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.     

FTIR estimation of free fatty acid content in crude oils extracted from damaged soybeans

A user-interactive computer-assisted Fourier transform infrared (FTIR) method has been developed for estimation of free fatty acids (FFA) in vegetable oil samples by deconvolution of the infrared (IR) absorbances corresponding to the triglyceride ester and FFA carbonyl bonds. Peak areas were used to determine FFA as a percentage of the total carbonyl areas in weighed standards of refined, bleached, deodorized soybean oil containing from 0 to 5% added oleic acid. These data for percent FFA by FTIR were compared to corresponding FFA data obtained by two titration methods-the AOCS Official Method Ca 5a-40 and the Official Method with a slight modification. Correlation coefficients were 0.999 for the Ca 5a-40, 0.999 for the modified and 0.989 for the FTIR methods. FFA in samples of crude soybean oils extracted from damaged beans (0.5 to 2.1% FFA) were measured by FTIR and compared to data obtained by titration of the same samples (correlation coefficient, 0.869). To whom correspondence should be addressed at National Center for Agricultural Utilization Research, Agriculture Research Service, U.S. Department of Agriculture, 1815 North University Street, Peoria, IL 61604. ¹The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

Pan-heating of low-linolenic acid and partially hydrogenated soybean oils

Genetically modified low-linolenic acid soybean oil (LL-SBO) was compared to partially hydrogenated soybean oil (PH-SBO). Samples were heated on a Teflon pan at ∼180°C until a selected end point of ≥20% polymer content was reached. High-performance size-exclusion chromatography analysis indicated the PH-SBO contained >20% polymer after 20 min of heating, whereas the LL-SBO sample contained >20% polymer after 10 min. Supercritical fluid chromatography analysis indicated degradation rates of 0.161±0.011 min⁻¹ for LL-SBO and 0.086±0.004 min⁻¹ for PH-SBO. The volatile compounds were identified and quantitated with static head-space-GC-MS. 1-Heptene (239.9 ppm) and hexanal (1486.1 ppm) were present at the greates concentration among the volatile compounds in LL-SBO. The volatile compounds present in the greatest concentrations in heated PH-SBO were hexanal (376.9 ppm) and pentane (82.1 ppm). After 10 min of heating, the LL-SBO oil FFA value (2.66%), p-anisidine value (386.5 abs/g oil), Food Oil Sensor reading (18.75), and color intensity (Y=4.0, R=1.0) were significantly greater than those of PH-SBO after 14 min of heating (4.28%, 298.5 abs/g oil, 16.08, Y=1.0, R=0.1, respectively). There was a significant difference in the degradation rates between LL-SBO and PH-SBO (P<0.05). The PH-SBO was more stable than the LL-SBO.     

Determination of free fatty acids in palm oil by near-infrared reflectance spectroscopy

A near-infrared (NIR) spectroscopy calibration was developed for the determination of free fatty acids (FFA) in crude palm oil and its fractions based on the NIR reflectance approach. A range of FFA concentrations was prepared by hydrolyzing oil with 0.15% (w/w) lipase in an incubator at 60°C (200 rpm). Sample preparation was performed in Dutch cup, and the spectra were measured in duplicate for each sample. The optimized calibration models were constructed with multiple linear regression analysis based on C=O overtone regions from 1850–2050 nm. The best wavelength combinations were 1882, 2010, and 2040 nm. Multiple correlation coefficients squared (R ²) were: 0.994 for crude palm oil, 0.961 for refined-bleached-deodorized (RBD) palm olein, and 0.971 for RBD palm oil. Calibrations were validated with an independent set of 8–10 samples. R ² of validation were 0.997, 0.943, and 0.945, respectively. The developed method was rapid, with a total analysis time of 5 min, and environmentally friendly, and its accuracy was generally good for raw-material quality control.     

