Evaluation of methodologies to determine vegetable oil species present in oil mixtures: Proposition of an approach to meet the EU legislation demands for correct vegetable oils labelling

Refined vegetable oils are widely used in the food industry as ingredients or components in many processed food products in the form of oil blends. To date, the generic term 'vegetable oil' has been used in the labelling of food containing oil blends. With the introduction of new EU Regulation for Food Information (1169/2011) due to take effect in 2014, the oil species used must be clearly identified on the package and there is a need for development of fit for purpose methodology for industry and regulators alike to verify the oil species present in a product. The available methodologies that may be employed to authenticate the botanical origin of a vegetable oil admixture were reviewed and evaluated. The majority of the sources however, described techniques applied to crude vegetable oils such as olive oil due to the lack of refined vegetable oil focused studies. Nevertheless, DNA based typing methods and stable isotopes procedures were found not suitable for this particular purpose due to several issues. Only a small number of specific chromatographic and spectroscopic fingerprinting methods in either targeted or untargeted mode were found to be applicable in potentially providing a solution to this complex authenticity problem. Applied as a single method in isolation, these techniques would be able to give limited information on the oils identity as signals obtained for various oil types may well be overlapping. Therefore, more complex and combined approaches are likely to be needed to identify the oil species present in oil blends employing a stepwise approach in combination with advanced chemometrics. Options to provide such a methodology are outlined in the current study.

Identifying oil species in oil mixtures

Detection of adulteration of non-processed vegetable oil with lesser value seed oils (classic example is hazelnut in virgin olive oil) has been in the centre of scientific attention for many years and several chemical methods were proposed. The recent EC Regulation 1169/2011, however, introduces necessity for different analytical method in a more complicated matrix. From the end of 2014, food businesses required to declare the composition of the refined oil mixture in the food product label. This creates a gap since there is no analytical method currently available to perform such analysis. In the first phase the work focused on 100% oil blends of various oil species of palm oil (and derivatives), sunflower and rapeseed oil before expanding to foodstuffs. Chromatographic methods remain highly relevant although suffer from various limitations which derive from natural compositional variation. Modern multivariate techniques based on machine learning algorithms, however, when applied in FTIR, Raman spectroscopic data have a strong potential in tackling the problem.

Development and application of NMR techniques to study water-in-CO2 microemulsions

Self-assembly is a phenomenon that occurs frequently throughout the universe. In this work, two self-assembling systems were studied: the formation of reverse micelles in isooctane and in supercritical CO2 (scCO2), and the formation of gels in organic solvents. The goal was the physicochemical study of these systems and the development of an NMR methodology to study them. In this work, AOT was used as a model molecule both to comprehensively study a widely researched system water/AOT/isooctane at different water concentrations and to assess its aggregation in supercritical carbon dioxide at different pressures. In order to do so an NMR methodology was devised, in which it was possible to accurately determine hydrodynamic radius of the micelle (in agreement with DLS measurements) using diffusion ordered spectroscopy (DOSY), the micellar stability and its dynamics. This was mostly assessed by 1H NMR relaxation studies, which allowed to determine correlation times and size of correlating water molecules, which are in agreement with the size of the shell that interacts with the micellar layer. The encapsulation of differently-sized carbohydrates was also studied and allowed to understand the dynamics and stability of the aggregates in such conditions. A W/CO2 microemulsion was prepared using AOT and water in scCO2, with ethanol as cosurfactant. The behaviour of the components of the system at different pressures was assessed and it is likely that above 130 bar reverse microemulsions were achieved. The homogeneity of the system was also determined by NMR. The formation of the gel network by two small molecular organogelators in toluene-d8 was studied by DOSY. A methodology using One-shot DOSY to perform the spectra was designed and applied with success. This yielded an understanding about the role of the solvent and gelator in the aggregation process, as an estimation of the time of gelation.

Lipase from marine Aspergillus awamori BTMFW032: Production, partial purification and application in oil effluent treatment

Marine fungus BTMFW032, isolated from seawater and identified as Aspergillus awamori, was observed to produce an extracellular lipase, which could reduce 92% fat and oil content in the effluent laden with oil. In this study, medium for lipase production under submerged fermentation was optimized statistically employing response surface method toward maximal enzyme production. Medium with soyabean meal- 0.77% (w/v); (NH4)2SO4-0.1 M; KH2PO4-0.05 M; rice bran oil-2% (v/v); CaCl2-0.05 M; PEG 6000-0.05% (w/v); NaCl-1% (w/v); inoculum-1% (v/v); pH 3.0; incubation temperature 35 8C and incubation period-five days were identified as optimal conditions for maximal lipase production. The time course experiment under optimized condition, after statistical modeling, indicated that enzyme production commenced after 36 hours of incubation and reached a maximum after 96 hours (495.0 U/ml), whereas maximal specific activity of enzyme was recorded at 108 hours (1164.63 U/mg protein). After optimization an overall 4.6- fold increase in lipase production was achieved. Partial purification by (NH4)2SO4 precipitation and ion exchange chromatography resulted in 33.7% final yield. The lipase was noted to have a molecular mass of 90 kDa and optimal activity at pH 7 and 40 8C. Results indicated the scope for potential application of this marine fungal lipase in bioremediation.

