Evaluation of the bellier test in the detection of olive oil adulteration with vegetable oils

Virgin olive oil was mixed with eight vegetable oils (sunflower, soya bean, palm, linseed, cottonseed, corn, sesame, and olive residue) at various levels. The Bellier test was applied to find the minimum detectable adulteration level and the ‘sensitivity score’ for each oil. The test was inapplicable to sunflower and linseed oils regardless of the level in olive oil. It was successful in detecting olive residue, soya bean, palm, cottonseed, corn, and sesame oils at minimal levels of 730, 150, 130, 90, 60 and 10 g kg^?1, respectively. The rancidity level of the adulterant oils did not affect the performance of the test in the case of sunflower, linseed and sesame oils. The sensitivity of the test decreased considerably with increasing peroxide value of the adulterant oil: soya bean, palm, cottonseed, corn and olive residue. However, the change in sensitivity level commenced at so high a peroxide value that it has no significance for practical purposes; at such levels of peroxidation the adulterated olive would be unmarketable and rejected by inspectors due to its poor sensory quality.     

MALDI-TOF mass spectrometry detection of extra-virgin olive oil adulteration with hazelnut oil by analysis of phospholipids using an ionic liquid as matrix and extraction solvent

The adulteration of extra virgin olive oil (EVOO) with hazelnut oil (HO) is frequent and constitutes a serious concern both for oil suppliers and consumers. The high degree of similarity between the two oils as regards triacylglycerol, total sterol and fatty acid profile, complicates the detection of low percentages of HO in EVOO. However, phospholipids (PLs) are usually present in seed oils at a concentration range of 10–20 g/kg, while the amounts of PLs in VOOs are 300–400 times lower. Thus, in this work a sample pretreatment procedure focused towards the selective PLs extraction was developed; the Bligh–Dyer extraction procedure was modified introducing the ionic liquid resulting from the combination of TBA (tributylamine) and CHCA (α-Cyano-4-hydroxycinnamic acid) as extraction solvent. The selective extraction and enrichment of phospholipids from EVOO and HO samples was then achieved. The relevant extracts were analyzed by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) using the same ionic liquid TBA-CHCA as MALDI matrix, that was found to be very suitable for PLs analysis. In fact, a remarkable increase of the phospholipids signals, with a simultaneous decrease of those relevant to triacylglycerols and diacylglycerols, was observed in the relevant mass spectra. The applicability of the whole method to the individuation of the presence of HO in EVOO was demonstrated by the analysis of EVOO samples progressively adulterated with variable quantities of HO, that was still detectable at a 1% contamination level.     

The potential of different techniques for volatile compounds analysis coupled with PCA for the detection of the adulteration of olive oil with hazelnut oil

This paper investigates the effectiveness of three rapid methods of volatile compounds analysis with subsequent principal component analysis (PCA) treatment of data for differentiation between virgin olive oil samples adulterated with hazelnut oil. Tested methods included comparison of chromatograms of volatiles obtained using SPME-fast GC-FID, volatiles analysis by electronic nose based on MOS sensors (HS-Enose), and by direct coupling of SPME to MS (SPME-MS). Volatile compounds were analyzed also by SPME-GC/MS technique. Data obtained as a result of SPME-GC/MS was subjected to PCA. SPME-GC–MS analysis with subsequent PCA yielded good results, however being time consuming. The three methods of analysis of volatiles, with subsequent PCA treatment of data, allowed detection of olive oil adulteration with different contents of hazelnut oil ranging from 5 to 50% (v/v).     

A contribution to the study of the enantiomeric composition of a chiral constituent in hazelnut oil used in the detection of adulterated olive oil

 A method is proposed for the determination of the adulteration of olive oil with hazelnut oil which is based on the study of the enantiomeric makeup of (E)-5-methylhept-2-en-4-one (filbertone). The possibilities of either using a sample preparation technique or performing direct injection of the samples (i.e., without any kind of sample pretreatment) are considered and both simultaneous distillation extraction followed by gas chromatographic analysis and direct injection in on-line coupled reverse-phase liquid chromatography to gas chromatography are used. In both cases, a chiral stationary phase is employed in the gas chromatography step and the determination of the enantiomeric composition of filbertone is recommended for an accurate evaluation and quick control for detecting the adulteration of olive oil with hazelnut oil. Received: 9 October 1998 / Revised version: 22 March 1999     