Evaluation of SafTestTM methods for monitoring frying oil quality

The feasibility of applying methods developed by Safety Associates, Inc., to monitor oil degradation products, including malondialdehydes (AldeSafe^TM), FFA (FASafe^TM), and peroxides (PeroxySafe^TM), in fresh and heat-abused deep-fat frying oil was evaluated. Based on performance qualification studies, the AldeSafe method was the most suitable SafTest^TM assay for monitoring the quality of frying oil because of its high accuracy, precision, linearity, and reproducibility, and low detection/quantitation limits. A strong correlation (r=0.924) between the AldeSafe method and its counterpart, AOCS Official Method Cd 19-90, also supported the suitability of the SafTest method for monitoring oil quality. Moreover, the FASafe method had a moderately strong relationship with AOCS Official Method Ca 5a-40 (r=0.761). Our studies suggest that this test can be applied for monitoring frying oil; however, certain method performance limitations must be considered for routine analysis purposes. In contrast, the PeroxySafe method probably should not be used to monitor heat-abused oil without further development because of high variability, low accuracy, and low correlation (r=0.062) with the AOCS Official Method Cd 8-53 assay.     

Determination of phospholipids in vegetable oil by fourier transform infrared spectroscopy

A method was developed to determine the total phospholipid content in vegetable oil by Fourier transform infrared spectroscopy (FTIR). Calibration curves of I-α-phosphatidylcholine (PC), I-α-phosphatidylethanolamine (PE), and I-α-phosphatidylinositol (PI) in hexane were generated at different concentrations. The optimal phospholipid absorption bands between 1200–970 cm⁻¹ were identified and used for quantitative determination. High R ²≥0.968 were observed between band areas and phospholipid standard concentrations. Phospholipids from crude soybean oil were obtained by water degumming, and purification was performed on a silicic acid column. The phospholipid contents of purified phospholipid extract, degummed and crude soybean oil determined from calibration equations were >90, 0.0113, and 1.77%, respectively. High correlations of determination (R ²≥0.933) were observed between the FTIR method and thin-layer chromatography-imaging densitometry method for the determination of phospholipid content. FTIR was found to be a useful analytical tool for simple and rapid quantitative determination of phospholipids in vegetable oil.     

Determination of free fatty acids in crude palm oil and refined-bleached-deodorized palm olein using fourier transform infrared spectroscopy

A rapid direct Fourier transform infrared (FTIR) spectroscopic method using a 100 μ BaF₂ transmission cell was developed for the determination of free fatty acid (FFA) in crude palm oil (CPO) and refined-bleached-deodorized (RBD) palm olein, covering an analytical range of 3.0–6.5% and 0.07–0.6% FFA, respectively. The samples were prepared by hydrolyzing oil with enzyme in an incubator. The optimal calibration models were constructed based on partial least squares (PLS) analysis using the FTIR carboxyl region (C=O) from 1722 to 1690 cm⁻¹. The resulting PLS calibrations were linear over the range tested. The standard errors of calibration (SEC) obtained were 0.08% FFA for CPO with correlation coefficient (R ²) of 0.992 and 0.01% FFA for RBD palm olein with R ² of 0.994. The standard errors of performance (SEP) were 0.04% FFA for CPO with R ² of 0.998 and 0.006% FFA for RBD palm olein with R ² of 0.998, respectively. In terms of reproducibility (r) and accuracy (a), both FTIR and chemical methods showed comparable results. Because of its simpler and more rapid analysis, which is less than 2 min per sample, as well as the minimum use of solvents and labor, FTIR has an advantage over the wet chemical method.     

Comparative study of the extraction and measurement of cottonseed free fatty acids

Crude oil was extracted from cottonseed by three different methods to study the influence of extraction technique on the free fatty acid (FFA) concentration. Extraction procedures that recovered more oil had higher levels of FFA. In addition, the highest concentration of FFA was found in oil recovered by Soxhlet reextraction of a meal initially defatted by a room-temperature extraction process. The FFA concentrations of oils recovered by Soxhlet extraction were highly correlated with the FFA concentration of oils recovered by the other extraction methods studied (R ²>0.96). Titration of oil and gas chromatography of silylated oil were compared as methods to determine FFA concentration. The methods compared well (R ²=0.998) with the titration method, giving ∼5% higher values for FFA than the chromatography method. Half of this difference appeared to be due to the oleic acid approximation used in the titration approach. The other half of the difference is likely due to the detection of other acidic components in crude oil.     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. v. shape memory effect

