WO2004108869A1 - Virgin olive oil with modified sensory attributes and method of obtaining same - Google Patents

Virgin olive oil with modified sensory attributes and method of obtaining same Download PDF

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Publication number
WO2004108869A1
WO2004108869A1 PCT/ES2004/070040 ES2004070040W WO2004108869A1 WO 2004108869 A1 WO2004108869 A1 WO 2004108869A1 ES 2004070040 W ES2004070040 W ES 2004070040W WO 2004108869 A1 WO2004108869 A1 WO 2004108869A1
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oil
chlorophyll
olives
virgin olive
sensory characteristics
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PCT/ES2004/070040
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Spanish (es)
French (fr)
Inventor
José María GARCIA MARTOS
María del Carmen MARTINEZ PELAEZ
María del Carmen PEREZ CAMINO
Luis Carlos Sanz Martinez
Ana Gracia Perez Rubio
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Consejo Superior De Investigaciones Científicas
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Publication of WO2004108869A1 publication Critical patent/WO2004108869A1/en

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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23DEDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00Other edible oils or fats, e.g. shortenings, cooking oils
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00Production of fats or fatty oils from raw materials
    • C11B1/02Pretreatment
    • C11B1/04Pretreatment of vegetable raw material

Definitions

  • the object of the present invention is a virgin olive oil with sensory characteristics (mainly color and flavor) modified and its obtaining procedure.
  • the present invention allows to modulate the intensity of the attributes that determine the sensory quality of virgin olive oil by reducing attributes such as bitterness and spiciness, or the aroma of grass, and the increase of its fruity aroma and its content in chlorophylls and carotenes without significantly affecting the parameters that define its commercial category.
  • bitterness and spiciness would be due to the action of first of glucosidases, which would first break the glycosidic bond of oleuropein giving secoiride derivatives of phenols and then these could be attacked by esterases producing free phenols (Ital J. Food Sci. 1998, 10 , 99-115).
  • the formation of volatiles responsible for the aroma of virgin olive oil are due to enzymatic activities that develop during the process of extraction.
  • the smell of grass or green of hexanal and other compounds with 6 carbon atoms is due to enzymatic activities involved in the degradative pathway of fatty acids, such as lipoxygenase, and the characteristic aromas of mature fruit, due to various esters are originated by different alcohol-acyl transferases (J. Agric.Food Chem. 1993, 41, 2368-2373).
  • the green pigmentation of the oil depends on its content of chlorophylls a and b, these are found in the chloroplasts of the olive mesoderm cells and dissolve in the oil during the crushing of the fruit, but the action of the chlorophyllase determines its destruction and the consequent loss of said coloration in the oil.
  • the content of carotenoids depends on the opposing action of two types of enzymes, the anabolic ones responsible for their synthesis and the catabolic ones that determine their destruction (J. Agrie, Food Chem. 1994, 42, 1089-1095). Since these sensory attributes depend on different enzymatic activities, it would be enough to alter them to modify them at the convenience of a physical method, which does not detract from the concept of virgin olive oil, but this treatment should not be applied during the grinding and beating of the fruit , because it would determine an excessive deterioration of its quality when the oil is exposed to atmospheric oxygen.
  • the intact oleuropein is less soluble in the
  • a first object of the present invention is a virgin olive oil with modified sensory characteristics obtained from olives of any variety and ripening index less than or equal to 3.0, such that said oil, without mixing with any other oil or compound, presents simultaneously the following contents in compounds related to odor, taste and coloring: total polyphenols (mmoles / Kg of oil): ⁇ 2,0 secoiridoid derivatives (mmoles / Kg of oil): ⁇ 1, 0 chlorophyll b (mg / Kg of oil): ⁇ 5 chlorophyll a (mg / Kg of oil): ⁇ 30
  • Also constituting an object of the present invention is a virgin olive oil with modified sensory characteristics obtained from olives of any variety with ripening index> 3, so that said oil without mixing with any other oil or compound presents simultaneously the following contents in compounds related to odor, taste and coloring: total polyphenols (mmoles / Kg of oil): ⁇ 1.0 secoiridoid derivatives (mmoles / Kg of oil): ⁇ 5.5 lutein (mg / Kg of oil): ⁇ 1 , 5 chlorophyll b (mg / Kg of oil): ⁇ 0.5 chlorophyll a (mg / Kg of oil): ⁇ 2.0 pheophytin b (mg / Kg of oil): ⁇ 0.05 pheophytin a (mg / Kg) of oil): ⁇ 0.3 ⁇ -carotene (mg / Kg of oil): ⁇ 0.3
  • Another method of the present invention is a method for obtaining a virgin olive oil with the characteristics indicated above.
  • Said process includes a step of milling the olives and later separating the oil by means of solid-liquid separation techniques applied to the pulp obtained after milling and differs from the usual procedure
  • the paste obtained after grinding is not subjected to any heat treatment and the oil obtained after the solid-liquid separation is not mixed with any other oil or with any compound that induces modifications in its smell, taste or color. It has been found that by the process object of the present invention the oil extraction efficiency increases between 3% and 7% with respect to the yield obtained when the olives are not subjected to heat treatment
  • the object of this invention is to provide a virgin olive oil obtainable by a process that allows to reduce the excess of bitterness, spiciness and smell of grass and increase the content of chlorophylls, carotenes and fruity aroma of virgin olive oil, without reducing its commercial category.
  • a heat treatment for example, immersion or shower with
  • the temperature of the water or water vapor may range between 40 and 150 ° C and the time of action between 30 seconds and 120 minutes. It must be ensured that the fruit is perfectly submerged or impregnated by the water or water vapor used, so that the heat transfer is as fast and efficient as possible during the entire time of the process.
  • the power of the same should be between 200 and 1200 Watts and the exposure time between 10 and 300 seconds
  • the method to be used, the time and the temperature of the test will depend of the intensity that you want to eliminate and the intensity of green color that you want to achieve, as well as the degree of maturity and variety of the olive used. The more immature and resistant the fruit, the greater the temperature and the time necessary to carry out the operation.
  • the process of extracting the oil should be delayed as little as possible after the treatment, to avoid recovering the altered enzymatic activities.
  • the procedure consists in distributing 100 olives of the sample considered in groups with the following characteristics: Group 0. - fruits with green skin; Group 1. - fruits with green-yellow skin; Group 2.- Green fruits with a red or purple spot; Group 3.- Fruits completely red-purple; Group 4.- Black fruits with completely white pulp. Group 5.- Black fruits with ⁇ 50% dark pulp; Group 6.- Black fruits with> 50% pulp
  • the olives are also characterized by their consistency, which is evaluated for its resistance to penetration as described in J. Agrie. Food Chem. 1996, 44, 264-267 by using a Zwlck 3300 10 densimeter (Zwlck GMBH & Company, Ulm, Germany) for the force required to introduce a 2.4 mm diameter disc into the fruit. The results are expressed in N / cm 2 .
  • the absolute sensory quality of the oil is determined by an analytical panel of 25 12 tasters according to the method described in Annex XII of the European Union Regulation (EEC / 2568/91). Each oil was evaluated according to a scale of 9 points, the value “1” being the one that evaluates the bad quality and "9" the one of the optimum one.
  • the descriptive quantitative analysis of the sensory attributes, including bitterness and spiciness, is carried out simultaneously with the absolute quality assessment, using a structured scale of 6 points, where "0" represents the absence of the attribute, "1 " the
  • the intensity of bitterness and spiciness can also be evaluated by the oil content of the hydroxytyrosol and tirasol secoiride derivatives: the dialdehydic form of the decarboxymethyl of the aglucone of the oleurope ⁇ a, the aldehyde form of oleuropein aglucone, the dialdehyde form of liglusoside aglucone carboxymethyl and the aldehydic form of ligustroside aglucone which are closely related to the intensity of this attribute and are quantified according to J. Agrie. Food Chem.
  • the elution is prepared with a flow of 1 mL / min., Using as a mobile phase a mixture of water: acetic acid (97: 3, v / v) (solvent A) and methanol: acetonitrile (1: 1, v / v) ) (solvent B).
  • the solvent gradient changes according to the following conditions: From 95% (A) - 5% (B) to 70% (A) - 30% (B) in 25 mi ⁇ ., To 60% (A) - 40% (B) ) in 5 min., and 30% (A) - 70% (B) in 10 min. Finally, it remains 100% (B) for 5 mi ⁇ . until the end of the process.
  • the quantification of the phenols is carried out at 280 nm and the results are expressed in moles per Kg.
  • the parameters that measure the commercial quality of virgin olive oil (titratable acidity, peroxide index, specific extinction coefficients at 232 and 270 nm (K2 3 2 and K27 0 ) composition of fatty acids, esteral, erythrodiol + uvaol, alcohols linear, triterpenic, methyl sterols, and trans isomers are determined according to the standardized European Union methods (Annexes II and IX in European Community Regulation EEC / 2568/91 and in Document I20 / 11 of the IOC).
