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 oxidizing enzymes like lipoxygenase (Britton
are considered very important to maintain health et al., 1995a; Mercadante, 2008; Caris-Veyrat,
and to reduce the risks of severe diseases (Krinsky 2008). The mechanisms involved in carotenoids
and Johnson, 2005). The carotenoid content degradation in food are similar with the degrada­
in plant derived food is influenced by several tion of pure compounds and occur mainly through
factors such as: genetic origin, environmental oxidation, geometrical isomerisation, but also by
conditions, cultivation practice and post-harvest rearrangement of 5,6-epoxides and dehydration
treatment. Post-harvest treatment is a key step in (Mercadante, 2008; Rodriguez-Amaya, 2016).
preserving the nutritional value of plant food. Due Enzymic oxidation is due to the contact of caro­
to the polyenic system (conjugated double bonds), te­noids with lipoxygenase which leads to the
carotenoids are susceptible to degradation under bleaching of pigments, while non-enzymic oxida­
high temperature, light, acidic pH and presence tion results in the formation of different epoxides
of reactive oxygen species. It was proved that and apocarotenals. High temperature, light and
carotenoids are more stable in vegetables and presence of acids determine the geometrical
fruit than in isolated form and disruption of the isomerisation of carotenoids (Mercadante, 2008).
94 POP et al

Apricots are largely consumed worldwide as 2.3 Separation of carotenoids by RP-HPLC

fresh, canned or dried fruits. The total world fresh HPLC analysis of carotenoids was performed
apricot production was 4,038,520 tons in 2012, on Shimadzu LC20 AT high performance liquid
with Turkey as main producer of both fresh and chromatograph with a SPDM20A diode array
dried fruits (FAOSTAT). Due to the short shelf life detector. An YMC C30 column (250x4.6 mm; 5
of fresh apricots, these are subjected to different μm) was used and the mobile phases consisted
preservation methods, the most common being in: solvents A: methanol/tert-butyl methyl ether/
canning or drying (open air sun drying, hot air water (81:15:4) and solvent B: tert-butyl methyl
drying, microwave drying or combined methods) ether/methanol/water (90: 7:3). The gradient
(Garcia-Martinez et al., 2012). Beside their was: 0 min 0 % solvent B, 20 min 0 % B; 130 min –
pleasant taste, apricots are associated with health 82 % B; 132 min 0 % B, followed by equilibration
benefits such as anti-inflammatory, antioxidant or of column for 10 min. The flow rate was fixed at 0.8
antimicrobial effects (Erdogan-Orhan and Kartal, ml/min and the DAD detector was set at 450 nm.
2013). Carotenoids, polyphenols, vitamin C, Standard compounds β-cryptoxanthin, β-carotene
mono- and polysaccharides, volatiles and minerals and lycopene were provided by ChromaDex, USA;
are among the most important constituents of β-cryptoxanthin palmitate was obtained by semi
apricot fruits (Ruiz et al., 2005; Sass-Kiss et al., synthesis and purified by HPLC in our laboratory
2005; Dragovic-Uzelac et al., 2007; Aubert and (Pintea et al., 2013). The chromatographic data and
Chanforan, 2007; Kurtz et al., 2008; Erdogan- UV-VIS spectra were compared using Shimadzu
Orhan and Kartal, 2013). Even if several studies LC software. Calibration curves were made
investigated the effect of drying method on the for β-cryptoxanthin, β-carotene and β-crypto­
total and individual content of carotenoids in xanthin palmitate by plotting peak area against
apricots (Ihns et al., 2011; Garcia-Martinez et concentration. The identification of cis isomers
al., 2012; Turkyilmaz et al., 2013; Fratianni et was based on the specific absorption maxima
al., 2013) there are no reported data regarding which appears in the UV region of the absorption
the stability of individual carotenoids in dried spectra of carotenoids (Britton et al., 1995b).
apricots during storage. Our aim was to monitor Statistical analysis. The results are presented
the carotenoid content and profile during one year as the mean ± SD. Significant differences between
storage period of commercially available dried samples were analysed with one-way ANOVA post
apricots using an HPLC-PDA method. hoc tests, and pairwise multiple comparisons
were onducted using Tukey’s test. Significant
differences were reported based on P ≤ 0.05.
MATERIAL AND METHODS Statistical analyses were performed using the
2.1 Plant material SPSS programme (SPSS Inc., Chicago, IL, USA).
Dried apricots (Prunus armeniaca L.) were
purchased from a local organic product store. The RESULTS AND DISCUSSIONS
fruits were divided and kept in individual sealed The total carotenoid content, estimated by
polyethylene bags, at room temperature (25ºC), in the spectrophotometric method in dried apricots
dark for twelve months. Samples were taken each at the beginning of the experiment was 6.72
month for carotenoid extraction. mg/100 g. This value is relatively low compared
2.2 Carotenoid extraction and quantification to fresh fruits, where a total carotenoid content
The dried fruits (20 g) were extracted with ranging between 1.5-16 mg/100 g fresh weight
a mixture of methanol/ethyl acetate/ petroleum was reported for various cultivars (Ruiz et al.,
ether (1: 1: 1, v/v/v) as described previously 2005; Sass-Kiss et al., 2005; Dragovic-Uzelac et
(Pop et al., 2015). Total carotenoids content al., 2007; Kurtz et al., 2008). Taking into account
was determined using the spectrophotometric that β-carotene is the major compound in
method with an UV-VIS Spectrophotometer (Jasco apricots, the carotenoid concentration is close to
V-530) (Britton et al., 1995a). The concentration values found by Alagoz et al. (2015), 4.1- 6.7 mg
of total carotenoids was expressed as mg β-carotene/100 g in dried apricots from Turkey.
carotenoids/100 g dried fruits. All experiments Higher concentrations of β-carotene (10.4-12.8
were performed under subdued light. mg/100 g d.w), were found in dried apricots (with

