13

Soybean Oil
Earl G. Hammond, Lawrence A. Johnson, Caiping Su, Tong Wang, and Pamela J. White
Iowa State University Ames, Iowa

1. INTRODUCTION The amounts of soybeans and total vegetable oil crops have been rising for a number of years. World production of soybeans in 2003 was estimated to be 184.49 million MT out of 317.89 million MT total for vegetable oil crops, making soybeans the worlds largest oilseed crop, rivaled only by palm oil (1). The 2003 crop of soybeans was expected to yield 29.85 million MT of soybean oil out of a total of 91.79 million MT of vegetable oil worldwide. The U.S. production of soybean oil was estimated at 8.59 million MT for 2002, of which 7.86 million MT was consumed domestically. During 20022003, Brazil produced 4.90 million MT and Argentina 4.12 million MT of soybean oil (2). The U.S. price of crude soybean oil has varied from $0.24/kg to $0.62/kg over the past 5 years with the lower prices being more recent (1). Soybeans owe their dominance of the oilseed market to the value of their protein, which is much greater than that of other oilseeds. Of the oilseed meals produced in 2003, 129.58 million MT out of a total of 185.69 milllion MT was soybean meal (1). Of the money made on extracting soybeans, the meal accounted for between 51% and 76% of the total in the last 10 years. Soybean oil of typical composition performs well as a salad oil, but it is usually hydrogenated for use as a margarine stock or frying oil. Soybean oils stability to oxidation also is limited by its content
Baileys Industrial Oil and Fat Products, Sixth Edition, Six Volume Set. Edited by Fereidoon Shahidi. Copyright # 2005 John Wiley & Sons, Inc.

577

578

SOYBEAN OIL

of linolenic acid. Recent decades have witnessed numerous attempts to manipulate the fatty acid composition of soybean oil to help it compete better in various uses, but the cost of growing, segregating, and testing special varieties and resistance to genetically modied oils have limited the appeal of these altered varieties.

2. COMPOSITION OF SOYBEANS Table 1 shows the average composition of soybean seed (oil, protein, and some amino acids) grown in the United States during recent years (3). Aside from varietal differences, the composition is affected by various geographic/environmental factors. According to Hurburgh (5), oil is much more variable than protein from yearto-year. States most distant from the center of the Corn Belt (probably those with the greatest weather extremes) experience the most variability in composition. Table 2 lists some of the environmental and cultivation practices that have an

TABLE 1. Typical Composition (wt% std. dev.) of Soybeans (dry weight basis) (3). Protein Lysine Methionine Cysteine Tryptophane Threonine Oil Ash Carbohydrate 40.69 0.51 2.56 0.11 0.57 0.03 0.72 0.06 0.52 0.05 1.54 0.07 21.38 0.64 4.56 0.34 (4) 29.4 3.29 (4)

TABLE 2. Soybean Protein and Oil Responses to Various Environmental and Cultivation Practices (3). Variable High temperatures Early season drought Late season drought Early frost/cold temperature Additional soil nitrogen Increased fertility (P ,S) Late planting Insect defoliation Insect depodding Rhizobium inoculation
a b

Protein ?
a

Oil b ?

? inconclusive; increase; decrease. Oil is reduced because of rening loss to remove chlorophyll.

COMPOSITION OF SOYBEANS

579

observable effect on soybean protein and oil percentages. Maestri et al. (6) grew soybean cultivars in several regions of Argentina and concluded that the protein and oil contents were positively correlated with altitude. Protein was negatively correlated with latitude and precipitation, and oil was negatively correlated with temperature and precipitation. Oil content in soybeans tends to be negatively correlated with protein, but breeding soybeans for high protein while maintaining oil content has been a priority of the U.S. soybean producers, and some progress has been achieved (7, 8). The variety Prolina reportedly produces 22.7% oil and 45.5% protein on a dry weight basis. There also has been interest in reducing the oligosaccharides that cause atulence and reduce the digestibility and nutritive value of soybeans. Isoavones are minor constituents of soybeans whose consumption is believed to have benecial effects (911). The benets of isoavones have encouraged the direct consumption of soy protein in the United States. The concentration of isoavones changes with variety and growing conditions and has been reported to be 1.22.5 mg/g in U.S. beans (9), 0.52.3 mg/g in Korean beans (10), and 0.23.5 mg/g in Japanese beans (11). Table 3 shows the typical composition of the lipid phase of soybeans. Triacylglycerols are the primary component. The 3.7% phospholipids content in the soy beans is higher than that usually found in hexane-extracted oil, which is typically

TABLE 3. Typical Composition of Crude Soybean Oil. Component Triacylglycerol Phospholipids Unsaponifable matter (1315) Sterolsc (16) Campesterol Stigmasterol -Sitosterol 5-Avenasterol (17) 7-stigmasterol (17) 7-avenasterol (17) Tocopherols (16) Alpha Beta Gamma Delta Hydrocarbons (14, 15) Free fatty acids (18) Trace metals (18) Iron Copper
a b c

% 94.4 3.7b 1.31.6 0.236 0.059 0.054 0.123 0.005 0.005 0.002 0.123 0.0093 0.0018 0.0834 0.029 0.38 0.30.7 ppm 13 0.030.05
a

Std. Dev. 1.4 1.2 (12) 0.053 0.018 0.013 0.027

0.040 0.0044 0.0028 0.036 0.010

By difference. Based on 23 varieties chosen to represent a wide fatty acid composition. Based on 13 varieties chosen to represent a wide range of composition.

580

SOYBEAN OIL

1.852.75% (19). Of the unsaponiable matter of soybean oil, typically about 1.45% of the oil, 16% is sterols, 8.5% is tocopherols, and 26% is hydrocarbons. The remaining 50% of the unsaponiable matter consists of other minor and unidentied products. The sterols are about 52% -sitosterol, 25% campesterol, and 23% stigmasterol. Maestrl et al. (4) reported similar proportions on the three major sterols but also reported 5.4% 0.82 of 5-avenasterol, 3.8% 0.76 of 7stigmasterol, 1.3% 0.42 of 7-avenasterol, and traces of cholesterol in the total sterols. The tocopherols are about 7.6% a, 1.5% b, 67.8% g, and 23.6% d. There is considerable variation among plant varieties in the amounts and proportions of molecular species of sterols and tocopherols (4, 16, 20). Vlahakis and Hazebroeck (21) also have investigated the effects of planting locations and temperature on the sterol and total tocopherol contents of a number of soybean varieties. They found that growth temperature can cause as much as a 2.5-fold difference in sterol content, with higher temperatures favoring higher amounts of sterols, increasing the campesterol/-sitosterol ratio and decreasing total tocopherols. McCord et al. (22) examined a number of soybean lines with low and normal contents of linoleate. The low-linolenate lines averaged about 6% lower in tocopherol than the highlinolenate lines, but some reduced-linolenate lines were not signicantly different from normal-linolenate lines in tocopherols. The a- and g-tocopherols tend to be concentrated in the soybean germ, whereas d-tocopherol is concentrated in the endosperm (23). The hydrocarbon fraction of soybeans consists of n-hydrocarbons of chain length 14 to 33 plus squalene and small amounts of hexahydrofarnesylacetone (14, 15). The squalene content is reported to be about 0.014% of the oil. There seems to be considerable variation in the distribution of the hydrocarbon chain lengths with plant variety, judging from the two examples in the literature. Free fatty acids vary considerably with the age and soundness of the beans but are seldom lower than the 0.1% of the crude oil (18). Damaged beans can contain 18% free fatty acid as well as elevated iron and copper, 37 ppm and 0.080.18 ppm, respectively. Rened oil usually retains little phospholipid, but damaged beans can have a signicant content of phosphatidic acid, and the amount of iron in the oil is related to the amount of phosphorus (24). During deodorization, considerable amounts of sterol and tocopherol may be removed from the oil. The proportion removed depends on deodorization conditions, but a 30% to 40% decrease is not unusual (25). Much of the hydrocarbons and squalene are lost to the deodorizer distillate as well. Free fatty acids in fully rened oil are required to be <0.05% and unsaponiable matter <1.5% (26). Table 4 shows the percentages and standard deviations of the methyl esters of 21 typical rened soybean oil samples. This composition is typical of most presently commercial soybean varieties. The typical composition probably has been selected through plant breeding because it is associated with good yield and other important agronomic properties. It has been possible to change the composition of soybean oil considerably, and Table 4 also shows the ranges of percentages that have been reported for each methyl ester. Many of the changes in composition can be achieved without great losses in yield or oil content, but lines with high or low palmitate

