Discrimination of olive oil adulterated with vegetable oils using dielectric spectroscopy

The study focused on application of dielectric spectroscopy to identify the adulteration of olive oil. The dielectric properties of binary mixture of oils were investigated in the frequency range of 101 Hz–1 MHz. A partial least squares (PLS) model was developed and used to verify the concentrations of the adulterant. Furthermore, the principal component analysis (PCA) was used to classify olive oil sample as distinct from other adulterants based on their dielectric spectra. The results showed that the dielectric spectra of binary mixture of olive oil spiked with other oils increased with increasing concentration of soy, corn, canola, sesame, and perilla oils from 0% to 100% (w/w) over the measured frequency range. PLS calibration model showed a good prediction capability for the concentrations of the adulterant. For olive oil adulterated with soy oil, the results showed that the RMS was 0.053, sd(RMS), 0.017 and Q² value was 0.967. PCA classification plots for all oil samples showed clear performance in the differentiation for the different concentrations of the adulterant. Each of the oil samples could be easily grouped in different clusters using dielectric spectra. From the results obtained in this research, dielectric spectroscopy could be used to discriminate the olive oil adulterated with the different types of the oils at levels of adulteration below 5%.     

Extra-Virgin Olive Oil and Cheap Vegetable Oils: Distinction and Detection of Adulteration as Determined by GC and Chemometrics

Refined oils including corn, sunflower, soybean, and palm oils as well as low-quality olive oil such as refined lampante and pomace olive oils are commonly used for extra-virgin olive oil (EVOO) adulteration. Indeed, K ₂₇₀ could be used as a parameter for the detection of EVOO fraud for each type of the studied refined oils, 10 % olive, 4 % pomace olive, 10 % palm, 5 % corn, and 2 % soybean oils. Moreover, the adulteration could also be detected by the increase of the trans fatty acid contents with 10 % pomace olive, 3 % soybean, 3 % sunflower, 2 % corn, and 10 % palm oils. Actually, stigmasta-3,5-diene content is one of the most effective means of detecting refined oils in EVOO at low levels: 2 % olive, 0.4 % pomace olive, 1 % palm, 0.2 % soybean, 0.5 % sunflower, and 0.1 % corn oils. Finally, the application of linear discriminant analysis could represent an alternative and innovative tool for faster and cheaper evaluation of EVOO adulteration.     

A Cost-Efficient and Simple Plant Oil DNA Extraction Protocol Optimized for DNA-Based Assessment of Product Authenticity

DNA-based assays offer precision in ascertaining the species/cultivar origin of agro-food products. Yet, obtaining DNA of sufficient quality and quantity is the main challenge while performing DNA-based food authentication analyses. The aim of the present work was to standardize a cost-efficient, easy-to-apply, yet effective plant oil DNA isolation protocol that allows reliable downstream PCR-based analyses. Because capillary electrophoresis (CE) separation of species/cultivar discriminating genomic fragments is a widely adopted approach in food genomics, a CE system was utilized in order to assess the performance of the proposed cetyl trimethyl ammonium bromide (CTAB)-based protocol. A plastid intergenic spacer and a nuclear olive gene were used as targets in order to evaluate the amplificability of DNA extracted with the CTAB-based protocol. The plastid barcode not only allowed assessing the reproducibility of PCR amplifications from the extracted oil DNA samples (olive, hazelnut, corn, rapeseed, cottonseed, and soybean oils) but also proved successful in discriminating all tested oil crop species based on amplified fragment length polymorphisms. Moreover, the barcode assay proved successful in correctly identifying the tested olive oil: cottonseed oil blends as admixtures of the two oil species. Thus, it was also feasible to demonstrate the potential of the barcode sequence as a discriminatory analyte to detect adulteration in plant oils. In addition, application of a CAPS (cleaved amplified polymorphic sequence) assay designed to genotype a nuclear SNP (single nucleotide polymorphism) marker resulted in the successful identification of the two single-cultivar olive oils included in the study. As a result of the present work, it was feasible to standardize a reliable and cost-efficient DNA extraction protocol that works well with both unrefined (olive and hazelnut) and refined (corn, rapeseed, cottonseed, and soybean) oils.     

