Infrared spectroscopy for quantitative analysis and oil parameters of olive oil and virgin coconut oil: A review

Vegetable oils are major lipid sources with high nutritional and calorific values for human diet. Specifically, virgin coconut oil and extra virgin olive oil are the functional oils widely used in food and pharmaceutical products, either as vehicles or main components. The quality of edible oils is determined by its contents and parameters inherent in vegetable oils. Infrared spectroscopy is an ideal technique for quantitative analysis of vegetable oils as well as for determination of oils parameters as the changes in infrared spectra can be associated with the changes of oils parameters. Infrared spectra in complex samples are difficult to interpret, as a consequence, spectroscopist uses additional tools called with chemometrics to analyse edible oils qualitatively and quantitatively. This article reviews the use of infrared spectroscopy combined with chemometrics (multivariate analysis) for quantitative analysis and determination of oil parameters of virgin coconut oil and extra virgin olive oil. Although infrared spectra for edible oils are similar, they exhibit some differences which enable spectroscopist to differentiate due to the nature property of infrared spectroscopy spectra as fingerprint spectra which can be understood that there are no different edible oils having the same infrared spectroscopy spectra.     

鲜榨山茶油与特级初榨橄榄油营养价值的比较

以鲜榨山茶油和特级初榨橄榄油为研究对象,对其理化指标、脂肪酸组成和营养成分进行测定并比较。结果表明:鲜榨山茶油在理化指标上与特级初榨橄榄油相当,脂肪酸组成与特级初榨橄榄油相似,但油酸含量高于特级初榨橄榄油,棕榈酸和硬脂酸含量低于特级初榨橄榄油;在维生素E、角鲨烯、植物甾醇等天然生物活性物质方面媲美特级初榨橄榄油。     

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。     

Characterization of antioxidant olive oil biophenols by spectroscopic methods

BACKGROUND: Olive oil contains numerous phenolic components with well‐recognized health‐beneficial activity. The major phenolic compounds present in olives and virgin olive oil—hydroxytyrosol, oleuropein and the oleuropein aglycones 3,4‐DHPEA‐EA and 3,4‐DHPEA‐EDA—as well as some of their metabolites were studied in the present work, regarding their main structural preferences. Vibrational spectroscopy (Raman) coupled to theoretical methods were used, aiming at fully characterizing the systems and therefore enabling their quick and reliable identification in food samples. RESULTS: The Raman data, assisted by the theoretical simulations, allowed us to obtain the main geometrical and spectroscopic features of the olive oil constituents under study, which determine their known antioxidant and chemoprotective properties. In fact, it was verified that the spectra comprise distinctive bands for each compound, allowing their ready detection and differentiation. CONCLUSION: This is the first reported study on the structural behaviour of olive oil phenolic compounds, and it established Raman spectroscopy as a rapid, non‐destructive and reliable analytical technique for identifying these bioactive components in dietary extracts. It can surpass other analytical methods currently used, once it allows the concomitant identification of several olive oil components in a particular sample. Copyright © 2010 Society of Chemical Industry     

Has the use of talc an effect on yield and extra virgin olive oil quality?

The maximization of both extraction yield and extra virgin olive oil quality during olive processing are the main objectives of the olive oil industry. As regards extraction yield, it can be improved by both acting on time/temperature of malaxation and using physical coadjuvants. It is well known that, generally, increasing temperature of malaxation gives an increase in oil extraction yield due to a reduction in oily phase viscosity; however, high malaxation temperature can compromise the nutritional and health values of extra virgin olive oil, leading to undesirable effects such as accelerated oxidative process and loss of volatile compounds responsible for oil flavor and fragrance. The addition of physical coadjuvants in olive oil processing during the malaxation phase, not excluded by EC regulations owing to its exclusively physical action, is well known to promote the breakdown of oil/water emulsions and consequently make oil extraction easier, thus increasing the yield. Among physical coadjuvants, micronized natural talc is used for olive oil processing above all for Spanish and Italian olive cultivars. The quality of extra virgin olive oil depends on numerous variables such as olive cultivar, ripeness degree and quality, machines utilized for processing, oil storage conditions, etc. However, the coadjuvants utilized in olive processing can also influence virgin olive oil characteristics. The literature highlights an increase in oil yield by micronized natural talc addition during olive processing, whereas no clear trend was observed as regards the chemical, nutritional and sensory characteristics of extra virgin olive oil. Although an increase in oil stability was reported, no effect of talc was found on the evolution of virgin olive oil quality indices during storage. © 2016 Society of Chemical Industry     

