2007 Cumin Noir Food Chem

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Food

Chemistry
Food Chemistry 101 (2007) 673–681
www.elsevier.com/locate/foodchem

Nigella sativa L.: Chemical composition and


physicochemical characteristics of lipid fraction
Salma Cheikh-Rouhou a, Souhail Besbes a,*, Basma Hentati b, Christophe Blecker c,
Claude Deroanne c, Hamadi Attia a
a
Département de biologie, Ecole Nationale d’Ingénieurs de Sfax, Unité Analyses Alimentaires, Route de Soukra, B. P. W., 3038 Sfax, Tunisia
b
Institut de Biotechnologie de Sfax, Unité de Biotechnologie et pathologie, Route de Soukra, 3038 Sfax, Tunisia
c
Faculté Universitaire des Sciences Agronomiques de Gembloux, Unité de Technologie des Industries Agro-alimentaires, passage des Déportés 2,
5030 Gembloux, Belgium

Received 16 October 2005; received in revised form 16 December 2005; accepted 20 February 2006

Abstract

Physicochemical properties of two Nigella seed varieties, having a Tunisian and Iranian origin, were determined. Physical and chem-
ical analyses of crude oils extracted from the seeds by a cold solvent method were also performed. The following results (on a dry-weight
basis) were obtained for Tunisian and Iranian varieties, respectively: protein 26.7% and 22.6%, oil 28.48% and 40.35%, ash 4.86% and
4.41%, and total carbohydrate 40.0% and 32.7%. The major unsaturated fatty acids were linoleic acid (50.3–49.2%), followed by oleic
acid (25.0–23.7%), while the main saturated fatty acid was palmitic acid (17.2–18.4%). Myristic, myristoleic, palmitoleic, margaric, marg-
aroleic, stearic, linolenic, arachidic, eicosenoic, behenic and lignoceric acids were also detected. Thermal profiles of both Nigella seed
varieties, determined by their DSC melting curves, revealed different thermograms. Sensorial profiles of Tunisian and Iranian seed oils
were defined through the CieLab (L*, a*, b*) colour, oxidative stability by Rancimat test and viscosity. Physicochemical properties of the
oils for Tunisian and Iranian varieties, respectively, include: saponification number 211 and 217, peroxide value 5.65 and 4.35, iodine
index 120 and 101, and an acidity of 22.7% and 18.6%. Results suggested that Nigella seed oil could deserve further consideration
and investigation as a potential new multi-purpose product for industrial, cosmetic and pharmaceutical uses.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Nigella seeds; Oil; Fatty acids; Thermal properties; Sensorial properties

1. Introduction and ‘Shunez’ (Burits & Bucar, 2000). In Tunisia, they are
called ‘Sinouj’. Nigella sativa seeds are used for edible
Nigella (Nigella sativa L.) is an annual herbaceous plant and medicinal purposes in many countries, including
belonging to the Ranunculaceae family (Al-Gaby, 1998; Egypt, Syria, Iran and to a slight extent in Tunisia. They
Atta, 2003) growing in countries bordering the Mediterra- are used as a condiment in bread and other dishes (Abou-
nean Sea (Gad, El-Dakhakhny, & Hassan, 1963). It tastes tabl, El-Azzouny, & Hammerschmidt, 1986; Merfort et al.,
slightly bitter and peppery with a crunchy texture. Seeds 1997). They are also used in the preparation of a traditional
are angular, of generally small size (1–5 mg), dark grey or sweet dish, composed of black cumin paste, which is sweet-
black colour. They represent the useful product. They are ened with honey or syrup, and in flavouring of foods, espe-
known in Arabia as ‘Al-Habba Al-Sawdaa’ or ‘Al-Kam- cially bakery products and cheese. Nigella seed oil or
moon Al-Aswad’ (Al-Gaby, 1998), ‘Habbet el Baraka’ extract has protective and curative actions.
The composition and properties of this species have
*
Corresponding author. Tel.: +216 74 274 088; fax: +216 74 275 595. been fairly well investigated, particularly in Tunisia.
E-mail address: [email protected] (S. Besbes). Nigella seed oil is considered as one among newer sources