A series of new shape memory polymers are synthesized by the cationic copolymerization of regular soybean oil, low saturation soybean oil (LoSatSoy oil), and/or conjugated LoSatSoy oil with styrene and divinylbenzene, norbornadiene, or dicyclopentadiene initiated by boron trifluoride diethyl etherate or related modified initiators. The shape memory properties of the soybean oil polymers are characterized by the deformability (D) of the materials at temperatures higher than their glass‐transition temperatures (T_g), the degree to which the deformation is subsequently fixed at ambient temperature (FD), and the final shape recovery (R) upon being reheated. It is found that a T_g well above ambient temperature and a stable crosslinked network are two prerequisites for these soybean oil polymers to exhibit shape memory effects. Good shape memory materials with high D, FD, and R values are prepared by controlling the crosslink densities and the rigidity of the polymer backbones. The advantage of the soybean oil polymers lies in the high degree of chemical control over the shape memory characteristics. This makes these materials particularly promising in applications where shape memory properties are desirable. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1533–1543, 2002; DOI 10.1002/app.10493     

Rapid Determination of Degradation in Frying Oils with Near-Infrared Spectroscopy

Measures of free fatty acids (FFA), total polar materials (TPM), and conjugated dienoic acids (CDA), typical indices of oil degradation, were analyzed in daily oil aliquots taken from soybean oils with different linolenic acid concentrations used to fry French fries. The oils also were scanned with a reflectance near-infrared spectrometer using a wavelength range of 350–2,500 nm. By using partial least squares and one-out cross validation, calibrations were developed to quantitatively determine FFA, TPM, and CDA by near-infrared spectroscopy (NIRS). The coefficients of determination (R ²) when compared to the standard methods were 0.973 for FFA, 0.984 for TPM, and 0.902 for CDA. NIRS was an accurate and fast method to determine FFA, TPM, and CDA in oxidized oils. The ability to obtain different parameters simultaneously makes NIRS a potentially valuable tool for food quality assurance.     

Effects of Introducing Crude and Modified Soybean Oil into Polyurethane Structures on the Soil-Burial Biodegradation Process

Synthetic and natural acrylate oligomers blends and their blends with different ratios of crude soybean oil were studied as environmentally degradable and eco-compatible materials. Two of the components acrylated epoxidized soybean oil (AESO) and crude soybean oil are bio-sourced oligomers. Their biodegradability under soil burial in natural condition was characterized by FT-IR and mechanical properties and was further confirmed by SEM analyses. A high content of modified and crude soybean oil present in the sample composition had enhanced the adhesion of microorganism onto the polymer surface, which in turn resulted in high biodegradation rates under soil burial conditions.     

Comparative study on the stability of crude and refined rice bran oil during long‐term storage at room temperature

The effect of the full refining process on the stability of rice bran oil during storage at room temperature was studied. Crude and refined rice bran oil were kept in the dark and were exposed to light for 240 days, and every 10 days samples were drawn and analysed. The storage stability of crude and fully refined rice bran oil was determined and compared with respect to fatty acid composition, tocopherols, tocotrienols, sterols and γ‐oryzanol content. In addition, the oxidative status was evaluated by determining the concentration of polar compounds and the oil stability index (OSI). A good correlation between the decrease of total tocopherols and the OSI was found. α‐Tocopherol had the highest correlation coefficient (r² = 0.9653) in crude rice bran oil kept in the dark, and γ‐tocopherol showed the lowest in the refined sample (r² = 0.4722). The order of stability of tocopherols and tocotrienols in crude oil was completely different from that in refined oil. In comparison to tocopherols, sterols showed a better stability during the entire storage period. The exposure to daylight heavily affected the composition and the stability of both crude and refined rice bran oil.     

Plasma Polymerization Modified Polyvinylidene Fluoride (PVDF) Membrane Development and Characterization for Degumming of Soybean Oil

Unmodified and surface‐modified polyvinylidene fluoride (PVDF) membranes were tested for their ability to degum soybean crude oil and crude oil miscellas. The membrane was modified with 1,1,1,3,3,3‐hexafluoro‐2‐propanol or hexamethyldisiloxane (HMDSO) by radio‐frequency plasma polymerization at 10–100 W glow discharge power and 1–30 min contact time. The membranes were characterized by contact angle measurements, attenuated total reflectance Fourier transform infrared spectroscopy, atomic force microscopy, and scanning electron microscopy. Modification of the PVDF membrane with HMDSO at 60 W power for 5 min increased the interfacial free energy between water and solid surface from 30 ± 2 to 64 ± 2 mJ/m². This membrane was tested for permeate flux and phospholipid rejection with crude oil and different concentrations of miscella. Although formation of the polymer film on the membrane tended to decrease membrane pore size, the modified membrane had an oil flux as good as the unmodified membrane did. In addition, the modified‐membrane improved the phospholipid rejection and removed 76 % of the phospholipids from the crude oil and 81–90 % of the phospholipids from crude oil miscellas.     

