Determination of 3‐MCPD esters in edible oil – methods of analysis and comparability of results

The discovery of fatty acid esters of 3‐chloropropane‐1,2‐diol (3‐MCPD) in edible oil products initiated food monitoring campaigns in many EU Member States. As the determination of 3‐MCPD esters was new to most laboratories, questions on the reliability of the produced analysis data were raised. In response to this, the Institute for Reference Materials and Measurements (IRMM) of the European Commission's Joint Research Centre (JRC) organised a proficiency test on the determination of 3‐chloropropane‐1,2‐diol esters (3‐MCPD esters) in edible oils. The aim of this proficiency test was to scrutinise the capabilities of official food control laboratories, private food control laboratories as well as laboratories from food industry to determine the 3‐MCPD esters content of edible oils. The study was carried out in accordance with “The International Harmonised Protocol for the Proficiency Testing of Analytical Chemistry Laboratories” and ISO Guide 43. The test materials dispatched to the participants were: refined palm oil, extra virgin olive oil spiked with 3‐chloropropane‐1,2‐dioleate and 3‐MCPD standard solution in sodium chloride. Altogether 41 laboratories from 11 EU Member States, Switzerland and Macedonia subscribed for participation in the study. The analysis task was to determine the 3‐MCPD esters content as total 3‐MCPD content of the test samples. Participants were free to choose their analysis methods. In total, 34 laboratories reported results to the organisers of the study. The performance of laboratories in the determination of 3‐MCPD esters in edible oils was expressed by z‐scores. About 56% of the participants performed satisfactorily in the determination of 3‐MCPD esters in palm oil and 85% for the spiked extra virgin olive oil test sample. The study revealed that the direct transesterification of the sample without the prior removal of glycidol esters might lead to strong positive bias.     

Quantitative determination of diesel oil in contaminated edible oils using high-performance liquid chromatography

A simple and reliable high-performance liquid chromatography method for the analysis of diesel oil in contaminated edible oils is described. Analysis performed using a diol column with a mobile phase of heptane and isopropanol (94∶6, vol/vol). Although baseline separation between diesel and other background fluorescent components was not achieved, quantitation was still possible using baseline integration. The method is linear over the range of 5–1000 μg/g with a correlation coefficient (r ²) of 0.9984. Average recoveries from spiked edible oils were 94.4–101.3%, with a limit of quantitation (LOQ) of 5 μg/g for sunflower oil, palm olein, and groundnut oil. Corn oil has a higher content of ester components, thus, LOQ was slightly worse (40 μg/g). The applicability of the method was confirmed by gas chromatography-mass spectroscopic detection to show the presence of diesel hydrocarbons in the suspected contaminated crude palm oil. This procedure provides a simple and sensitive method for determining diesel oil concentration in contaminated edible oils without prior sample cleanup or extraction.     

Influence of Zataria multiflora Boiss. essential oil on oxidative stability of sunflower oil

In this study, the influence of the application of 0.025%, 0.05% and 0.075% of Zataria multiflora Boiss. essential oil (EO) on oxidative stability of sunflower oil was examined and the EO was compared to butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) during storage at 37°C and 47°C. The main components of EO were identified as carvacrol (45.6%), p‐cymene (18.1%) and thymol (16.3%). Peroxide value (PV), anisidine value (AnV) and thiobarbituric acid (TBA) value measurement in sunflower oil showed that all concentrations of EO had a lower antioxidant effect in comparison to BHA and BHT. Samples supplemented with EO concentration of 0.075% were the most stable during storage at both temperatures (p<0.05). Furthermore, Totox value, antioxidant activity (AA), stabilization factor (F) and antioxidant power (AOP) determination confirmed efficacy of this EO as antioxidant in sunflower oil. EO also was able to reduce the stable 2,2‐diphenyl‐1‐picrylhydrazyl free radical (DPPH ^. ) with a 50% inhibition concentration (IC₅₀) of 34.3 ± 0.8 µg/mL. The results indicate that EO could be used as a natural antioxidant in oils for food uses.     