  • the pigment content of the oils was evaluated according to J. Agrie. Food Chem. 1997, 45, 3733-3737: 100 mg of oil are dissolved in 370 ⁇ L of ethyl acetate. An aliquot of this solution is injected into an HPLC system equipped with a UV ⁇ is diode array detector, a Rheodyne valve injector with 20 ⁇ L loop and a 30 ° C octadecyl reverse phase (C ⁇ 8 ) column Lichrospher 100RP -18 (2.0 mm id x 250 mm) with a particle size of 5 ⁇ m (Merck, Darmstadt, Germany).
  • the elution is prepared using a mixture of acetonitrile: water (90: 10, v / v) (solvent A) and ethyl acetate (solvent B) as the mobile phase.
  • the solvent gradient changes according to the following conditions: With a flow of 0.5 mUmin. an eluent concentration of 90% (A) - 10% (B) is maintained for 5 minutes then the eluent concentration varies up to 80% (A) - 20% (B) in 5 min. and finally up to 16% ( A) - 84% (B) in 20 min. with the end of the process.
  • the quantification of pigments is carried out at 430 and 466 nm and the results are expressed in mg per Kg of oil.
  • the volatiles were adsorbed on a DVB / Carboxem / PDMS fiber. Subsequently, the volatile components collected in the fiber were released directly into the gas chromatograph injector, equipped with a DB-Wax silica capillary column (30 m x 0.25 mm). The quantification was performed using individual calibration curves for identified compound. The identification of the compounds was carried out with a GC-MS equipment equipped with a similar stationary phase and two different lengths 30 and 60 m. The compounds were separated by their different retention times and identified individually according to the spectrum collection of the Wiley / NBS database.
  • a sample of 50 kg of olive of the variety 'Manzanilla' with maturity index between 0 and 1 and a consistency of 45 N / cm 2 is divided randomly into 2 sub-samples of 10 kg each. The first one is processed directly and its oil is extracted, using it as a control. The rest are immersed for 3 minutes in water at 68 D Cy and then also processed as above. The physical, chemical and sensory parameters that measure the quality category obtained by these oils are presented in Table I.
  • Table III shows the effect of the treatment on the content of oil pigments, which are considerably increased.
  • Figure 1 compares the profile of volatile components of the oil obtained from the olives treated with the control, observing the decrease in the number of components and the intensity thereof, not observing the appearance of any component unrelated to the control, that could indicate the development of any strange smell of virgin olive oil.
  • the volatile compounds of the oil aroma that are most affected by the heat treatment of the olive correspond to the chromatographic peaks: (1) methyl acetate. (2) methanol. (3) 2-methylbutanal. (4) ethanol. (5 and 6) pentene dimers. (7) 1-penten-3-one. (8 and 9) pente ⁇ o dimers. (10) hexanal. (11) Z2-pentenal. (12) E3-hexenal. (13) Z3-hexenal. (14) 1-penten-3-ol. (15) Z2- hexenal. (16) £ 2-hexenal. (17) unknown. (18) unknown. (19) Z3-hexenyl acetate. (20) £ 2-pe ⁇ tenol. (21) Z2-pentenol. (22) hexanol. (23) Z3-hexenol. (24) unknown. (25) acetic acid.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

The invention relates to a virgin olive oil with modified sensory attributes (mainly colour and flavour) and to the method of obtaining same. The invention can be used to modulate the intensity of the attributes that determine the sensory quality of the virgin olive oil, by reducing attributes such as bitterness and spiciness or the herby aroma thereof, and increasing the fruity aroma and the chlorophyll- and carotene-content of same, without significantly affecting the parameters that define the commercial category of said oil. The method of obtaining the aforementioned oil is different from the standard method used in that the olives are subjected to a heat treatment process prior to crushing, thereby also improving the oil extraction yield.

Description

TITULOTITLE
Aceite de oliva virgen con características sensoriales modificadas y procedimiento de obtención.Virgin olive oil with modified sensory characteristics and obtaining procedure.
OBJETO DE LA INVENCIÓNOBJECT OF THE INVENTION
El objeto de la presente invención es un aceite de oliva virgen con características sensoriales (color y sabor principalmente) modificadas y su procedimiento de obtención. La presente invención permite modular la Intensidad de los atributos que determinan la calidad sensorial del aceite de oliva virgen mediante la reducción de atributos como el amargor y el picante, o el aroma a hierba, y el aumento de su aroma frutado y de su contenido en clorofilas y carotenos sin que se afecten significativamente los parámetros que definen su categoría comercial.The object of the present invention is a virgin olive oil with sensory characteristics (mainly color and flavor) modified and its obtaining procedure. The present invention allows to modulate the intensity of the attributes that determine the sensory quality of virgin olive oil by reducing attributes such as bitterness and spiciness, or the aroma of grass, and the increase of its fruity aroma and its content in chlorophylls and carotenes without significantly affecting the parameters that define its commercial category.
ESTADO DE LA TÉCNICASTATE OF THE ART
Aunque el amargor y el picante no son atributos indeseables en el aceite de oliva virgen y forman parte inherente de sus características sensoriales definitorias, su exceso reduce su comerciabilidad, sobre todo ante consumidores no habituados a este tipo de aceite. De la misma forma el exceso de olor a hierba o verde enmascara el aroma más suave del frutado maduro, desequilibrando el conjunto aromático de este producto.Although bitterness and spiciness are not undesirable attributes in virgin olive oil and are an inherent part of their defining sensory characteristics, their excess reduces their marketability, especially before consumers not used to this type of oil. In the same way, the excess of grass or green odor masks the softest aroma of ripe fruity, unbalancing the aromatic set of this product.
Por otra parte, el concepto que relaciona el aceite de oliva virgen con el de ser básicamente la fracción oleosa de un zumo de aceituna, obtenido por medios exclusivamente físicos se ve mejor reflejado con una coloración verde, propia de las clorofilas, que da idea de mayor frescura y de utilización de un fruto más verde y menos susceptible al deterioro, que la coloración dorada, más propia del fruto maduro.On the other hand, the concept that relates virgin olive oil to that of being basically the oily fraction of an olive juice, obtained by exclusively physical means is best reflected with a green coloration, typical of chlorophylls, which gives an idea of greater freshness and use of a greener fruit and less susceptible to deterioration, than the golden coloration, more typical of ripe fruit.
Este aumento de la pigmentación verde no debe suponer una reducción del contenido en carotenos, que aportan un apreciable valor nutricíonal al aceite de oliva virgen. This increase in green pigmentation should not lead to a reduction in the carotene content, which contributes an appreciable nutritional value to virgin olive oil.
Tanto los atributos amargo y picante relacionados con compuestos fenólicos derivados de la hidrólisis de la oleuropeína, como el aroma o la pigmentación del aceite de oliva están condicionados por actividades enzimáticas que se desarrollan durante el proceso de triturado y batido de la aceituna, durante el proceso de extracción del aceite de oliva virgen (J. Am. Oil Chem. Soc. 1998, 75673-681).Both the bitter and spicy attributes related to phenolic compounds derived from the hydrolysis of oleuropein, as well as the aroma or pigmentation of olive oil, are conditioned by enzymatic activities that develop during the process of crushing and whipping the olive, during the process for extraction of virgin olive oil (J. Am. Oil Chem. Soc. 1998, 75673-681).