0308-8146/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2006.02.022
674 S. Cheikh-Rouhou et al. / Food Chemistry 101 (2007) 673–681

of edible oils, thanks to its important role in human nutri- screens and then were preserved in hermetic bags at
tion and health. This seed oil has been reported to possess 20 C until analysis.
antitumor activity (Worthen, Ghosheh, & Crooks, 1998),
antioxidant activity (Burits & Bucar, 2000), anti-inflamma- 2.2. Oil extraction and preservation
tory activity (Houghton, Zarka, de la Heras, & Hoult,
1995), antibacterial activity (Morsi, 2000) and a stimula- Black cumin seeds (50 g) were placed in a dark flask
tory effect on the immune system (Salem & Hossain, (capacity = 1 l) and homogenized with 250 ml of hexane.
2000). Few works have considered physicochemical charac- After mixing for 4 h in a shaker (Selecta, Spain) at a rate
teristics of black cumin seed oil. Proximate analysis of of 180 U/min, the mixture was centrifuged for 15 min at
whole mature Nigella seeds showed that the moisture con- 1000g at ambiant temperature (20 C). The supernatent
tent ranged from 5.52% to 7.43%, crude protein from 20% was then filtered through a filtering paper (Whattman
to 27%, ash from 3.77% to 4.92%, carbohydrates from No. 2). The extraction procedure was repeated twice and
23.5% to 33.2% and ether-extractable lipid from 34.49% the collected solvent was removed using a rotary evapora-
to 38.72% (Abdel-Aal & Attia, 1993; Salem, 2001; Takruri tor at 40 C. The seed oils obtained finally were drained
& Dameh, 1998). This last fraction contains high amounts under a stream of nitrogen and then stored in a freezer
of linoleic, oleic and palmitic acids (Abdel-Aal & Attia, (20 C) for subsequent physico-chemical analyses.
1993; Babayan, Koottungal, & Halaby, 1978; Gad et al.,
1963). Actually, a great deal of attention has been focused 2.3. Analytical methods
on black cumin seed oils, and thus their consumption has
increased, especially in Middle East countries. As men- 2.3.1. General
tioned in the literature, the oil has been usually produced All analytical determinations were performed at least in
by a hot solvent extraction method at 40–60 C (Al-Gaby, triplicate. Values were expressed as the mean ± standard
1998; Burits & Bucar, 2000; D’Antuono, Moretti, & deviation ðx  SDÞ.
Lovato, 2002; Ramadan & Mörsel, 2003; Takruri &
Dameh, 1998) and even at 70 C (Ramadan & Mörsel, 2.3.2. Chemical analysis of powdered seeds
2004), using the Soxhlet extractor. This hot method of 2.3.2.1. Dry matter. The dry matter was determined accord-
extraction could affect the oil properties and may induce ing to the Association of Official Analytical Chemists
partial alteration of the majority of minor constituents that (AOAC, 1990).
have many functional, antioxidative and pro-oxidative
effects (Espin, Rivas, & Wichers, 2000; Koski et al., 2002; 2.3.2.2. Fat content. Oil was extracted from 15 g of seed
Tasioula-Margari & Okogeri, 2001). powder in a Soxhlet extractor for 8 h using hexane as a sol-
To our knowledge, the study of thermal and sensorial vent. The result was expressed as the percentage of lipids in
aspects of black cumin seed oil has not yet been done, the dry matter of seed powder.
though they would provide much information about the
oil. The availability of such data would facilitate the esti- 2.3.2.3. Protein content. Total protein was determined by
mation of the oil shelf-life and the determination of its the Kjeldahl method. Protein was calculated using a nitro-
quality. gen conversion factor of 6.25 (Al-Gaby, 1998). Data were
This investigation was undertaken to obtain informa- expressed as percent of dry weight.
tion about the chemical composition of Nigella seeds
cultivated in Tunisia and Iran and to determine fatty 2.3.2.4. Ash and mineral contents. To remove carbon, about
acid profiles, thermal profiles and sensorial profiles of 0.5 g of powdered seed samples were ignited and inciner-
their lipid fraction obtained by cold solvent ated in the muffle furnace at 550 C for about 12 h. The
extraction. ashes were dissolved in HNO3 (Larrauri, Rupérez, Bor-
roto, & Saura-Calixto, 1996) and the mineral constituents
2. Materials and methods (Ca, Na, K, Mg, Fe, Zn, Cu and Mn) were determined
using an atomic absorption spectrophotometer (Hitachi Z
2.1. Seed material 6100, Japan). For the phosphorus content, the phospho-
molybdovanadate method was used (AOAC, 1990). The
Two varieties of mature black cumin (Nigella sativa L.) total ash was expressed as percent of dry matter.
seeds were purchased from a herbal market in Menzel
Temim, a little town situated in the North East of Tunisia. 2.3.2.5. Carbohydrate content. Carbohydrate was estimated
One sample was reported to be imported from Iran, and by difference of mean values, i.e. [total solids 
the other was a Tunisian variety. The samples were directly (protein + lipids + minerals)].
stored at 15 C for maximum 3 days. Then, they were
soaked in water, washed and air-dried. For the determina- 2.3.3. Analysis of oil extract
tion of black cumin fractions, seed samples were separately 2.3.3.1. Fatty acid composition. Fatty acid composition was
milled in a heavy-duty grinder for 2 min, to pass 1–2 mm analysed by gas-liquid chromatography after derivatisation
S. Cheikh-Rouhou et al. / Food Chemistry 101 (2007) 673–681 675