Edible and non-edible olive oils discrimination by the application of a sensory olfactory system based on tin dioxide sensors

An array of semiconductor sensors has been developed to discriminate virgin olive oil samples based on their organoleptic characteristics. The multisensor, developed at laboratory, is composed by 14 sensing elements of tin dioxide thin layers (doped with Cr and In, and undoped) deposited by the reactive sputtering technique. The sensors are stable and show good repeatability. Off-flavors and extra-virgin olive oil samples, taken at the outlet of the vertical centrifuge of a small experimental olive oil mill and sensory evaluated, have been used. A good discrimination of edible (extra-virgin and virgin) from non-edible (lampante) olive oils has been obtained through the statistical method of principal component analysis (PCA).     

Chemical stability of extra-virgin olive oil added with oregano essential oil

Extra virgin olive oil is highly consumed and well known for its nutritional and health benefits. However, it is fatty food highly susceptible to lipid oxidation. The objective of this study was to evaluate the preserving effect of oregano (Origanum vulgare L. spp vulgare called "oregano compacto") essential oil on physical and chemical properties in extra virgin olive oil during storage. Oregano essential oil composition was analyzed by GC-MS. This essential oil was added into extra virgin olive oil at 0.05%. The samples were stored in 3 different conditions: darkness, light exposure, and temperature (60 °C). Chemical indicators of lipid oxidation (peroxide value, p-anisidine value, conjugated dienes, free fatty acidity, and carotenoid and chlorophyll contents) were measured. High content in carvomenthol (22.52%), terpinolene (19.77%), thymol (13.51%), and γ-terpinene (10.30%) were detected in oregano essential oil. Olive oil samples without oregano essential oil stored at 60 °C and exposure at artificial light had the highest peroxide values during storage. Higher p-anisidine and K232 values after day 7 of storage were detected in temperature, darkness, and light exposure treatments. Light treatment was the main factor that degraded chlorophyll causing loss of color. The highest chlorophyll content (3.87 mg/kg) was observed in olive oil with essential oil at the end of storage. In general, olive oil samples added with oregano essential oil had lower peroxide, conjugated dienes, and p-anisidine values and higher chlorophyll and carotenoid contents during storage. Oregano essential oil retards lipid oxidation process in olive oil prolonging its shelf life. PRACTICAL APPLICATION: Oregano essential oil was and is used with the purpose of flavoring and aromatizing food. This essential oil due to its composition has shown antioxidant activity. Synthetic antioxidants such as butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA) are thought to be promoters of carcinogenesis. Extra virgin olive oil is widely consumed because of its nutritional benefits and sensory properties which are very important to be preserved in the product. In this study, the oregano essential oil showed remarkable antioxidant activity in olive oil. Therefore, this essential oil could be considered for the industry as natural antioxidant not only to be used in olive oil but also in other fatty food products to substitute synthetic ones.     

基于光谱法的特级初榨橄榄油快速鉴伪技术

本文研究了特级初榨橄榄油中掺入不同比例橄榄果榨油(精炼橄榄油)、菜籽油、玉米油和大豆油的光谱特征,采用荧光光谱和紫外光谱,对掺假样品及纯油样品进行了快速检测。结果表明,特级初榨橄榄油的光谱特征与其他植物油之间差异较大,且掺假体积与吸光度之间存在良好的线性关系(R²>0.89),实现了特级初榨橄榄油的定性鉴别与定量检测,建立了特级初榨橄榄油质量控制体系及其掺假检测分析技术,最低检出限为1%,线性范围为5%～100%(v/v)。系统聚类分析将所有特级初榨橄榄油准确地分为一个亚类,也佐证了此方法的稳定性与可靠性。这种简单快捷的检测技术,有助于特级初榨橄榄油实时、在线橄榄油检测分析技术的研发,为我国橄榄油品质鉴定及产业发展提供有利的技术保障。     

Role of polyphenol oxidase and peroxidase in shaping the phenolic profile of virgin olive oil

The main objective of this study was to assess the ability of polyphenol oxidase (PPO) and peroxidase (POX) enzymatic activities present in olive fruit tissues to oxidize main phenolic compounds related to the process to obtain virgin olive oil (VOO) in order to ascertain their involvement in shaping the phenolic profile of this product. In the two olive cultivars under study, Arbequina and Picual, olive PPO activity was found to be largely present in the fruit mesocarp whereas most olive POX activity is in the seed. Moreover, both enzymatic activities display relatively constant values after the onset of fruit ripening when the fruit is harvested for VOO production. Results showed that both PPO and POX activities present in olive fruit at ripening stages are able to oxidize main phenolic glycosides present in the fruit as well as those phenolic compounds arising during the industrial process to obtain the oil, especially secoiridoid compounds derived from oleuropein that mainly determine VOO nutritional and sensorial properties. Experimental data suggest a key role for endogenous olive PPO and POX enzymatic activities in determining the phenolic profile of VOO.     