El amargor y el picante serían debidos a la acción primero de glucosidasas, que romperían primero el enlace glucosídico de la oleuropeína dando derivados secoirideos de fenoles y después éstos podrían ser atacados por esterasas produciendo fenoles libres (Ital. J. Food Sci. 1998, 10, 99-115). La formación de volátiles responsables del aroma del aceite de oliva virgen son debidos a actividades enzimáticas que se desarrollan durante el proceso de su extracción. Así, el olor a hierba o verde propio del hexanal y otros compuestos con 6 átomos de carbono se debe a actividades enzimáticas que intervienen en la ruta degradativa de los ácidos grasos, como la lipoxigenasa, y los aromas característicos del fruto maduro, debidos a diversos esteres son originados por diferentes alcohol-acil transferasas (J. Agric.Food Chem. 1993, 41 , 2368-2373). La pigmentación verde del aceite depende del contenido en el mismo de clorofilas a y b, éstas se hallan en los cloroplastos de las células del mesodermo de la aceituna y se disuelven en el aceite durante el triturado del fruto, pero la acción de las clorofilasas determina su destrucción y la consiguiente pérdida de dicha coloración en el aceite. El contenido en carotenos depende de la acción contrapuesta de dos tipos de enzimas, las anabólicas encargadas de su síntesis y las catabólicas que determinan su destrucción (J. Agrie. Food Chem. 1994, 42, 1089-1095). Dado que estos atributos sensoriales dependen de sendas actividades enzímáticas, bastaría con alterar las mismas para modificarlos a conveniencia por un método físico, que no desvirtúe el concepto de aceite de oliva virgen, pero este tratamiento no debe ser aplicado durante la molienda y batido del fruto, pues determinaría un deterioro excesivo de su calidad al estar expuesto el aceite al oxígeno atmosférico. La oleuropeína intacta es menos soluble en el The bitterness and spiciness would be due to the action of first of glucosidases, which would first break the glycosidic bond of oleuropein giving secoiride derivatives of phenols and then these could be attacked by esterases producing free phenols (Ital J. Food Sci. 1998, 10 , 99-115). The formation of volatiles responsible for the aroma of virgin olive oil are due to enzymatic activities that develop during the process of extraction. Thus, the smell of grass or green of hexanal and other compounds with 6 carbon atoms is due to enzymatic activities involved in the degradative pathway of fatty acids, such as lipoxygenase, and the characteristic aromas of mature fruit, due to various esters are originated by different alcohol-acyl transferases (J. Agric.Food Chem. 1993, 41, 2368-2373). The green pigmentation of the oil depends on its content of chlorophylls a and b, these are found in the chloroplasts of the olive mesoderm cells and dissolve in the oil during the crushing of the fruit, but the action of the chlorophyllase determines its destruction and the consequent loss of said coloration in the oil. The content of carotenoids depends on the opposing action of two types of enzymes, the anabolic ones responsible for their synthesis and the catabolic ones that determine their destruction (J. Agrie, Food Chem. 1994, 42, 1089-1095). Since these sensory attributes depend on different enzymatic activities, it would be enough to alter them to modify them at the convenience of a physical method, which does not detract from the concept of virgin olive oil, but this treatment should not be applied during the grinding and beating of the fruit , because it would determine an excessive deterioration of its quality when the oil is exposed to atmospheric oxygen. The intact oleuropein is less soluble in the
aceite que en el agua, por lo que apenas se halla presente en el aceite de oliva virgen tras su extracción. Por el contrario, las clorofilas a y b y los carotenos intactos se disuelven perfectamente en el aceite de oliva virgen y se presentan en éste tras su extracción. La diferente respuesta de las actividades enzimáticas responsables de los aromas al tratamiento físico puede determinar la obtención de un conjunto más equilibrado de componentes aromáticos.oil than in water, so it is hardly present in virgin olive oil after extraction. On the other hand, the chlorophylls a and b and the intact carotenes dissolve perfectly in the virgin olive oil and appear in it after extraction. The different response of the enzymatic activities responsible for the aromas to the physical treatment can determine the obtaining of a more balanced set of aromatic components.
EXPLICACIÓN DE LA INVENCIÓNEXPLANATION OF THE INVENTION
Constituye un primer objeto de la presente invención un aceite de oliva virgen con características sensoriales modificadas obtenido de aceitunas de cualquier variedad e índice de maduración menor o igual que 3,0 , de forma que dicho aceite, sin mezclar con ningún otro aceite o compuesto, presenta simultáneamente los siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifenoles totales (mmoles/Kg de aceite): ≤ 2,0 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 1 ,0 clorofila b (mg/Kg de aceite): ≥ 5 clorofila a (mg/Kg de aceite): ≥ 30A first object of the present invention is a virgin olive oil with modified sensory characteristics obtained from olives of any variety and ripening index less than or equal to 3.0, such that said oil, without mixing with any other oil or compound, presents simultaneously the following contents in compounds related to odor, taste and coloring: total polyphenols (mmoles / Kg of oil): ≤ 2,0 secoiridoid derivatives (mmoles / Kg of oil): ≤ 1, 0 chlorophyll b (mg / Kg of oil): ≥ 5 chlorophyll a (mg / Kg of oil): ≥ 30
Cuando la variedad de la aceituna de la cual se obtiene el aceite es Hojiblanca con un índice de maduración ≤ 3,0 y una resistencia a la penetración comprendida entre 35 y 60 N/cm2, el aceite sin mezclar con ningún otro aceite o compuesto presenta simultáneamente los siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifenoles totales (mmoles/Kg de aceite): ≤ 0,9 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 0,7 luteína (mg/Kg de aceite): ≥ 5,0 clorofila b (mg/Kg de aceite): ≥ 5,0 clorofila a (mg/Kg de aceite): ≥ 30,0 feofitina b (mg/Kg de aceite): > 0,1 feofitina a (mg/Kg de aceite): ≥ 5,0 β- caroteno (mg/Kg de aceite): ≥ 2,5 When the variety of the olive from which the oil is obtained is Hojiblanca with a ripening index ≤ 3.0 and a penetration resistance between 35 and 60 N / cm 2 , the oil without mixing with any other oil or compound simultaneously presents the following contents in compounds related to odor, taste and coloring: total polyphenols (mmoles / Kg of oil): ≤ 0.9 secoiridoideos derivatives (mmoles / Kg of oil): ≤ 0,7 lutein (mg / Kg of oil): ≥ 5.0 chlorophyll b (mg / Kg of oil): ≥ 5.0 chlorophyll a (mg / Kg of oil): ≥ 30.0 pheophytin b (mg / Kg of oil):> 0, 1 pheophytin a (mg / Kg of oil): ≥ 5.0 β-carotene (mg / Kg of oil): ≥ 2.5
Cuando la variedad de la aceituna de la cual se obtiene el aceite es 'Manzanilla' con un índice de maduración ≤ 3,0 y una resistencia a la penetración comprendida entre 35 y 60 N/cm2, el aceite sin mezclar con ningún otro aceite o compuesto presenta simultáneamente los siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifeπoles totales (mmoles/Kg de aceite): ≤ 2,0 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 1 ,0 luteína (mg/Kg de aceite): > 6,0 clorofila b (mg/Kg de aceite): ≥ 8,0 clorofila a (mg/Kg de aceite): ≥ 30,0 feofitina b (mg/Kg de aceite): ≥ 0,1 feofitina a (mg/Kg de aceite): ≥ 7,0 β- caroteno (mg/Kg de aceite): ≥ 2,5When the olive variety from which the oil is obtained is 'Chamomile' with a ripening index ≤ 3.0 and a resistance to penetration between 35 and 60 N / cm 2 , the oil without mixing with any other oil or compound presents simultaneously the following contents in compounds related to odor, taste and coloring: total polifeπols (mmoles / Kg of oil): ≤ 2.0 secoiridoideos derivatives (mmoles / Kg of oil): ≤ 1, 0 lutein ( mg / Kg of oil):> 6.0 chlorophyll b (mg / Kg of oil): ≥ 8.0 chlorophyll a (mg / Kg of oil): ≥ 30.0 pheophytin b (mg / Kg of oil): ≥ 0,1 pheophytin a (mg / Kg of oil): ≥ 7,0 β-carotene (mg / Kg of oil): ≥ 2,5
Cuando la variedad de la aceituna de la cual se obtiene el aceite es 'Picual' con un índice de maduración ≤ 3,0 y una resistencia a la penetración comprendida entre 35 y 60 N/cm2, el aceite sin mezclar con ningún otro aceite o compuesto presenta simultáneamente los siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifenoles totales (mmoles/Kg de aceite): ≤ 0,8 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 0,5 luteína (mg/Kg de aceite): ≥ 5,0 clorofila b (mg/Kg de aceite): ≥ 9,0 clorofila a (mg/Kg de aceite): ≥ 35,0 feofitina b (mg/Kg de aceite): ≥ 0,1 feofitina a (mg/Kg de aceite): ≥ 5,0 β- caroteno (mg/Kg de aceite): ≥ 1 ,5When the olive variety from which the oil is obtained is 'Picual' with a ripening index ≤ 3.0 and a penetration resistance between 35 and 60 N / cm 2 , the oil without mixing with any other oil or compound simultaneously presents the following contents in compounds related to odor, taste and coloring: total polyphenols (mmoles / Kg of oil): ≤ 0.8 secoiridoid derivatives (mmoles / Kg of oil): ≤ 0.5 lutein ( mg / Kg of oil): ≥ 5.0 chlorophyll b (mg / Kg of oil): ≥ 9.0 chlorophyll a (mg / Kg of oil): ≥ 35.0 pheophytin b (mg / Kg of oil): ≥ 0,1 pheophytin a (mg / Kg of oil): ≥ 5,0 β-carotene (mg / Kg of oil): ≥ 1, 5
Cuando la variedad de la aceituna de la cual se obtiene el aceite es 'Verdial' con un índice de maduración < 3,0 y una resistencia a la penetración comprendida entre 35 y 60 N/cm2, el aceite sin mezclar con ningún otro aceite When the variety of the olive from which the oil is obtained is 'Verdial' with a ripening index <3.0 and a penetration resistance between 35 and 60 N / cm 2 , the oil is not mixed with any other oil