to fatty methyl esters (FAMEs) with 2 M KOH in metha- the colour becomes more saturated or chromatic, but these
nol at room temperature according to the IUPAC standard values approach zero for neutral colours (white, grey or
method (IUPAC, 1992). Analyses of FAMEs were carried black). Absorbance of oil solutions in hexane were mea-
out with a Hewlett-Packard 5890 Series II gas chromato- sured with a spectrophotometer UV-240 (Shimmadzu Cor-
graph (H.P. Co., Amsterdam, The Netherlands) equipped poration, Kyoto, Japan) with light of wavelengths between
with a hydrogen flame ionisation detector and a capillary 205 and 800 nm.
column: HP Inovax cross-linked PEG (30 m ·
0.32 mm · 0.25 lm film). The column temperature was 2.3.3.6. Index determination. AOCS official methods
programmed from 180 to 240 C at 5 C/min and the injec- (American Oil Chemists’ Society, AOCS, 1997) were used
tor and detector temperatures were set at 250 C. Identifi- to evaluate the peroxide, iodine, saponification and acidity
cation and quantification of FAMEs was accomplished values (method number Cd 8–53, Cd 3d-63, Cd 3–25 and
by comparing the retention times of peaks with those of Cd 3d-63, respectively). Determination of refractive index
pure standards purchased from Sigma and analyzed under (at 40 C) was determined with a refractometer (type Abbe
the same conditions. The results were expressed as a per- optic system).
centage of individual fatty acids in the lipid fraction.
2.3.3.7. Specific extinction. K232 and K270 extinction coeffi-
2.3.3.2. Differential scanning calorimetry (DSC). Thermal cients were calculated from absorbances at 232 and
characteristics of black cumin seed oils were performed 270 nm, respectively, with UV spectrophotometer (SECO-
using a modulated differential scanning calorimeter (DSC MAN, Type: ANTHELIE 70 MI 0291, No. 344, France),
2920 Modulated DSC-TA Instruments, Newcastle, DE, using a 1% solution of oil in cyclohexane and a path length
USA). Oil samples (2 ± 0.10 mg) were weighed directly of 1 cm.
into a DSC-pan (SFI-Aluminium, TA Instrument
T11024). The samples were quickly cooled to 50 C with 2.3.3.8. Chlorophyll and polyphenolic compounds. Chloro-
a speed of 15 C/min, maintained at this temperature for phyll (mg/kg) was quantified by spectrophotometry
15 min and heated to 90 C with a heating speed of (SECOMAN, Type: ANTHELIE 70 MI 0291, No. 344,
15 C/min. The same operation (cooling and heating) was France), following the methodology described by Mı́nguez,
repeated and the DSC thermographs were recorded during Rejano, Gandul, Higinio, and Garrido (1991). The pheno-
the second melting. An empty DSC-pan was used as refer- lic compounds of Nigella seed oils were determined
ence. The instrument was calibrated for temperature and colorimetrically at 725 nm, using the Folin–Ciocalteau
heat flow using eicosane (Tp = 36.80 C, H = 247.70 J/g) reagent as previously done by Gutfinger (1981) on virgin
and dodecane (Tp = 9.65 C, H = 216.73 J/g). Results olive oil.
are the averages of triplicate samples.
2.3.3.9. Viscosity determination. Viscosity of the oil samples
2.3.3.3. Oxidative stability. Oxidative stability was evalu- was measured with a Stress Tech Rheologica Rheometer
ated by the Rancimat method (Gutiérrez, 1989). Stability (Rheologica Instruments AB, Lund, Sweden). Measure-
was expressed as the oxidation induction time (h), with ments were performed at 25 C with a steel cone-plate
the use of the Rancimat 679 apparatus (Metrohm AG, (C40/4) at a constant shear rate of 100 s1.
Herison, Switzerland). A flow of air (15 l/h) was bubbled
through the oil (2.5 g) heated at 100 C and the volatile 3. Results and discussion
degradation products were trapped in distilled water,
increasing the water conductivity. The induction time was 3.1. Chemical characteristics of black cumin seeds
defined as the time necessary to reach the inflection point
of the conductivity curve (Halbault, Barbé, Aroztegui, & The average compositions of the two different Nigella
De La Torre, 1997). seed samples are shown in Table 1. Proximate analysis of
Tunisian Nigella seeds showed that moisture content
2.3.3.4. UV – spectrophotometric analyses. Absorbances of (8.65%), crude protein (26.7%), ash content (4.86%) and
oil solutions in hexane were measured with UV-240 spec- total carbohydrates (40.0%) were slightly higher than the
trophotometer (Schimmadzu-Corporation, Kyoto, Japan). amounts of the Iranian variety, while the lipid fraction of
the TNS variety was relatively lower than the INS one
2.3.3.5. Colour. The CieLab coordinates (L*, a*, b*) were (28.48% against 40.35%). Such variation in nutrient con-
measured with a spectrophotometer MS/Y-2500 (Hunter- centrations among species and varieties may be related to
lab, In., Reston, VA, USA), calibrated with a white tile. the variations of cultivated regions, storage conditions
Under the tristimulus colour coordinate system, the L* and maturity stage. It may also be due to geographical
value is a measure of lightness and varies from 100 and climatic differences where Nigella seeds had been
(black) to +100 (white), the a* value varies from 100 grown (Atta, 2003). Data on nutrient contents mention
(green) to +100 (red), and the b* value varies from 100 that Nigella seeds are considered as a beneficient source
(blue) to +100 (yellow). As the values of a* and b* rise, of oil and many minerals.
676 S. Cheikh-Rouhou et al. / Food Chemistry 101 (2007) 673–681