Deacidification of high-acid rice bran oil by reesterification with monoglyceride

Autocatalytic esterification of free fatty acids (FFA) in rice bran oil (RBO) containing high FFA (9.5 to 35.0% w/w) was examined at a high temperature (210°C) and under low pressure (10 mm Hg). The study was conducted to determine the effectiveness of monoglyceride in esterifying the FFA of RBO. The study showed that monoglycerides can reduce the FFA level of degummed, dewaxed, and bleached RBO to an acceptable level (0.5±0.10 to 3.5±0.19% w/w) depending on the FFA content of the crude oil. This allows RBO to be alkali refined, bleached, and deodorized or simply deodorized after monoglyceride treatment to obtain a good quality oil. The color of the refined oil is dependent upon the color of the crude oil used.     

Quantitative differential scanning calorimetric analysis for determining total polar compounds in heated oils

A new differential scanning calorimetry (DSC) method was developed for the determination of total polar compounds (TPC) in heated oils. Three different types of edible oils, refined, bleached, and deodorized corn oil (CO), palm olein (RBDPO), and soybean oil (SO), were used in this study, Each type of edible oil was heated at 180°C in a deep fryer to obtain a range of TPC concentrations. In this study, the cooling thermograms of oil samples at a scanning rate of 1°C/min from −30 to −85°C showed a well-defined single crystallization peak. The study found that six DSC parameters, namely, peak temperature (PT), enthalpy (EN), onset (ON) and offset (OF) temperatures, peak height (HT), and the range of temperatures (RT) (the difference between onset and offset temperature) of this single crystallization peak could predict well the TPC of heated oils by using stepwise multiple linear regression analysis. These six parameters were used as independent variables while values from standard method were used as dependent variables. The coefficient of determination (R ²) of calibration models for CO, RBDPO, and SO were 0.9996, 0.9709, and 0.9980, respectively. Calibration models were validated with an independent set of samples. The R ² of validation models were 0.9995, 0.9559, and 0.9961, respectively. Based on the results obtained, DSC appears to be useful instrumental method in determining the TPC of edible oils, and it may have the potential to replace the time- and chemical-consuming standard method.     

Prediction of crude sunflower oil deterioration after seed drying and storage processes

The effects of air-drying temperature and storage time on several characteristics of crude sunflower oil were evaluated in terms of FFA and PV. Long storage affected oil content to a greater extent than air-drying temperature. FFA and PV varied between 0.53 and 1.22% and between 10.7 and 23.3. meq O₂/kg, respectively, when samples of uniform initial moisture content (approximately 28%) were dried at various temperatures between 25 and 90°C to approximately 7% moisture content, stored for 8 mon, and then analyzed. Both oil quality characteristics increased exponentially with air-drying temperature (T) and linearly with storage time (t). Mathematical functions of the form A·exp(B·T)+C·t (where A, B, and C are parameters adjusted from experimental data) most closely predicted the experimental loss of quality of sunflower oil in terms of FFA and PV with variations in T and t. Statistical analysis showed SE of the estimated parameters of 0.08 and 1.19 and coefficients of determination, R ², of 0.922 and 0.939 for FFA and PV, respectively, which were significant at 95% confidence. High-oleic seeds from a similar experiment were used to validate the proposed equation. The results of applying the mathematical function proposed above showed a reasonable ability to predict the experimental values with SE of 0.037 and 0.808 and R ² of 0.983 and 0.972 for FFA and PV, respectively, which were significant at 95% confidence. Plots of residuals showed random distribution. The results obtained suggested that the equation proposed could be used as a quality-loss model in sunflower drying simulations.     