橄榄油掺伪的气相色谱质谱鉴别方法研究

采用气相色谱质谱法测定了某品牌橄榄油、棕榈油、菜籽油、大豆油、玉米油、花生油、葵花籽油的脂肪酸组成与含量,并采用聚类分析软件对其相似性进行了分析。实验模拟了掺假过程,向橄榄油中加入不同比例的低价值植物油包括棕榈油、菜籽油、大豆油、玉米油、花生油、葵花籽油,初步建立了橄榄油掺伪鉴别的气相色谱质谱法。掺入低价值植物油后,肉豆蔻酸、α-亚麻酸、山嵛酸、反式亚油酸、花生酸、花生一烯酸等脂肪酸含量随着掺加比例的增加呈现线性上升趋势。根据上述脂肪酸指标含量进行判定,棕榈油、菜籽油、大豆油、玉米油、花生油、葵花籽油最低掺假检出限分别为5.27%、5.61%、6.35%、4.53%、1.93%和9.21%。通过对不同植物油中其脂肪酸特征组分及含量的分析,可达到鉴别橄榄油掺假的目的。      

Fatty acids and sensory characteristics of Spanish dry-cured loin enriched in acid α-linolenic and α-tocopherol

The effects of using α-linolenic and α-tocopherol acid-enriched pork on the fatty acids and sensory characteristics of Spanish dry-cured loins were investigated. For the study, five batches of Spanish dry-cured loins were manufactured using pork loin enriched in polyunsaturated n − 3 fatty acids and α-tocopherol. Tissues were obtained from pigs fed on diets with the same ingredients, except for the oil source which corresponded to: [sunflower (C), linseed (L) and linseed and olive (1/1, w/w) (LO)] and two different amounts of α-tocopheryl acetate [20 (C, L and LO) or 200 (LOE and LE) mg/kg diet]. Dry-cured loins with polyunsaturated fatty acid n6/n3 ratios below 4 were obtained from linseed and linseed/olive oil-enriched batches. Dry-cured loin manufactured with pork from animals fed on diets enriched only with linseed oil presented the worst sensory characteristics and higher TBAR values than did dry-cured loins from animals fed on diets enriched with linseed and olive oil and linseed oil plus tocopheryl acetate.     

Development of a SCAR marker for the identification of Olea europaea L.: A newly detected adulterant in commercial Mediterranean oregano

A recent pharmacognostic survey on the European food market highlighted a previously unreported adulteration of Mediterranean oregano. Dried crushed leaves, silvery grey in colour but devoid of glandular hairs and with unequivocal xerophytic adaptations were copiously spotted (20–30% w/w) in a number of commercial samples. Microscopical investigations narrowed the range of suspect candidates to Olea europaea L. and a method based on Sequence-Characterised Amplified Regions markers (SCARs) was developed from Random Amplified Polymorphic DNA markers (RAPDs) specific for O. europaea, in order to authenticate the contaminant and set up a fast, sensitive, reliable and low-cost screening of dried commercial Mediterranean oregano samples. The method enabled the unequivocal detection of low amounts (up to 1%) of olive leaves in both artificial and commercial batches, allowing the preemptive rejection of suspect samples and reducing the number of samples to be subjected to more careful pharmacognostic analyses. The relatively short dimension of the amplicons is suitable for the analysis of potentially degraded DNA obtained from dried and processed commercial plant material and given their specificity the method may be enforceable also in case of forensic disputes even in case of finely ground material.     

The potential of plastid trnL (UAA) intron polymorphisms for the identification of the botanical origin of plant oils

This work describes a methodology for the identification of the botanical origin of plant oils emphasising on the detection of adulteration of olive oil with sesame oil. This methodology comprises a PCR-based assay that exploits the polymorphisms found in the plastid genome combined with a capillary electrophoresis system to discriminate a range of 11 plant species commonly used for oil extraction on the basis of differential length of their corresponding PCR amplicons. The assay takes advantage of universal primers that amplify a region from the trnL (UAA) intron of every plant species. The results showed that amplicons from all species can be accurately discriminated apart from olive and avocado. Single-base primer extension was then proposed as an additional methodology to discriminate the two species and to confirm the results of the former approach. These assays were successfully applied on olive and sesame oils, thus confirming the validity of this approach.     