Table 1 Table 2
Chemical characteristics (dry basis) of the Tunisian Nigella seeds (TNS) Fatty acid compositions (g/100 g of total fatty acid) of TNS and INS oils
and the Iranian variety (INS)
Fatty acid TNS INS
Component TNS INS
Myristic C14:0 0.35 ± 0.02 0.41 ± 0.05
Dry matter (%) 91.35 ± 0.26 95.92 ± 0.70 Myristoleic C14:1 Tr. Tr.
Oila 28.48 ± 0.05 40.35 ± 0.16 Palmitic C16:0 17.2 ± 0.15 18.4 ± 0.25
Crude proteina 26.7 ± 0.35 22.6 ± 0.24 Palmitoleic C16:1 1.15 ± 0.05 0.78 ± 0.25
Asha 4.86 ± 0.06 4.41 ± 0.01 Margaric C17:0 Tr. Tr.
Potassiumb 783 ± 6.61 708 ± 7.98 Margaroleic C17:1 Tr. Tr.
Magnesiumb 235 ± 4.87 260 ± 48.70 Stearic C18:0 2.84 ± 0.08 3.69 ± 0.12
Calciumb 572 ± 21.5 564 ± 33.4 Oleic C18:1 25.0 ± 0.24 23.7 ± 0.06
Phosphorusb 48.9 ± 0.04 51.9 ± 0.01 Linoleic C18:2 50.31 ± 0.25 49.15 ± 0.06
Sodiumb 20.8 ± 2.21 18.5 ± 3.17 Linolenic C18:3 0.34 ± 0.06 0.32 ± 0.05
Ironb 8.65 ± 0.65 9.42 ± 0.88 Arachidic C20:0 0.14 ± 0.02 0.22 ± 0.01
Copperb 1.65 ± 0.03 1.48 ± 0.21 Eicosenoic C20:1 0.32 ± 0.04 0.34 ± 0.05
Zincb 8.04 ± 0.21 7.03 ± 0.49 Behenic C22:0 1.98 ± 0.08 2.60 ± 0.05
Manganeseb 4.43 ± 0.11 3.37 ± 0.21 Lignoceric C24:0 Tr. Tr.
Total carbohydratea 40.0 ± 0.46 32.7 ± 0.41 SAFA 22.7 ± 0.37 25.5 ± 0.69
All values given are means of three determinations. MUFA 26.6 ± 0.39 25.0 ± 0.58
a
In % dry matter basis. PUFA 50.7 ± 0.70 49.8 ± 0.20
b
In mg/kg of dry matter. All values given are means of three determinations.
SAFA, saturated fatty acids; MUFA, monounsaturated fatty acids;
PUFA, polyunsaturated fatty acidsl; Tr., trace amounts (less than 0.2%).
Nigella seeds contained significant amounts of impor-
tant mineral elements. Potassium is the most abundant ele-
ment in the black cumin seeds, followed by phosphorus tained oleic and linoleic acids at relatively high levels
and calcium. The other elements, in descending order by (18.9–20.1 and 47.5–49.0, respectively) but these are lower
quantity, were Mg, Na, Fe, Zn, Mn and Cu. These results than those corresponding to the Tunisian variety (25.0 and
agree with those found by Takruri and Dameh (1998) for 50.3, respectively) and to the Iranian variety (23.7 and 49.2,
five varieties of black cumin seeds (Iranian, two Syrian, respectively) (Table 2). In this study, saturated acids
Turkish and Jordanian). Nigella seeds provide relatively accounted for 25.5% and 22.7% of total fatty acids, for
high amounts of minerals (Mn, Zn, Cu and Fe). However, INS and TNS oils, respectively. Among them, the main sat-
the nutritional status of these minerals cannot be predicted urated normal chain fatty acids were palmitic, stearic,