Optimization of the chemoenzymatic epoxidation of soybean oil

The lipase Candida antarctica (Novozyme 435) immobilized on acrylic resin was used as an unconventional catalyst for in situ epoxidation of soybean oil. The reactions were carried out in toluene. The peracid used for converting TG double bonds to oxirane groups was formed by reaction of FFA and hydrogen peroxide. The reaction conditions were optimized by varying the lipase concentration, solvent concentration, molar ratio of hydrogen peroxide to double bond, oleic acid concentration, and reaction temperature. The kinetic study showed that 100% conversion of double bonds to epoxides can be obtained after 4 h. The addition of free acids was not required for the reaction to proceed to conversions exceeding 80%, presumably owing to generation of FFA by hydrolysis of soybean oil. The enzyme catalyst was found to deteriorate after repeated runs.     

Methanolysis of triacylglycerols by organic basic catalysts

Methanolysis of rapeseed and soybean oil was studied using organic basic catalysts at boiling with reflux. The molar ratio methanol/free fatty acids (FFA) amounted to approx 2.8 : 1. The catalyst (guanidine carbonate) is used at concentrations between 0.5 and 1.3 wt‐% with respect to the oil. During boiling at reflux, guanidine carbonate disintegrates into guanidine and gaseous carbon dioxide. This is a very special reaction; other alcohols such as ethanol, propanol, etc. do not react in this way with guanidine carbonate. Under these conditions, the reaction mixture consists of two phases. The catalyst is mainly dissolved in the methanol phase. The rate of the phase transfer reaction is increased by stirring. With guanidine carbonate as a catalyst, neutralized rapeseed oil yielded, within 45 min and in one step, a product that meets the European Norm for biodiesel. Degummed and dried crude rapeseed oil contains ca. 1 wt‐% FFA, whereas crude degummed and dried soybean oil contains 0.3–0.7 wt‐% FFA. During catalysis with guanidine carbonate, the FFA are transformed into their methyl esters to about 60–70% at low concentrations in the crude oil (approximately up to 1–1.5%). Neutralization of the degummed and dried crude oil proved to be unnecessary in such cases.     

A DSC study of Z<Subscript>2</Subscript>−Z<Subscript>3</Subscript> viscosity blown soybean oil

The thermal oxidation of four commercially available neat blown soybean oil samples and a heat-bodied soybean oil sample, obtained from various manufacturers, having Gardner bubble viscosities between Z₂ and Z₃ was investigated using nonisothermal DSC under a constant oxygen flow and a heating rate (β) ranging from 3 to 20°C/min. The extrapolated onset temperatures (T _e1 and T _e2 ) and maximum temperature of heat flow (T _p2 ) at different β were determined from the DSC curves and used in conjunction with the Ozawa-Flynn-Wall method to estimate the kinetic parameters of oil thermal oxidation. At a β of 10°C/min, the calculated activation energies (E _a ) for the blown soybean oil samples investigated ranged between 57.7 and 74.3 kJ/mol for T _e1 , 37.6 and 55.3 kJ/mol for T _e2 , and 54.7 and 63.0 kJ/mol for T _p2 . For comparison, a Z ₂ −Z ₃ heat-bodied soybean oil sample had activation energies of 72.5, 39.8, and 61.9 for T _e1 , T _e2 , and T _p2 , respectively. By ¹H NMR, the amount of allylic and bis-allylic hydrogens present in the blown soybean oil samples relative to an unmodified soybean oil sample was determined to range from 40.3 to 48.2% and 14.9 to 22.4%, respectively.     

Determination of low trans levels in refined oils by fourier transform infrared spectroscopy

A Nicolet 410 Fourier (FTIR) spectrophotometer, equipped with a DGTS detector and a sample cell with NaCl windows (nominal pathlength=50 μm), was used for the development of an FTIR method for routine analysis of low trans levels in physically refined oils. The approach of the study differed from those previously described in that a separate calibration curve was established for each type of oil. Quantitation was established by use of Basic Quant Software® and by measuring the peak height at 967 cm^?1 relative to a baseline drawn between 1002 and 932 cm^?1. The slope of the different calibration curves established in six vegetable oils (soybean, corn, sunflower, high-oleic sunflower, low-erucic rapeseed, and high-erucic rapeseed) was close to 1 (0.9942–1.0041), and correlation coefficients (r ²) were rather good (0.9990–0.9999). FTIR spectra of 20 soybean oil samples were collected and quantitated with the different calibrations. Compared to previous reported literature data, increased accuracy (mean difference=0.05%; standard deviation of difference=0.11%) and reproducibility (r ²=0.09–0.12%) were obtained when the FTIR spectra were quantitated with a calibration curve based on 10 physically refined soybean oil samples.