o compuesto presenta simultáneamente los siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifenoles totales (mmoles/Kg de aceite): ≤ 0,9 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 0,8 luteína (mg/Kg de aceite): > 9,0 clorofila b (mg/Kg de aceite): ≥ 12,0 clorofila a (mg/Kg de aceite): ≥ 40,0 feofitina b (mg/Kg de aceite): ≥ 0,1 feofitina a (mg/Kg de aceite): ≥ 5,0 β- caroteno (mg/Kg de aceite): ≥ 4,5or compound simultaneously presents the following contents in compounds related to odor, taste and coloring: total polyphenols (mmoles / Kg of oil): ≤ 0.9 secoiridoid derivatives (mmoles / Kg of oil): ≤0.8 lutein ( mg / Kg of oil):> 9.0 chlorophyll b (mg / Kg of oil): ≥ 12.0 chlorophyll a (mg / Kg of oil): ≥ 40.0 pheophytin b (mg / Kg of oil): ≥ 0,1 pheophytin a (mg / Kg of oil): ≥ 5,0 β-carotene (mg / Kg of oil): ≥ 4,5
Constituye igualmente un objeto de la presente invención un aceite de oliva virgen con características sensoriales modificadas obtenido de aceitunas de cualquier variedad con índice de maduración >3, de forma que dicho aceite sin mezclar con ningún otro aceite o compuesto presenta simultáneamente los siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifenoles totales (mmoles/Kg de aceite): ≤ 1 ,0 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 0,5 luteína (mg/Kg de aceite): ≥ 1 ,5 clorofila b (mg/Kg de aceite): ≥ 0,5 clorofila a (mg/Kg de aceite): ≥ 2,0 feofitina b (mg/Kg de aceite): ≥ 0,05 feofitina a (mg/Kg de aceite): ≥ 0,3 β- caroteno (mg/Kg de aceite): ≥ 0,3Also constituting an object of the present invention is a virgin olive oil with modified sensory characteristics obtained from olives of any variety with ripening index> 3, so that said oil without mixing with any other oil or compound presents simultaneously the following contents in compounds related to odor, taste and coloring: total polyphenols (mmoles / Kg of oil): ≤1.0 secoiridoid derivatives (mmoles / Kg of oil): ≤5.5 lutein (mg / Kg of oil): ≥ 1 , 5 chlorophyll b (mg / Kg of oil): ≥ 0.5 chlorophyll a (mg / Kg of oil): ≥ 2.0 pheophytin b (mg / Kg of oil): ≥ 0.05 pheophytin a (mg / Kg) of oil): ≥ 0.3 β-carotene (mg / Kg of oil): ≥ 0.3
Constituye otro objeto de la presente invención un procedimiento de obtención de un aceite de oliva virgen con las características indicadas anteriormente. Dicho procedimiento incluye una etapa de molienda de las aceitunas y posterior separación del aceite mediante técnicas de separación sólido-líquido aplicadas a la pasta obtenida tras la molienda y se diferencia del procedimiento habitual Another method of the present invention is a method for obtaining a virgin olive oil with the characteristics indicated above. Said process includes a step of milling the olives and later separating the oil by means of solid-liquid separation techniques applied to the pulp obtained after milling and differs from the usual procedure
en que antes de la molienda las aceitunas se someten a un tratamiento térmico que puede aplicarse de diversas formas, por ejemplo:in which before grinding the olives are subjected to a heat treatment that can be applied in various ways, for example:
- inmersión de las aceitunas en agua a una temperatura comprendida entre 40°C y 150°C durante un periodo comprendido entre 30 segundos y 120 minutos.- Immersion of the olives in water at a temperature between 40 ° C and 150 ° C for a period between 30 seconds and 120 minutes.
- ducha de las aceitunas con agua o vapor de agua a una temperatura comprendida entre 40°C y 150°C durante un periodo comprendido entre 30 segundos y 120 minutos.- showering the olives with water or steam at a temperature between 40 ° C and 150 ° C for a period between 30 seconds and 120 minutes.
- irradiación con microondas, con una potencia comprendida entre 200 y 1200 Watios y un tiempo de exposición comprendido entre 10 y 300 segundos- irradiation with microwaves, with a power between 200 and 1200 Watts and an exposure time between 10 and 300 seconds
La pasta obtenida tras la molienda no es sometida a ningún tratamiento térmico y el aceite obtenido tras la separación sólido-líquido no se mezcla con ningún otro aceite o con cualquier compuesto que induzca modificaciones en su olor, sabor o coloración. Se ha constatado que mediante el procedimiento objeto de la presente invención el rendimiento de extracción de aceite aumenta entre un 3% y un 7% respecto al rendimiento obtenido cuando las aceitunas no se someten a tratamiento térmicoThe paste obtained after grinding is not subjected to any heat treatment and the oil obtained after the solid-liquid separation is not mixed with any other oil or with any compound that induces modifications in its smell, taste or color. It has been found that by the process object of the present invention the oil extraction efficiency increases between 3% and 7% with respect to the yield obtained when the olives are not subjected to heat treatment
BREVE DESCRIPCIÓN DE LA FIGURABRIEF DESCRIPTION OF THE FIGURE
Resultados del análisis por cromatografía gas-líquido de alta resolución del aceite control y del aceite obtenido de aceitunas sometidas a inmersión en agua a 68°C durante 3 minutos.Results of the analysis by high-resolution gas-liquid chromatography of the control oil and the oil obtained from olives subjected to immersion in water at 68 ° C for 3 minutes.
DESCRIPCIÓN DETALLADA DE LA INVENCIÓNDETAILED DESCRIPTION OF THE INVENTION
El objeto de esta invención es aportar un aceite de oliva virgen obtenible mediante un procedimiento que permita reducir el exceso de amargor, picante y olor a hierba y aumentar el contenido en clorofilas, carotenos y aroma afrutado del aceite de oliva virgen, sin reducir por ello su categoría comercial. Para ello, se han llevado a cabo estudios y pruebas que han conducido al desarrollo de un procedimiento que ha permitido lograr este objetivo, mediante la aplicación de un tratamiento térmico (por ejemplo inmersión o ducha con The object of this invention is to provide a virgin olive oil obtainable by a process that allows to reduce the excess of bitterness, spiciness and smell of grass and increase the content of chlorophylls, carotenes and fruity aroma of virgin olive oil, without reducing its commercial category. For this, studies and tests have been carried out that have led to the development of a procedure that has allowed to achieve this objective, by applying a heat treatment (for example, immersion or shower with
agua caliente o vapor de agua, irradiación con microondas etc.) a la aceituna, de forma previa a su procesamiento para la obtención de aceite, sin que se deterioraran por ello significativamente los parámetros que determinan su calidad comercial. En el caso de que el tratamiento se aplique mediante inmersión o ducha de las aceitunas, la temperatura del agua o vapor de agua podrá oscilar entre 40 y 150 °C y el tiempo de actuación entre 30 segundos y 120 minutos. Debe asegurarse que el fruto esté perfectamente sumergido o impregnado por el agua o vapor de agua empleado, para que la transferencia de calor sea lo más rápida y eficaz posible durante todo el tiempo del proceso.hot water or water vapor, irradiation with microwaves, etc.) to the olive, prior to its processing to obtain oil, without significantly deteriorating the parameters that determine its commercial quality. In the case that the treatment is applied by immersion or showering the olives, the temperature of the water or water vapor may range between 40 and 150 ° C and the time of action between 30 seconds and 120 minutes. It must be ensured that the fruit is perfectly submerged or impregnated by the water or water vapor used, so that the heat transfer is as fast and efficient as possible during the entire time of the process.
En el caso de que el tratamiento se efectúe mediante irradiación con microondas, la potencia de las mismas debe estar comprendida entre 200 y 1.200 Watios y el tiempo de exposición entre 10 y 300 segundos El método a utilizar, el tiempo y la temperatura del ensayo dependerán de la intensidad que se quiera eliminar y de la intensidad de color verde que se pretenda conseguir, así como del grado de madurez y la variedad de la aceituna que se emplee. Conforme más inmaduro y resistente sea el fruto mayor será la temperatura y el tiempo necesario para efectuar la operación. El proceso de extracción del aceite debe demorarse lo menos posible tras el tratamiento, para evitar que se recuperen las actividades enzimáticas alteradas.In the case that the treatment is carried out by irradiation with microwaves, the power of the same should be between 200 and 1200 Watts and the exposure time between 10 and 300 seconds The method to be used, the time and the temperature of the test will depend of the intensity that you want to eliminate and the intensity of green color that you want to achieve, as well as the degree of maturity and variety of the olive used. The more immature and resistant the fruit, the greater the temperature and the time necessary to carry out the operation. The process of extracting the oil should be delayed as little as possible after the treatment, to avoid recovering the altered enzymatic activities.
Para la realización del tratamiento térmico a las aceitunas es preciso por tanto conocer el grado de maduración de las aceitunas, que se evalúa por el color de su piel y de su pulpa de acuerdo con la escala descrita en J. Agrie. Food Chem. 1996, 44, 264-267, que se usa rutinariamente por la industria almazarera.To carry out the heat treatment of the olives, it is therefore necessary to know the degree of maturation of the olives, which is evaluated by the color of their skin and their pulp according to the scale described in J. Agrie. Food Chem. 1996, 44, 264-267, which is routinely used by the almazarera industry.