from the quantity of black cumin consumed (Takruri & behenic, myristic and arachidic, with minute amounts of
Dameh, 1998). margaric and lignoceric acids. Margaric and margaroleic
acids were not detected in previously published data
3.2. Profiles of black cumin seed oil (Abdel-Aal & Attia, 1993; Atta, 2003; Babayan et al.,
1978; Gad et al., 1963; Üstun, Kent, Çekin, & Clvelekoglu,
3.2.1. General 1990). A negligible amount of eicosenoic acid (0.33%)
Since the lipid fraction was found to be the most abun- was detected and was in accordance with that reported
dant one in black cumin seeds, it is very interesting to study by Ramadan and Mörsel (2002) but was absent in the study
its physicochemical characteristics in order to seek its done by Babayan et al. (1978). The source of variability
added value. We were interested in determining fatty acid may be genetic (plant cultivar, variety grown), seed quality
composition, thermal, sensorial and physical descriptors (maturity, harvesting-caused damage and handling/storage
of Nigella seeds. conditions), oil processing variables, or accuracy of detec-
tion, lipid extraction method and quantitative techniques
3.2.2. Fatty acid composition (Ramadan & Mörsel, 2002).
Fatty acid composition of Nigella seed oil is given in
Table 2, which shows that linoleic, oleic and palmitoleic 3.2.3. Thermal profile
acids account for more than 73% of the total fatty acids DSC provides information on the excess specific heat
for INS oil and 76% for TNS oil. They represent the main over a wide range of temperatures (Gloria & Aguilera,
unsaturated fatty acids. The ratio of linoleic acid to oleic 1998). Any endothermic or exothermic event is registered
acid was more than 2:1. This result agreed with those as a peak in the chart, and its area is proportional to the
reported in soybean oil (C18:2 = 52%, C18:1 = 25%) and in enthalpy gained or lost, respectively. Nigella seed oils, of
corn oil (C18:2 = 58.7%, C18:1 = 26.6%) (Ramadan & Mör- both Iranian and Tunisian varieties, showed different
sel, 2002). The ratio of saturated to unsaturated fatty acids DSC melting profiles (see Fig. 1). The INS oil exhibited a
(S/U%) was 34.1% in INS oil and 29.4% in TNS oil. These simple thermogram with a single peak having the following
ratios were higher than that reported by Ramadan and characteristics: melting peak (29.34 C), melting enthalpy
Mörsel (2003) for black cumin seed oil (25.7%). Atta (60.68 J/g) and onset temperature (33.41 C). Therefore,
(2003) showed that the oils of black cumin varieties con- the TNS oil thermogram presented two distinct peaks: a
S. Cheikh-Rouhou et al. / Food Chemistry 101 (2007) 673–681 677