COMPOSITION OF SOYBEANS

581

TABLE 4. The Averages and Standard Deviations of Methyl Esters from Typical Soybean Oils and the Range Reported for each Methyl Ester. Methyl Ester Myristate Palmitate Palmitoleate Stearate Oleate Linoleate Linolenate Arachidate Gondoate Behenate Lignocerate Furanoid IIb Furanoid IIIc Saponication Value Iodine Value
a b

Typical Value %a (27) 0.04 0.5 (27) 10.57 0.43 (27) 0.02 0.04 (27) 4.09 0.34 (27) 22.98 2.01 (27) 54.51 1.54 (27) 7.23 0.78 (27) 0.33 0.14 (27) 0.18 (28) 0.25 0.20 (27) 0.1 (29) 0.014 0.0086 (30) 0.015 0.0076 (30) 190.4 (31, 32) 132.7(31, 32)

Range Achieved % trace0.03 (4) 3.226.4 (33, 34) trace0.7 (29) 2.632.6 (33, 35) 8.679.0 (36, 37) 35.264.8 (3537) 1.719.0 (38, 39) trace0.7 (28) trace0.6 (4) trace1.0 (4) 0.00330.0290 (30) 0.00840.0272 (30) 188.5201.6 (31, 32) 114.0138.5 (31, 32)

Based on 21 commercial samples. 10,13-epoxy-11,12-dimethyloctadeca-10,12-dienoate. c 12,15-epoxy-13,14-dimethyloctadeca-12,14-dienoate.

percentages tend to have reduced oil contents (33, 40, 41). Lines with high stearate percentages suffer from low yields and sporadically from poor germination. Wang et al. (42) tested lines with elevated palmitate or stearate in a number of tests of germination and seedling vigor at three temperatures and found that, although the high-saturate seed did well in these tests, vigor was negatively correlated with saturate percentage. Most of the changes reported in Table 4 were attained by traditional plant breeding or use of mutagenic agents. The high-oleic mutant is an exception and was attained by direct genetic manipulation (37). High-oleate lines developed by traditional plant breeding have been reported, but their oleate percentage varies widely with growth environment, which limits their commercial value (38). The fatty acid composition of soybean oil changes considerably with maturity and with seed oil deposition (15, 35, 43, 44). In typical soybean triacylglycerols, the palmitate and linolenate tend to decrease with maturity, whereas linoleate increases. Oleate tends to increase to a maximum and then decline slightly. Soybeans selected for atypical fatty acid compositions show quite different patterns of change with maturity from typical soybeans. Seitz (31) and Wesolowski (32) measured the saponication and iodine values of a number of samples from various geographic locations, and their ranges and typical values are shown in Table 4. Harp and Hammond (45) explored the stereospecic distribution of acyl groups on the three positions of the glycerol molecule for soybean triacylglycerols with a wide range in fatty acid composition. They found that the amount of an acyl group

582

SOYBEAN OIL

on a particular position was linearly related to the amount of that acyl group in the whole triacylglycerol. At low concentrations of palmitate, stearate, oleate, and linoleate in the total triacylglycerols, the amounts on the sn-1 > sn-3, but the reverse was true at higher total concentrations. Palmitate and stearate were conned to the sn-1 and sn-3 positions, whereas the oleate concentration was similar on all three positions. Linoleate concentrations at the sn-2 position were generally greater than those at the sn-1 and sn-3 positions, but the amount of linoleate on the sn-2 position seemed to be strongly and negatively correlated with the amounts of saturates on the sn-1 and sn-3 positions. Plots of linolenate concentrations at particular positions versus the concentrations in the whole triacylglycerol showed considerably more scatter than plots for the other acyl groups, but they generally showed the amount of linolenate on sn-2 > sn-1 > sn-3. The saturate percentages also seemed to inuence the amounts of linolenate on the sn-2 position positively and on the sn-3 position negatively. Table 5 shows the stereospecic distribution of typical soybean triacylglycerols. Theoretically, stereospecic data can be used to predict the acylglycerol structure using the 1-random-2-random-3-random distribution theory (47), if one assumes the fatty acid composition of the three glycerol positions are individually controlled but that the combinations of the three positions are random. However, the change in fatty acid composition with maturity, described in the previous paragraph, shows that the triacylglycerol composition is unlikely to be truly random in the combination of the three glycerol positions. In addition, soybeans from the same plant or pod can have slightly different acyl group compositions, so pooled oil from many seeds and plants is unlikely to be exactly random in its glycerol position combinations. Thus, such a calculation can lead only to approximate compositions. Neff et al. (48, 49) partially separated the triacylglycerols of soybean oils with a wide range of fatty acid compositions using high-performance liquid

TABLE 5. Stereospecic Distribution of Acyl Groups in the Triacylglycerols, Phosphatidylcholine, Phosphatidylethanolamine, and Phosphatidylinositol of a Typical Soybean (45, 46). Compound/Acyl group Triacylglycerols sn-1 sn-2 sn-3 Phosphatidylcholine sn-1 sn-2 Phosphatidylethanolamine sn-1 sn-2 Phosphatidylinositol sn-1 sn-2 16:0 11.8 19.3 2.9 14.9 11.2 16.0 4.1 16.0 28.5 3.5 22.2 45.1 4.6 18:0 4.6 7.5 0.8 6.4 11.9 22.6 3.7 8.3 17.1 2.4 19.3 35.2 3.4 18:1 29.4 25.4 27.9 34.8 8.6 7.3 9.9 6.8 5.0 8.7 6.1 5.3 5.9 18:2 47.1 39.6 61.1 38.9 58.6 38.3 71.1 57.3 42.4 73.8 43.4 17.1 70.9 18:3 7.2 7.8 7.4 5.0 9.9 6.0 11.2 11.7 7.1 11.7 9.3 2.4 15.3

COMPOSITION OF SOYBEANS

583

chromatography, and their results are shown in Table 6. These data show how the amounts of the triacylglycerol species change with fatty acid composition. The primary phosphatides of soybean oil are phosphatidylcholine, phosphatidylethanolamine, and phosphotidylinositol, which generally make up 55.3%, 26.3%, and 18.4% of the total phosphatides, respectively (50). The stereospecic distribution of the acyl groups in these phospholipids for a typical soybean lipid is shown in Table 5. In all the phospholipids, the saturated acyl groups are concentrated in the

TABLE 6. Acyl and Triacylglycerol Composition in mol% of Soybean Oils Having a Wide Range of Fatty Acyl Compositions (48, 49). Sample Number 1 2 3 4 5 3.9 3.3 28.5 61.8 2.5 2.0 30.0 1.7 0.4 26.9 0.4 6.4 0.1 0.1 13.9 3.6 3.7 0.8 4.6 2.6 0.9 0.8 0.2 0.7 0.3 0.1 21.4 3.3 23.6 49.0 2.7 1.2 0.1 11.5 1.5 1.7 14.4 0.5 20.7 1.0 7.3 2.6 16.3 8.6 2.1 2.3 3.2 2.2 1.7 0.5 0.2 0.4 23.6 19.0 9.3 38.0 10.0 1.4 0.1 0.4 3.7 0.8 6.9 3.6 0.1 17.5 1.4 1.5 1.3 7.7 7.4 13.8 1.0 3.9 0.6 16.0 1.2 0.1 0.3 6.5 1.3 0.6 0.6 0.2 28.2 3.9 13.9 43.8 10.2 3.2 0.2 0.6 9.6 2.0 9.4 8.7 0.3 21.4 2.1 2.0 3.1 2.0 12.2 14.8 0.8 1.3 1.0 3.0 1.5 0.2 0.3 0.2 8.5 26.5 18.0 38.9 8.2 2.6 0.1 0.1 6.5 1.9 2.2 7.1 0.3 11.6 0.4 0.1 2.5 13.0 6.4 2.0 1.1 11.8 0.5 8.8 0.3 2.1 12.3 1.4 0.6 3.4 0.1 0.1

