Transfer of phenolic compounds during olive oil extraction in relation to ripening stage of the fruit

The transfer of phenolic compounds of Olea europaea L. cv. Arbequina variety during olive oil extraction in relation to ripening stage was investigated. The parameters of oil extraction by the Abencor system are shown together with mass balances of the products and by products from the olive oil extraction in relation to olive paste. The phenolic compounds in olive paste, pomace, oil and wastewater were identified and measured by HPLC. Throughout the study, the concentrations of simple phenols, secoiridoids and flavonoids were higher in the olive paste and pomace phases than in oil and wastewater phases. High concentrations of 4‐(acetoxyethyl)‐1,2‐dihydroxybenzene (3,4‐DHPEA‐AC) and secoiridoid derivatives such as the dialdehydic form of elenolic acid linked to 3,4‐DHPEA (hydroxytyrosol) or p‐HPEA (tyrosol) (3,4‐DHPEA–EDA, p‐HPEA–EDA, where EDA is elenolic acid dialdehyde) and an isomer of oleuropein aglycone (3,4‐DHPEA–EA, where EA is elenolic acid aldehyde) were found in olive oil, together with lignan compounds. It was observed that 3,4‐DHPEA–EDA was the most abundant polyphenol present in the wastewater phase. This indicates that biotransformation occurred during olive extraction, especially in the crushing and malaxation operations, and reflects the possible chemical changes that lead to the formation of new compounds. Moreover, the distribution of compounds showed their affinities toward different phases. Copyright © 2005 Society of Chemical Industry     

Antioxidant activity of virgin olive oil phenolic compounds in a micellar system†

The antioxidant activity of two virgin olive oils, obtained from the same olive (Olea europaea sativa) batch but processed with different hammer crushing conditions, was evaluated by measuring their protective action towards linoleic acid peroxidation in a micellar system. The antioxidant efficiency (AE) of the oil phenolic fraction was higher when the olives were processed with a higher hammer crusher rotation rate. HPLC analysis demonstrated that one of the main derivatives of oleuropein, indicated as 3,4-DHPEA-EDA (the dialdehydic form of elenolic acid linked with 3,4-dihydroxyphenylethanol), is present only in the oil with higher AE. 3,4-DHPEA-EDA showed the greatest antioxidant ability among virgin olive oil phenols. Its greater efficiency in the micellar system in comparison with 3,4-dihydroxyphenylethanol (3,4-DHPEA) is related to its greater lipophilicity. It is suggested that the behaviour in the water–micellar environment is representative of that in a real system such as tomato-based sauce with added virgin olive oil. © 1999 Society of Chemical Industry     

酶处理对初榨橄榄油品质及抗氧化活性的影响

将纤维素酶、果胶酶应用于橄榄油提取工艺,旨在生产具有较高总酚含量及较强抗氧化活性的高质量初榨橄榄油。随着果胶酶和纤维素酶添加量的提高,橄榄油的过氧化值及K_(232)均出现下降的趋势,油酸比例有一定程度提高,并在添加0.2%纤维素酶时油酸比例达到最高(65.85%)。结合主成分分析,确定了在油橄榄融合过程中添加0.5%纤维素酶得到的初榨橄榄油总酚含量和抗氧化活性最高。这是由于果胶酶和纤维素酶能有效降解橄榄细胞壁,减少亲水酚类物质与细胞壁多糖的络合,有助于橄榄果皮中的游离酚的释放,从而提高橄榄油中总酚含量及抗氧化活性。     

Characterisation of phenolic extracts from olive pulp and olive pomace by electrospray mass spectrometry

Methanol extracts of olive pomace (two‐phase olive oil extraction) and olive pulp were analysed by reverse phase HPLC and the eluted fractions were characterised by electrospray ionisation mass spectrometry. This technique allowed the identification of some common phenolic compounds, namely, verbascoside, rutin, caffeoyl‐quinic acid, luteolin‐4‐glucoside and 11‐methyl‐oleoside. Hydroxytyrosol‐1′‐β‐glucoside, luteolin‐7‐rutinoside and oleoside were also detected. Moreover, this technique enabled the identification, for the first time in Olea europaea tissues, of two oleoside derivatives, 6′‐β‐glucopyranosyl‐oleoside and 6′‐β‐rhamnopyranosyl‐oleoside, and of 10‐hydroxy‐oleuropein. Also, an oleuropein glucoside that had previously been identified in olive leaves was now detected in olive fruit, both in olive pulp and olive pomace. With the exception of oleoside and oleuropein, the majority of phenolic compounds were found to occur in equivalent amounts in olive pulp and olive pomace. Oleoside was the main phenolic compound in olive pulp (31.6 mg g^?1) but was reduced to 3.6 mg g^?1 in olive pomace, and oleuropein (2.7 mg g^?1 in the pulp) almost disappeared (<0.1 mg g^?1 in the pomace). Both these phenolic compounds were degraded during the olive oil extraction process. Copyright © 2004 Society of Chemical Industry     