Quantification of soybean oil adulteration in extra virgin olive oil using portable raman spectroscopy

Extra virgin olive oil is produced through either a cold press procedure or a centrifugation with no thermal and chemical treatments and it is considered as the best quality oil under the category of olive oils. The superior properties of olive oil due to its rich in phenolic and antioxidant content and its contribution to prevent several health problems has increased the demand for olive oil over the years. Consequently, it is nowadays sold at remarkably higher price than regular vegetable oils in the market. Unfortunately, extra virgin olive oil (EVOO) has been adulterated with other cheap oils due to potential high commercial profit. Even though, there are methods available to detect the adulteration in EVOO (such as chromatographic methods and PCR), alternative simpler and faster methods are being studied. In this study, performance of portable Raman spectroscopy to quantify soybean oil (SO) adulteration [up to 25?% (w/w)] in EVOO has been evaluated. Partial Least Square Regression (PLSR) calibration models were developed and both internally (using cross-validation, leave-one-out approach) and externally (using an independent sample set) validated. The model gave standard error of prediction (SEP) of 1.34?% (w/w) SO in EVOO and correlation coefficient of prediction (rPred) of 0.99. Additionally, the residual predictive deviation (RPD) value calculated for the model was found to be 5.71, indicating that the model was considered as “good” and could be used for routine analysis and quality control applications.     

Implementation of physicochemical and sensory analysis in conjunction with multivariate analysis towards assessing olive oil authentication/adulteration

The authenticity of products labeled as olive oils, and in particular as virgin olive oils, stands for a very important issue both in terms of its health and commercial aspects. In view of the continuously increasing interest in virgin olive oil therapeutic properties, the traditional methods of characterization and physical and sensory analysis were further enriched with more advanced and sophisticated methods such as HPLC-MS, HPLC-GC/C/IRMS, RPLC-GC, DEPT, and CSIA among others. The results of both traditional and "novel" methods were treated both by means of classical multivariate analysis (cluster, principal component, correspondence, canonical, and discriminant) and artificial intelligence methods showing that nowadays the adulteration of virgin olive oil with seed oil is detectable at very low percentages, sometimes even at less than 1%. Furthermore, the detection of geographical origin of olive oil is equally feasible and much more accurate in countries like Italy and Spain where databases of physical/chemical properties exist. However, this geographical origin classification can also be accomplished in the absence of such databases provided that an adequate number of oil samples are used and the parameters studied have "discriminating power."     

基于PCA-SVM结合共聚焦拉曼光谱的特级 初榨橄榄油掺伪压榨菜籽油定量分析

为了促进国内橄榄油市场的健康发展，对掺伪同样存在天然类胡萝卜素的低温压榨菜籽油的特级初榨橄榄油进行了定量鉴别研究。采用共聚焦拉曼光谱技术对不同掺伪浓度油样进行测试，基于密度泛函理论对油样的拉曼光谱峰的归属进行了理论分析，并对拉曼光谱数据进行主成分分析（PCA），然后利用支持向量机（SVM）构建PCA-SVM模型。另外，对PCA-SVM模型的检出限进行了研究。结果表明：特级初榨橄榄油与低温压榨菜籽油的拉曼光谱存在一定差异，最明显的光谱差异主要集中在谱峰1 008、1 161、1 528 cm-1和谱段2 800～3 000 cm-1内，与密度泛函理论对不同油样拉曼光谱峰的分析一致；不考虑类胡萝卜素特征信号建立的PCA-SVM模型决定系数大于0.989，均方根误差小于2.990%，检出限为2%（低温压榨菜籽油体积分数）;在特级初榨橄榄油掺伪定量分析中，考虑类胡萝卜素的特征信号有助于提高模型预测精度，但仅限于掺伪低价植物油中无类胡萝卜素存在的情况;PCA-SVM模型在不考虑类胡萝卜素特征信号的情况下依然具有良好的定量预测效果。综上，所建立的PCA-SVM模型可以用于掺伪2%以上低温压榨菜籽油的特级初榨橄榄油的定量鉴别。     