Acyl group Palmitate (P) Stearate (S) Oleate (O) Linoleate (L) Linolenate (Ln) Triacylglycerol Species LnLL LnLnO LnLnP LLL LnLO LnLP LLO LnOO LLP LnOP LnPP LOO LLS LOP PLP OOO LOS POO SLP LnSS POP PPP SOO SLS SOP PPP SOS PSS SSS

584

SOYBEAN OIL

sn-1 position and the unsaturated acyl groups, especially linoleate, on the sn-2 position. Phosphatidylinositol tends to be richest in palmitate and stearate, whereas phosphatidylcholine has the least palmitate. Wang et al. (51) reported the stereospecic distribution of the acyl groups in the various phospholipids types and the amounts of particular acyl combinations for soybean lipids with a wide variety of fatty acid compositions. Some phosphatidic acid and lysophospholipids also may be present as a result of hydrolysis of the phospholipids (52). The amounts of the hydrolytic products usually increase with age and damage to the beans (53). Soybeans also contain 170 47 ppm of cerebrosides in which the sugar is glucose and the chief fatty acid is 2-hydroxy palmitic acid (54). Traces of ceramides also are present. These are believed to play a role in cell signaling in the soybean plant. Crude soybean oil contains about 1.9 ppm of Vitamin K1 or phylloquinone (55). This vitamin plays a role in blood coagulation and bone metabolism. During rening, some Vitamin K1 may be lost (56, 57), especially during deodorization. Hydrogenation of the fat converts some of the Vitamin K1 to 20 ,30 -dihydrovitamin K1 (58). Wilson et al. (7, 8, 39, 59) have reviewed the genetic control of fatty acid biosynthesis in soybeans and discussed the advantages of soybean oil with special compositions. Oil with reduced palmitate is available presently in a limited market. The commercial introduction of low-linolenate soybeans has been inhibited by the availability of corn oil, which has a composition like very low-linolenate soybean oil. The price differential between these oils often is smaller than the costs of contract growing, segregating, and processing low-linolenate soybeans. High-oleate soybean oil is stable under frying conditions, but this trait alters the avor of the fried products (60). The acceptance of high-oleate soybean oil also suffers from public concern about the growth and consumption of plants produced by direct genetic modication. There are small amounts of two acyl groups containing furan rings in soybeans (30). These oils are reported to be the sources of the odorous compound 3-methyl2,4-dione by photo-oxidation (61), but Kao et al. (62) were not able to nd differences in avor of photo-oxidized varieties with high and low content of these acyl groups.

3. PHYSICAL PROPERTIES OF SOYBEAN OIL The physical properties of fatty acids vary with their chain length, unsaturation, and other substituents and change with temperature. Numerous attempts have been made to develop equations that will predict these properties. Soybean oils properties should reect its constituents and, especially, its fatty acid composition, and physical properties have frequently been measured for typical soybean oils, but there have been fewer measurements of soybean oils with modied fatty acid compositions. Table 7 shows the values of physical properties of soybean oil of typical composition. Seitz (31) examined 77 samples of soybean oil from various parts of the

PHYSICAL PROPERTIES OF SOYBEAN OIL

585

TABLE 7. Some Physical Properties of Typical Soybean Oil. Density 20 C Specic Heat Capacity 20 C Melting Point Cloud Point Pour Point Heat of Combustion Heat Transfer Coefcient Surface Tension 30 C Viscosity 20 C Refractive Index nD20 C Vapor Pressure Heat of Vaporization Electrical Resistivity 24 C Dry Water Saturated Smoke Point Flash Point Fire Point 0.9165 to 0.9261 g/mL (31, 32) Decreases 0.000643 to 0.000668 g/mLC (6367) 0.448 cal/g C Increases 0.000616 cal/g C (68) 0.6 C (35) 9 C (69) 12 to 16 C (69, 70) 9450-9388 cal/g (71) 9135 91 cal/g (72) 269.7 watts/ K M2 at 180 C (73) 27.6 dyne/cm Decreases 0.077 dyne/cm C (63, 64) 58.562.2 cP (31) 1.47331.4760 (32) 1m at 254 C (74) 44,200 cal/mol (74) 23.7 Tohm cm (75) 7.25 Tohm cm (75) $245 C (76) $324 C (76) $360 C (76)

world over a seven-year period and reported densities at 20 C ranging from 0.9165 g/mL to 0.9210 g/mL. Wesolowski (32) examined the density of 53 Polish soybean oils at 19.9 C and reported values ranging from 0.9202 g/mL to 0.9165 g/mL. The following correlations of density and other variables were found: with refractive index 0.62, with iodine value 0.64, with saponication value 0.34, and with acid value 0.59. Yokota and Tachimori (77, 78) also reported a close relation between density and iodine value. Halvorsen et al. (79) and Rodenbush et al. (80) developed equations to predict the density of vegetable oils that took their fatty acid compositions into account and predicted densities of soybean oils with <0.1% error. The density of vegetable oils changes approximately linearly with temperature, and Kravchenko et al. (65, 66) found the density decreased 0.000668 g/mL C between 0 C and 100 C, whereas Alvarado (63, 64) found a value 0.000643 between 20 C and 70 C, and Noureddini et al. (67) found 0.0006674 between 23.9 C and 110 C. The densities of soybean oil-solvent mixtures at various temperatures are important for engineering calculations and have been reported for hexane, ethylene dichloride, and tricholoroethylene at 25 C, 37.8 C, and 50 C (81); Skellysolve B at 20 C, 10 C, 0 C, 10 C, 25 C, and 40 C (82); dichloromethane at 25 C (83); and hexane at 25 C (84). The specic heat capacity of soybean oil was measured by Clark et al. (85) and varied from 0.448 cal/g C to 0.666 cal/g C between 1 C and 271 C. Specic heat increased linearly with temperature at 0.00070 cal/g C. Tochitani and Fujimoto (68) measured the specic heat capacity of soybean oil from about the

586

SOYBEAN OIL

approximate melting point to 150 C and found a linear increase that t the following equation: Sp: Heat Capacity in cal=g C 0:4353 0:000616 T; 1

where T is the temperature in  C. Their data agreed closely with those of Clark et al. (85) but were slightly higher than those reported by Kasprzycka-Guttman et al. (86), who made measurements between 70 C and 140 C. Wang and Briggs (87) estimated the heat capacities of soybean oils of various compositions based on an equation by Morad et al. (88). They calculated that high-oleate oils should have a slightly higher heat capacity and low-saturate oils a slightly lower heat capacity than typical soybean oil, and the change with temperature should be 0.00057 cal/ g C. Their equation agreed with their experimental values within 5%. Miller et al. (73) determined the heat-transfer coefcient for soybean oil at frying temperatures and found that they varied from 261.3 watts/ KM2 to 276.2 watts/  KM2 between 170 C and 190 C, where M2 is square meters of surface. The melting of natural fats and oils usually occurs over a considerable temperature range, and soybean oils typical melting range is below 0 C. The availability of differential scanning calorimetry (DSC) at low temperatures has made information on melting of soybean oil available, and interest in using vegetable oils as fuels has also sparked measurements of their cloud and pour points. Table 8 (41) gives the temperatures of onset, maximum, and end of melting for various types of soybean oil. Table 7 gives the cloud and pour points of typical soybean oil. Wang and Briggs (87) also gave DSC curves for the melting of high-oleate, low-saturate, and lowlinolenate soybean oil. Hagura and Suzuki (89, 90) used the change in electrical capacitance of oil samples to obtain the melting range of soybean oil and found the results agreed with those obtained by DSC. Seitz (31) measured the viscosity at 20 C of 77 soybean oils from four geographic locations, and the range of variation was 58.1cP to 62.2cP (Table 7). Viscosity decreases with temperature, and the relation is not linear. Kinematic values (viscosity/density) have been reported at 20 C and 80 C by Chiof (91) and by Miller et al. (73) at frying temperatures (170190 C); dynamic viscosities have been reported between 0 C and 100 C by Kravchenko et al. (65, 66), between 23.9 C and 110 C by Nourreddini et al. (67), between 20 C and 70 C by Alvarado