紫外光谱结合化学计量学检测初榨橄榄油掺伪研究

以紫外光谱为技术手段,结合偏最小二乘法和BP人工神经网络2种化学计量学方法建立了初榨橄榄油/混合橄榄油二元掺伪体系的定量预测模型.试验结果表明,2种统计模型定量预测性能良好,偏最小二乘模型的训练集交叉验证均方根误差RMSEcv和预测集均方根误差RMSEP均达到0.011,预测值与真实值相关性达到0.996 2;BP人工神经网络迭代次数为61步,训练集拟合残差为9.684×10-5,网络预测值和真实值相关系数为0.998 3,对于5％以上掺伪比例的油样BP神经网络能够精确地预测.     

气相色谱仪结合数据分析软件鉴别橄榄油掺杂

目的基于气相色谱仪和数据分析软件来鉴别橄榄油掺杂。方法取5种橄榄油分别与市售葵花籽油、大豆油、菜籽油、玉米油和花生油以不同的比例混合来模拟掺杂。运用气相色谱-氢火焰检测器检测其脂肪酸甲酯含量,结合数据分析软件(mass profiler professional,MPP)进行数据处理,以偏最小二乘判别分析法建立预测模型。结果 1%(体积比)掺杂样品的鉴别准确率在90%以上。结论通过此方法对各类掺杂橄榄油都能很好地鉴别是否掺杂。     

Potential use of extra virgin olive oil in bakery products rich in fats: a comparative study with refined oils

The lipid fraction of bakery products undergoes a significant degradation during baking, with an increase in undesirable oxidised substances, that can act as catalysts for further oxidative reactions during storage reducing the product shelf life. The use of extra virgin olive oil in bakery products rich in fat in place of refined oils was studied, assessing the evolution of the oxidative and hydrolytic degradation during storage. Two‐way analysis of variance, followed by Tukey's HSD test for multiple comparisons, covariance and principal component analyses were carried out to compare the effect of the type of oils. The data obtained showed that the evolution of the oxidation levels in the analysed samples during storage was related to the type of oil used in the production process. Particularly, the use of extra virgin olive oil led to significantly lower values of hydroperoxides, ultraviolet absorption constants, triacylglycerol oligopolymers and oxidised triacylglycerols.     

Use of lambda DNA as a marker to assess DNA stability in olive oil during storage

Filtered olive oil samples spiked with three different concentrations of λDNA were stored at 25 °C under a 12 h photoperiod for up to a year. These samples were used for DNA extraction and PCR amplification of λDNA amplicons of 107, 415 and 691 bp length. The amplification signal was gradually decreased with longer storage periods, while the strength of the signal was related to the initial concentration of spiking λDNA particularly during longer storage periods. The 107 bp amplicon was the only one successfully amplified from all the samples, regardless of both concentration of spiking λDNA and storage period. The amplification of 415 and 691 bp amplicons was not successful for samples stored longer than a threshold period of 20 and 10 days, respectively. These results suggest that detection of polymorphic markers requiring DNA templates shorter than 100 bp might have a wider range of applications in DNA fingerprinting of olive oil. In addition, the DNA extracts were tested for the presence of inhibitors in PCR amplification reactions of yeast DNA amplicons. The inhibitory effect of olive DNA extracts was partial and gradually increased with the storage period of the olive oil samples used for the DNA extraction.     

基于吸光度线性混合模型的橄榄油掺杂定量分析方法

提出了橄榄油掺杂的吸光度线性混合模型,利用朗伯-比尔吸收机理推导出掺杂比的计算公式,可以定量分析二组分橄榄油掺杂油的组分比例构成。通过误差分析理论分析了掺杂比的计算误差,确定了在橄榄油和掺入油的吸光度差值最大的波长区具有最小的检测误差。实验中利用构建的可见近红外光谱采集系统对橄榄油掺杂玉米油、花生油和大豆油的情况进行了验证,对于掺杂10%以上的掺杂混合油的掺杂比计算值和实际配比值的相关系数分别达到0.999 2、0.999 6和0.999 7,标准误差分别为0.008 2、0.005 9和0.005 1,相对误差可以控制在5%以内。实验结果表明根据吸光度线性混合模型计算橄榄油掺杂其他食用油的掺杂比例是准确可行的,可以用于橄榄油掺杂的组分定量检测。     