基于紫外可见光谱技术和色素组成区分橄榄油与其他食用油

目的 通过紫外可见光谱技术和色素组成,探究区分橄榄油与其他食用油的方法。方法 选择市售橄榄油(特级初榨橄榄油、混合橄榄油)和其他食用油(菜籽油、玉米油、葵花籽油、大豆油、花生油、调和油)作为研究对象,分别在220~800 nm的波长范围内进行全光谱扫描以及在波长为450 nm和670 nm处进行光度测量;通过比较不同食用油的紫外可见吸收光谱并结合主成分分析(principal component analysis, PCA)和偏最小二乘法判别(partial least squares discriminant analysis, PLS-DA)对不同橄榄油和其他食用油进行比较区分。结果 通过观察比较各食用油紫外可见吸收光谱的最大吸收波长所在位置,可以对不同食用油进行初步区分。并且PCA和PLS-DA结果显示,以波长450 nm和670 nm处的吸光度A450和A670以及A450/A670为变量,可用于区分不同橄榄油和其他食用油。结论 基于紫外可见光谱技术对不同食用油中色素的检测结果可以对食用油进行分类,并且A450、A670和A450/A670可以作为区分橄榄油与其他食用油的标记。     

Aroma and physical characteristics of cakes prepared by replacing margarine with extra virgin olive oil

The effect of margarine substitution by extra virgin olive oil on the quality of Madeira cakes was studied. Three cakes containing either extra virgin olive oil or extra virgin olive oil/margarine mixture or margarine were prepared. The use of extra virgin olive oil increased batter density and cake volume while decreased the weight loss (%) during baking. Texture profile analysis also showed that the replacement of margarine by extra virgin olive oil affected significantly hardness and cohesiveness of the cakes. Headspace solid phase microextraction was applied in order to analyze the aroma of the three cakes. The addition of extra virgin olive oil produced a wide range of volatile compounds, which were analyzed by gas chromatography/mass spectrometry and were originated either from extra virgin olive oil or were produced during the baking process. Hedonic sensory tests were also conducted revealing that the cake prepared with extra virgin olive oil/margarine mixture was highly appreciated by the consumers as it got scores similar to control.     

Oxidation Processes in Sicilian Olive Oils Investigated by a Combination of Optical and EPR Spectroscopy

Abstract: Extra virgin olive oil (EVOO) is recognized as one of the healthiest foods for its high content of antioxidants, which forestall and slow down radical formation. Free radical‐initiated oxidation is considered one of the main causes of rancidity in fats and oils. As a consequence, reliable protocols for the investigation of oil oxidation based on selective, noninvasive, and fast methods are highly desirable. Here we report an experimental approach based on UV‐Vis absorbance, steady‐state fluorescence, and electron paramagnetic resonance (EPR) spectroscopy for studying oxidation processes induced by temperature for a period up to 35 d on Sicilian EVOO samples. We followed the decrease in β‐carotene content during incubation time and observed changes in polyphenols and tocopherols during the oxidation processes, focusing on the time scale of those changes. Using EPR spectroscopy, the free radical formation in different oil samples is reported, providing a fingerprint for both the antioxidant content and temporal features of the oxidation process at its early stage. Practical Application: We monitor β‐carotene and chlorophyll in an auto‐oxidation process. A protocol based on spectroscopic measurements is presented and can be used for the quality control process of commercial olive oil.     

A comparison between olive oil and extra-virgin olive oil used as covering liquids in canned dried tomatoes: hydrolytic and oxidative degradation during storage

The hydrolytic and oxidative degradation of olive oil and extra‐virgin olive oil, used as covering liquids in canned dried tomatoes, was studied during storage by means of conventional (acidity, peroxide value, p‐anisidine value) and non conventional (polar compounds) analyses. The effects of the addition of spices were also considered. The hydrolysis and oxidation of olive oil increased faster and was higher than that of extra‐virgin olive oil in terms of absolute values but some other indices, such as percentage of oligopolymers and percentage of oxidized triglycerides, increased faster in extra‐virgin olive oil than in olive oil. The antioxidant effect given by a higher concentration of polyphenols in the extra‐virgin olive oil was shown by a reduced amount of secondary oxidation. However, olive oil and extra‐virgin olive oils showed similar behaviour in terms of peroxide formation.     