Microwave heating of different commercial categories of olive oil: Part I. Effect on chemical oxidative stability indices and phenolic compounds

The effect of microwave heating of extra virgin olive oil (EVOo), olive oil (Oo) and pomace olive oil (Po) in domestic appliances, was investigated in terms of chemical oxidative indices (peroxide, p-anisidine and Totox values), free acidity, water content, total phenol content and different classes of phenolic compounds.     

The role of olive β-glucosidase in shaping the phenolic profile of virgin olive oil

The main objective of this work was to investigate the biochemical factors directly affecting the phenolic profile of virgin olive oil (VOO) such as the content of phenolic glycosides and the β-glucosidase activity present in the olive fruit. The phenolic compositions of VOO from two olive cultivars, Arbequina and Picual, were studied throughout the ripening phase. Picual oils displayed significantly higher phenolic content than Arbequina oils at all ripening stages; however, the total phenolic content of Arbequina fruits was consistently higher than that of Picual fruits. The most abundant phenolic glucosides found in olive fruits were oleuropein, present in both cultivars, and demethyloleuropein, only detected in Arbequina fruits. Nevertheless, the content of phenolic glycosides can hardly be regarded as a limiting factor given that the total secoiridoid content in VOOs represents an average of 1–4% of the secoiridoid glycosides present in the fruits. Although the level of β-glucosidase activity does not seem to be a limiting factor in these two cultivars, experimental data on the selectivity of the enzyme towards olive phenolic glucosides and its product specificity suggest that olive β-glucosidase plays a critical role in shaping the phenolic profile of VOO. A hypothesis on the biochemical formation of the dialdehydic form of decarboxymethyloleuropein (3,4-DHPEA-EDA) from oleuropein is proposed.     

Phenolic compounds in olive oil and olive pomace from Cilento (Campania,Italy) and their antioxidant activity

Virgin olive oil (VOO) has nutritional and sensory characteristics that make it unique and a basic component of the Mediterranean diet. Its importance is mainly attributed to its richness in polyphenols, which act as natural antioxidants and may contribute to the prevention of several human diseases. In this paper we report the determination and quantification of oleocanthal, one of the main substances responsible for the bitter taste of olive oil, together with a quali-quantitative analysis by HPLC analytical methods of phenolics from Cilento VOO and olive oil pomace. The total phenolic content was also determined and the in vitro antioxidant and free-radical scavenging activities by DPPH test was evaluated. A superoxide anion enzymatic assay was also carried out and the results were confirmed by the inhibition of xanthine oxidase activity assay. The possible protective role played by VOO secoiridoids on injurious effects of reactive oxygen metabolites on the intestinal epithelium, using Caco-2 human cell line, was investigated.     

Acrylamide formation in a cookie system as influenced by the oil phenol profile and degree of oxidation

The purpose of this study was to investigate the effect of the olive oil phenolic compounds as well as of thermoxidised oil on the formation of acrylamide in a cookies system. Three virgin olive oils having different phenolic profile and a thermoxidised sunflower oil were selected. Cookies were baked at 190 °C for different times (8–16 min) following a basic recipe where type of oil was the variable. Additionally to acrylamide (AA), other parameters such as colour, moisture, antioxidant activity (AOA), and hydroxymethylfurfural (HMF) were measured. Results showed that concentration and composition of phenolic moiety of virgin olive oil significantly affect the acrylamide formation, particularly at prolonged baking time. Virgin olive oil with a higher dihydroxy/monohydroxy ratio was more efficient in the AA mitigation and AA was reduced up to 20%. Colour and AOA were not significantly different among the three types of oils. However, AA is dramatically increased when thermoxidised oil is used with a parallel increase of browning and HMF. It was concluded that lipid oxidation products should be considered as an important factor in acrylamide formation during baking of fat-rich products.     