Composition and distribution of fatty acids in triglycerides from goat infant formulas with milk fat

Most infant formulas use vegetable oils in place of milk fat to provide an overall fatty acid profile similar to that of breast milk. Vegetable oils have 5 to 20% saturated fatty acids in the sn-2 position of triglycerides unless they are modified by interesterification. Interesterification is increasingly used for the fat for infant formulas to raise the level of saturated fatty acids in the sn-2 position to 40 to 60%. The objective of this study was to verify an alternative approach to providing the appropriate fatty acid profile, including in the sn-2 position, for a goat infant formula. In this method, 55% of total fat was made from goat milk fat and 45% from a mixture of unmodified high oleic sunflower, canola, and sunflower oils in a ratio of 44:30:26. The fatty acid profile was measured by gas-liquid chromatography and the relative percentage of fatty acids in the sn-2 position of triglycerides was measured via partial deacylation with Grignard reagent using trimethylsilyl derivatives of monoacylglycerols. Mixing goat milk fat with vegetable oils produced a formula with a profile of essential fatty acids and a ratio of linoleic:α-linolenic fatty acids within the required interval of 5 to 15:1 recommended for infant formula. The proportion of palmitic acid in the sn-2 position was 31%.     

Production of n-3 fatty acid enriched pork liver pâté

Five batches of pâté were manufactured using back fat and liver enriched in polyunsaturated n-3 fatty acids and α-tocopherol. Tissues were obtained from animals fed on diets with the same ingredients excepting the oil source which were: [sunflower (C), linseed (L) and linseed and olive (1/1, w/w) (LO)] and two different amounts of α-tocopherol [20 (C, L and LO) or 200 (LOE and LE) mg/kg diet]. A pâté with a healthier polyunsaturated fatty acid n-6/n-3 ratio (<4) was obtained from linseed enriched batches than from those of both the control (9.32) and several commercial pâtés (8.64). The α-tocopherol enriched batches showed a higher lipid stability against oxidation. No differences of chemical composition, TBARs values, textural or sensory features were found.     

Evaluation and characterisation of Citrullus colocynthis (L.) Schrad seed oil: Comparison with Helianthus annuus (sunflower) seed oil

The physicochemical properties, fatty acid, tocopherol, thermal properties, ¹H NMR, FTIR and profiles of non-conventional oil extracted from Citrullus colocynthis (L.) Schrad seeds were evaluated and compared with conventional sunflower seed oil. In addition, the antioxidant properties of C. colocynthis seed oil were also evaluated. The oil content of the C. colocynthis seeds was 23.16%. The main fatty acids in the oil were linoleic acid (66.73%) followed by oleic acid (14.78%), palmitic acid (9.74%), and stearic acid (7.37%). The tocopherol content was 121.85 mg/100 g with γ-tocopherol as the major one (95.49%). The thermogravimetric analysis showed that the oil was thermally stable up to 286.57 °C, and then began to decompose in four stages namely at 377.4 °C, 408.4 °C, 434.9 °C and 559.2 °C. The present study showed that this non-conventional C. colocynthis seed oil can be used for food and non-food applications to supplement or replace some of the conventional oils.     

Silphium L. extracts – composition and protective effect on fatty acids content in sunflower oil subjected to heating and storage

The influence of ethanol and hexane extracts from leaves, inflorescences, and rhizomes of Silphium perfoliatum, Silphium trifoliatum, Silphium integrifolium on fatty acid content changes in sunflower oil subjected to heating and storage was studied in comparison to the synthetic antioxidant – butylated hydroxyanisole (BHA). A positive effect of extracts made of above-ground and underground organs of Silphium on the durable quantitative composition of fatty acids was proven. Tested extracts elevated the value of change inhibition with reference to linoleic acid to a level comparable with BHA, and sometimes, in appropriate systems, they were characterized by better values (for oil stored for 180 days at room temperature, the inhibition coefficient for linoleic acid changes reached 4.6% for 0.04% BHA, and 7.09% for hexane extract made of S. trifoliatum inflorescences, 400 μl/2 g; for oil heated for 120 h, the inhibition coefficient of linoleic acid changes amounted to 11.32% for 0.06% BHA, and 15.69% for hexane extract made of S. perfoliatum rhizomes, 600 μl/2 g). It was found that active substances groups such as phenolic acids, flavonoids and terpenes were present in tested extracts.     

Rapid Quantitative Determination of Walnut Oil Adulteration with Sunflower Oil Using Fluorescence Spectroscopy

Adulteration of walnut oil with sunflower oil is a major issue for the walnut oil industry. In this paper, the potential use of total synchronous fluorescence (TSyF) spectra to differentiate walnut oil from sunflower oil and synchronous fluorescence spectra combined with multivariate analysis to assess the adulteration of walnut oil is demonstrated. TSyF spectra were acquired by varying the excitation wavelength in the region 250–700 nm and the wavelength interval (Δλ) in the region from 10 to 100 nm. TSyF contour plots for walnut oil, in contrast to sunflower oil, show an extra fluorescence region in the excitation wavelength lower than 280 nm. Fifty-one oil mixtures were prepared by adulterating walnut oil with sunflower oil at varying levels (0–100 %). The partial least-squares regression model was used for the quantification of adulteration using wavelength intervals of 20, 40, 60 and 80 nm. This technique is useful for the detection of sunflower oil in walnut oil at levels down to 0.3 % (v/v) in just 2.5 min using an 80-nm wavelength interval.     