Bovine serum albumin produces a synergistic increase in the antioxidant activity of virgin olive oil phenolic compounds in oil-in-water emulsions

Virgin olive oil is valued for its flavor, but unacceptable off-flavors may develop on storage in food products containing this oil due to oxidation. The oxidative stability of oil-in-water emulsions containing bovine serum albumin (BSA) and virgin olive oil phenolic compounds was studied. Four oil-in-water emulsions with and without BSA and phenols isolated from virgin olive oil were prepared. These model systems were stored at 60 degrees C to speed up lipid oxidation. Primary and secondary oxidation products were monitored every three days. Peroxide values and conjugated diene contents were determined as measures of the primary oxidation products. p-Anisidine values and volatile compounds were determined as measures of the secondary oxidation products. This latter determination was carried out by headspace solid-phase microextraction coupled with gas chromatography. Although olive oil phenolic compounds and BSA contributed some antioxidant activity when present as individual additives, the combination of BSA with phenols in an emulsion showed 58-127% synergy, depending on which analytical method was used in the calculation. The emulsion containing phenolic compounds and BSA showed a low level of deterioration after 45 days of storage at 60 degrees C.

Solid phase microextraction of volatile oxidation compounds in oil-in-water emulsions

Headspace solid phase microextraction (HS-SPME) has been used to isolate the headspace volatiles formed during oxidation of oil-in-water emulsions. Qualitative and quantitative analyses with an internal standard were performed by GC-FID. Four sample temperatures for adsorption (30, 40, 50 and 60 C) and adsorption times in the range 10-25 min were tested to determine the conditions for the volatile concentration to reach equilibrium. The optimum conditions were at 50 C for 20 min. The method was applied to monitor changes in volatile composition during oxidation of an o/w emulsion. SPME was a simple, reproducible and sensitive method for the analysis of volatile oxidation products in oil-in-water emulsions. (c) 2004 Elsevier Ltd. All rights reserved.

Albumin causes a synergistic increase in the antioxidant activity of green tea catechins in oil-in-water emulsions

Model oil-in-water emulsions containing epicatechin (EC) and epigallocatechin gallate (EGCG) showed a synergistic increase in stability in emulsions containing added albumin. EGCG showed a stronger synergy (35%) with ovalbumin than did EC. Oxidation of the oil was monitored by determining peroxide values and hexanal contents. The effect of bovine serum albumin (BSA) on model oil-in-water emulsions containing each of the green tea catechins [epicatechin gallate (ECG), EGCG, EC and epigallocatechin (EGC)] was studied during storage at 30 degrees C. The green tea catechins showed moderate antioxidant activity in the emulsions with the order of activity being ECG approximate to EGCG > EC > EGC. Although BSA had very little antioxidant activity in the absence of phenolic antioxidants, the combination of BSA with each of the catechins showed strong antioxidant activity. BSA, in combination with EC, EGCG or EGC, showing the strongest antioxidant activity with good stability after 45 days storage. Model experiments with the catechins stored with BSA in aqueous solutions confirmed that protein-catechin adducts with antioxidant activity were formed between the catechins and protein. The antioxidant activity of the separated protein-catechin adducts increased strongly with storage time and was stronger for EGCG and ECG than for EC or EGC. (c) 2006 Elsevier Ltd. All rights reserved.

Production of haploids and doubled haploids in oil palm

Background: Oil palm is the world’s most productive oil-food crop despite yielding well below its theoretical maximum. This maximum could be approached with the introduction of elite F1 varieties. The development of such elite lines has thus far been prevented by difficulties in generating homozygous parental types for F1 generation. Results: Here we present the first high-throughput screen to identify spontaneously-formed haploid (H) and doubled haploid (DH) palms. We secured over 1,000 Hs and one DH from genetically diverse material and derived further DH/mixoploid palms from Hs using colchicine. We demonstrated viability of pollen from H plants and expect to generate 100% homogeneous F1 seed from intercrosses between DH/mixoploids once they develop female inflorescences. Conclusions: This study has generated genetically diverse H/DH palms from which parental clones can be selected in sufficient numbers to enable the commercial-scale breeding of F1 varieties. The anticipated step increase in productivity may help to relieve pressure to extend palm cultivation, and limit further expansion into biodiverse rainforest.