The utilisation solutions of olive mill by-products in the terms of sustainable olive oil production: a review

Despite the high economic and nutritional value as major positive aspects, olive oil production has an unfavourable side, which is the negative environmental impact caused by the generation of significant amounts of liquid and solid wastes. Therefore, the implementation of sustainable technologies to add value to the olive oil production process is a matter of great interest. This study aimed to review novel solutions dealing with the utilisation of olive oil production by-products while taking into account sustainable waste management options. The most promising technologies for the production of high-added value products from olive oil production by-products have been described with a special attention to the sustainable nonthermal technologies for the extraction of bioactive phenolic compounds, and the key findings of such investigations were reviewed. All described technologies are environmentally friendly and show great potential. Nevertheless, further researches are required to optimise and increase their applicability.     

橄榄油的质量分级检测技术研究进展

橄榄油是地中海饮食的特点之一,具有极高的营养价值。按照加工工艺橄榄油分为初榨橄榄油和精炼橄榄油。初榨橄榄油的品质较好营养价值较高,因此价格较为昂贵。精炼橄榄油由于品质较差,价格较低。橄榄油的质量分级与经济价值直接相关,已成为目前橄榄油研究的热点。掺伪、造假者的主要目标是特级初榨橄榄油,所以该产品标准的检测十分重要。但由于掺入的食用油在脂肪酸组成等方面与橄榄油非常接近,因此识别起来十分困难。为了规范橄榄油市场,维护消费者的合法权益,研究者采用了多种检测方法来对初榨橄榄油和精炼橄榄油进行鉴别。本研究从标志性成分、模式识别和组学技术3个角度对橄榄油的质量分级检测技术的最新进展情况进行了综述,并对橄榄油的质量分级检测技术的研究方向进行了展望。     

28份国产特级初榨橄榄油中多酚含量及其变化规律北大核心CSCD

为了对我国油橄榄产业提供基础数据支持,采用国际油橄榄理事会推荐的HPLC法检测特级初榨橄榄油中的多酚含量,分析了我国不同产地的28份市售食用特级初榨橄榄油样品的多酚含量,并对不同生产年度和不同产地单果级特级初榨橄榄油中多酚含量变化规律进行了分析。结果表明:市售国产特级初榨橄榄油中均含有较为丰富的多酚类化合物,多酚含量范围为(63.885±2.345)mg/kg~(307.325±6.865)mg/kg;特级初榨橄榄油中多酚含量受贮存时间的影响较大,同时不同产地中适合生产高多酚含量特级初榨橄榄油的品种具有差异。不同特级初榨橄榄油样品之间多酚含量波动较大,需要通过多种方法来防止油脂中多酚类化合物的降解,以保证油品的质量,并因地制宜对油橄榄品种进行优化筛选。     

Sensory attribute preservation in extra virgin olive oil with addition of oregano essential oil as natural antioxidant

Four commercial varieties of oregano are farmed in Argentina: "Compacto,"Cordobes,"Criollo," y "Mendocino." Oregano essential oil is known for antioxidant properties. The objective of this study was to evaluate changes in the intensities of positive and negative attributes in extra virgin olive oil with addition of essential oil obtained from the 4 Argentinean oregano types. Oregano essential oil was added into olive oil at 0.05% w/w. The samples were stored in darkness and light exposure during 126 d at room temperature. The intensity ratings of fruity, pungency, bitterness, oregano flavor, and rancid flavor were evaluated every 21 d by a trained sensory panel. In general, samples with addition of oregano essential oil in olive oil exhibited higher and lower intensity ratings of positive and negative attributes, respectively, during storage compared with the control samples. The first 2 principal components explained 72.3% of the variability in the olive oil samples. In general, positive attributes of olive oil were highly associated with the addition of oregano essential oil in darkness, whereas rancid flavor was negatively associated with them. Olive oil with oregano "Cordobes" essential oil was oppositely associated with light exposure treatments and negative attribute (rancid flavor) suggesting better performance as natural antioxidant of this essential oil in olive oil. The result of this study showed that the presence of oregano essential oil, specially "Cordobes" type, preserve sensory quality of extra virgin olive oil prolonging the shelf life of this product. Practical Application: Extra virgin olive oil is highly appreciated for its health benefits, taste, and aroma. These properties are an important aspect in this product quality and need to be preserved. The addition of natural additives instead of synthetic ones covers the present trend in food technology. This research showed that the addition of oregano essential oil preserved the intensity ratings of positive attributes in extra virgin olive oil during storage. The essential oil of the oregano variety called "Cordobes" exhibited better protecting effect on sensory properties of olive oil than the other oregano varieties. The addition of oregano essential oil should be considered for the food industry as a natural source of antioxidant additives for preserving sensory properties in extra virgin olive oil and other similar food products.