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

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 decrease of absorption at λmax 448 nm and an in­
cultivar by different drying methods (Garcia- crease of absorption in the UV region (300-400
Martinez et al., 2012). Also, Türkyilmaz and nm). These changes are associated with a decrease
coworkers (2013) found concentrations ranging of carotenoid concentration and with changes in
between 26.6 and 36.2 mg/ 100 g d.w. depending the profile of carotenoids, mainly with the cis-
on SO2 content in one cultivar of dried Turkish trans isomerization and appearance of “cis-peak”
Malatya apricots. As it can be observed in Figure (Britton et al., 1995b).
1, significant changes occurred in the absorption A significant decrease of total carotenoid
spectra of total carotenoid extract, with a marked 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 97

Tab. 1. Variation of residual concentration of major carotenoids (mean ± S.E) in dried apricots during
storage
Compound Month 1 Month 4 Month 8 Month 12

β-cryptoxanthin 97.2 ± 5.7a 75.2 ± 4.2b 45.0± 2.3c 37.2 ± 2.3c

13-cis β-carotene 97.1 ± 3.8a 71.3 ± 3.5b 38.8 ± 2.1c 25.4 ± 1.5d
all trans β-carotene 95.5 ± 3.8a 57.4 ± 1.5b 25.4 ± 0.9c 15.7 ± 1.4d
9-cis β-carotene 98.3 ± 3.7a 67.3 ± 3.4b 39.1 ± 1.5c 27.3 ± 1.7d
β-cryptoxanthin palmitate 98.4 ± 4.3a 85.2 ± 4.1b 61.4 ± 2.4c 58.2 ± 3.3c

Note: Different letters within a column denote significant differences (P < 0.05).

A study performed on different fruits and esterified form of xanthophylls - β-cryptoxanthin,

vegetables monitored the changes induced by lutein, zeaxanthin, capsanthin and capsorubin –
thermal treatment (heating at 98ºC) or freezing showed increased thermal and storage stability
(-20ºC) on the content of anthocyanins, carotenoids compared to their non-esterified counterparts in
and ascorbic acid. In the case of apricots, the paprika (Schweiggert et al., 2007) and tamarillo
concentration of individual carotenoids was nectar (Mertz et al., 2010).
estimated spectrophotometrically based on the
wavelength of maximum absorption and on CONCLUSIONS
their molar absorptivity coefficients, without a In the present work, we demonstrated that
chromatographic separation. Using this method significant losses in total carotenoid content occurs
the authors have shown that the highest decrease during the storage of dried apricots, only 20.35 %
was produced by lyophilization, for all carotenoids of the initial concentration remaining after twelve
the final concentration being approximately 50% of months. This is the first report regarding the
the initial one. Heating at 98ºC resulted in a greater comparative stability of carotenes, xanthophylls
reduction of hydrocarbon carotenoid (β-caro­ and their esters in dried apricots, by using an
tene, α-carotene and lycopene) and a mode­rate HPLC method. The degree of degradation depends
fall in the case of xanthophylls (β-crypto­xanthin on the chemical nature of compounds, β-carotene
and lutein) (Leon et al., 2012). In the case of sun being more sensitive than β-cryptoxanthin and
dried Malatya apricots preserved with potassium β-cryptoxanthin palmitate.
sorbate, it has been observed that the decrease
in the content of β-carotene is dependent on the Acknowledgements: This work was supported
storage temperature. Thus, for fruits stored at 4ºC, by a grant of the Romanian National Authority for
10ºC and 20ºC, a significant decrease (up to 64 % ) Scientific Research, CNCS – UEFISCDI, project PN-
of β-carotene after 10 months was recorded, while II-ID-PCE-2011-3-0721
for fruits stored at 30°C there was no significant
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