Table 4
Oxidation induction time, viscosity, phenolic content and chlorophyll
pigments of TNS and INS oils
TNS INS
Induction time (h) 12.0 ± 0.05 50.33 ± 2.48
Viscosity (mPa s) 11.23 ± 0.08 5.99 ± 0.03
Polyphenols (as mg gallic acid/kg of oil) 245 ± 9.16 309 ± 12.31
Chlorophyll (mg/kg) 6.04 ± 0.06 2.26 ± 0.06
All values given are means of three determinations.

Fig. 1. Melting thermograms of TNS oil (- - -) and INS oil (—) studied.

first low temperature melting peak (LTMP) with a melting


temperature of 14.2 C, a melting enthalpy of 59.52 J/g
and an onset temperature of 19.96 C, followed by a sec-
ond high temperature melting peak (HTMP) having a melt-
ing temperature of 24.77 C, a melting enthalpy of 18.37 J/
g and an onset temperature of 8.54 C (Table 3). The pres-
ence of two distinct peaks may be due to the appearance of
a second, more stable, polymorphic form or to the presence
of higher-melting triacylglycerols. The presence of this
HTMP could explain the presence of some crystals at room
temperature (25 C), leading to a higher viscosity (11.23
against 5.99 mPa s for TNS and INS oils, respectively) Fig. 2. CieLab coordinates (L*, a*, b*) of nigella seed oils from the two
studied varieties (h: L, n: a, : b).
(Table 4). In fact, contrary to the INS oil, TNS oil is not
entirely in the liquid state at 25 C (see Fig. 1).
shows that Nigella seed oil b* values were higher than those
3.2.4. Sensorial and physical profiles of other vegetable oils. Thus, Nigella seed oils were more
3.2.4.1. General. To determine sensorial and physical yellow-coloured than vegetable oils studied by Hsu and
descriptors of black cumin seed oils, colour, oxidative sta- Yu (2002). This may suggest the presence of more yellow
bility, viscosity and physicochemical parameters were pigments (carotenoids) in Nigella seed oils. The INS oil
studied. showed other colour particularity: Hunter a* negative value
(1.08) was markedly lower than the Hunter a* of common
3.2.4.2. Colour. In this study, we compared L*, a* and b* vegetable oils.
parameters of TNS and INS oils (see Fig. 2). The TNS UV absorption, although outside the visible spectrum,
variety showed a higher a* value and lower L* and b* val- was related to colour changes (Mazza & Qi, 1992; Melton,
ues. This means that the TNS oil was lighter-coloured and Jafar, Sykes, & Trigiano, 1994). TNS oil absorbed in the
more yellow; otherwise, it contained more yellow pigments UV-C (100–290 nm), UV-B (290–320 nm) and UV-A
than did the INS oil. Such a colour seems to attract con- (320–400 nm) ranges, while the INS oil showed absorbance
sumers (Hsu & Chung, 1998). The CieLab (L*, a*, b*) val- only in the UV-C and UV-B ranges (see Fig. 3). Thus,
ues of other vegetable oils, such as palm, soybean, Nigella seed oil can be used to give protection against
sunflower, olive and corn, ranged from 63.4 to 69.5, 3.8 UV radiations with relatively high shielding power (SPF)
to 4.4 and 9.2 to 10.4, respectively (Hsu & Yu, 2002). This and protection factor (PFA) scores. Nigella seed oil may

Table 3
Thermal parameters, from DSC melting curves, of seed oil from the two studied Nigella varieties
Parameter TNS INS
First peak Second peak First peak Second peak
Onset temperature (C) 19.96 ± 0.2 8.54 ± 5.37 33.41 ± 0.03 –
Peak temperature (C) 14.2 ± 0.07 24.77 ± 2.38 29.34 ± 0.21 –
Melting enthalpy (J/g) 59.52 ± 0.04 18.37 ± 0.48 60.68 ± 0.72 –
All values given are means of three determinations.
678 S. Cheikh-Rouhou et al. / Food Chemistry 101 (2007) 673–681

3 degeneration, the main cause of their alteration (Aparicio,


Roda, Albi, & Gutiérrez, 1999).
Absorbance

2 The results of the Rancimat test are shown in Table 4.


Stability, expressed as the oxidation induction time, was
1 about 55 h for INS oil and about 12 h for TNS oil. This dif-
ference could be attributed to a higher natural antioxidants
0 content in INS oil, since no significant difference in the
200 245 290 fatty acid profile, essentially in MUFA and PUFA con-
1 tents, was observed. Aparicio et al. (1999) mentioned a sig-
nificant correlation of phenols, oleic/linoleic ratio and
tocopherols, with oil stability measured by Rancimat, in
Absorbance

0.5 virgin olive oil. A high direct correlation was observed


between total phenol content and oxidative stability by
Rancimat (Gutfinger, 1981; Salvador, Aranda, Gómez-
0 Alonso, & Fregapane, 2001). The INS oil had a higher phe-
290 335 380 nolic compounds content than had TNS oil (309 mg/kg
1 against 245 mg/kg, respectively), which mainly determine
a greater resistance to auto-oxidation (Baldioli, Servili,
Perretti, & Montedoro, 1996; Perrin, 1992; Tsimidou,
Absorbance