Functional milk beverage fortified with phenolic compounds extracted from olive vegetation water, and fermented with functional lactic acid bacteria

Functional milk beverages (FMB100 and FMB200) fortified with phenolic compounds (100 and 200 mg/l) extracted from olive vegetable water, and fermented with γ-amino butyric acid (GABA)-producing (Lactobacillus plantarum C48) and autochthonous human gastro-intestinal (Lactobacillus paracasei 15N) lactic acid bacteria were manufactured. A milk beverage (MB), without addition of phenolic compounds, was used as the control. Except for a longer latency phase of FMB200, the three beverages showed an almost similar kinetic of acidification, consumption of lactose and synthesis of lactic acid. Apart from the beverage, Lb. plantarum C48 showed a decrease of ca. Log 2.52-2.24 cfu/ml during storage. The cell density of functional Lb. paracasei 15N remained always above the value of Log 8.0 cfu/ml. During fermentation, the total concentration of free amino acids markedly increased without significant (P > 0.05) differences between beverages. The concentration of GABA increased during fermentation and further storage (63.0 ± 0.6-67.0 ± 2.1 mg/l) without significant (P > 0.05) differences between beverages. After fermentation, FMB100 and FMB200 showed the same phenolic composition of the phenol extract from olive vegetable water but a different ratio between 3,4-DHPEA and 3,4-DHPEA-EDA. During storage, the concentrations of 3,4-DHPEA-EDA, p-HPEA and verbascoside of both FMB100 and FMB200 decreased. Only the concentration of 3,4-DHPEA increased. As shown by SPME-GC-MS analysis, diactetyl, acetoin and, especially, acetaldehyde were the main volatile compounds found. The concentration of phenolic compounds does not interfere with the volatile composition. Sensory analyses based on triangle and paired comparison tests showed that phenolic compounds at the concentrations of 100 or 200 mg/l were suitable for addition to functional milk beverages.     

Contribution of olive seed to the phenolic profile and related quality parameters of virgin olive oil

BACKGROUND: Conflicting results have been reported about the effect of fruit de‐stoning on the virgin olive oil (VOO) phenolic profile. The aim of the present study was to determine whether olive seed plays any role in the synthesis of this oil phenolic fraction. RESULTS: Increases of around 25% of total phenolic compounds were observed in oils obtained from de‐stoned olive fruits in three main Spanish cultivars. To investigate the involvement of olive seed in determining the phenolic profile of VOO, whole intact olive fruits were added with up to 400% olive stones. Excellent regression coefficients were found in general for the decrease of total phenolic compounds and, particularly, of o‐diphenolics in the resulting oils. On the other hand, it was found that olive seed contains a high level of peroxidase (POX) activity (72.4 U g^?1 FW), accounting for more than 98% of total POX activity in the whole fruit. This activity is able to modify VOO phenolics in vitro, similar to the effect of adding stones during VOO extraction. CONCLUSION: Olive seed plays an important role in determining VOO phenolic profile during the process to obtain an oil that seems to be associated with a high level of POX activity. Copyright © 2007 Society of Chemical Industry     

Effect of oxygen reduction during malaxation on the quality of extra virgin olive oil (Cv. Carboncella) extracted through “two-phase” and “three-phase” centrifugal decanters

Quality and composition of virgin olive oil (VOO) are strictly dependent on complex processes that take place during the olive fruit crushing and malaxation of the olive paste. In this work, modulation of O₂ levels within malaxation chambers (R1: unmodified atmosphere; R2: oxygen: 12.73–4.64 kPa from the beginning to the end of malaxation; R3: 10.46–2.27 kPa; R4: 9.87–0.69 kPa) in two continuous “two-phase” and “three-phase” oil extraction plants was performed. Combined effects on the biosynthesis of nutritionally bioactive molecules and aroma volatiles and on the resulting sensory properties of the produced oils were investigated. Results showed that the type of oil extraction plant markedly affected the level of the phenolic compounds in the oil (and the related sensory attributes of bitter, pungency, astringency and bitter and pungency persistence). Reduction of O₂ concentration in the malaxing chamber, while having a minor impact on the presence of phenolic compounds, significantly affected the formation of all the examined volatiles. Particularly, lowered levels of oxygen hindered the formation of lipoxygenase derived volatiles weakening odours and flavours of artichoke, fresh fruity, and fresh cut grass.     

Occurrence of C15-C45 mineral paraffins in olives and olive oils.