Migrated phthalate levels into edible oils

The determination of phthalates in edible oils (virgin olive oil, olive oil, canola oil, hazelnut oil, sunflower oil, corn oil) sold in Turkish markets was carried out using gas chromatography–mass spectrometry. Mean phthalate concentrations were between 0.102 and 3.863 mg L^?1 in virgin olive oil; 0.172 and 6.486 mg L^?1 in olive oil; 0.501 and 3.651 mg L^?1 in hazelnut oil; 0.457 and 3.415 mg L^?1 in canola oil; 2.227 and 6.673 mg L^?1 in sunflower oil; and 1.585 and 6.248 mg L^?1 in corn oil. Furthermore, the influence of the types of oil and container to the phthalate migration was investigated. The highest phthalate levels were measured in sunflower oil. The lowest phthalate levels were determined in virgin olive oil and hazelnut oil. The highest phthalate levels were determined in oil samples contained in polyethylene terephthalate.     

基于稳定碳同位素示踪技术的商品植物油掺杂鉴别研究

本文旨在运用所建立的纯植物油的脂肪酸组成及其稳定碳同位素比值判别标志对广州市售商品植物油是否掺杂进行判识。先在广州某大型超市购得18种商品植物油(包括3种茶籽油、5种花生油、2种葵花油、2种玉米油和6种橄榄油);然后采用气相色谱-质谱联用仪(GC-MS)、气相色谱-同位素比值质谱仪(GC-IRMS)和元素分析-同位素比值质谱仪(EA-IRMS)对这18种商品油的脂肪酸组成和全油及其脂肪酸的稳定碳同位素比值进行测定;最后将本次检测所获得的数据与作者之前建立的判别标志进行对比分析。对比结果表明,本批商品植物油的品质总体较好,但其中50%的植物油商品存在掺杂。因此,将植物油脂肪酸组成数据与其稳定碳同位素比值数据相结合,可灵敏地确定待检植物油是否存在掺杂。     

Thermal Stability and Kinetic Study on Thermal Decomposition of Commercial Edible Oils by Thermogravimetry

Thermal stability and kinetic parameters of commercial edible oils were investigated by non‐isothermal thermogravimetry/derivative thermogravimetry (TG/DTG). Kinetic parameters were calculated by integral and approximation methods. Results obtained indicated that these parameters were dependent on composition of fatty acids, being influenced by the presence of natural and artificial antioxidants. According to the thermogravimetric curves, the following thermal stability sequence was suggested: corn > sunflower > soybean > rice > soybean + olive > sunflower + olive > canola > olive; while the activation energy indicated the following stability order: sunflower > corn > soybean > rice > soybean + olive > canola > sunflower + olive > olive.     

Authentication of Olive Oil Adulterated with Vegetable Oils Using Fourier Transform Infrared Spectroscopy

Determination of the authenticity of extra virgin olive oils has become more important in recent years following some infamous adulteration and contamination scandals. The study focused on application of Fourier transform infrared spectroscopy to identify the adulteration of olive oils. Single-bounce attenuated total reflectance measurements were made on pure olive oil and olive oil samples adulterated with varying concentrations of sunflower oil (20-100 mL vegetable oil/L of olive oil). Discriminant analysis using 12 principal components was able to classify the samples as pure and adulterated olive oils based on their spectra. A partial least squares model was developed and used to verify the concentrations of the adulterant. Furthermore, the discriminant analysis method was used to classify olive oil samples as distinct from other vegetable oils based on their infrared spectra.     