0.5 Papadopoulos, & Boskou, 1992). The amount of phenols


in crude seed oils is an important factor when evaluating
the quality of the oil because these compounds have been
0 correlated with sensory quality, the shelf life of oil and in
400 600 800 particular, its resistance to oxidation (Cinquanta, Esti, &
(nm) La Notte, 1997).
Fig. 3. Ultraviolet/visible spectra of TNS oil (- - -) and INS oil (—). Figure The oxidative stability of INS oil was higher than that of
derived from scans (k = 200–290) of oil diluted 1:800; from scans most vegetable oils and comparable to some varieties of
(k = 290–400) of oil diluted 1:100 and from scans (k = 400–800) of oil olive oil and date seed oil, mainly because they have high
diluted 1:10, all in hexane. phenolics contents (Aparicio et al., 1999; Besbes et al.,
2004a, 2004b, 2004c, 2005). The oxidation induction time
of sunflower oil, under the same experimental conditions,
provide protection against both UV-A (an origin of skin is only about 7.7 h (Farag, El-Baroty, & Basumy, 2003).
oxidative stress) and UV-B. The optical transmission of Salvador et al. (2001) reported that the induction time of
Nigella seed oil, especially in the UV range (290–400 nm) olive oil varied from 9 to 143 h. Besbes et al. (2004a,
was comparable to those of date seed oil, raspberry seed 2004b, 2004c) found that date seed oil presented a high oxi-
oil and titanium dioxide preparations, which can be used dation stability (33–45 h), measured by Rancimat under
as sun protection factors for UV-B (SPF) and protection the same conditions. This high stability was explained by
factors for UV-A (PFA) (Besbes, Blecker, Deroanne, the relatively low content of PUFA and a high content of
Drira, & Attia, 2004a; Oomah, Ladet, Godfrey, Liang, & natural antioxidants, such as phenolic compounds. The
Girard, 2000). contribution of phenolic and orthophenolic compounds
The strong absorptivity of TNS oil at 450 nm, a wave- in the oxidation stability of olive oil was about 51%, fatty
length which is approximately at the lower limit of detect- acids 24% and, in less percentages a-tocopherols, carote-
ability for the human eye, corresponded to high levels of noids and chlorophylls (Aparicio et al., 1999).
yellow pigments in this oil. TNS oil contained more yel- A study of phenolic, tocopherol and sterol profiles of
low-colouring than did INS oil, as indicated by the absor- Nigella sativa L. seed oil should be undertaken because
bance (0.7 against 0.25) at 440–460 nm for 1% oil in they are of capital importance for achieving high oxidative
hexane. stability; and they could also present some functional mol-
This confirms the results obtained with the CieLab ecules having a high added value, improving economic util-
Miniscan instrument. These yellow colours, which include ity of Nigella sativa seeds as a source of edible lipids.
carotenoids, are beneficial, since they simulate the appear-
ance of butter without the use of primary colorants, such as 3.2.4.4. Viscosity. Table 3 shows that the viscosity of INS
carotenes and annattos, commonly used in the oil and fat oil was lower than that of TNS oil (5.99 against 11.23
industry (Oomah et al., 2000). mPa s). This result was in agreement with DSC results
which showed the presence of HTMP in TNS oil at room
3.2.4.3. Oxidative stability. Oxidative stability is an impor- temperature. From fundamental physics of polymers, it is
tant parameter in evaluating the quality of oils and fats, as known that the viscosity has a power dependence on
it gives a good estimation of their susceptibility to oxidative molecular weight (Gloria & Aguilera, 1998). It is worth
S. Cheikh-Rouhou et al. / Food Chemistry 101 (2007) 673–681 679