El procedimiento consiste en distribuir 100 aceitunas de la muestra que se considere en grupos con las siguientes características: Grupo 0.- frutos con piel verde; Grupo 1.- frutos con piel verde-amarilla; Grupo 2.- Frutos verdes con una mancha roja o morada; Grupo 3.- Frutos completamente rojo-púrpuras; Grupo 4.- Frutos negros con pulpa completamente blanca. Grupo 5.- Frutos negros con < 50% de pulpa oscura; Grupo 6.- Frutos negros con > 50% de pulpa The procedure consists in distributing 100 olives of the sample considered in groups with the following characteristics: Group 0. - fruits with green skin; Group 1. - fruits with green-yellow skin; Group 2.- Green fruits with a red or purple spot; Group 3.- Fruits completely red-purple; Group 4.- Black fruits with completely white pulp. Group 5.- Black fruits with <50% dark pulp; Group 6.- Black fruits with> 50% pulp
oscura y Grupo 7.- Frutos con el 100% de la pulpa oscura. El índice de maduración se calcula mediante la fórmula: I.M. = ∑(in¡) / 100 Donde "i" es el número que identifica al grupo y "n," el número de 5 aceitunas que corresponden a este grupo.dark and Group 7.- Fruits with 100% dark pulp. The ripening index is calculated by the formula: I.M. = Σ (in¡) / 100 Where "i" is the number that identifies the group and "n," the number of 5 olives that correspond to this group.
Las aceitunas quedan también caracterizadas por su consistencia, que se evalúa por su resistencia a la penetración según se describe en J. Agrie. Food Chem. 1996, 44, 264-267 mediante el uso de un densímetro Zwlck 3300 10 (Zwlck GMBH & Company, Ulm, Germany) por la fuerza requerida para introducir un disco de 2,4 mm de diámetro en el fruto. Los resultados se expresan en N/cm2.The olives are also characterized by their consistency, which is evaluated for its resistance to penetration as described in J. Agrie. Food Chem. 1996, 44, 264-267 by using a Zwlck 3300 10 densimeter (Zwlck GMBH & Company, Ulm, Germany) for the force required to introduce a 2.4 mm diameter disc into the fruit. The results are expressed in N / cm 2 .
La extracción física del aceite de oliva se realiza a escala de laboratorio 15 mediante un analizador de rendimientos "Abencor" (Comercial Abengoa S.A., Sevilla, España), que simula a pequeña escala el proceso industrial de la extracción de aceite (Grasas y Aceites 1975, 26, 379 - 385). Se ha constatado un aumento en el rendimiento de la extracción de aceite cuando se utilizan aceitunas previamente sometidas a tratamiento térmico, en 20 comparación al rendimiento obtenido cuando no se ha aplicado dicho tratamiento térmico.The physical extraction of olive oil is done on a laboratory scale 15 by means of a performance analyzer "Abencor" (Comercial Abengoa SA, Seville, Spain), which simulates the industrial process of oil extraction on a small scale (Greases and Oils 1975 , 26, 379-385). An increase in the yield of oil extraction has been observed when olives previously subjected to heat treatment are used, in comparison with the yield obtained when said thermal treatment has not been applied.
Determinación de la calidad sensorial del aceiteDetermination of the sensory quality of the oil
La calidad sensorial absoluta del aceite se determina por un panel analítico de 25 12 catadores de acuerdo con el método descrito en el Anexo XII de la Regulación de la Unión Europea (EEC/2568/91). Cada aceite fue evaluado de acuerdo a una escala de 9 puntos, siendo el valor "1" el que evalúa la calidad pésima y "9" el de la óptima. El análisis cuantitativo descriptivo de los atributos sensoriales, entre los que se incluyen el amargor y el picante se realiza 30 simultáneamente con la valoración de calidad absoluta, empleando una escala estructurada de 6 puntos, donde "0" representa la ausencia del atributo, "1" la The absolute sensory quality of the oil is determined by an analytical panel of 25 12 tasters according to the method described in Annex XII of the European Union Regulation (EEC / 2568/91). Each oil was evaluated according to a scale of 9 points, the value "1" being the one that evaluates the bad quality and "9" the one of the optimum one. The descriptive quantitative analysis of the sensory attributes, including bitterness and spiciness, is carried out simultaneously with the absolute quality assessment, using a structured scale of 6 points, where "0" represents the absence of the attribute, "1 " the
simple percepción, "2" presencia ligera, "3" intensidad media, "4" intensidad fuerte y "5" intensidad máxima. Cada prueba se realiza al menos por duplicado.simple perception, "2" light presence, "3" medium intensity, "4" strong intensity and "5" maximum intensity. Each test is performed at least in duplicate.
Determinación de parámetros relacionados con el amargor y picante La intensidad de amargor y picante también se puede evaluar por el contenido en el aceite de los derivados secoirideos de hidroxitirosol y tirasol: la forma dialdehídica del decarboximetil de la aglucona de la oleuropeíπa, la forma aldehldlca de la aglucona de la oleuropeína, la forma dialdehidica del carboximetil de la aglucona del ligustrósido y la forma aldehídica de la aglucona del ligustrósido los cuales están estrechamente relacionados con la intensidad de este atributo y se cuantifican de acuerdo con J. Agrie. Food Chem. 2001, 49, 2185-2192: Se disuelven 2,5 g de aceite de oliva en 6 mL de hexano que se hace pasar por una columna de extracción de fase sólida con fase diol (Superclean, Normal Phase SPE, LC-Diol de 500 mg y 3 mL) previamente acondicionada sucesivamente con 6 mL de metaπol y 6 mL de hexaπo. Se lava sucesivamente con 3 mL de hexano. Después se continúa lavando con 3 mL de una mezcla de Hexano : Acetato de etilo (90 : 10, v/v). Finalmente se eluye con 10 mL de metanol, recogiéndose esta fracción, que se evapora hasta sequedad en un rotavapor. El residuo se disuelve en 500 μL de una mezcla metanol : agua (1 : 1, v/v). Una alícuota de esta solución se inyecta en un sistema de HPLC equipado con un detector de diodo array U.V., un inyector con válvula Rheodyne con loop de 20 μL y una columna a 30 °C de fase inversa de octadecilo (Cíe) Llchrospher 100RP-18 (4,0 mm i.d. x 250 mm) con un tamaño de partícula de 5 μm (Merck, Darmstad, Germany). La elusión se prepara con un flujo de 1 mL /min., usando como fase móvil una mezcla de agua : ácido acético (97 : 3, v/v) (solvente A) y metanol : acetonitrilo (1:1, v/v) (solvente B). El gradiente de solventes cambia según las condiciones siguientes: Desde 95 % (A) - 5 % (B) hasta 70 % (A) - 30 % (B) en 25 miπ., a 60 % (A) - 40 % (B) en 5 min., y a 30 % (A) - 70 % (B) en 10 min. Finalmente se mantiene 100 % (B) durante 5 miπ. hasta el final del proceso. La cuantificación de los fenoles se lleva a cabo a 280 nm y los resultados son expresados en moles por Kg. Determination of parameters related to bitterness and spiciness The intensity of bitterness and spiciness can also be evaluated by the oil content of the hydroxytyrosol and tirasol secoiride derivatives: the dialdehydic form of the decarboxymethyl of the aglucone of the oleuropeíπa, the aldehyde form of oleuropein aglucone, the dialdehyde form of liglusoside aglucone carboxymethyl and the aldehydic form of ligustroside aglucone which are closely related to the intensity of this attribute and are quantified according to J. Agrie. Food Chem. 2001, 49, 2185-2192: Dissolve 2.5 g of olive oil in 6 mL of hexane passed through a solid phase extraction column with diol phase (Superclean, Normal Phase SPE, LC- Diol of 500 mg and 3 mL) previously conditioned successively with 6 mL of meta-piol and 6 mL of hexaπo. Wash successively with 3 mL of hexane. Then continue washing with 3 mL of a mixture of Hexane: Ethyl Acetate (90: 10, v / v). Finally elute with 10 mL of methanol, collecting this fraction, which is evaporated to dryness in a rotary evaporator. The residue is dissolved in 500 μL of a methanol: water mixture (1: 1, v / v). An aliquot of this solution is injected into an HPLC system equipped with a UV diode array detector, a Rheodyne valve injector with 20 μL loop and a 30 ° C octadecyl reverse phase (Cie) column, Llchrospher 100RP-18 (4.0 mm id x 250 mm) with a particle size of 5 μm (Merck, Darmstadt, Germany). The elution is prepared with a flow of 1 mL / min., Using as a mobile phase a mixture of water: acetic acid (97: 3, v / v) (solvent A) and methanol: acetonitrile (1: 1, v / v) ) (solvent B). The solvent gradient changes according to the following conditions: From 95% (A) - 5% (B) to 70% (A) - 30% (B) in 25 miπ., To 60% (A) - 40% (B) ) in 5 min., and 30% (A) - 70% (B) in 10 min. Finally, it remains 100% (B) for 5 miπ. until the end of the process. The quantification of the phenols is carried out at 280 nm and the results are expressed in moles per Kg.