Different classes of olive oils and other olive samples (olives, olive paste and olive pomace) collected during their production were analysed for mineral paraffins in the range of C(15)-C(45). None of the 22 extra virgin olive oils contained mineral paraffins above the detection limit of 1 mg kg(-1). Also, lampante virgin olive oil from the olive mill showed no detectable amounts, but olive oil from the market contained 6-30 mg kg(-1). This contamination cannot be attributed to the refining step, which, on the contrary, partially removes the more volatile hydrocarbons, but could result from transport. Olive-pomace oils obtained by second centrifugation contained 16-145 mg kg(-1) mineral paraffins, presumably because of contamination during storage of the pomace. All olive-pomace oils from solvent extraction contained more than 100 mg kg(-1) mineral paraffins, also mainly from storage. Deposition of particulate matter from the air, vehicle exhaust emissions and direct contamination from the bulldozers used to move the pomace were identified as potential sources.     

Evolution of major and minor components and oxidation indices of virgin olive oil during 21 months storage at room temperature

This article reports the evolution of major and minor components and oxidation indices of seven samples of virgin olive oil (VOO) which differ in their initial contents of natural antioxidants, during 21 months of storage at room temperature and in darkness. As expected, statistically significant differences in the antioxidant contents were observed, with initial concentrations ranging from 0.33 to 0.55 mmol/kg for α-tocopherol and from 1.08 to 3.88 mmol/kg for total phenols. The quality indices PV, K₂₃₂ and K₂₇₀ increased linearly during the storage time studied (21 months), which should make it possible to predict the shelf-life of a VOO sample by extrapolation from the results obtained during a relatively short period of storage (i.e. several weeks). K₂₃₂ was the first parameter that exceeded the established upper limit for extra VOO and therefore seems to be the most relevant index for analysis and monitoring to determine the commercial category of the olive oil. The reduction of total phenolic compounds ranged from 43% to 73%, and it was remarkable that the decrease was higher in samples whose initial phenol contents were greater. Hydroxytyrosol increased linearly in most samples, whereas its complex forms decreased considerably, with the exception of two in which the hydroxytyrosol content decreased continuously or diminished after an initial increase. This fact was probably due to the low initial concentration of hydroxytyrosol secoiridoid forms: i.e. 0.32 mmol/kg for the sum of 3,4-DHPEA-EDA and 3,4-DHPEA-EA in one of these samples as compared to between 0.65 and 2.06 mmol/kg in the others. Finally, there was a slight and apparently linear fall in the α-tocopherol content of all samples, with a reduction ranging from 0.054 mmol/kg (12%) to 0.127 mmol/kg (23%), although there may be a short lag phase at the beginning of the assay.     

Distribution of olive oil phenolic compounds in rat tissues after administration of a phenolic extract from olive cake

Scope The distribution and accumulation of olive oil phenolic compounds in the body are topics lacked of information. The aim of this study was to evaluate the bioavailability, metabolism and distribution of phenolic compounds from olive cake. Methods and results The metabolism and distribution of phenolic compounds were examined by UPLC‐MS/MS after an acute intake of a phenolic extract from olive cake, analyzing plasma and tissues (heart, brain, liver, kidney, spleen, testicle and thymus) 1, 2 and 4 h after ingestion using Wistar rats as the in vivo model. The results showed a wide distribution of phenolic compounds and their metabolites in the tissues, with a main detoxification route through the kidneys. Highlighting the quantification of the free forms of some phenolic compounds, such as oleuropein derivative in plasma (Cmax 4 h: 24 nmol/L) and brain (Cmax 2 h: 2.8 nmol/g), luteolin in kidney (Cmax 1 h: 0.04 nmol/g), testicle (Cmax 2 h: 0.07 nmol/g) and heart (Cmax 1 h: 0.47 nmol/g); and hydroxytyrosol in plasma (Cmax 2 h: 5.2 nmol/L), kidney (Cmax 4 h: 3.8 nmol/g) and testicle (Cmax 2 h: 2.7 nmol/g). Conclusion After a single ingestion of olive oil phenolic compounds, these were absorbed, metabolized and distributed through the blood stream to practically all parts of the body, even across the blood‐brain barrier.     

Classification of ‘Chemlali’ accessions according to the geographical area using chemometric methods of phenolic profiles analysed by HPLC-ESI-TOF-MS

The present work describes a classification method of Tunisian ‘Chemlali’ olive oils based on their phenolic composition and geographical area. For this purpose, the data obtained by HPLC-ESI-TOF-MS from 13 samples of extra virgin olive oils, obtained from different production area throughout the country, were used for this study focusing in 23 phenolics compounds detected. The quantitative results showed a significant variability among the analysed oil samples. Factor analysis method using principal component was applied to the data in order to reduce the number of factors which explain the variability of the selected compounds. The data matrix constructed was subjected to a canonical discriminant analysis (CDA) in order to classify the oil samples. These results showed that 100% of cross-validated original group cases were correctly classified, which proves the usefulness of the selected variables.     