Effects of caffeic acid and bovine serum albumin in reducing the rate of development of rancidity in oil-in-water and water-in-oil emulsions

The antioxidant properties of caffeic acid and bovine serum albumin in oil-in-water and water-in-oil emulsions were studied. Caffeic acid (5 mmol/kg emulsion) showed good antioxidant properties in both 30% sunflower oil-in-water (OW) and 20% water-in-sunflower oil emulsions (WO), pH 5.4, during storage at 50 ºC. Although bovine serum albumin (BSA) (0.2%) had a slight antioxidant effect, the combination of caffeic acid and BSA showed a synergistic reduction in the rate of development of rancidity, with significant reductions in concentration of total volatiles, peroxide value (PV) and p-anisidine value (PA) for both emulsion types. The synergistic increase in stability of the OW and WO emulsions containing BSA and caffeic acid was 102.9 and 50.4 % respectively based on TOTOX values, which are calculated as 2PV + PA, with greater synergy calculated if based on formation of headspace volatiles, The OW emulsion was more susceptible to the development of headspace volatiles by oxidation than the WO emulsion, even though the degree of oxidation assessed by the TOTOX value was similar.

Physicochemical changes occuring in oil when atmospheric frying is combined with post-frying vacuum application

The aim of this study was to investigate the effect of atmospheric frying followed by drainage under vacuum on the stability of oil, compared to similar frying with drainage at atmospheric pressure. Changes in the oil were assessed by the free fatty acid (FFA) content, p-anisidine value (AnV), colour, viscosity, fatty acid profile and concentration of tocols. The rate of FFA formation in the case of vacuum drainage was found to be about half that of atmospheric drainage. Oil deterioration by oxidation and polymerisation was also reduced by the use of vacuum drainage. The AnV of the oil after vacuum drainage was lower by about 12%, the total colour difference was improved by 14% and viscosity was slightly reduced after 5 days of frying, compared to the values for oil that had been drained at atmospheric pressure. There was a reduction in the loss of polyunsaturated fatty acids in the case of vacuum drainage after 5 days of frying but differences in retention of tocols were only evident in the first two days of frying.

Antioxidant properties of three aromatic herbs (rosemary, thyme and lavender) in oil-in-water emulsions

Lipid oxidation is the major form of deterioration in foods because it decreases food quality and nutritional value, and may have negative health implications. Selected aromatic plant extracts from leaves, flowers and stems of rosemary, thyme and lavender were investigated for their antioxidant activity. The total polyphenol content was determined by the Folin-Ciocalteu assay and the antioxidant capacity was determined by the Trolox equivalent antioxidant capacity, 1,1-diphenyl-2-picrylhydrazyl, oxygen radical absorbance capacity and ferric-reducing antioxidant power assays. For all four antioxidant assays, the extracts from thyme flowers, lavender leaves and thyme leaves had the highest antioxidant activity, followed by rosemary stems, rosemary leaves, and lavender stems, and the lavender flowers and thyme stems had the lowest antioxidant activity. The antioxidant activity was correlated with the polyphenol content, although minor deviations were observed. In oil-in-water emulsion, extracts from rosemary leaves and thyme leaves were most effective at retarding oxidation followed by the rosemary stems and thyme flowers. Extracts from thyme flowers and lavender leaves were less effective in the emulsion than predicted by the homogeneous antioxidant assays. This study demonstrated the potential use of plants extract as substitutes for synthetic antioxidants.

Dissolved radioelements in (oil) water wells in Parana basin, Brazil

This paper describes the results of a study on groundwaters from Tubarao Group at the Parana sedimentary basin, São Paulo State, Brazil. The purpose of this study was to integrate chemical and U-isotopes data in order to evaluate the models for quantifying different relative volumes of mixing waters in a resultant water. Despite it was possible to generate a typical triangle involving U-238 and its daughter U-234, the U-isotopes model failed to interpret the major hydrochemical facies observed in the studied localities.

Ultrasonic characterization of emulsions: milk and water in oil

Measurements of ultrasonic attenuation and velocity in milk and low concentration water-in-oil (W/O) emulsion were conducted, using a measurement cell with a double-element transducer that eliminates diffraction losses. The milk is characterized by the attenuation coefficient, while in the case of water-in-oil emulsions, the characterization is best represented by the propagation velocity.

Selective factors involved in oil flotation isolation of black yeasts from the environment

The oil flotation isolation technique has been successfully applied to recover chaetothyrialean black yeasts and relatives from the environment. The selective mechanisms playing a role in isolation are unknown. The fungi concerned are supposed to occupy specialized microniches in nature, taking advantage of (1) oligotrophism. Mineral oil as a main selective agent may be based on (2) hydrophobicity or on (3) assimilation. All three hypotheses are tested in this paper. Results show that cell wall hydrophobicity is unlikely to be a selective factor. Incubation under poor nutrient conditions provides competitive advantage for black yeasts, especially for Exophiala strains, which are subsequently enriched by mineral oil which enhances growth in this group of fungi. Incubation under mineral media and mineral oil can be used as selective factor.

Simple and direct potentiometric determination of potassium ions in biodiesel microemulsions at a glassy carbon electrode modified with nickel(II) hexacyanoferrate nanoparticles

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)