Determinación de los parámetros que miden la calidad comercial del aceiteDetermination of the parameters that measure the commercial quality of the oil
Los parámetros que miden la calidad comercial del aceite de oliva virgen (acidez titulable, índice de peróxidos, coeficientes de extinción específica a 232 y 270 nm (K232 y K270). composición de ácidos grasos, esterales, eritrodiol + uvaol, alcoholes lineales, triterpénicos, metil esteróles, e isómeros trans se determinan de acuerdo a los métodos normalizados de la Unión Europea (Anexos II y IX en la Regulación de la Comunidad Europea EEC/2568/91 y en el Documento T20/11 del COI).The parameters that measure the commercial quality of virgin olive oil (titratable acidity, peroxide index, specific extinction coefficients at 232 and 270 nm (K2 3 2 and K27 0 ) composition of fatty acids, esteral, erythrodiol + uvaol, alcohols linear, triterpenic, methyl sterols, and trans isomers are determined according to the standardized European Union methods (Annexes II and IX in European Community Regulation EEC / 2568/91 and in Document I20 / 11 of the IOC).
Determinación del contenido en pigmentosDetermination of pigment content
El contenido en pigmentos de los aceites fue evaluado de acuerdo a J. Agrie. Food Chem. 1997, 45, 3733 - 3737: Se disuelven 100 mg de aceite en 370 μL de acetato de etilo. Una alícuota de esta solución se inyecta en un sistema de HPLC equipado con un detector de diodo array U.V.Λ is, un inyector con válvula Rheodyne con loop de 20 μL y una columna a 30 °C de fase inversa de octadecilo (Cι8) Lichrospher 100RP-18 (2,0 mm i.d. x 250 mm) con un tamaño de partícula de 5 μm (Merck, Darmstad, Germany). La elusión se prepara usando como fase móvil una mezcla de acetonitrilo : agua (90 : 10, v/v) (solvente A) y acetato de etilo (solvente B). El gradiente de solventes cambia según las condiciones siguientes: Con un flujo de 0,5 mUmin. se mantiene una concentración de eluyente de 90 % (A) - 10 % (B) durante 5 minutos a continuación la concentración de eluyente varía hasta 80 % (A) - 20 % (B) en 5 min.y finalmente hasta 16 % (A) - 84 % (B) en 20 min. con el final del proceso. La cuantificación de pigmentos se lleva a cabo a 430 y 466 nm y los resultados son expresados en mg por Kg de aceite.The pigment content of the oils was evaluated according to J. Agrie. Food Chem. 1997, 45, 3733-3737: 100 mg of oil are dissolved in 370 μL of ethyl acetate. An aliquot of this solution is injected into an HPLC system equipped with a UVΛ is diode array detector, a Rheodyne valve injector with 20 μL loop and a 30 ° C octadecyl reverse phase (Cι 8 ) column Lichrospher 100RP -18 (2.0 mm id x 250 mm) with a particle size of 5 μm (Merck, Darmstadt, Germany). The elution is prepared using a mixture of acetonitrile: water (90: 10, v / v) (solvent A) and ethyl acetate (solvent B) as the mobile phase. The solvent gradient changes according to the following conditions: With a flow of 0.5 mUmin. an eluent concentration of 90% (A) - 10% (B) is maintained for 5 minutes then the eluent concentration varies up to 80% (A) - 20% (B) in 5 min. and finally up to 16% ( A) - 84% (B) in 20 min. with the end of the process. The quantification of pigments is carried out at 430 and 466 nm and the results are expressed in mg per Kg of oil.
Determinación de componentes volátilesDetermination of volatile components
Los componentes volátiles se analizaron empleando el método descrito en J. Agrie. Food Chem. 2002, 50, 4037-4042: Una muestra de 0,5 g de aceite se colocó en un tubo de 10 mL cerrado herméticamente, que se colocó en un baño de agua a 40 °C. Tras 10 min. de tiempo de equilibrio, se dejó que The volatile components were analyzed using the method described in J. Agrie. Food Chem. 2002, 50, 4037-4042: A sample of 0.5 g of oil was placed in a sealed 10 mL tube, which was placed in a 40 ° C water bath. After 10 min. of equilibrium time, it was left to
durante 50 min. los volátiles se adsorbieran en una fibra DVB/ Carboxem/ PDMS. Posteriormente, los componentes volátiles recogidos en la fibra fueron liberados directamente en el inyector del cromatógrafo de gases, equipado con una columna capilar de sílice DB-Wax (30 m x 0,25 mm). La cuantificación fue realizada usando curvas individuales de calibración para compuesto identificado. La identificación de los compuestos fue realizada con un equipo GC-MS equipado con una fase estacionaria similar y dos diferentes longitudes 30 y 60 m. Los compuestos fueron separados por sus diferentes tiempos de retención e identificados individualmente de acuerdo con la colección de espectros de la base de datos Wiley/NBS.for 50 min. the volatiles were adsorbed on a DVB / Carboxem / PDMS fiber. Subsequently, the volatile components collected in the fiber were released directly into the gas chromatograph injector, equipped with a DB-Wax silica capillary column (30 m x 0.25 mm). The quantification was performed using individual calibration curves for identified compound. The identification of the compounds was carried out with a GC-MS equipment equipped with a similar stationary phase and two different lengths 30 and 60 m. The compounds were separated by their different retention times and identified individually according to the spectrum collection of the Wiley / NBS database.
MODO DE REALIZACIÓN DE LA INVENCIÓN Ejemplo 1MODE OF EMBODIMENT OF THE INVENTION Example 1
Una muestra de 50 Kg de aceituna de la variedad 'Manzanilla' con índice de madurez entre 0 y 1 y una consistencia de 45 N/cm2 se divide aleatoriamente en 2 submuestras de 10 Kg cada una. La primera de ellas es procesada directamente y le es extraído su aceite, utilizándose como control. Las restantes se sumergen durante 3 minutos en agua a 68 DCy a continuación también se procesa como la anterior. Los parámetros físicos, químicos y sensoriales que miden la categoría de calidad obtenida por estos aceites se presenta en la Tabla I. A sample of 50 kg of olive of the variety 'Manzanilla' with maturity index between 0 and 1 and a consistency of 45 N / cm 2 is divided randomly into 2 sub-samples of 10 kg each. The first one is processed directly and its oil is extracted, using it as a control. The rest are immersed for 3 minutes in water at 68 D Cy and then also processed as above. The physical, chemical and sensory parameters that measure the quality category obtained by these oils are presented in Table I.
Figure imgf000013_0001
Figure imgf000013_0001
Los tratamientos térmicos no determinan en ningún caso que se produzca una pérdida de categoría comercial del aceite de oliva virgen obtenido, ya que los valores alcanzados en los distintos parámetros se mantienen dentro de los límites exigidos para el virgen extra.The thermal treatments do not determine in any case that there is a loss of commercial category of the virgin olive oil obtained, since the values reached in the different parameters are kept within the limits required for the extra virgin.
En la Tabla II se muestra como el tratamiento térmico provoca una reducción de las intensidades de amargo y picante determinados sensorialmente así como del contenido en derivados secoirideos de hidroxitirosol y tirasol del aceite obtenido.In Table II it is shown how the heat treatment causes a reduction of the sensorially determined bitter and spicy intensities as well as the content of hydroxytyrosol and sunflower derivatives of the obtained oil.
TABLA IITABLE II
Figure imgf000014_0001
Figure imgf000014_0001
En la Tabla III se muestra el efecto del tratamiento sobre el contenido en pigmentos del aceite, los cuales se ven considerablemente incrementados.Table III shows the effect of the treatment on the content of oil pigments, which are considerably increased.
TABLA IIITABLE III
Figure imgf000014_0002
Figure imgf000014_0002
En la Figura 1 se compara el perfil de componentes volátiles del aceite obtenido a partir de las aceitunas tratadas con el control, observándose la disminución del número de componentes y en la intensidad de los mismos, no observándose la aparición de ningún componente ajeno al control, que pudiera indicar el desarrollo de cualquier olor extraño al aceite de oliva virgen. Figure 1 compares the profile of volatile components of the oil obtained from the olives treated with the control, observing the decrease in the number of components and the intensity thereof, not observing the appearance of any component unrelated to the control, that could indicate the development of any strange smell of virgin olive oil.
