Edible oil quality as measured by thermal release of pentane

As part of their thermal decomposition products, fatty hydroperoxides produce normal hydrocarbons. The extent of hydrocarbon formation can be measured and associated with the quality and potential stability of an oil. Edible oils containing linoleic acid develop 13-hydroperoxy-9,11-octadecadienoic acid as one product of autoxidation. On thermal decomposition this hydroperoxide yields pentane; the amount released has been correlated with the flavor scores of fresh and aged soybean and cottonseed oils and with the peroxide values of these oils. The quantity of pentane released has an inverse linear relationship to flavor score and a direct linear relationship to peroxide values. Edible oils exposed to light exhibit a different relationship between flavor score and thermally derived pentane than do the same oils when autoxidized in the dark. Presented at AOCS Meeting, New Orleans, May 1967.     

Effect of processing on the oxidative stability of low erucic acid turnip rapeseed (Brassica rapa) oil

The effect of various processing conditions on the composition and the oxidative stability of mechanically pressed (90–95°C) rapeseed oil was investigated. The five different rapeseed oils included crude (nondegummed), superdegummed, steam stripped (at 140°C for 4h, nondegummed), physically refined (degummed, bleached and deodorized at 240°C), and cold pressed (40°C) oils. Oils were autoxidized in the dark at 60°C and under light at 25°C. Oxidation was followed by measuring changes in the peroxide values (PV) and the consumption of tocopherol and carotenoid was measured. In the dark the oils reached PVs of 10 meq/kg in the order: cold pressed > superdegummed > steam stripped ≅ crude > refined. However, under light conditions the order changed as follows: cold pressed > crude ≅ steam stripped > superdegummed > refined. Processing had no effect on fatty acid composition nor α-tocopherol content of the oils. Superdegumming and steam stripping decreased the carotenoid content of the oils while cold pressing and refining reduced also chlorophyll, γ-tocopherol and phosphorus content of the oils.     

Studies on the flavor of autoxidized soybean oil

The flavor components of soybean oil in the early stages of autoxidation were isolated by distillation in a molecular still. The distillate consisted of an aqueous layer and an oily film. The oily film did not reproduce the autoxidized flavor when added to freshly deodorized oil. Gas chromatographic and organoleptic analysis indicated that the oily film contained hexanal, vinylamyl ketone, andtrans,cis-2,6-nonadienal. The aqueous layer reproduced the autoxidized flavor when added to freshly deodorized oil, and the flavor had a retention time on butandiol succinate columns between those of pentanal and hexanal. Mixtures of vinylethyl ketone and pentanal gave a flavor to freshly deodorized oil similar to the flavor of oil in the early stages of autoxidation. Vinylethyl ketone was identified in the distillate from autoxidized soybean oil as the 2,4-dinitrophenylhydrazone. Presented at the AOCS Meeting, Minneapolis, 1963.     

Adaptation of the AOCS official method for measuring hydroperoxides from small-scale oil samples

An adaptation of the American Oil Chemists' Society Official Method Cd 8–53 for determining peroxides in fats and oils using a 0.5-g sample is described. Comparisons of the Official Method and the small-scale method were performed by analyzing soybean oil samples spiked with t-butyl hydroperoxide and autoxidized soybean oil samples. A linear relationship between the Official Method and the small-scale method was obtained with an R ² of 0.998. The small-scale method is sensitive, precise, and suitable for small sample sizes and uses only about 10% of the chemicals necessary for the Official Method.     