Valorization of olive oil solid waste using high pressure–high temperature reactor

The production of olive oil leads to considerable amounts of solid wastes rich in bioactive compounds with antioxidant properties, which have been partly used as inefficient polluting heating fuels for many years. This work was aimed to study the effect of extraction time and temperature on phenolics recovery from olive pomace. For this propose, different tests were performed, varying time from 15 to 120 min and temperature from 100 to 180 °C, using a high pressure–high temperature agitated reactor under a modified atmosphere. Total polyphenols, o-diphenols and total flavonoids were quantified. Maximum total polyphenols yield (45.2 mg_CAE/g_DP) was achieved at 180 °C and 90 min. HPLC analysis showed that oleuropein (2433 mg/100 g_DP) and tyrosol (485 mg/100 g_DP) were predominant phenolics in the extracts. Methanolic extracts, after additional purification processes, can be used in food, cosmetic and pharmaceutical industries. Solid residues, after phenolics extraction, are considered to have little environmental impact.     

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     

Phenolic profile and antioxidant activities of olive mill wastewater

Olive trees play an important role in the Moroccan agro-economy, providing both employment and export revenue. However, the olive oil industry generates large amounts of wastes and wastewaters. The disposal of these polluting by-products is a significant environmental problem that needs an adequate solution. On one hand, the phytotoxic and antimicrobial effects of olive mill wastewaters are mainly due to their phenolic content. The hydrophilic character of the polyphenols results in the major proportion of natural phenols being separated into the water phase during the olive processing. On other hand, the health benefits arising from a diet containing olive oil have been attributed to its richness in phenolic compounds that act as natural antioxidants and are thought to contribute to the prevention of heart diseases and cancers. Olive mill wastewater (OMW) samples have been analysed in terms of their phenolic constituents and antioxidant activities. The total phenolic content, flavonoids, flavanols, and proanthocyanidins were determined. The antioxidant and radical scavenging activity of phenolic extracts and microfiltred samples was evaluated using different tests (iron(II) chelating activity, total antioxidant capacity, DPPH assays and lipid peroxidation test). The obtained results reveal the considerable antioxidant capacity of the OMW, that can be considered as an inexpensive potential source of high added value powerful natural antioxidants comparable to some synthetic antioxidants commonly used in the food industry.     

Effect of growing location,malaxation duration and citric acid treatment on the quality of olive oil

BACKGROUND: The total phenolic compounds of olive oil exert antiradical activity at cellular level and can prevent cardiovascular disease, metabolic syndrome and cancer. Increased awareness of its health benefits has increased the consumption of olive oil around the world. An alternative processing technique effective in increasing the amount of oil extracted while maintaining the oil quality is needed to meet the rising global demand for olive oil. RESULTS: Addition of 0.3 g mL^?1 citric acid at 1:1000 (v/w) to olive paste followed by a 30 min malaxation period significantly increased the oil recovery, concentration of total phenolic compounds and antiradical activity by 46.23, 120.27 and 31.48% respectively. While there was no significant effect on the acidity, the peroxide value was significantly reduced by 63.85%. The organoleptic characteristics of the olive oil extracted with citric acid were also comparable to those of the control. CONCLUSION: Addition of 0.3 g mL^?1 citric acid (i.e. 30% w/v) at 1:1000 (v/w) to olive paste followed by a 30 min malaxation period in a Blixer^® 4.0 blender is the most promising extraction technique to improve the oil recovery, concentration of total phenolic compounds and antiradical activity of the extracted olive oil without compromising other quality parameters. © 2012 Society of Chemical Industry     

Effect of crushing on olive paste and virgin olive oil minor components

The present study focuses on the influence of the olive crushing technique on the minor composition of olive pastes and their corresponding virgin olive oils since these compounds are strongly related to their quality and characteristics. Two different cultivars, Arbequina and Cornicabra—known for their different minor component composition—were processed at laboratory scale using hammer mills at various breakage forces and grid hole diameters, a blade cutter and a mortar. Crushing and kneading produce a profound change in the composition of the phenolic compounds in the olive paste and in the final oil. Hydroxytyrosol derivatives in virgin olive oil were most affected by the crushing conditions. The stronger the crushing conditions (i.e. hammer crushers using smaller grid holes and a higher rotation speed), the higher the phenolic content in both olive paste and oil in both varieties. Interestingly, the effect on volatile compounds of milder or stronger crushing conditions was opposite to that described for the phenolic compounds.