Edible oils and fats play an important role regarding human nutrition, consequently human health. Oils and fats are considered as one of the food products which are characterized with high energy content. It contains also relative high level of essential fatty acids and soluble fat vitamins (A, D, E, K). Moreover, it gives different food products its desired and accepted sensory properties, such as taste, odour, colour, flavour, consistency...etc.
Extra virgin olive oil (EVOO) has unique nutritional and sensory characteristics. The importance of EVOO is mainly attributed to its high content of oleic acid and its richness in phenolic compounds, which act as natural antioxidants. On the other hand, EVOO is expensive owing to the hard and time-consuming tasks involved in the cultivation of olive trees, the harvesting of the fruits, and the extraction of the oil. For these reasons, adulterations of EVOO with olive oils of lower quality are occasionally detected.
Adulteration EVOO, either by adding lower-grade olive oils or adding other less expensive oils such as sunflower (SO), corn (CO), sesame and soybean oils.
The adulteration practice in oils is difficult to detect, when the oil adulterant has close similarity in terms of chemical composition and color to that of the original oil. The development of a fast and reliable technique for qualitative and quantitative analyses of high value oils like EVOO is one of the interest aspects for researchers.
The present study aims to carried out by blending the EVOO with the less expensive oils commonly used for cheating, such as SO and CO, where the EVOO was obtained by extracting it using the methods approved from the fresh olive fruits, while the other oils were purchased after making sure of their conformity to the correct storage conditions and from then prepare binary mixtures (w / w) of olive oil and SO in similar proportions to the expected cheat levels (5, 15 and 25%) and binary mixtures of olive and CO in the same proportions. Each samples were analyzed for important physical and chemical properties such as: unsaponifiable matter%, , color, refractive index, viscosity, specific weight, acidity%, peroxide value, iodine value,
saponification number, total phenols, flavonoids and tocopherols,
fatty acid profile and oxidative stability then comparing the data
obtained with data previously known by Codex Alimentarius
Standard, The Egyptian Standards, and IOC. Applications of UV
at wavelengths 274, 266, 270, 232 nanometer and calculation ΔK
and FTIR spectroscopy to assess the adulteration of EVOO with
SO and CO.
The obtained results can be summarized as follows:
1- Fatty acid profile:
Results shown that the most prevalent fatty acids in EVOO were C16:0 (12.95%), C18:1 (70.42%) and C18:2 (13.13%). The percentage of total saturated fatty acids of EVOO were (14.80%).
The palmitic acid as a major saturated fatty acid, followed by stearic acid their percentages were (12.95 and 1.55%), respectively. While, the percentage of total unsaturated fatty acids were (85.20%), it is clear that oleic acid (C18:1) was the most common unsaturated fatty acid (70.42%) followed by linoleic acid (C18:2) (13.13%).
Adulterations EVOO with SO by addition of different concentrations 5, 15 and 25% from SO with to EVOO showed remarkable changes in the main constituents and the predominant saturated fatty acids and unsaturated fatty acids composition of EVOO. The concentration level of C16:0 and C18:1 was gradual decreased corresponding with increasing the SO content in the oil blends. The blend samples for EVOO and SO (95:5%), (85:15%) and (75:25 %) recorded 12.67, 12.14 and 11.24% for palmitic acid, respectively, while oleic acid were 67.88, 64.0 and 58.49%, respectively. Linoleic acid had a lesser percentages in EVOO (13.13%), but with added SO showed a gradual increase with increasing the SO concentrations. The adulterations EVOO with SO ratios (95:5%), (85:15%) and (75:25 %) recorded 16.28, 20.61 and 27.18% linoleic acid, respectively.
On the other hand, the addition of different concentrations 5, 15 and 25% from CO (as adulterations oil) to EVOO showed slight changes in the main constituents and the predominant saturated fatty acids and unsaturated fatty acids composition of EVOO. The concentration level of C16:0 and C18:1 was slight decreased with increasing the CO content in the oil blends. The blend samples for EVOO and CO (95:5%), (85:15%) and (75:25%) recorded 12.92, 12.80 and 12.60% for palmitic acid, respectively, while oleic acid were 65.05, 60.90, and 56.63%
respectively. Also, can noted that linoleic acid had a lesser percentages in EVOO (13.13%), but with added CO showed a gradual increase with increasing the CO concentrations. The blends for EVOO and CO (95:5%), (85:15%) and (75:25 %) recorded 19.20, 23.40 and
27.20% linoleic acid respectively, because CO contained higher levels of linoleic acid (57.84%).
Total unsaponifiable matter (%):
From the obtained results it is noticed that EVOO was the highest total unsaponifiable matter among the authentic oils. The addition of different concentrations 5, 15 and 25% from SO and CO to EVOO showed remarkable changes in total unsaponifiable matter of EVOO. The blend various concentrations of EVOO with SO and EVOO with CO recorded (0.60, 0.50 and 0.40%) and (0.60, 0.50, and 0.48%) for concentrations 5, 15 and 25%, respectively.
Natural antioxidants content of virgin olive oil:-
From the obtained results noticed that EVOO the highest value of total phenols, flavonoids and tocopherols content among the authentic SO and CO samples were recorded (850, 70 and 45 mg/kg.), (230, 25 and 20 mg/kg) and (10.2, 6.8 and 6.4 mg/kg), respectively.
The binary admixtures from (EVOO and SO) and (EVOO and CO) showed remarkable changes in the natural antioxidants content of EVOO as follows:
- Total phenols content of blend samples gradual decrease with increase the addition of SO and CO at 5, 15 and 25% ratio recorded (810, 730 and 650 mg/kg) and (808, 720 and 640 mg/kg) respectively.