Analysis of polymers from autoxidized marine oils by gel permeation HPLC using a light-scattering detector

A high-performance gel-permeation chromatographic method was developed for the isolation and quantification of polymers from autoxidized fish oils. The chromatographic system consists of a single pump, a 500 Å styrene/divinylbenzene column, and a light-scattering “mass” detector. Dichloromethane was used as the mobile phase, and quantifications were carried out using glycerol as internal standard. The polymer content of commercially available fish oils was found to be around 2%, but the value increased rapidly during oxidation at 35°C in air under light. The oxidized oils were also characterized by peroxide value, thiobarbituric acid value, ultraviolet (UV) measurements, thin-layer chromatography (TLC)/densitometry, and capillary gas chromatography. No correlation between polymer content and standard oxidation assessment parameters for the fish oils analyzed was found. However, a relationship between the polymer increase and the decrease of total fatty acids was observed, indicating that the polymers may be the main oxidation product in autoxidized marine oils.     

Efficiency of Gold Nano Particles on the Autoxidized Soybean Oil Polymer: Fractionation and Structural Analysis

Polyunsaturated plant oils have gained great interest as monomers to produce biodegradable polymers obtained from renewable resources due to the limited existing sources of petroleum oil and environmental issues. Soybean oil was autoxidized by exposure to atomospheric oxygen at room temperature with or without the presence of gold nanoparticles (Au NPs) 5–41 days. When the autoxidation process was catalyzed with Au NPs, the molecular weight of the oxidized oil was increased in 5 days. In contrast to this, without Au NPs, the oxidized oil was still a fluidized liquid. Autoxidized soybean oil polymer in toluene solution with gold NP showed a surface plasmon resonance at λ_max = 540 nm in a UV–VIS spectrometer and a fluorescence emission spectrum at λ_max = 450 nm, when it was irradiated at λ_max = 390 nm. The higher molecular weight of the polymeric oils was successively fractionated by the extraction from the solvent‐non‐solvent mixture CHCl₃/petroleum ether with the volume ratio of 5:15. Three polymeric oils fractions with different molecular weight (ca 1000, 4000, and 40,000 g/mol) were obtained. GC–MS analysis, ¹H‐NMR and GPC techniques were used in the structural analysis of the fractionated polymeric oils.     

Refractive index as an objective method for evaluation of rancidity in edible oils and fats

Common edible oils and fats (refined peanut oil, seasame oil, safflower oil, and butter oil, ghee) were exposed to direct sunlight, fluorescent light and Schaal Test. Data collected on refractive indices (N _D ²⁵ ) show an increase of the order of 0.001±0.0003 at the stage of development of perceptible rancid odor. The pattern of changes in refractive indices and peroxide values of these edible oils, autoxidized at 100±5 C, show that refractive indices indicate more precisely the termination of the induction periods than peroxide values.     

Interference of peroxides with the determination of total carbonyls in autoxidized fats

The contribution of hydroperoxides to the carbonyl content of autoxidized fats measured by a colorimetric 2,4-dinitrophenylhydrazone procedure has been studied. Carbonyls were determined in radiation oxidized methyl myristate, in autoxidized methyl esters of oleie, linoleic and linolenic acids and in autoxidized oils, before and after reduction of hydroperoxides to hydroxyl groups. The results indicate that hydroperoxides decompose to carbonyl compounds during the carbonyl determination and give carbonyl contents that are too high. The extent of the interference depends on the nature of the peroxides and, therefore, on the fatty acid composition of the material and on other factors probably associated with the conditions during autoxidation and subsequent storage. For these reasons it is not possible to apply a correction for peroxide interference based on the determined peroxide value. Carbonyl determinations on autoxidized lipids should be preceded by reduction of the peroxides to non-carbonyl compounds, and care should be taken to prevent losses of low molecular weight carbonyls during this procedure. Presented at the AOCS meeting, Houston, 1965.     

Influence of interesterification on the oxidative stability of marine oil triacylglycerols

To understand the relationship between triacylglycerol structure of marine oils and their oxidative stability, peroxide values and absorbed oxygen levels of whale, sardine, cod liver and skipjack oils, interesterified by lipase and NaOCH₃, were compared with those of native oils during storage at 40°C. Triacylglycerol structures of marine oils were characterized by high-performance liquid chromatography and differential scanning calorimetry analyses. Enzymatically interesterified fish oils were more stable than native oils because the level of highly unsaturated triacylglycerols was decreased. However, the oxidative stability of interesterified whale oil was more susceptible to oxidation than the native oil.     