TABLE 8. The Onset, Maximum Rate, and Termination of Melting Temperatures of Soybean Oil with Various Fatty Acid Compositions % (41). Class Typical 18:0 " 16:0 & 18:0 " 16:0 " 16:0 # Onset 39.6 13.7 17.1 21.8 46.1 Maximum Termination 9.4 18.3 16.8 8.4 13.8 0.6 20.7 18.9 11.6 8.1 16:0 11.4 10.1 24.6 28.0 3.4 18:0 4.2 22.8 18.7 4.7 2.6 18:1 26.1 17.3 8.6 13.8 18.0 18:2 50.3 42.2 37.5 42.1 64.8 18:3 7.9 7.7 10.7 11.4 11.2

PHYSICAL PROPERTIES OF SOYBEAN OIL

587

(63, 64), and between 1 C and 60 C by Arissen (92). Dahlberg et al. (93) were able to predict the viscosity of soybean and other oils from the Fourier transform infrared spectra. Rodenbush et al. (80) calculated the viscosity of oils by relating viscosity to a function they termed the reduced density, which they could calculate from the fatty acid composition. Several authors have t their viscosity-temperature data to equations (6367, 87, 94). Some of these come with a claim of theoretical signicance, but all have enough variables to t the data well. One of Alavarados equations (63, 64) is ln m ln m0 E=RT; 2

where E/R was 3262 and ln m0 was 6.997 for soybean oil. Wang and Briggs (87) reported graphically the change of viscosity with temperature from 10 C to 90 C for soybeans with altered fatty acid compositions. They found the viscosity of higholeic soybean oil higher and low-saturated soybean oil lower than that of typical soybean oil. Miller et al. (73) determined the kinematic viscosity of soybean oil at temperatures of 170 C, 180 C, and 190 C, and obtained values of 3.151 cm2/sec, 2.880 cm2/sec, and 2.614 cm2/sec, respectively. The viscosities of soybean oil-hexane (Skellysolve B) mixtures at temperatures between 20 C and 40 C were investigated by Magne et al. (84). Ibemesi and Igwe (95) examined the reduced viscosity (viscosity/concentration) of solutions of soybean oil in toluene, xylene, cyclohexane, and tetrahydrofuran. They found an anomalous reduced viscosity increase at concentrations below about 0.12 g/mL that they attributed to clustering of the fat molecules in the solvent. Erhan et al. (96) determined the kinematic viscosity of blends of typical soybean oil with polyalphaolens and isobutyrl oleate and high-oleic soybean oil with isotrideceyl adipate and mineral oil to achieve viscosities suitable for lubricants. The surface tension of soybean oil at 20 70 C was reported by Alvarado (63, 64) and is given in Table 7. The surface tension decreased linearly with temperature at 0.077 dyne/cm C. Wesolowski (32) examined the refractive index of 53 samples of soybean oil from Poland, and the range is given in Table 7. Sietz (31) reported average values for samples from several geographic locations, and these values (1.47471.4752) fall near the mean of Weslowskis samples. Refractive index depends on chain length and unsaturation (97) and often has been used to follow hydrogenation (98102). Refractive index also has been used to follow autoxidation (103). A closely related quantity, the dielectric capacitance also has been used to assess the quality of frying oil (104). Perry et al. (74) measured the vapor pressure of soybean oil at various temperatures and found that the data t the equation: log P 18:3 9650=T; 3

where P is the pressure in microns and T is in K. The also estimated the heat of vaporization (Table 7).

588

SOYBEAN OIL

Tomoto and Kusano (105, 106) measured the solubility of carbon dioxide, nitrogen, hydrogen, and oxygen in soybean oil between 0.2 atm and 1 atm and between 30 C and 70 C. The Bunsen coefcient (volume of gas at standard conditions / volume of soybean oil at 760 mm) at 30 C was 1.018 for carbon dioxide, 0.086 for nitrogen, and 0.048 for hydrogen. The Bunsen coefcient of oxygen at 30 C was 0.141 but increased with temperature, probably because of oxidation during the measurement. The Bunsen coefcient decreases linearly to zero at zero gas pressure. The natural logarithm of the Bunsen coefcient versus 1/T in K is linear, and the constant is the heat of solution of the gases divided by the gas constant. These heats of solution are 2.42 kcal/mol for carbon dioxide, 2.58 kcal/mol for nitrogen, and 3.86 kcal/mol for hydrogen. From this relation, one can calculate the solubility at any temperature and pressure in the range of the study. Comparison of the values for soybean oil with olive and linseed oil suggested that the Bunsen coefcients are inuenced by the degree of unsaturation of the oil. The viscosity of soybean oil decreased with the amount of carbon dioxide dissolved, but dissolved nitrogen slightly increased the viscosity. Loncin (107) reviewed the data on the solubility of water in fats and oils. For typical soybean oil, the solubility of water was 0.11% by weight at 22 C and rose to 0.19% at 60 C. The solubility of water decreases with fatty acid chain length and increases with the percentage of free fatty acids. The vapor pressures of soybean oil-hexane mixtures between 75 C and 120 C were reported (108, 109), and similar data for soybean oil with commercial hexanes was reported by Smith (110). Arnold and Breuklander (83) measured the boiling point of dichloroethylene-soybean oil mixtures and found the log (V.P.) was a linear relation of the mole fraction of oil. Kusano (111, 112) measured the vapor pressure (P) of soybean oil-solvent mixtures that included hexane, benzene, and carbon tetrachloride between 20 C and 50 C and found linear relations between log P and 1/ T. Anikin et al. (113, 114) measured the vapor pressure of mixtures of soybean oil with the khladon 113 (trichlorotriuoroethane) between 30 C and 100 C. Aeberhard and Spekuljak (115, 116) measured the vapor pressure of hexane in hexanesoybean oil mixtures and found the vapor pressure at 25 C could be predicted by the equation P 9128x 0:2807x2 0:004695x3 ; 4

where P is the vapor pressure in Torr and x is the weight percentage of solvent in the mixture. Tekin and Hammond (75) measured the resistivity of soybean oil and found it decreased logarithmically with temperature from about 100 Tohm cm at 5 C to 0.251 Tohm cm at 100 C. The resistivity was decreased by saturating the oil with water and the addition of oleic acid, a-tocopherols, b-carotene, phospholipids, and monoacylglycerol. The smoke, ash, and re points of soybean oil have been determined by the Cleveland Cup method and show considerable variation. Dickhart (117) reported a smoke point of 138 C while Detwiler and Markley (76) reported 241250 C.

GRADING

589

Detwiler and Markley (76) found that the smoke point varied considerably with the degree of rening, especially the removal of free fatty acids, and also with the mode of oil extraction. Yen et al. (118) found a smoke point of 191 C, which was raised several degrees by the addition of phenolic antioxidants. The ash point of soybean oil, the temperature at which vapors coming from the oil will catch re from an ignition source, were reported as 304 C (117), 326331 C (76), 174 C (69), 318 C (70), and 320 C (119). The low value reported by Ali et al. (69) was obtained by using a Pensky-Martens closed tester and ASTM method 093-90. The ash points of hexane-soybean oil mixtures were determined and correlated with headspace gas chromatography data (120). Fire points or self-ignition temperatures (SITs) for soybean oil by using the Cleveland Cup method, which uses a brass cup, were reported to be 356363 C (76) and 400 C using a stainless-steel cup apparatus (71). The burning rate of soybean oil was 4.3 g/m2sec, ame height 129 mm, and irradiance 0.153 kW/m2 (71). Kowalski (119) studied the self-ignition temperature in a differential scanning calorimeter heated at rates of 4090 C/min and under 8002800 kPa of oxygen pressure and found values of 260290 C for soybean oil. He found the addition of copper wire to the sample decreased the self-ignition temperature by 515 C. The self-ignition temperature was inversely related to oxygen pressure. Wakakura (121, 122) used a scanning calorimeter at an oxygen pressure of 980 kPa with soybean oil spread on glass wool and in bulk and found self-ignition temperatures of 147 C and 376 C, respectively.