Lipid oxidation inhibiting capacities of blackseed essential oil and rosemary extract

Lipid oxidation is the main deterioration process that occurs in vegetable oils containing lipid molecules with polyunsaturation. The aim of the present study was to investigate the possible effects of blackseed (Nigella sativa L.) essential oil (BEO) and rosemary (Rosmarinus officinalis L.) extract (RE) on stabilization of sunflower oil under accelerated storage conditions. RE was obtained by soxhlet extraction using methanol, whereas BEO was hydrodistilled from the blackseed extract obtained by extraction using petroleum ether (b.p. 40–60°C). The results indicate that both extracts stabilize sunflower oil to a certain extent, the extent being greater with RE than with BEO based on measurements of peroxide value, p‐anisidine value, amount of nonoxidized linoleic acid in saponified oil samples by HPLC‐DAD, concentration of conjugated diene hydroperoxide, and UV light absorption. The oil stabilizing effect of BEO against lipid oxidation, especially at concentrations of 0.06 and 0.1 g/100 g oil was found to increase as the temperature increased, according to principal component analysis results. Based on its strong lipid oxidation inhibiting capacity, RE can be used as a potential natural extract for stabilizing sunflower oil against oxidation. BEO, at carefully selected concentrations, can be suggested as an alternative supplement of plant origin for improving oil stabilization. Practical applications: Sunflower oil is a widely used vegetable oil for cooking and frying, and has a high linoleic acid content of about 40–70%. Here we show that sunflower oil can be stabilized by adding rosemary and blackseed extracts. The treatment can be useful especially in applications which require heating the oil to high temperatures.     

Pan-frying stability of NuSun oil,a mid-oleic sunflower oil

Pan-frying is a popular frying method at home and in many restaurants. Pan-frying stabilities of two frying oils with similar iodine values (IV)—mid-oleic sunflower oil (NuSun oil; IV=103.9) and a commercial canola oil (IV=103.4)—were compared. Each oil sample was heated as a thin film on a Teflon-coated frying pan at ∼180°C to a target end point of ≥20% polymer. High-performance size-exclusion chromatography analysis of the mid-oleic sunflower and canola oil samples indicated that the heated samples contained 20% polymer after approximately 18 and 22 min of heating, respectively. The food oil sensor values increased from zero to 19.9 for the canola sample and from zero to 19.8 for the mid-oleic sunflower sample after 24 min of heating. The apparent first-order degradation rate for the mid-oleic sunflower sample was 0.102±0.008 min⁻¹, whereas the rate for the canola sample was 0.092±0.010 min⁻¹. The acid value increased from approximately zero prior to heating to 1.3 for the canola sample and from zero to 1.0 for the mid-oleic sunflower sample after 24 min of heating. In addition, sensory and volatile analyses of the fried hash browns obtained from both oils indicated there were no significant differences between the two fried potato samples.     

Determination of seed oil content and fatty acid composition in sunflower through the analysis of intact seeds, husked seeds, meal and oil by near-infrared reflectance spectroscopy

A methodological study was conducted to test the potential of near-infrared reflectance spectroscopy (NIRS) to estimate the oil content and fatty acid composition of sunflower seeds. A set of 387 intact-seed samples, each from a single plant, were scanned by NIRS, and 120 of them were selected and further scanned as husked seed, meal, and oil. All samples were analyzed for oil content (nuclear magnetic resonance) and fatty acid composition (gas chromatography), and calibration equations for oil content and individual fatty acids (C_16:0, C_16:1, C_18:0, C_18:1, and C_18:2) were developed for intact seed, husked seed, meal, and oil. For intact seed, the performance of the calibration equations was evaluated through both cross- and external validation, while cross-validation was used in the rest. The results showed that NIRS is a reliable and accurate technique to estimate these traits in sunflower oil (validation r ² ranged from 0.97 to 0.99), meal (r ² from 0.92 to 0.98), and husked seeds (r ² from 0.90 to 0.97). According to these results, there is no need to grind the seeds to scan the meal; similarly accurate results are obtained by analyzing husked seeds. The analysis of intact seeds was less accurate (r ² from 0.76 to 0.85), although it is reliable enough to use for pre-screening purposes to identify variants with significantly different fatty acid compositions from standard phenotypes. Screening of intact sunflower seeds by NIRS represents a rapid, simple, and cost-effective alternative that may be of great utility for users who need to analyze a large number of samples.     