Identification of 3-MCPD esters to verify the adulteration of extra virgin olive oil

ABSTRACT

The adulteration of olive oil is an important issue around the world. This paper reports an indirect method by which to identify 3-monochloropropane-1,2-diol (3-MCPD) esters in olive oils. Following sample preparation, the samples were spiked with 1,2-bis-palmitoyl-3-chloropropanediol standard for analysis using gas chromatograph-tandem mass spectrometry. The total recovery ranged from 102.8% to 105.5%, the coefficient of variation ranged from 1.1% to 10.1%, and the limit of quantification was 0.125 mg/kg. The content of 3-MCPD esters in samples of refined olive oil (0.97–20.53 mg/kg) exceeded those of extra virgin olive oil (non-detected to 0.24 mg/kg). These results indicate that the oil refining process increased the content of 3-MCPD esters, which means that they could be used as a target compound for the differentiation of extra virgin olive oil from refined olive oil in order to prevent adulteration.     

Detection of olive oil adulteration with some plant oils by GLC analysis of sterols using polar column

A new method was developed to determine the presence of some refined vegetable oils in olive oil based on the sum of campesterol and stigmasterol percentages. Model systems of corn, soybean, sunflower and cotton seed oils in olive oil at levels of 5%, 10% and 20% were prepared. The unsaponifiables of these model systems were analysed by GLC using polar column with high thermal stability. An olive oil authenticity factor based on the summation of campesterol and stigmasterol percentages was established as an indicator of olive oil adulteration with vegetable oils. The results indicate the possibility to detect the presence as little as 5% of these plant oils in olive oil.     

Identification and quantification of the migration of chemicals from plastic baby bottles used as substitutes for polycarbonate

The results of a study on the analytical identification and quantification of migration of chemicals from plastics baby bottles found in the European Union market made of materials that are now present as substitutes for polycarbonate (PC) are reported. A total of 449 baby bottles with a focus on first age or sets of bottles were purchased from 26 European Union countries, Canada, Switzerland and the USA. From this collection, which contained several duplicates, a total of 277 baby bottles were analysed. The materials included different types of plastic such as PC, polyamide (PA), polyethersulphone (PES), polypropylene (PP), but also silicone, and from the United States a co-polyester marketed under the trade name Tritan?. The bottles were subjected to the conventional migration test for hot fill conditions, i.e. 2?h at 70°C. The simulant used was that specified in European Union legislation (2007/19/EC) for milk, i.e. 50% ethanol. In a first phase 1, migration was conducted since the scope of this investigation was a screening rather than a true compliance testing check. Second and third migrations were performed on selected articles when migrated substances exceeded limits specified in the legislation. In order to verify some materials, a portion of the bottle was cut to run an FT-IR fingerprint to confirm the nature of the polymer. The migration solutions in general showed a low release of substances. Results showed that bottles made of PP and silicones showed a greater number of substances in the migration solutions and in greater quantity. Chemicals from PP included alkanes, which could be found in >65% of the bottles at levels up to 3500?µg?kg^?1; and benzene derivatives in 17% of the baby bottles and found at levels up to 113?µg?kg^?1. Some substances were found on a regular basis such as plasticisers, esters and antioxidants (e.g. tris(2,4-di-tert-butylphenyl)phosphate, known as Irgafos 168. Some substances found were not included in the Community positive list, which means that those should not be found even in the first migration. Such substances included 2,6-di-isopropylnaphthalene (DIPN), found in 4% of the bottles at levels up to 25?µg?kg^?1, 2,4-di-tert-butyl phenol (in 90% of the bottles at levels up 400?µg?kg^?1). Moreover, bisphenol A (BPA) was detected and quantified in baby bottles made of PA, but limited to one brand and model specific (but labelled BPA free). Results for baby bottles made of silicone also indicated the presence of components, e.g. potentially coming from inks (benzophenone, diisopropyl naphtahalene – DIPN, which could come for example from the presence of instruction leaflets in the bottles). In the case of silicone, phthalates were also found in relevant concentrations, with levels for DiBP and DBP from the first migration test of 50–150?µg?kg^?1 and DEHP at levels 25–50?µg?kg^?1.     