4. GRADING To facilitate soybean marketing, the U.S. Federal Grain Inspection Service (FGIS) established grading standards for soybeans (Table 9) (123), and the FGIS website (124) provides much more detailed information than can be provided here (124).

TABLE 9. Ofcial Grades and Grade Requirements of the Federal Grain Inspection Service, United States Department of Agriculture. Maximum Limits Damaged Kernels Soybeans Heat Foreign of Other Damaged Total Material Splits Colors (%) (%) (%) (%) (%) 0.2 0.5 1.0 3.0 2.0 3.0 5.0 8.0 1.0 2.0 3.0 5.0 10.0 20.0 30.0 40.0 1.0 2.0 5.0 10.0

Grade U.S. No. 1 U.S. No. 2 U.S. No. 3 U.S. No. 4 U.S. Sample Grade

Minimum Test Weight per Bushel (lbs) 56.0 54.0 52.0 49.0

590

SOYBEAN OIL

Soybeans are classied into two classes based on color, Yellow Soybeans and Mixed Soybeans. There are four numerical grades (U.S. No. 1, 2, 3, and 4) and a U.S. Sample Grade for each class. Sample Grade designates those soybeans that do not meet the requirements of any of the numerical grades. Six factors are considered in assigning a grade designation: test weight, amounts of beans that are damaged or heat damaged, and amounts of foreign material, splits, and soybeans of other colors. Although important to processors because they affect yields and qualities of nished products, the FGIS ofcial grades do not consider moisture, protein, and oil contents, but these factors may be specied on contracts in some markets. Near infrared transmission (NIT) spectroscopy is widely used to rapidly estimate (within less than 2 min after sampling and without any sample preparation required) moisture, protein, and oil contents. Brumm and Hurburgh (125) developed a computer program to estimate the process value of soybeans based on their composition and selling prices of oil and meal. In some cases, price premiums are offered for soybeans high in oil content or high in both oil and protein contents, and details of the program are available on the Internet (126). Beans low in test weight may contain less oil. Test weight is the weight in pounds of grain per Winchester bushel (35.2 L) and is determined by using an Ofcial Test Weight Apparatus and a 11/4-quart (1.18 L) sample before removing foreign material. All other grading factors are measured as percentages of total sample weight. Foreign material, which is other grains, weed seeds, pods, leaves, stems, etc., reduces oil and protein contents and storage life. Foreign material is determined by sieving a sample. All materials, including soybeans and soybean pieces that readily pass through an 8/64-inch (3.2-mm) round-hole sieve and all material other than soybeans remaining on the sieve after sieving are considered to be foreign matter. Split soybeans, which result from mechanical damage during handling and over drying, reduce storage life and oil yield, and increase losses during oil rening. Splits (typically the cotyledon splits into two halves) and broken beans (more than two pieces) increase free fatty acid (FFA), phosphatides, iron, and peroxide contents of the crude oil. Heat-damaged beans have high-FFA content and darken the oil color, both changes in oil quality increase rening loss (127). Splits are dened as beans with more than one-fourth of the bean removed and are not damaged. Splits are determined by sieving a portion of the grain after removing the foreign material. Damaged beans reduce the storage life of the beans and oil yield in processing, cause the oil to be dark-colored and poor in avor, and increase losses during oil rening (128). Soybeans and soybean pieces that are badly damaged by the ground, weather, frost, heat, insects (stinkbug-stung kernels are considered at one-fourth the actual percentage), mould, or sprouting are considered to be damaged. Damaged beams are determined by hand picking after removing foreign material. Soybeans of other colors may affect oil color by contributing undesirable pigments and are those beans that are green, black, brown, or have multiple colors. Almost 27 million MT of soybeans were exported from the United States during the 2002 crop year, of which 4.8% was U.S. No. 1, 94.6% was U.S. No. 2, 0.4% was U.S. No. 3, and 0.1% was U.S. No. 4. By comparison, Brazilian soybeans are

RECOVERY OF OIL FROM SOYBEANS

591

typically slightly higher in oil content (6-yr average of 1.2% higher oil content), foreign matter, damage, free fatty acid, and moisture contents and lower in test weight (129).

5. RECOVERY OF OIL FROM SOYBEANS Soybeans are economically important because of their high qualities and quantities of oil and protein. From one bushel of soybeans (60 lb, 27.2 kg), crushers typically recover 11.1 lb (5.0 kg) of crude oil, 44.3 lb (20.1 kg) of meal (48% protein), and 3.3 lb (1.5 kg) of hulls with the remainder being shrinkage. According to the U.S. Department of Agriculture statistics, the oil accounts for about one-third of the returns in processing soybeans with the protein in the form of meal accounting for the remainder (130). Over the past ve years, the meal (48% protein) has ranged in yearly average prices of $153289/MT (6.913.1 cents/lb), whereas the oil has ranged $311569/MT (14.125.8 cents/lb). Hulls have limited outlets, mostly in cattle feeds, and sell for about $66/MT (3 cents/lb) and return $4.04/MT of soybeans ($0.11/bu). During the same period, the average price of soybeans in the United States ranged from $167270/MT ($4.547.35/bu) and crushing margins, the difference in soybean price and crusher returns, averaged $23.1 56.2/MT ($0.631.53/bu). Farmers often store their soybeans in metal bins on the farm or in concrete silos at local elevators for a fee. This allows farmers to sell their crop later in the year when prices usually increase. Soybeans should be stored at less than 13% moisture to assure safe storage and preservation of the quality. This moisture content is usually achieved by drying in the eld before harvesting. Lower moisture contents increase the tendency of soybeans to split during handling to form two half pieces of cotyledon. Higher moisture content during storage can lead to mold damage or heating damage due to seed respiration (131). These forms of damage can affect soybean grade and oil quantity and quality when processed. The processing of soybeans has been described in more detail elsewhere than can be done here (132134). Oil is recovered today by either mechanical means or through the use of organic solvents. In the preindustrial revolution period, soybeans were merely pressed with lever or animal-driven screw-operated batch presses. Around the turn of the Twentieth Century, when soybeans became a viable commercial crop in the United States, steam-powered hydraulic batch presses were used. Today, electric-powered continuous screw-presses, often referred to as expellers (but this is a trademarked name for screw presses manufactured by one supplier), or continuous countercurrent solvent extractors are used. In either case, soybeans are pretreated prior to oil recovery to either make oil recovery easier or more complete, or to increase the value of the defatted solids known as meal. Usually, soybeans arriving from the farm or elevator are cleaned to remove stems, leaves, pods, broken grain, dirt, stones, and extraneous seeds using shaker screens and aspirators. It is usually advantageous to remove the major portion of the hulls because they are low in oil (<1%) and protein. The hulls of

592

SOYBEAN OIL

soybeans account for 78% of the weight. Dehulling reduces the material going downstream into costly operations and increases the protein content of the meal. Dehulling raises the meal protein content by about four percentage points (i.e., from 44% for undehulled solvent-extracted soybean meal to 4849%) and reduces ber content (from 7.0% to <3.3%). The formulated feed market prefers high-protein and low-ber meal, especially in manufacturing swine and poultry feeds. The hulls are relatively easy to remove from soybeans compared with those of other oilseeds, simply cracking the bean into 68 pieces to free the hull using corrugated roller mills and aspirating the hulls away from the oil- and protein-rich cotyledon, known as meat, is effective. Consistent bean size is important to proper cracking and drought-caused shrinking and wrinkling make dehulling much more difcult and less efcient (135). Often, the aspirated hulls go to gravity tables to scavange any small meats aspirated with the hulls. Usually, cleaned soybeans are conditioned prior to cracking to improve dehulling efciency by heating and drying the beans to about 9.5% moisture and allowing the moisture to equilibrate for 17 days within the bean to loosen the hull. Various hot-dehulling schemes have also been devised to increase dehulling efciency, and are often used in northern latitudes where the protein contents of soybeans, and, consequently, meal protein levels, may be lower and specied protein levels cannot be achieved without more complete hull removal. In the 1930s, soybeans were widely processed by screw pressing after cooking the seed. A typical process diagram for screw pressing soybeans is shown in Figure 1 and a plant photo is shown in Figure 2. The beans are heated and the oil is squeezed out. The pressed oil usually goes to settling basins to reduce ne

Soybeans

CLEANING

Foreign Matter CRACKING ASPIRATING Meats Hulls

( DRYING OR COOKING

optional)

Foots

SCREW PRESSING

Cake

MEAL GRINDING

SETTLING POLISH FILTERING Foots

MEAL COOLING Partially Defatted Meal

Crude Oil
Figure 1. Process ow diagram for screw pressing soybeans.