Microbial mediated dimerization of fattyacids of sunflower oil: An effective role of lipase and biosurfactant

This study emphasizes microbial mediated transformation of sunflower oil to an adhesive product and characterization in detail. Marine bacterial isolates Bacillus (MTCC 5514), when grown in mineral medium, releases both hydrolytic enzymes and surface‐active components during the log phase of growth. When this species was grown in the presence of sunflower oil at an optimized concentration of 5% (w/v) under room temperature, enzymatic hydrolysis of oil proceeds with the release of fatty acids and glycerol. Further, on increasing the incubation period, the presence of surface‐active components, lipase and glycerol, influence the dimerization of the fatty acids, which further, transformed to a polymerized product sunflower oil‐based adhesive product with adhesive nature. Liquid chromatography‐mass spectrometry (electrospray ionization) analysis further authenticates the presence of dimeracids. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40555.     

Study and optimization of a soaking treatment to reduce migration from plasticized polyvinyl chloride

Commercial sunflower oil was epoxidized, and epoxidized sunflower oil (ESO) was used as a thermal stabilizer for polyvinyl chloride (PVC). This work describes a process capable to reduce the additives migration between plasticized PVC stabilized with ESO and food simulants. For that purpose, samples were first soaked in n‐heptane and then dried. Soaking temperature and drying temperature with time were optimized by using the methodology of experiment plans. The optimal conditions found were applied to study the migration of additives in a fatty simulant (olive oil) at 40°C. The test conditions were 12 days. Twelve circular samples of plasticized PVC were immersed in 120 mL of olive oil. A circular sample and 10 mL of food simulant were taken off every day to be analyzed. The rate of mass variation was followed. The specific migrations of the present additives were investigated by using Fourier transform infrared spectroscopy, atomic absorption spectrometry and gas chromatography‐ mass spectrometry. The results showed that the studied process reduced considerably the additives migration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Reactive extraction of itaconic acid using tri‐n‐butyl phosphate and aliquat 336 in sunflower oil as a non‐toxic diluent

Itaconic acid finds a place in various industrial applications. It can be produced by biocultivation in a clean and environment friendly route but recovery of the acid from the dilute stream of the bioreactor is an economic problem. Reactive extraction is a promising method to recover carboxylic acid but suffers from toxicity problems of the diluent and extractant employed. So there is need for a non‐toxic extractant and diluent or a combination of less toxic extractants in a non‐toxic diluent that can recover acid efficiently. Effect of different extractants: tri‐n‐butylphosphate (TBP) (an organophosporous compound) and Aliquat 336 (a quaternary amine) in sunflower oil was studied to find the best extractant–sunflower oil combination. Equilibrium complexation constant, K_E, values of 1.789 and 2.385 m³ kmol^?1, respectively, were obtained for itaconic acid extraction using TBP and Aliquat 336 in sunflower oil. The problem of toxicity in reactive extraction can be reduced by using a natural non‐toxic diluent (sunflower oil) with the extractant. Copyright © 2010 Society of Chemical Industry     

Correlation of viscosities of vegetable oil blends with selected esters and hydrocarbons

Blending is often used to reduce the viscosity of vegetable oil lubricants. Experimental rheological results were compared with traditional blending charts and calculation methods. Kinematic viscosities of 90% oleic sunflower, canola, and soybean oils blended with adipates, oleates, polyalphaolefins, and mineral oil were determined at 40°C using capillary viscometers. Blending charts related the viscosities to blend composition with 5% inaccuracy compared with more than 10% deviation made by the cubic equation of Kendall and Monroe. Even more accurate and simpler correlations could be derived. A semilog relationship between viscosities and composition was more accurate than a cubic model. Higher accuracy was also achieved when relating viscosities to volume fractions rather than to weight or mole fractions. Mineral oil blends did not follow the observed rules.     