反向传播神经网络算法结合拉曼荧光光谱法定量检测特级初榨橄榄油掺假

目的 建立基于反向传播神经网络算法结合拉曼荧光光谱技术定量检测低等级橄榄油掺假特级初榨橄榄油的分析方法。方法 制备11种不同掺伪浓度的特级初榨橄榄油混合油样各10份,在相同时间、空间及目标的前提下,使用同台光谱探测系统,采集样品的拉曼光谱和荧光光谱。经过卷积神经网络去除拉曼光谱的基线,实现拉曼光谱和荧光光谱的数据预处理。根据分子光谱与电子光谱的特征差异,人为干预并设定拉曼光谱的权重,建立低等级橄榄油掺假特级初榨橄榄油的反向传播神经网络回归模型。结果 综合评估了反向传播神经网络回归模型的评价参数,特级初榨橄榄油掺假的反向传播神经网络模型的测试集决定系数为0.9716,均方根误差为0.0569,模型预测效果较好。结论 本研究提出的反向传播神经网络算法结合拉曼光谱与荧光的探测方法,满足快速检测低等级橄榄油掺假特级初榨橄榄油的定量分析需求,为评价或跟踪特级初榨橄榄油的品质提供了一种无损伤、高效率、低成本的新检测思路。     

Tocopherol speciation as first screening for the assessment of extra virgin olive oil quality by reversed-phase high-performance liquid chromatography/fluorescence detector

A method based on reversed-phase high-performance liquid chromatography with fluorescence detector has been developed for the determination of tocopherols in vegetable oils. Oils were diluted in acetonitrile/tetrahydrofuran (THF) and injected directly onto HyPurity C₁₈ column. Methanol and THF (90:10) mixture was used as a mobile phase. Tocopherols were detected by fluorescence detector. The method had good limit of detection (LOD) (7 ng/g for α-tocopherol and 6 ng/g for β-, γ- and δ-tocopherols) and reproducibility (CV% < 2.8%).     

Determination of (E)‐5‐methylhept‐2‐en‐4‐one in deodorised hazelnut oil. Application to the detection of adulterated olive oils

The presence of (E)‐5‐methylhept‐2‐en‐4‐one (filbertone) in a hazelnut oil, deodorised in a laboratory system using nitrogen as stripping gas, is studied regarding its usefulness as a chiral marker for detecting adulterations of olive oil. The analytical method involves the use of both simultaneous distillation–solvent extraction as a sample concentration step and a chiral stationary phase in the subsequent gas chromatographic analysis. The procedure is simple, rapid, effective for detecting adulterations of olive oil with hazelnut oil and can reduce falsely negative results obtained if conventional parameters included in current regulations are exclusively considered when establishing purity in olive oils. © 2000 Society of Chemical Industry     

橄榄油中农药多残留前处理方法研究及其应用于气相色谱、气质联用测定效果评估

建立了串联双柱净化前处理方法用于橄榄油中313种农药多残留的测定。橄榄油样品采用正己烷溶解,正己烷-乙腈-盐水三相分配除去部分杂质,农药组分转移至乙腈中,经串联双柱净化后供气相色谱仪(GC)和气相色谱-质谱仪(GC-MS)分析。气相色谱法采用火焰光度检测器(FPD)和电子捕获检测器(ECD)测试,外标法定量,适用于有机磷、有机氯和拟除虫菊酯等部分农药的测定。气相色谱-质谱法采用选择离子监测方式(SIM),外标法定量,适用于本法中所有313项农药的测定。在优化后的条件下进行分析,气相色谱-质谱法的检出限(S/N≥3)为0.01～0.03 mg/kg,在加标水平为0.01、0.05、0.20 mg/kg时,平均回收率为57.5%～148.4%(百菌清为44.3%),其中回收率在70%～120%之间的占93.9%,相对标准偏差为2.1%～17.8%。方法准确、灵敏、快速,可满足橄榄油中多种农药残留的风险监控需求并可扩展到其他植物油检测。     

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.