Alkyl aryl ethers in lignite solubilization: 2. Analysis of oil fractions

The FT-i.r. and ¹H n.m.r. spectroscopic analyses of oils or maltenes from a Spanish lignite (Utrillas, Teruel), are reported. These oils were obtained by depolymerization with alkyl aromatic ethers (anisole, 3-methylanisoleand 1,3-dimethoxybenzene) catalyzed by Lewis acids ZnCl₂, AlCl₃, SbCl₃and BF₃ (as boron trifluoride etherate), at atmospheric pressure and temperatures <220 °C. Bands due to aromatic ethers in the i.r. and n.m.r. spectra of the oils obtained by depolymerization indicate solvent incorporation. Oils obtained by direct lignite extraction showed 25% aromatic H and some H_α (≈3%) without OH groups. These appeared in some oils obtained by depolymerization with AlCl₃ and were due to secondary reactions with the aromatic extract. Oils derived from processes with good yields showed increases in aromaticity. The extent of substitution of aromatic rings in oils obtained by depolymerization was less than for oils directly extracted. All the oils studied show a low degree of condensation.     

Radicals generated in autoxidized methyl linoleate by light irradiation

The structure of free radicals generated in the autoxidation of methyl linoleate (ML) was studied by the spin trapping technique using deuterated nitrosodurene, (CD₃)₄C₆HNO, as the spin trap. The secondary alkyl radicals were trapped after irradiation of ML with UV light. The formation rate of secondary alkyl radicals increased upon shortening the wavelength of irradiation light and was closely correlated with the peroxide value of autoxidized ML when a UV light longer than 250 nm was employed. When hydroperoxides separated from autoxidized ML were added to ML, the relationship between the formation rate of secondary alkyl radicals and the amounts of added hydroperoxides was nearly linear. These results suggest that secondary alkyl radicals are generated by proton abstraction of the active radicals, such as RO and HO, which are produced by the photolysis of hydroperoxides with UV light. The spin trapping technique can be applied to the study of lipid oxidation and/or photolysis of autoxidized lipid.     

Supercritical CO2 degumming and physical refining of soybean oil

A hexane-extracted crude soybean oil was degummed in a reactor by counter-currently contacting the oil with supercritical CO₂ at 55 MPa at 70°C. The phosphorus content of the crude oil was reduced from 620 ppm to less than 5 ppm. Degummed feedstocks were fed (without further processing,i.e., bleaching) directly to a batch physical refining step consisting of simultaneous deacidification/deodorization (1 h @ 260°C and 1–3 mm Hg) with and without 100 ppm citric acid. Flavor and oxidative stability of the oils was evaluated on freshly deodorized oils both after accelerated storage at 60°C and after exposure to fluorescent light at 7500 lux. Supercritical CO₂-processed oils were compared with a commercially refined/bleached soybean oil that was deodorized under the same conditions. Flavor evaluations made on noncitrated oils showed that uncomplexed iron lowered initial flavor scores of both the unaged commercial control and the CO₂-processed oils. Oils treated with .01% (100 ppm) citric acid had an initial flavor score about 1 unit higher and were more stable in accelerated storage tests than their uncitrated counterparts. Supercritical CO₂-processed oil had equivalent flavor scores, both initially and after 60°C aging and light exposure as compared to the control soybean oil. Results showed that bleaching with absorbent clays may be eliminated by the supercritical CO₂ counter-current processing step because considerable heat bleaching was observed during deacidification/deodorization. Colors of salad oils produced under above conditions typically ran 3Y 0.7R.     