On the importance of total polar phenols to monitor the stability of Greek virgin olive oil

A large number of virgin olive oil samples obtained from different areas in Greece were analyzed for various quality parameters. The work focuses on the colorimetric determination of total phenols with the Folin‐Ciocalteu reagent and its importance in predicting shelf life of virgin olive oil. The results indicate a good correlation of total polar phenol content with the stability of the oil. Colorimetric determination of ortho‐diphenol content does not seem to be a better means for predicting virgin olive oil stability. RP‐HPLC quantification of hydroxytyrosol and tyrosol in their free form gives poor results in the case of freshly extracted oils. It is concluded that until an easy‐to‐manage HPLC method will be available, which will quantify accurately both free and bound forms of hydroxytyrosol and other phenolics, the colorimetric method for the determination of total polar phenols remains a good practical means to evaluate the stability of virgin olive oil.     

Cyclic fatty acids in sunflower oils during frying of frozen foods with oil replenishment

Frying of frozen foods has become popular because it considerably reduces cooking time. Polymers and cyclic fatty acid monomers (CFAM) formed during frying are potentially toxic and therefore their production should be minimized. Twenty discontinuous fryings of different frozen foods were carried out over ten consecutive days, in sunflower oil (SO) and in high‐oleic acid sunflower oil (HOSO), by adding fresh oil after each frying to bring the volume of the fryer oil back to 3 L. CFAM methyl ester derivates were hydrogenated, isolated, concentrated and quantified by HPLC using a reverse‐phase column, followed by gas chromatography. After 20 fryings, significantly higher contents of polar material, polymers and CFAM (all p <0.001) were found in SO than in HOSO. Bicyclic compound formation was four times higher in SO (p <0.001). The fat from the fried potatoes presented a polymer content very similar to that of their corresponding oils. The 100‐g rations of the SO‐fried potatoes from the 20^th frying supply 49 or 15%, respectively, more polymers and CFAM and 1 mg more bicyclic fatty acids than the 100‐g rations of HOSO‐fried potatoes. Because digestion and absorption of polar material, polymers and CFAM occur, the data clearly show the advantageousness and advisability of frying with HOSO rather than SO.     

Zinc and nickel determination in liquid edible oils by FAAS after the extraction

A new method has been developed for the extraction and determination of zinc and nickel in liquid edible oils by using the complexation of these metals with [N,N′‐bis(salicylidene)‐2,2′‐dimethyl‐1,3‐propanediaminato]. Zn(II) and Ni(II) complexes with a tetradentate Schiff base have been investigated spectrophotometrically. Experimental extraction conditions for these metals from liquid oil standards were optimized using central composite design. Optimum conditions for Zn(II) and Ni(II) extractions from oil have been found close to each other. The ratio of the volume of used Schiff base solution to the amount of oil (V_LDM/m_oil; mL/g), the stirring time and the temperature were round about 1.00 mL/g, 55 min, 32°C, respectively, for simultaneous determination of both metals in same sample. The recovery percentages at the optimum experimental conditions were found 98.9 ± 2.8 and 101.8 ± 4.7 for Zn(II) and Ni(II), respectively. The proposed method was applied on the raw and spiked samples such as olive oil, sunflower oil, corn oil, canola oil and obtained recovery values were between 93.7–107.2 and 93.1–101.1% for Zn(II) and Ni(II), respectively. Practical applications: There is interest in the determination of metals in liquid edible oils because of their catalytic effect on the oxidation reaction of oils. A new method for the determination of Zn(II) and Ni(II) in liquid edible oils which does not require any digestion or decomposition was developed. This study offeres a cheap, rapid, accurate, sensitive, risk‐free, and practical metal determination method after the extraction.     