RECOVERY OF OIL FROM SOYBEANS

593

Figure 2. Photograph inside a modern soybean screw-press plant (courtesy of West Central Cooperative, Ralston, IA). (This gure is available in full color at http://www.mrw.interscience. wiley.com/biofp.)

solids content, with the nes being recycled to the screw press. The oil then goes to polish lters before being placed into storage for shipment to a renery. Today, in the United States, there are less than a half-dozen traditional screw press plants (excluding extrusion-expelling, which will be discussed later). Only one screwpress plant crushing more than 800 MT/day exists, and it is located in Ralston, IA. Under optimum processing, the meal can contain as low as 46% residual oil, which contributes metabolizable energy to livestock consuming screw-pressed meal. As a result of the heat treatment during cooking and screw pressing, increased rumen-bypass characteristics improves feed efciency in high producing dairy cattle. Thereby, the meal may sell for premium prices over solvent-extracted meal when adequate numbers of dairy animals are located nearby. As this meal is used to feed ruminants, the beans are not usually dehulled. Direct solvent extraction is the most widely used oil-recovery method for soybeans, but it also requires considerable capital and large scale to compete. In actual practice, solvent extraction is used to crush over 98% of the soybean processed in the United States. Process ow diagrams are shown in Figures 3 and 4. Most soybean solvent-extraction plants process more than 2,500 MT/day (Figure 5), and some are capable of processing as much as 5,000 MT/day (especially newly constructed plants in Brazil). Direct-solvent-extraction plants smaller than 1,000 MT/day have difculty competing in the United States. At various times, soybeans have been extracted commercially with petroleum distillate fractions that resemble gasoline, acetone, carbon disulde, ethanol, trichloroethylene, and even water,

594

SOYBEAN OIL

Soybeans CLEANING CRACKING ASPIRATING ( optional) Meats Cracked Meats CONDITIONING FLAKING Flakes EVAPORATING Miscella (oil and solvent) STRIPPING Crude Oil Solvent ( EXPANDING optional) Collets Foreign Matter GRAVITY TABLING

Hulls

SOLVENT EXTRACTING Marc (solids and solvent) ( optional) FLASH DESOLVENTIZING White Flakes GRINDING MEAL DESOLVENTIZING TOASTING COOLING GRINDING Toasted Meal Enzyme-active Flour Solvent

Figure 3. Process ow diagram for direct solvent-extracting soybeans.

which is not a true solvent but facilitates oil separation by creaming. A petroleum distillate containing a mixture of hexane isomers having a typical boiling range of 65 C to 71 C is the only solvent used today. These products typically contain 45% to 70% n-hexane. n-Hexane is considered a neurotoxin in the United States and has proven toxicity at high concentrations. The U.S. Occupational and Safety Administration has set the maximum workplace exposure level at 500 ppm and a timeweighted average not to exceed 50 ppm (136). In recent years, there has been considerable interest by the soybean industry in alternative solvents to hexanes because of increasing environmental and safety concerns. Alternative solvent technologies have been extensively reviewed (137139).

Figure 4. Depiction of equipment and process ow diagram for direct solvent-extracting soybeans (courtesy of French Oil Mill Machinery Co., Piqua, OH).

595

596

SOYBEAN OIL

Figure 5. Photograph of a modern soybean-extraction plant (courtesy of Bunge North America, Council Bluffs, IA). (This gure is available in full color at http://www.mrw.interscience.wiley. com/biofp.)

Cleaned and dehulled soybeans are conditioned by heating to 74 C to soften the meat prior to aking using smooth roller mills. Proper cracking and conditioning are important to achieve the desired cell distortion or cell rupture that is necessary for efcient extraction and to prevent production of excessive amounts of ne meat particles that impede proper aking or extraction. Highly distorted cells are desired (140) so that cell walls and pseudo-membranes around oil bodies are sufciently ruptured, and the oil can be easily contacted by the solvent and leached out. Soybeans are typically aked to 0.25 mm (1012 thousandths of an inch) to achieve the desired distortion (141). The akes may be conveyed directly to the extractor or to an expander. In recent years, expanders have been adopted to achieve increased cell distortion and to produce an easily extractable porous pellet (collets) that is more dense than aked soybeans. Thereby, more mass of material can be placed into the xed volume of the extractor, the oil is more quickly extracted reducing extraction time, and the solvent drains more completely reducing the load on meal desolventizing equipment. All of these factors increase plant throughput capacity (142144). Plants vary in the amounts of akes that are expanded, typically about one-third of the ake production, but in a few cases, all akes are expanded. Although there is not universal agreement, expanding may also improve oil quality by quickly inactivating phospholipases, which cause phospholipids to become nonhydratable. In the authors opinion, adoption of expanders is the most signicant change in solvent extraction during the past quarter century.

RECOVERY OF OIL FROM SOYBEANS

597

Figure 6. Photograph inside a modern direct solvent-extraction plant processing soybeans (courtesy of Crown Iron Works, Minneapolis, MN). (This gure is available in full color at http://www.mrw.interscience.wiley.com/biofp.)

Soybeans are exclusively extracted in the percolation mode as opposed to the immersion mode used during early days of soybean extraction. A photograph of a modern chain extractor is shown in Figure 6. The percolating solvent ows by gravity through the bed. Solvent is always passed countercurrent to the transport of meal solids. There are several different types of extractors, including chain and basket types, and shallow- and deep-bed types. Soybean akes or collets are extracted for 30 45 min in six or more stages. The best quality oil, low in non-triacylglycerole components, is extracted rst, and with more exhaustive extraction, poorer quality oil is recovered. Thus, at lowresidual oil levels, the proportions of phosphatides, free fatty acid, and pigments that are extracted are greater and so is the rening loss. However, the current industry practice strives for the most complete extraction possible, typically in the range or 0.5% to 1.25% residual oil. For this reason, exhaustive laboratory devices, such as a Soxhlet extractor with ground material, are not very useful when trying to achieve oil that is representative of that produced by a commercial extractor, and, for best results, the solvent should be percolated in stages through a bed of aked material. The full miscella (oil-rich extract) containing 2030% oil drains from the freshest aked or expanded meats and is sent to solvent-recovery operations. The operations include two-stage evaporators and an oil stripper. The oil content exiting the rst-stage evaporator is 6570% oil and is heated with vapors from the desolventizer-toaster. After the second-stage evaporator, the oil content is 90 95% oil. The oil stripper uses steam-injection vapor, high heat, and high vacuum to remove the