Chemiluminescence as a method for oxidative rancidity assessment in autoxidized marine oils

Chemiluminescence based on light emission from excited oxygen species,e.g. singlet oxygen and triplet carbonyls, has been used to measure the oxidative rencidity of fish oils. The luminescence was recorded after sodium hypochlorite addition to the oils dissolved intert-butanol. In addition to high sensitivity and ability to detect small changes in rancidity, the method is fast and may be used as a supplement to the standard chemical methods for quality assessment and antioxidant evaluation. However, care has to be taken in interpretation of the chemiluminescence data of different fish oils, as the light emission depends on both the composition and the rancidity level of the oil. The autoxidized oils were also characterized by peroxide value, thiobarbituric acid value, anisidine value, Kreis rancidity index, iodine value, ultraviolet measurements, capillary gas chromatography, size-exclusion chromatography and sensoric evaluation.     

Effects of filtration through activated carbons on peroxide,thiobarbituric acid and carbonyl values of autoxidized soybean oil

Effects of filtration bleaching on peroxide value (PV), thiobarbituric acid value (TAV) and carbonyl value (CV) of autoxidized soybean oil were investigated by using twenty-three kinds of activated carbon in order to improve oil quality. From the decreases in PV, TAV and CV and from the physical and chemical properties of activated carbons, it was suggested that hydroperoxides, aldehydes and ketones were adsorbed on the acid sites distributed over the surface or within the pores of the activated carbons while the autoxidized soybean oil flowed through the packed column. The residual tocopherols in autoxidized soybean oil and treated soybean oil were determined during storage. The decrease in oxidative stability of treated soybean oil seemed to be caused by elimination ofα-,β-andγ-tocopherols.δ-Tocopherol was chemically more stable thanα-,β- andγ-tocopherols in autoxidized soybean oil.     

Effects of the cold percolation system on the quality of virgin olive oil

The effects of the cold percolation system on the quality of virgin olive oil from two different Italian cultivars (Coratina and Oliarola) were determined. The quality was also compared with that of oil extracted with the current centrifugation system using a two‐phases decanter. Tests were performed in an industrial oil mill equipped with the two extraction systems. The oils extracted with cold percolation system showed, in all cases, lower free acidity, peroxide value, and ultraviolet (UV) absorption (K₂₃₂ and K₂₇₀) and higher polyphenol contents in comparison to oils obtained by two‐phases centrifugation. These results were confirmed by the autoxidation stability of the oils examined.     

High oleic oils by selective hydrogenation of soybean oil

High oleic (monoene) oils were obtained from soybean oil by selective hydrogenation with copper catalysts. A mixture of nickel and copper chromite catalyst had activity suitable for producing the high monoene oils. A new catalyst (copper-on-Cab-O-Sil) prepared in the Laboratory was more active than commercial copper catalysts. Hydrogenated oils contained 61–72% monoenoic and 14–24% dienoic acids, and there was essentially no increase in stearic acid. Thetrans-isomer content of these oils varied between 17% to 32%. Double bonds in the monoene were distributed along the molecule from C₆ to C₁₅, but were located preferentially in the C₉ position for thecis-monoene and in the C₁₀ and C₁₁ positions for thetrans-monoene. When the iodine value of these high monoene oils was about 90–95, they remained liquid above 28 C. Citric acid treatment reduced the copper content of hydrogenated oils to a level that was comparable to that of the original soybean oil. Presented at the AOCS Meeting, Chicago, October 1967. Food and Agricultural Organization representative from Rumania. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Content of chlorophylls and carotenes in rapeseed oil