Lipid oxidation of stored eggs enriched with very long chain n−3 fatty acids,as affected by dietary olive leaves (Olea europea L.) or α-tocopheryl acetate supplementation

The antioxidant potential of dietary olive leaves or α-tocopheryl acetate supplementation on lipid oxidation of refrigerated stored hen eggs enriched with very long-chain n−3 fatty acids, was investigated. Ninety-six brown Lohmann laying hens, were equally assigned into three groups. Hens within the control group were given a typical diet containing 3% fish oil, whereas other groups were given the same diet further supplemented with 10 g ground olive leaves/kg feed or 200 mg α-tocopheryl acetate/kg feed. Results showed that α-tocopheryl acetate or olive leaves supplementation had no significant effect on the fatty acid composition and malondialdehyde (MDA) levels of fresh eggs but reduced their lipid hydroperoxide levels compared to controls. Storage for 60 d decreased the proportions of polyunsaturated fatty acids (PUFAs) but increased those of monounsaturated fatty acids (MUFAs) in eggs from the control group, while had no effect on the fatty acid composition of the eggs from the other two groups, which showed decreased levels of lipid hydroperoxides and MDA. Therefore, the very long chain n−3 PUFAs in eggs were protected from undergoing deterioration partly by olive leaves supplementation and totally by α-tocopheryl acetate supplementation. In addition, incorporating tocopherols into eggs might also provide a source of tocopherols for the human diet.     

Detection of adulteration of extra-virgin olive oil by chemometric analysis of mid-infrared spectral data

This study focuses on the detection and quantification of extra-virgin olive oil adulteration with different edible oils using mid-infrared (IR) spectroscopy with chemometrics. Mid-IR spectra were manipulated with wavelet compression previous to principal component analysis (PCA). Detection limit of adulteration was determined as 5% for corn–sunflower binary mixture, cottonseed and rapeseed oils. For quantification of adulteration, mid-IR spectral data were manipulated with orthogonal signal correction (OSC) and wavelet compression before partial least square (PLS) analysis. The results revealed that models predict the adulterants, corn–sunflower binary mixture, cottonseed and rapeseed oils, in olive oil with error limits of 1.04, 1.4 and 1.32, respectively. Furthermore, the data were analysed with a general PCA model and PLS discriminant analysis (PLS-DA) to observe the efficiency of the model to detect adulteration regardless of the type of adulterant oil. In this case, detection limit for adulteration is determined as 10%.     

High-power gradient diffusion NMR spectroscopy for the rapid assessment of extra-virgin olive oil adulteration

A high gradient diffusion NMR spectroscopy was applied to measure diffusion coefficients (D) of a number of extra-virgin olive, seed, and nut oils in order to ascertain the suitability of this rapid and direct method for discrimination of adulterated olive oils. Minimum adulteration levels that could be detected by changes in D were 10% for sunflower (SuO) and soybean oil (SoO), and 30% for hazelnut (HO) and peanut oil (PO). Qualitative and quantitative prediction of adulteration was achieved by discriminant analysis (DA). The highest prediction accuracy (98–100%) was observed only when two DA models were concomitantly used for sample classification. The first DA model provided recognition of high adulterated EVOO with more than 20% of SuO or SoO, and 30% with PO, whilst the second model could differentiate EVOO adulterated with 10% of SuO or SoO, and more than 30% of HO. The validation test performed with an independent set of randomly adulterated EVOO samples gave 100% classification success. The high accuracy levels together with minimal requirements of sample preparation, and short analyses time, prove the high-power gradient diffusion NMR spectroscopy as an ideal method for rapid screening of adulteration in valuable olive oils.     

Production of conjugated linoleic acid by Propionibacterium freudenreichii

Two strains each of Propionibacterium freudenreichii ssp. shermanii and P. freudenreichii ssp. freudenreichii were tested for their ability to produce conjugated linoleic acid (CLA) in sodium lactate medium (SLM), De Man-Rogosa-Sharpe (MRS) medium and skim-milk. Data showed that both strains were able to produce CLA in three media supplemented with different concentrations of sunflower oil. Maximum production of CLA (78.8 μg/ml) was observed after 36 h of incubation in MRS containing 12 mg/ml of sunflower oil by P. freudenreichii ssp. shermanii. Moreover, the growths of both strains were inhibited by sunflower oil and a positive relationship between CLA production and ability to tolerate sunflower oil was observed. At the same time, it was also observed that the inhibitory effects on P. freudenreichii ssp. shermanii and P. freudenreichii ssp. freudenreichii in three media follow the order SLM > skim-milk > MRS and SLM > MRS > skim-milk, respectively. Micro aerobic conditions were in favour of increasing the amounts of CLA. The amounts of CLA increased from 0 to 36 h under micro aerobic conditions and no significant (p > 0.05) increases in total CLA levels were observed after 80 h of incubation. Results showed that P. freudenreichii may have potential for producing CLA.