598

SOYBEAN OIL

solvent to less than 0.2% remaining in the oil. The temperature of the oil in the stripper should not exceed 115 C to prevent scorching the oil and causing dark color. Flash point determination is an easy method to assure that the solvent-evaporation equipment is operating as it should and the ash point should exceed 150 C. All evaporated solvent is recycled to the extractor. The oil should be sent to a vacuum dryer to remove any residual stripping steam condensate and the dry oil immediately cooled prior to placing into storage. As a result of natural antioxidants (i.e., phoshpahtides, tocopherols), crude soybean oil can be stored for a long time in large tanks provided the oil is rst cooled to ambient temperature and has limited access to air. The crude oil should be low in moisture to prevent hydrolysis. Gummy deposits of phosphatides may spontaneously form in the bottoms of storage tanks and tank cars used for shipping crude oil. There has been much speculation about using supercritical carbon dioxide because using this technology eliminates safety issues as carbon dioxide is not ammable and the oil is better quality (139), but no such plants have been constructed to process soybeans. This is due to the absence of a commercially feasible means of continuously feeding soybean akes into a high-pressure vessel and removing the spent akes. Recently, one company has developed a screw press in which supercritical carbon dioxide is injected into the barrel. This equipment has been successfully used to produce soybean meal with lower residual oil contents than typically produced by screw pressing and with little heat denaturation of the protein. The spent akes or collets are sent to a meal desolventizer-toaster (DT). Newer equipment incorporates countercurrent steam usage. The Schumacher-type desolventizer/toaster/dryer/cooler has become widely accepted in the soybean industry, and, with this equipment, residual levels of hexane should be less that 500 ppm. Both indirect and direct steam heating are used. Steam vapor and a modest vacuum carry away the solvent vapors for condensing. Condensed solvent is recycled to the extractor after separating water from the hexane. A desolventizer-toaster is a series of trays through which the meal ows. Soybean meal is unique in that it must be toasted to inactivate protease inhibitors (especially trypsin inhibitor) that would reduce feed efciency if not denatured and inactivated. Urease activity is used as a measure of adequate heating. The toasted meal typically has low-protein solubility as measured by protein dispersibility index (typically 45 PDI). The meal is then sent to a dryer-cooler to reduce the meal temperature for safe storage. The moisture content should be about 12% and the residual fat content less than 1.5%. The free extractable oil after extraction is less than 1.0%, but heating during desolventizingtoasting frees some bound fat that previously was not extractable with hexane. Overtoasting may reduce digestibility and nutritional value of the meal. The meal is then ground with a hammer mill to produce meal with uniform particle size. If dehulling is employed, as is typical for plants in the United States, the meal will contain around 48% protein. Additionally, dehulling reduces the ber content of the meal by over 50%. In some plants, a portion of the soybean hulls may be added back to the meal prior to grinding to adjust and precisely control meal protein content. Livestock feeders are concerned about having uniform protein and ber contents in order to formulate minimum-cost feeds for maximum feed efciency.

RECOVERY OF OIL FROM SOYBEANS

599

The meal is generally ground so that 95% passes a U.S. 10-mesh screen and a maximum of 3% to 6% passes through a U.S. 80-mesh screen. Some plants divert part of their spent ake production away from a desolventizer-toaster to a ash desolventizer, which is designed to produce white akes with high-protein solubility (PDI 70 90). White akes are used as the starting material for producing protein isolates or concentrates, which contain >90% and 65% protein, respectively, and are used as food ingredients. Some soybean extraction plants also degum their oil before shipping to centralized reneries. There is not sufcient market to make it protable to recover all of the soybean phosphatides and market them as soy lecithin. The gums are added back to the meal in the toaster to evaporate the water. The gums contribute to the metabolizable energy content of the meal and the soybean crusher can get meal prices for crude phosphatides. Quality standards and trading rules for solvent-extracted soybean meal and oil are designated by the National Oilseed Processors Association and are available at a website (145). Soybean products are remarkably uniform in their quality characteristics compared with alternative sources of oil and meal. Recently, a third process, known as extruding-expelling (or Express Systems as trademarked by the equipment manufacturer), was developed (Figures 7 and 8) (146, 147). In this process, a dry extruder, which generates heat solely through friction of the beans in the extruder, replaces steam generating and steam heating the beans. The heated beans then go to a screw press and the rest of the process is the same as in screw pressing. The plants typically process 550 MT/day.

Soybeans

CLEANING

Foreign Matter CRACKING ASPIRATING Meats Hulls

optional)

EXTRUDING EXPELLING (screw pressing) SETTLING POLISH FILTERING Foots Cake

Foots

MEAL GRINDING

MEAL COOLING Partially Defatted Meal

Crude Oil
Figure 7. Process ow diagram for extruding-expelling soybeans.

600

SOYBEAN OIL

Figure 8. Photograph inside a modern extruding-expelling plant processing soybeans. (This gure is available in full color at http://www.mrw.interscience.wiley.com/biofp.)

Approximately 70 extruding-expelling plants have been built over the past 10 years for crushing soybeans. Usually, these plants are farmer-owned and provide meal to nearby livestock feeders (148). The oil is sold to the large oil reneries, often at a discount despite the oil being of excellent or superior quality because high costs are incurred in handling small lots of oil. These plants are ideally suited to identitypreserved processing. There are niche opportunities for these plants to market certied organic or nonGMO soybean oil, for which there is a lucrative market in some countries. Other opportunities reside with genetically enhanced soybean oils and meals, such as low-linolenate, high- and low-saturates, and high-oleate oils. This process has even been proposed for producing soybean products during interplanetary exploration (149). NASA plans to grow soybean in space because some missions, such as Mars exploration, cannot be supported without growing food in space.

6. QUALITIES OF SOYBEAN OILS AND MEALS EXTRACTED BY DIFFERENT METHODS Wang and Johnson (150) compared the qualities of soybean oils and meals obtained by the three processing methods. Soybean oil and meal samples were collected at three times within a one-year period from 13 extruding-expelling plants, eight

QUALITIES OF SOYBEAN OILS AND MEALS EXTRACTED

601

TABLE 10. Quality Characteristics of Soybean Meals Produced by Different Oil-Extraction Processes. Processing Method Solvent Extraction Screw-Pressing Extruding-Expelling 11.65 1.2 48.8 0.04 89.1 44.5 36.0 69.1 5.46 5280 11.03 6.3 43.2 0.03 61.6 10.6 48.1 51.5 0.3 2000 6.94 7.2 42.5 0.07 88.1 18.1 37.6 65.8 5.52 12,250

Property Moisture, % Residual oil1, % Protein1, % Urease, pH Protein solubility in KOH, % Protein dispersibility index Rumen-bypass protein, % Hunter L color Trypsin inhibitor, mg/g Trypsin inhibitor, TIU/g
1

Reported at 12% moisture basis.

solvent-extraction plants, and one continuous screw-press plant. Their results are shown in Tables 10 and 11. Solvent extraction is by far the most efcient method of recovering oil from soybeans, typically only about 1.2% residual oil is left in the meal. Screw-pressing is slightly more efcient in recovering oil than is extrudingexpelling, leaving 6.3% oil in screw-pressed meal compared with a mean of 7.2% for extruded-expelled meals. Most solvent-extraction plants dehull soybeans to produce soybean meal with 48% or more protein and carefully control the moisture content at 12%. Solvent-extracted soybean meal is highly uniform, often much more so than either screw-pressed or extruded-expelled meal. The high-protein and low-ber contents of solvent-extracted soybean meal are desired when feeding poultry and swine, which consume 46% and 25% of the soybean meal produced, respectively. Most extrusion-expelling and screw-press plants have not invested in dehulling equipment, as their meal generally goes into feeding ruminant animals. Protein dispersibility indices, a measure of protein denaturation that is used in the food industry, are lower for extruded-expelled and screw-pressed meals. Protein

TABLE 11. Quality Characteristics of Soybean Oils Recovered by Different Processes. Processing Method Solvent Extraction Screw-Pressing Extruding-Expelling 0.31 277 1365 0.08 0.96 39.8 11.1 0.33 463 1217 0.05 1.76 36.2 17.5 0.21 75 1257 0.08 1.73 23.9 10.2

Property FFA, % Phosphorus, ppm Tocopherols, ppm Moisture, % PV, meq/kg AOM stability, h Lovibond color, red