Los compuestos volátiles del aroma del aceite que se ven más afectados por el tratamiento térmico de la aceituna corresponden a los picos cromatográficos : (1) acetato de metilo. (2) metanol. (3) 2-metilbutanal. (4) etanol. (5 y 6) dímeros de penteno. (7) 1-penten-3-ona. (8 y 9) dímeros de penteπo. (10) hexanal. (11) Z2-pentenal. (12) E3-hexenal. (13) Z3-hexenal. (14) 1-penten-3-ol. (15) Z2- hexenal. (16) £2-hexenal. (17) desconocido. (18) desconocido. (19) acetato de Z3-hexenilo. (20) £2-peπtenol. (21 ) Z2-pentenol. (22) hexanol. (23) Z3-hexenol. (24) desconocido. (25) ácido acético.The volatile compounds of the oil aroma that are most affected by the heat treatment of the olive correspond to the chromatographic peaks: (1) methyl acetate. (2) methanol. (3) 2-methylbutanal. (4) ethanol. (5 and 6) pentene dimers. (7) 1-penten-3-one. (8 and 9) penteπo dimers. (10) hexanal. (11) Z2-pentenal. (12) E3-hexenal. (13) Z3-hexenal. (14) 1-penten-3-ol. (15) Z2- hexenal. (16) £ 2-hexenal. (17) unknown. (18) unknown. (19) Z3-hexenyl acetate. (20) £ 2-peπtenol. (21) Z2-pentenol. (22) hexanol. (23) Z3-hexenol. (24) unknown. (25) acetic acid.
Ejemplo 2Example 2
A una muestra de 100 gramos de aceitunas, tomada de una matriz de 500 gramos de la variedad Hojiblanca, con un índice de maduración comprendido entre 3 y 4, se le sometió a la prueba de rendimiento mediante sistema ABENCOR, según las condiciones usuales, obteniendo en dicha prueba 18 gramos de aceite.A sample of 100 grams of olives, taken from a 500 gram matrix of the Hojiblanca variety, with a maturity index between 3 and 4, was subjected to the yield test by the ABENCOR system, according to the usual conditions, obtaining in said test 18 grams of oil.
A 100 gramos de aceitunas alícuotas de la misma matriz de 500 gramos, se le sometió a un tratamiento térmico por inmersión en agua a 85 °C, durante 90 segundos. Se enfrió de forma natural no forzada hasta los 40 °C antes de proceder a su molienda, para someterla a la prueba de rendimiento mediante sistema ABENCOR, al igual que antes según las condiciones usuales, obteniéndose en dicha prueba 18.8 gramos de aceite. To 100 grams of aliquots of the same matrix of 500 grams, it was subjected to a thermal treatment by immersion in water at 85 ° C, for 90 seconds. It was cooled in a natural unforced way until 40 ° C before proceeding to its grinding, to submit it to the performance test by ABENCOR system, as before according to the usual conditions, obtaining in this test 18.8 grams of oil.

Claims

REIVINDICACIONES
1.- Aceite de oliva virgen con características sensoriales modificadas obtenido de aceitunas de cualquier variedad e índice de maduración menor o igual que 3,0, caracterizado porque el aceite sin mezclar con ningún otro aceite o compuesto presenta simultáneamente los siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifenoles totales (mmoles/Kg de aceite): ≤ 2,0 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 1 ,0 clorofila b (mg/Kg de aceite): ≥ 5 clorofila a (mg/Kg de aceite): ≥ 301.- Virgin olive oil with modified sensory characteristics obtained from olives of any variety and maturity index less than or equal to 3.0, characterized in that the oil without mixing with any other oil or compound simultaneously has the following contents in compounds related to odor, taste and coloration: total polyphenols (mmol / kg of oil): ≤ 2.0 secoiridoid derivatives (mmol / kg of oil): ≤ 1.0 chlorophyll b (mg / kg of oil): ≥ 5 chlorophyll a (mg / Kg of oil): ≥ 30
2.- Aceite de oliva virgen con características sensoriales modificadas según la reivindicación 1 , caracterizado porque cuando la variedad de la aceituna de la cual se obtiene el aceite es Hojiblanca con un índice de maduración ≤ 3,0 y una resistencia a la penetración comprendida entre 35 y 60 N/cm2, el aceite sin mezclar con ningún otro aceite o compuesto presenta simultáneamente los siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifeπoles totales (mmoles/Kg de aceite): ≤ 0,9 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 0,7 luteína (mg/Kg de aceite): ≥ 5,0 clorofila b (mg/Kg de aceite): ≥ 5,0 clorofila a (mg/Kg de aceite): ≥ 30,0 feofitina b (mg/Kg de aceite): ≥ 0,1 feofitina a (mg/Kg de aceite): ≥ 5,0 β- caroteno (mg/Kg de aceite): ≥ 2,52.- Virgin olive oil with modified sensory characteristics according to claim 1, characterized in that when the olive variety from which the oil is obtained is Hojiblanca with a ripening index ≤ 3.0 and a resistance to penetration between 35 and 60 N / cm 2 , the oil without mixing with any other oil or compound simultaneously has the following contents in compounds related to odor, taste and coloration: total polypheols (mmoles / Kg of oil): ≤ 0.9 Sequoia derivatives (mmoles / Kg of oil): ≤ 0.7 lutein (mg / Kg of oil): ≥ 5.0 chlorophyll b (mg / Kg of oil): ≥ 5.0 chlorophyll a (mg / Kg of oil) : ≥ 30.0 pheophytin b (mg / Kg oil): ≥ 0.1 pheophytin a (mg / Kg oil): ≥ 5.0 β-carotene (mg / Kg oil): ≥ 2.5
3.- Aceite de oliva virgen con características sensoriales modificadas según la reivindicación 1 , caracterizado porque cuando la variedad de la aceituna de la cual se obtiene el aceite es 'Manzanilla' con un índice de maduración ≤ 3,0 y una resistencia a la penetración comprendida entre 35 y 60 N/cm2, el aceite sin mezclar con ningún otro aceite o compuesto presenta simultáneamente los 3.- Virgin olive oil with modified sensory characteristics according to claim 1, characterized in that when the olive variety from which the oil is obtained is 'Chamomile' with a ripening index ≤ 3.0 and a resistance to penetration comprised between 35 and 60 N / cm 2 , the oil without mixing with any other oil or compound simultaneously presents the
siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifenoles totales (mmoles/Kg de aceite): ≤ 2,0 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 1,0 luteína (mg/Kg de aceite): ≥ 6,0 clorofila b (mg/Kg de aceite): ≥ 8,0 clorofila a (mg/Kg de aceite): ≥ 30,0 feofitiπa b (mg/Kg de aceite): ≥ 0,1 feofltina a (mg/Kg de aceite): ≥ 7,0 β- caroteno (mg/Kg de aceite): ≥ 2,5following content in compounds related to odor, taste and coloration: total polyphenols (mmol / Kg of oil): ≤ 2.0 secoiridoid derivatives (mmol / Kg of oil): ≤ 1.0 lutein (mg / Kg of oil ): ≥ 6.0 chlorophyll b (mg / Kg of oil): ≥ 8.0 chlorophyll a (mg / Kg of oil): ≥ 30.0 pheophytine b (mg / Kg of oil): ≥ 0.1 pheophylline a (mg / Kg of oil): ≥ 7.0 β-carotene (mg / Kg of oil): ≥ 2.5
4.- Aceite de oliva virgen con características sensoriales modificadas según la reivindicación 1 , caracterizado porque cuando la variedad de la aceituna de la cual se obtiene el aceite es 'Picual' con un índice de maduración ≤ 3,0 y una resistencia a la penetración comprendida entre 35 y 60 N/cm2, el aceite sin mezclar con ningún otro aceite o compuesto presenta simultáneamente los siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifenoles totales (mmoles/Kg de aceite): ≤ 0,8 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 0,5 luteina (mg/Kg de aceite): ≥ 5,0 clorofila b (mg/Kg de aceite): ≥ 9,0 clorofila a (mg/Kg de aceite): ≥ 35,0 feofitina b (mg/Kg de aceite): ≥ 0,1 feofitina a (mg/Kg de aceite): ≥ 5,0 β- caroteno (mg/Kg de aceite): ≥ 1 ,54.- Virgin olive oil with modified sensory characteristics according to claim 1, characterized in that when the olive variety from which the oil is obtained is 'Picual' with a ripening index ≤ 3.0 and a resistance to penetration comprised between 35 and 60 N / cm 2 , the oil without mixing with any other oil or compound simultaneously has the following contents in compounds related to odor, taste and coloration: total polyphenols (mmoles / Kg of oil): ≤ 0 , 8 secoiridoid derivatives (mmoles / Kg of oil): ≤ 0.5 lutein (mg / Kg of oil): ≥ 5.0 chlorophyll b (mg / Kg of oil): ≥ 9.0 chlorophyll a (mg / Kg of oil): ≥ 35.0 pheophytin b (mg / Kg oil): ≥ 0.1 pheophytin a (mg / Kg oil): ≥ 5.0 β-carotene (mg / Kg oil): ≥ 1.5
5.- Aceite de oliva virgen con características sensoriales modificadas según la reivindicación 1 , caracterizado porque cuando la variedad de la aceituna de la cual se obtiene el aceite es 'Verdial' con un índice de maduración ≤ 3,0 y una resistencia a la penetración comprendida entre 35 y 60 N/cm2, el aceite sin mezclar con ningún otro aceite o compuesto presenta simultáneamente los 5.- Virgin olive oil with modified sensory characteristics according to claim 1, characterized in that when the variety of the olive from which the oil is obtained is 'Verdial' with a ripening index ≤ 3.0 and a resistance to penetration comprised between 35 and 60 N / cm 2 , the oil without mixing with any other oil or compound simultaneously presents the
siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifenoles totales (mmoles/Kg de aceite): ≤ 0,9 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 0,8 luteína (mg/Kg de aceite): ≥ 9,0 clorofila b (mg/Kg de aceite): ≥ 12,0 clorofila a (mg/Kg de aceite): ≥ 40,0 feofitina b (mg/Kg de aceite): ≥ 0,1 feofitlna a (mg/Kg de aceite): ≥ 5,0 β- caroteno (mg/Kg de aceite): ≥ 4,5following content of compounds related to odor, taste and coloration: total polyphenols (mmol / Kg of oil): ≤ 0.9 secoiridoid derivatives (mmol / Kg of oil): ≤ 0.8 lutein (mg / Kg of oil ): ≥ 9.0 chlorophyll b (mg / Kg of oil): ≥ 12.0 chlorophyll a (mg / Kg of oil): ≥ 40.0 pheophytin b (mg / Kg of oil): ≥ 0.1 pheophytin a (mg / Kg of oil): ≥ 5.0 β-carotene (mg / Kg of oil): ≥ 4.5
6.- Aceite de oliva virgen con características sensoriales modificadas obtenido de aceitunas de cualquier variedad con índice de maduración >3, caracterizado porque el aceite sin mezclar con ningún otro aceite o compuesto presenta simultáneamente los siguientes contenidos en compuestos relacionados con el olor, el sabor y la coloración: polifenoles totales (mmoles/Kg de aceite): ≤ 1 ,0 derivados secoiridoideos (mmoles/Kg de aceite): ≤ 0,5 luteína (mg/Kg de aceite): ≥ 1 ,5 clorofila b (mg/Kg de aceite): ≥ 0,5 clorofila a (mg/Kg de aceite): ≥ 2,0 feofitina b (mg/Kg de aceite): ≥ 0,05 feofitiπa a (mg/Kg de aceite): ≥ 0,3 β- caroteno (mg/Kg de aceite): ≥ 0,36.- Virgin olive oil with modified sensory characteristics obtained from olives of any variety with a maturity index> 3, characterized in that the oil, not mixed with any other oil or compound, simultaneously has the following contents in compounds related to odor, taste and the coloration: total polyphenols (mmoles / Kg of oil): ≤ 1, 0 secoiridoid derivatives (mmoles / Kg of oil): ≤ 0.5 lutein (mg / Kg of oil): ≥ 1.5 chlorophyll b (mg / Kg of oil): ≥ 0.5 chlorophyll a (mg / Kg of oil): ≥ 2.0 pheophytin b (mg / Kg of oil): ≥ 0.05 pheophytine a (mg / Kg of oil): ≥ 0, 3 β-carotene (mg / Kg of oil): ≥ 0.3
7.- Procedimiento de obtención de un aceite de oliva virgen con características sensoriales modificadas según las reivindicaciones 1-6 que incluye una etapa de molienda de las aceitunas y posterior separación del aceite mediante técnicas de separación sólido-líquido aplicadas a la pasta obtenida tras la molienda caracterizado porque antes de la molienda las aceitunas se someten a un tratamiento térmico consistente en la inmersión de las aceitunas en agua a una temperatura comprendida entre 40°C y 150°C durante un periodo comprendido entre 30 segundos y 120 minutos. 7.- Procedure for obtaining a virgin olive oil with modified sensorial characteristics according to claims 1-6, which includes a milling step of the olives and subsequent oil separation by means of solid-liquid separation techniques applied to the paste obtained after the milling characterized in that before milling the olives are subjected to a heat treatment consisting of immersing the olives in water at a temperature between 40 ° C and 150 ° C for a period of between 30 seconds and 120 minutes.
8.- Procedimiento de obtención de un aceite de oliva virgen con características sensoriales modificadas según la reivindicaciones 1-6 que incluye una etapa de molienda de las aceitunas y posterior separación del aceite mediante técnicas de separación sólido-líquido aplicadas a la pasta obtenida tras la molienda caracterizado porque antes de la molienda las aceitunas se someten a un tratamiento térmico consistente en la ducha de las aceitunas con agua o vapor de agua a una temperatura comprendida entre 40°C y 150°C durante un periodo comprendido entre 30 segundos y 120 minutos.8.- Procedure for obtaining a virgin olive oil with modified sensory characteristics according to claims 1-6, which includes a milling step of the olives and subsequent oil separation by means of solid-liquid separation techniques applied to the paste obtained after the milling characterized in that before milling the olives are subjected to a thermal treatment consisting of showering the olives with water or steam at a temperature between 40 ° C and 150 ° C for a period of between 30 seconds and 120 minutes .
1010
9.- Procedimiento de obtención de un aceite de oliva con características sensoriales modificadas virgen según la reivindicaciones 1-6 que incluye una etapa de molienda de las aceitunas y posterior separación del aceite mediante técnicas de separación sólido-líquido aplicadas a la pasta obtenida tras la 15 molienda caracterizado porque antes de la molienda las aceitunas se someten a un tratamiento térmico consistente en la Irradiación con microondas con una potencia comprendida entre 200 y 1.200 Watios durante un periodo comprendido entre 10 y 300 segundos9.- Procedure for obtaining an olive oil with virgin modified sensory characteristics according to claims 1-6, which includes a milling step of the olives and subsequent oil separation by means of solid-liquid separation techniques applied to the paste obtained after the 15 milling characterized in that before milling the olives undergo a heat treatment consisting of microwave irradiation with a power of between 200 and 1,200 Watts for a period of between 10 and 300 seconds
20 10.- Procedimiento de obtención de un aceite de oliva virgen con características sensoriales modificadas según las reivindicaciones 7-9, caracterizado porque la pasta obtenida tras la molienda no es sometida a ningún tratamiento térmico.10.- Procedure for obtaining a virgin olive oil with modified sensory characteristics according to claims 7-9, characterized in that the paste obtained after grinding is not subjected to any heat treatment.
25 11.- Procedimiento de obtención de un aceite de oliva virgen con características sensoriales modificadas según las reivindicaciones 7-9, caracterizado porque el aceite obtenido tras la separación sólido-líquido no se mezcla con ningún otro aceite o con cualquier compuesto que induzca modificaciones en su olor, sabor o coloración.11.- Procedure for obtaining a virgin olive oil with modified sensory characteristics according to claims 7-9, characterized in that the oil obtained after the solid-liquid separation is not mixed with any other oil or with any compound that induces modifications in its smell, taste or coloration.
30 30
12.- Procedimiento de obtención de un aceite de oliva virgen con características sensoriales modificadas según las reivindicaciones 7-9, caracterizado porque el rendimiento de extracción de aceite aumenta entre un 3% y un 7% respecto al rendimiento obtenido cuando las aceitunas no se someten a tratamiento térmico. 12.- Procedure for obtaining a virgin olive oil with modified sensory characteristics according to claims 7-9, characterized in that the oil extraction yield increases between 3% and 7% with respect to the yield obtained when the olives are not subjected to heat treatment.
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WO2005087208A2 (en) * 2004-03-10 2005-09-22 Trustees Of Tufts College Synergistic effect of compositions comprising carotenoids selected from lutein, beta-carotene and lycopene
WO2006117826A2 (en) * 2005-05-02 2006-11-09 Sooft Italia Srl Composition comprising olive oil enriched and supplemented with lutein
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EP1211303A1 (en) * 2000-12-01 2002-06-05 Jean-Pierre Martel Method and apparatus for the integrated upgrading of oil-bearing drupes, especially olives and the products resulting therefrom
FR2840317A1 (en) * 2002-06-03 2003-12-05 Pierre Olivier Cogat Production of products from oleaginous drupes, especially olive oil, comprises processing whole fruits

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FR2840317A1 (en) * 2002-06-03 2003-12-05 Pierre Olivier Cogat Production of products from oleaginous drupes, especially olive oil, comprises processing whole fruits

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005087208A2 (en) * 2004-03-10 2005-09-22 Trustees Of Tufts College Synergistic effect of compositions comprising carotenoids selected from lutein, beta-carotene and lycopene
WO2005087208A3 (en) * 2004-03-10 2005-11-03 Tufts College Synergistic effect of compositions comprising carotenoids selected from lutein, beta-carotene and lycopene
WO2006117826A2 (en) * 2005-05-02 2006-11-09 Sooft Italia Srl Composition comprising olive oil enriched and supplemented with lutein
WO2006117826A3 (en) * 2005-05-02 2006-12-28 Sooft Italia Srl Composition comprising olive oil enriched and supplemented with lutein
US20210051971A1 (en) * 2018-01-31 2021-02-25 J -Oil Mills, Inc. Method for stabilizing oil or fat composition for frying use

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