The content of the green components in crude rapeseed oil, namely chlorophylls A and B, as well as the products of their decomposition pheophytins A and B, were determined by means of the spectrophotometric method of analysis. No chlorophyll A was found in any of the analyzed samples but the content of pheophytin A was quite high and amounted to from 17.99 to 25.65 ppm. Because of the fact that the oils were investigated 5 to 6 months after their extraction, the results obtained are not unexpected, bearing in mind that chlorophyll contained in oil easily changes into pheophytin. No chlorophyll B was found in some of the samples, investigated and in the remaining samples from 0.14 to 1.79 ppm was found. This can be explained by the hypothesis of slower change of chlorophyll B into pheophytin B. The content of pheophytin B in the investigated samples was between 0.52 and 6.15 ppm. This confirms the results obtained by Mingot (3). With old oils, the results of determining such components, whose content approaches nil in the sample, are less precise because of the influence of the oil which was used as a blank. The content of carotenes in crude rapeseed oils was also determined by the spectrophotometric method after isolating them by means of the column chromatography on Al₂O₃. In spite of the small amount of carotenes determined in rapeseed oils, a correlation can be observed between the quantity of chlorophylls and carotenes. It has been found that the higher the chlorophyll content, the higher also the carotene content, even if very slight in some cases, in all the investigated oils either extracted or pressed.     

Study on the oxidative rate and prooxidant activity of free fatty acids

Oleic, linoleic and linolenic acids were autoxidized more rapidly than their corresponding methyl esters. Addition of stearic acid accelerated the rate of autoxidation of methyl linoleate and the decomposition of methyl linoleate hydroperoxides. Therefore, the higher oxidative rate of FFA’s than their methyl esters could be due to the catalytic effect of the carboxyl groups on the formation of free radicals by the decomposition of hydroperoxides. Addition of stearic acid also accelerated the oxidative rate of soybean oil. This result suggests that particular attention should be paid to the FFA content that affects the oxidative stability of oils.     

Vegetable oil raw materials

Vegetable oils that are important to the chemical industry include both edible and industrial oils, which contribute 24% and 13.5%, respectively, compared to 55% for tallow, to the preparation of surfactants, coatings, plasticizers, and other products based on fats and oils. Not only the oils themselves but also the fatty acids recovered from soapstock represent a several billion pound resource. Coconut oil is imported to the extent of 700-1,000 million pounds per year. Its uses are divided about equally between edible and industrial applications. Safflower oil has a relatively small production, but 15–25% of the oil goes into industrial products. Soybean oil, the major edible oil of the world, is produced in the United States at the rate of 11,000 million pounds per year with more than 500 million pounds going into industrial uses, representing 5% of the total production. Castor oil is imported to the extent of about 100 million pounds per year. Linseed oil production has declined drastically over the last 25 years but still amounts to about 100 million pounds per year. Oiticica and tung oils are imported in lesser amounts than castor and linseed oils. New crops that have industrial potential, as well as the traditional vegetable oil crops, include seed oils from crambe,Limnanthes, Lesquerella, Dimorphotheca, Vernonia, andCuphea plants. Crambe oil contains up to 65% erucic acid. Oil fromLimnanthes contains more than 95% of fatty acids above C₁₈.Lesquerella oil contains hydroxy unsaturated acids resembling ricinoleic acid from castor oil.Dimorphotheca oil contains a conjugated dienol system.Vernonia oils contain as much as 80% epoxy acids. TheCuphea oils contain a number of short chain fatty acids. Of these, crambe,Limnanthes, andVernonia are probably the most developed agronomically. Competition between vegetable oils and petrochemicals for the traditional fats and oil markets has been marked over the past 25 years, but prices for petrochemicals have accelerated at a greater rate than those for vegetable oils; and, it is now appropriate to reexamine the old as well as the new markets for fatty acids.     

Modelling the temperature dependence of kinematic viscosity for refined canola oil

Viscosities of refined, bleached, deodorized (RBD) and refined, bleached, winterized (RBW) canola oils were measured at temperatures from 4 to 100°C. The viscosities of these refined canola oils were exponentially related to the oil temperature. Viscosity of the RBW oil was slightly greater than that of the RBD oil when the temperature was below 15°C. Compared to refined soybean oil, the canola oils were substantially more viscous. The viscosity of canola oil was modelled asv = exp(C₀ + C₁T + C₂T²). The maximum predicted error was less than 1.6% over the tested temperature range.