noting that the viscosity of Nigella seed oil is much lower Nigella seed oils are situated inside the interval range of the
than that of most vegetable oils. values mentioned by Tan, Che Man, Selamat, and Yusoff
(2002) in some edible oils (9.37–145 g of I2/100 g oil).
3.2.4.5. Polyphenols, induction time and chlorophylls. Iodine values of INS and TNS oils are similar to those
Nigella seed oil has a higher phenol content (Table 4) than reported by Atta (2003) (IV = 115–128), Babayan et al.
most edible oils, except for olive oil, which is considered to (1978) (IV = 125) and Abdel-Aal and Attia (1993)
be a rich source of phenolic compounds. Salvador et al. (IV = 107–110) for black cumin seed oils. A lower iodine
(2001) reported that total phenolic content of virgin olive value confers, to INS oil, more stability. Peroxide value
oil, measured by Folin–Ciocalteau method, ranged from of oil is a valuable measure of oil quality. Peroxide values
19 to 380 mg/kg and from 124 to 516 mg/kg according to of INS and TNS oils (4.3 and 5.65 meq O2/kg of oil,
Nissiotis and Tasioula-Margari (2002). This may explain respectively) are 3-fold lower than those reported by Atta
the fact that Nigella seed oil presents oxidation induction (2003) (PV = 10.7–13.5) but higher than those reported
times comparable to virgin olive oil. by Ramadan and Mörsel (2002) for black cumin seed oil
Total phenol levels of TNS and INS oils 10-fold higher (0.22–0.36).
than that of black cumin seed oil studied by Ramadan and TNS oil showed a higher absorptivity at 232 and
Mörsel (2004). Nigella seed oil, could be considered as a 270 nm, thus containing more oxidation primary (hydro-
potential source of natural phenolic compounds. Although peroxides) and secondary products than INS oil. Com-
their participation in conferring specific flavour to oil pared to TNS and INS oils, absorptivities at 232 and
(Caponio, Alloggio, & Gomes, 1999), phenolic compounds 270 nm of black cumin seed oil studied by Ramadan and
may have a positive effect in the prevention of coronary Mörsel (2004) were relatively higher (3.6 and 1.2,
heart disease and cancer (Owen et al., 2000; Tuck & Hay- respectively).
ball, 2002).
The content of chlorophyll pigments is an important
4. Conclusion
quality parameter because it correlates with colour, which
is a basic attribute for evaluating oil quality (Salvador
This study has revealed that Nigella sativa seeds are a
et al., 2001). These pigments are involved in autoxidation
rich source of many important nutrients that appear to
and photo-oxidation mechanisms (Gutierrez, Garrido,
have a very positive effect on human health. They consti-
Gallardo, Gandul, & Minguez, 1992; Mı́nguez-Mosquera,
tute a good alternative source of essential fatty acids com-
Gandul, & Garrido, 1990). The amounts of chlorophyll
pared with common vegetable oils and could contribute to
in TNS oil as mentioned in Table 4 was 6.04 ppm against
the overall dietary intake of the mineral elements studied.
2.26 ppm for INS oil. These amounts are situated inside
This preliminary study shows that Nigella seed oils con-
the interval range of the chlorophyll pigments in Cornic-
tain high relative percentages of linoleic acid. They are also
abra olive oils (2–27 ppm) (Salvador et al., 2001).
more yellow-coloured than other vegetable oils and they
can protect against UV light, which justifies their use in
3.2.4.6. Physical characteristics of Nigella seed oils. Physical
the cosmetic industry. Black cumin seed oils are very stable
characteristics of Nigella seed oils are presented in Table 5.
and could be conserved safely for a long time due to their
Refractive index of Nigella seed oil was similar to that of
considerable polyphenolic content. The use of Nigella seed
olive oils studied by Lalas and Tsakins (2002). The sapon-
oil for industrial applications could necessitate its exposure
ification value of about 211–218 is comparable to Xylopia
to high thermal treatments that could lead to changes in
aethiopica oil (Barminas, James, & Abubakar, 1999). The
quality characteristics of the oil. So, a study of thermo-oxi-
lower acidity of INS oil than TNS oil shows that it is edible
dation effects on physicochemical parameters of Nigella
and could have a long shelf life. The iodine index of 100–
seed oil must be undertaken.
120 indicates that Nigella oil is a highly unsaturated oil
and suggests that it contains high levels of oleic and linoleic
acids, as previously shown in Table 2. The iodine values of Acknowledgements

Authors thank Mr. Hammami Mohamed, responsible


Table 5
Physicochemical characterisation of TNS and INS oils
for U.S.C.R. spectrometry, for chromatographic analysis.
Parameter TNS INS
Refractive index (at 40 C) 1.47 ± 0.01 1.46 ± 0.01 References
FFA (%) 22.7 ± 0.35 18.6 ± 0.28
Saponification index (mg of KOH/g of oil) 211 ± 5.32 218 ± 8.24
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Iodine index (g of I2/100 g of oil) 119 ± 3.45 101 ± 2.72
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k232 1.07 ± 0.01 0.74 ± 0.03
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