.3 ± 3.5b 38.8 ± 2.1c 25.4 ± 1.5d
57.4 ± 1.5b 25.4 ± 0.9c 15.7 ± 1.4d
67.3 ± 3.4b 39.1 ± 1.5c 27.3 ± 1.7d
85.2 ± 4.1b 61.4 ± 2.4c 58.2 ± 3.3c
esterified form of xanthophylls - β-cryptoxanthin,
lutein, zeaxanthin, capsanthin and capsorubin –
showed increased thermal and storage stability
compared to their non-esterified counterparts in
paprika (Schweiggert et al., 2007) and tamarillo
nectar (Mertz et al., 2010).
CONCLUSIONS
In the present work, we demonstrated that
significant losses in total carotenoid content occurs
during the storage of dried apricots, only 20.35 %
of the initial concentration remaining after twelve
months. This is the first report regarding the
comparative stability of carotenes, xanthophylls
and their esters in dried apricots, by using an
HPLC method. The degree of degradation depends
on the chemical nature of compounds, β-carotene
being more sensitive than β-cryptoxanthin and
β-cryptoxanthin palmitate.
Acknowledgements: This work was supported
by a grant of the Romanian National Authority for
Scientific Research, CNCS – UEFISCDI, project PN-
II-ID-PCE-2011-3-0721
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