- Total flavonoids content of blend samples gradual decrease with increase the addition of SO and CO at 5, 15 and 25% ratio recorded (220, 200 and 180 mg/kg) and (220, 190 and 175 mg/kg), respectively
- Total tocopherols values of blend samples decrease with increase the addition of SO and CO at 5, 15 and 25% ratio recorded and (10.3, 9.7 and 9.1 mg/kg) and (9.5, 8.7 and 7.7 mg/kg), respectively.
The physical properties of oils samples
Colour index:
The EVOO extracted from authentic olive fruit was superior in their colour measurements which were found (10, 1 and 0.2 in the yellow, red and blue Lovibond scale), when compared with the colour units for the SO, CO were (8, 0.8) and (10, 1.1), respectively.
The colour metrics for the binary admixtures showed stability with increase SO and CO, it is also noted the appearance of the blue color in EVOO and its disappearance completely from all mixtures, this is due to EVOO showed the highest values among the authentic oils and the disappearance of the blue color from both authentic oils.
Refractive index
EVOO was the lowest value of the refractive index among the authentic oils. The refractive index for EVOO, SO and CO were 1.4675, 1.4723 and 1.4711, respectively.
The refractive index for oil blends at different concentrations 5, 15 and 25% from (SO to EVOO) and (CO to EVOO) were (1.4681, 1.4685 and 1.4693) and (1.4677, 1.4684 and 1.4689), respectively. The refractive index value of EVOO showed gradual increase with increase the of SO and CO up to 5%.
Viscosity
EVOO was the highest viscosity value among the authentic oils. The viscosity values of EVOO, SO and CO were 61, 40 and 42 cp., respectively. The addition of different concentrations 5, 15 and 25% from SO and CO to EVOO showed gradual decrease with increase the of SO and CO which recorded in the binary admixtures (EVOO and SO)
60, 55 and 50 cp. respectively, while, recorded in the binary admixtures (EVOO and CO) 60, 57 and 55 cp., respectively.
Specific gravity:
As for the specific weight, when applied to both authentic oils and their dual mixtures, it has been proven that it may play a role in detecting fraud in olive oil, but with less sensitivity if compared to some other tests, where fraud can be detected when there is SO and CO, starting from the ratio of 5% and by applying this test to randomized commercial olive oil samples, it was proven effective in detecting fraud, as it gave a positive result and gave readings outside the range specified in the standard specifications for olive oil.
The chemical properties of oils samples
Free fatty acid % (as oleic acid):
Free fatty acid % for samples of EVOO, SO and CO were 0.261, 0.036 and 0.085%, respectively. The addition of different concentrations 5, 15 and 25% from SO and CO to EVOO showed gradual decreased in free fatty acid% with increase the of SO and CO ratio, which recorded (0.250, 0.227 and 0.205%) and (0.252, 0.235 and 0.217%) for both of binary admixtures for oils under study.
Peroxide value
Peroxide values for samples of EVOO, SO and CO were 4.8, 0.2 and 0.2 meqO2/kg oil, respectively. EVOO was the highest peroxide value among the authentic oils under study; this is may be due to was not conducted refining process to EVOO such as refining SO and CO. The addition of different concentrations 5, 15 and 25% from SO and CO to EVOO showed gradual decreased in peroxide value with increase the of SO and CO ratio, which recorded (3.7, 2.5 and 2.3 meqO2/kg oil) and (4.8, 3.2 and 2.4 meqO2/kg oil) for both of binary admixtures for
oils under study.
Iodine value
Iodine values for samples of EVOO, SO and CO were 84, 129 and 121 gI2/100g oil respectively. The addition of different concentrations 5, 15 and 25% from SO and CO to EVOO showed gradual increased in iodine value with increase the SO and CO ratio, which recorded (86.2, 90.7 and 95.2 gI2/100g oil,) and (85.8, 89.5 and 93.2 gI2/100g oil) respectively, for both of binary admixtures for oils under study.
Oxidative stability (rancimat induction period)
The oxidative stability values of EVOO, SO and CO were 43.5, 16.4 and 25.1 (hr) respectively. the oxidative stability of the blends SO and CO with olive oil decreased with the increase of SO and CO at different concentrations 5, 15 and 25% were recorded (38.5, 32.4 and 25.5 hr) and (42.2, 39.3 and 35.8 hr), respectively.
Ultraviolet (UV) Spectroscopic Characteristics
Results revealed that the adulteration will be detected easily by UV absorbance at 270 nm because SO showed a shift out of the permitted range at 15% upward higher concentrations added to EVOO. Also, CO will be detected if present in 15% upward higher concentrations in blends with EVOO. The calculated ΔK allowed the detection of adulteration in EVOO at the concentration of 15% upward higher concentrations of adulterant SO and CO; and this is the lowest detectable value in adulterated EVOO.
Fourier Transform Infrared
A band around 2925 cm-1 along with its intensity (assigned to C–O stretching and symmetric stretching vibration of the aliphatic CH2 group) along with a very strong band along with its intensity located at 1743 cm-1 (assigned to the C=O stretching vibration of the ester group) were important to detect concentration of 5% adulterants SO and CO in EVOO.
Conclusion:
The present work successfully achieved its aim included in the applications of UV and FTIR spectroscopy as rapid, cheap, nondestructive, authenticity measuring tools to assess the adulteration of extra virgin olive oil with other edible oils such as corn and sunflower oils in detection limit 15% for UV and 5% for FTIR spectroscopy. Library searching in the FTIR region is a well established and powerful way which was used in comparison and matching of measured spectra.