Prediction of crude sunflower oil deterioration after seed drying and storage processes

The effects of air-drying temperature and storage time on several characteristics of crude sunflower oil were evaluated in terms of FFA and PV. Long storage affected oil content to a greater extent than air-drying temperature. FFA and PV varied between 0.53 and 1.22% and between 10.7 and 23.3. meq O₂/kg, respectively, when samples of uniform initial moisture content (approximately 28%) were dried at various temperatures between 25 and 90°C to approximately 7% moisture content, stored for 8 mon, and then analyzed. Both oil quality characteristics increased exponentially with air-drying temperature (T) and linearly with storage time (t). Mathematical functions of the form A·exp(B·T)+C·t (where A, B, and C are parameters adjusted from experimental data) most closely predicted the experimental loss of quality of sunflower oil in terms of FFA and PV with variations in T and t. Statistical analysis showed SE of the estimated parameters of 0.08 and 1.19 and coefficients of determination, R ², of 0.922 and 0.939 for FFA and PV, respectively, which were significant at 95% confidence. High-oleic seeds from a similar experiment were used to validate the proposed equation. The results of applying the mathematical function proposed above showed a reasonable ability to predict the experimental values with SE of 0.037 and 0.808 and R ² of 0.983 and 0.972 for FFA and PV, respectively, which were significant at 95% confidence. Plots of residuals showed random distribution. The results obtained suggested that the equation proposed could be used as a quality-loss model in sunflower drying simulations.     

A lipidomic approach for profiling and distinguishing seed oils of Hibiscus manihot L., flaxseed,and oil sunflower

As important oil crops in Inner Mongolia, sunflower, and flaxseed had distinct lipid profiles in seeds. As an emerging cash crop, Hibiscus manihot L. has strong potential market competitiveness. In this study, the lipidome, fatty acid composition and quality characteristics of flaxseed, H. manihot L., and sunflower seed oils were analyzed and compared. A total of 270 distinct lipids were identified and analyzed with an emerging detection approach—lipidomics, which illustrated the tremendous difference among the samples. triacylglycerol, diacylglycerol and polar lipids were the most abundant lipids in all samples. H. manihot L. seeds contained higher saturated and monounsaturated fatty acids and lower polyunsaturated fatty acids. H. manihot L. seed oil had the longest oxidative stability index time, high content of vitamin E and total phenolics, while flaxseed oil embodied the lowest oxidative stability. The peroxide value and acid value of the three oils were within the allowable range of Chinese national standards.     

Behaviour of cod liver oil during the autoxidation process

Prostaglandin‐like compounds, called isoprostanes, are generated by free enzyme‐independent radical peroxidation of the acids arachidonic (AA), eicosapentaenoic (EPA) and docosahexaenoic (DHA). Up to now, isoprostanes have been largely studied only in men and biological systems, but never in food. In this research, cod liver oil was used as a model system to study the oxidation mechanism in food containing high amounts of EPA and DHA. For comparison, under similar oxidation conditions, also the behaviour of a sunflower seed oil and an n‐3 long‐chain polyunsaturated fatty acid capsule supplement oil were studied. It was ascertained that EPA‐ and DHA‐derived compounds were formed during oxidation. These compounds were polar and easily isolatable by methanol from oxidised transmethylated oil. EPA and DHA oxidation derivatives showed maximal absorbance at 200 nm and were very potent pro‐oxidants at high temperatures. In oxidised sunflower oil, similar compounds did not form. Unfortunately, the chemical structures of the EPA and DHA oxidation derivatives were not discovered, but it is a realistic hypothesis that they could be isoprostane‐like compounds.     

Rapid and nondestructive determination of seed oil by pulsed nuclear magnetic resonance technique

The pulsed NMR technique for rapid and nondestructive determination of oil in oilseeds has been developed. The effects of spin-lattice relaxation time, spin-spin relaxation time, seed moisture, angular position of the seeds, sample tube thickness, and sample height upon the magnitude and reproducibility of the NMR signal were studied. Based upon these studies, various parameters for seed oil analysis have been fixed. The oil content of Brassica, peanut, and sunflower seeds was determined. The reproducibility of the measurement is ± 1 %. The technique was tested by measuring the oil content of the same seeds by the cold percolation method (CCl₄ extraction). It was further tested by determining the oil content of 60 Brassica seed samples independently at three laboratories. The results of these tests are given.     

Virgin sunflower oil

Sunflower oil is the second most important virgin oil in Europe but, from the nutritional point of view, the assessment of this oil has become increasingly poorer over the last few years because of the high amount of linoleic acid in traditional sunflower seeds. Today sunflower oil with a high oleic acid content is coming more into the focus of interest since the fatty acid composition is more comparable to rapeseed and olive oil. Another important aspect is that the high content of oleic acid results in a high oxidative stability, making this oil interesting for a wide range of applications. A special challenge is the production of high‐quality tasty virgin sunflower oil because, in contrast to other raw materials, about 30% of sunflower seeds consist of hulls that are covered by waxes. During oil processing these waxes are co‐extracted with the oil, resulting in undesired turbidity of the oil on storage. Pressing of the raw material is done in a screw press or expeller and results in residue fat contents between 7 and 15% depending on the pressing conditions. We discuss two possibilities to avoid or to remove waxes by dehulling of the seeds or winterisation of the resulting oil. Dehulling is carried out by an impact dehuller with removal of the hulls by airflow and gravity. Removal of hulls before pressing improves the sensory quality of the oil because it results in products with a mild sunflower seed‐like nutty taste, while oils from whole seeds often have a woody and bitter taste. In addition, the development of heat during pressing is reduced if dehulled seeds are used for oil production. Conventional sunflower seeds are processed mainly in big oil mills, whereas in small and medium‐sized facilities organic raw material is in use.     

Determination of Mineral Oil-Saturated Hydrocarbons (MOSH) in Vegetable Oils by Large Scale Off-Line SPE Combined with GC-FID

A method based on an off-line large-scale solid phase extraction (SPE) approach combined with conventional gas chromatographic-flame ionization detection (GC-FID) was developed to determine the mineral oil-saturated hydrocarbons (MOSH) in vegetable oils. A large-scale SPE column loaded with 10 g of activated silica gel impregnated with 1% silver nitrate which was used to retain lipids and olefins in vegetable oils and the MOSH in the oil samples was eluted with hexane. Then 2 μL concentrated solution was splitlessly injected into a common GC-FID instrument. The quantification limit reached 2.5 mg/kg when the MOSH fraction was concentrated to 0.1 mL. The accuracy of this procedure, as assessed by measuring the recoveries from spiked oil samples, was higher than 80%. This procedure was applied to analyze the MOSH in 38 commercial vegetable oils from Chinese market, which was the first survey of mineral oil contaminant in Chinese edible oils. The oil samples contaminated with different levels of MOSH, among which, 15 samples contained no mineral oils and 3 samples were contaminated with more than 50 mg/kg of MOSH. The highest contamination level was found in one of rice oils, in which the concentration of MOSH was up to 713.36 mg/kg. Of the 9 types of oils analyzed, camellia oil contained MOSH ranging between 6.76 and 78.49 mg/kg, averaging 46.72 mg/kg, indicating a higher contamination level than other types of oils. The results suggested that it is necessary to routinely detect mineral oil contamination in vegetable oils for food safety.