602

SOYBEAN OIL

solubilities in potassium hydroxide solution, a measure of protein denaturation and an indicator of overcooking that is used in the feed industry, are similar for extruded-expelled and solvent-extracted meals, but higher than that of screwpressed meal (62%). Rumen-bypass protein values are higher for the screw-pressed meals, indicating that more protein escapes the rumen and is not converted to microbial protein that has a lower nutritive value than the original soybean protein. All meals examined by Wang and Johnson (151), regardless of the processing method employed, had low-trypsin-inhibitor activity, which is important to proper protein digestion. Soybean trypsin inhibitors, especially in unheated soybeans, can inhibit the protease enzymes trypsin and chymotrypsin, reducing protein hydrolysis during digestion. There are two trypsin inhibitors in soybeans, Kunitz inhibitor and Bowman-Birk inhibitor. The Kunitz inhibitor is relatively easily inactivated by moist heat, comprises about 85% of the inhibitory activity, and acts only on trypsin; the Bowman-Birk inhibitor is much more stable to heat (due to six disulde cross linkages) and acts on both trypsin and chymotrypsin. The activity of the enzyme urease (easily measured as pH change) is often used as a quick and easy indicator of adequate cooking. A valuable resource for characteristics of soybean meal is http://www.stratsoy.uiuc.edu/epv/. Oil properties vary considerably between different types of plants (Table 11) and among plants of the same type and sampling times. The free fatty acid (FFA) content, a measure of hydrolytic degradation during seed storage and oil extraction, of extruded-expelled oil is signicantly lower than that of solvent-extracted oil, which may be due to the rapid inactivation of lipases during extrusion. Screw-pressed soybean oil typically contains 0.33% FFA, which is similar to that of typical solvent-extracted oil. The amounts of phospholipids in the oils after settling are much lower in extruded-expelled oil (75 ppm phosphorus) than in solvent-extracted oil (277 ppm phosphorus). Screw-pressed oil has much higher phospholipid content (463 ppm phosphorus) than does solvent-extracted oil. The phospholipid in extruded-expelled oil is readily hydratable and easy to settle, which are attributed to the rapid heat inactivation of the phospholipases. The tocopherol contents of crude extruded-expelled oils are slightly lower than those of crude solvent-extracted oil. Peroxide values (PVs), a measure of primary lipid oxidation products, are signicantly higher for crude extruded-expelled oil than for crude solvent-extracted oil, which is attributed to the high temperature used in extruding-expelling, the long period typically allowed for oil cooling, or the often poor oil-storage conditions and longer storage times at extruding-expelling plants. Oxidative stability, as measured by the Active Oxygen Method (AOM), of extruded-expelled oil is signicantly lower than that of solvent-extracted oil, probably because of the higher PV value and lower contents of phosphorus (phosphatides) and tocopherols in crude extruded-expelled oil. The colors of extruded-expelled and solvent-extracted oils are signicantly different. Although solvent-extracted oil tends to be slightly darker than extruded-expelled oil, screw-pressed oil is much darker in color than are the other two types, probably because of the more severe heat treatment of the screwpressed oil before pressing.

SOY PROTEIN INGREDIENTS

603

7. SOY PROTEIN INGREDIENTS Defatted soybean meal (white akes) may be heated to produce a variety of solubility and enzyme-activity characteristics, ground and sized to produce grits or our, and used as a food ingredient in bakery products, soymilk, and meat products. A historical accounting of the development of these products was published by Johnson et al. (151, 152). Soy our may be relecithinated or refatted with rened, bleached, and deodorized oil to achieve desirable functional properties. Soy our can also be texturized by using an extruder to produce meat-like products called TVP (texturized vegetable protein) that are often used to extend ground meat. Enzyme-active soy our is used in bread at 0.5% of the wheat our. Lipoxygenase in the soy our bleaches the carotenoids of wheat our to produce a whiter crumb and improves dough-mixing properties. White akes may be processed into soy protein isolates or concentrates (132, 153). Soy protein is poorly soluble in water at pH 4.5, the isoelectric point, and highly soluble at pH >8.0. These solubility characteristics can be used to isolate or concentrate soy protein. Untoasted and ash-desolventized meal in which the protein is undenatured and highly soluble (>70 PDI and preferably >90 PDI) is the preferred starting material in manufacturing soy protein isolates. Under some conditions, extruded-expelled meal can be used, but the yield of soy isolate is reduced. The meal is ground in water adjusted to pH 8.0 with sodium hydroxide and centrifuged to remove insoluble ber. The soluble fraction is acidied to pH 4.5, and the protein precipitates. The precipitated protein curd is separated from the soluble sugars by centrifuging. The protein curd may be washed, neutralized, and spray-dried. High protein solubility is not needed for protein concentrates and heating to insolubilize the protein and facilitate extracting the solubles (mostly sugars) with water is one way that has been used to prepare soy protein concentrates. Concentrates today, however, are normally made by extracting the sugars with either acid (pH 4.5) or aqueous ethanol (6080%). Aqueous ethanol is most frequently used because it produces the blandest product, but ethanol denatures the protein and leaves the protein with reduced functional properties unless the product is refunctionalized by jet cooking (154, 155) or by homogenizing under alkaline conditions (156). Soy protein concentrate must contain >65% protein on a dry basis. The soybean storage proteins glycinin and b-conglycinin, which often are recognized in the older literature as 11S and 7S proteins, respectively, based on their sedimentation during ultra centrifuging, comprise 6580% of the protein. Methods have even been developed to separate soy protein into fractions rich in individual proteins (157, 158). Some believe b-conglycinin has greater health benets than glycinin. Soy protein isolates are used in dairy analogs (milk replacers and beverage powders), meat-pumping solutions, luncheon meats, and infant formulas, whereas soy protein concentrates are used in dairy analogs (milk replacers, beverage powders, cheeses, coffee whiteners, frozen desserts, whipped toppings), baked goods, and meat products (156). These protein products are used for their functional properties such as solubility, water absorption and binding, viscosity control, gelation,

604

SOYBEAN OIL

cohesion-adhesion, elasticity, emulsication, fat absorption and binding, foaming, and color control. The solubility and thermal properties of these products were recently compared by Lee et al. (159). Some products have high solubility even though they were largely denatured. Many health benets have been attributed to soy protein products, either because of the proteins or accompanying phytochemicals, such as isoavones, saponins, etc. There is a growing body of evidence that soy protein products may impact hypertension and heart disease, osteoporosis and bone health, and certain cancers. The perception of such nutritional benets is driving an increased interest by food companies in the incorporation of soy protein products. In October 1999, the U.S. Food and Drug Administration (FDA) authorized a health claim for soy protein in cardiovascular disease. U.S. food labeling laws now permit a statement on the label that Diets low in saturated fat and cholesterol that include 25 grams of soy protein a day may reduce the risk of heart disease. One serving of (name of food) provides (list number) grams of soy protein. The health claim allowance is reported in the Federal Register (160) and is posted on the FDA website (161).

8. BASIC PROCESSING OPERATIONS As discussed in the previous section on soybean oil composition and Table 11, crude soybean oil can contain phospholipids, free fatty acids, lipid oxidation products, and unsaponicable matter, which includes chlorophyll and carotenoid pigments, tocopherols, sterols, and hydrocarbons. Some of these components negatively affect oil quality, and some may play positive roles in nutrition and functionality. The goal of oil rening is to remove the undesirable components so that a bland, stable, and nutritious product can be obtained. The basic processing operations in oil rening are (1) degumming, (2) neutralization, (3) bleaching, (4) hydrogenation, (5) deodorization, and (6) winterization or crystallization. These steps are outlined in a ow chart as shown in Figure 9. 8.1. Degumming Crude soybean oil contains a relatively high concentration of phospholipids compared with other vegetable oils. Degumming is a process of removing these components from crude soybean oil to improve its physical stability and facilitate further rening. Phospholipids can lead to dark-colored oils and they can also serve as precursors of off-avor (162) compounds. Free fatty acids, pigments, and other impurities are also partially removed by degumming. Soybean oil can also be neutralized directly without degumming if gum or lecithin recovery is not desired. Conventional belief holds that the loss of neutral oil in rening crude oil by direct neutralization is less than the combined losses of degumming and caustic rening of the degummed oil. The quality of crude soybean oil inuences the efcacy of degumming. Phospholipids can exist in a hydratable form, which can be readily removed by addition

BASIC PROCESSING OPERATIONS

605

Crude Soybean Oil Water FILTERING Foots GUMS HYDRATING CENTRIFUGING

Alkali

NEUTRALIZING CENTRIFUGING Soapstock (free fatty acids, phosphatides) Wash-water (residual soapstock) Moisture GUMS DRYING Lecithin Moisture

Water

WASHING CENTRIFUGING VACUUM DRYING

Bleaching Earth

BLEACHING FILTERING Spent Bleaching Earth (color, residual soapstock) DISTILLATE CONDENSING Deodorizer Distillate (off-flavor compounds, minor volatiles, free fatty acids)

Steam

DEODORIZING POLISH FILTERING

Salad & Cooking Oils

Figure 9. Diagram of conventional soybean oil rening.

of water, or in a nonhydratable form, which cannot be easily hydrated and removed. The nonhydratable phospholipids are considered to be the calcium and magnesium salts of phosphatidic acids, which are formed by enzymatic hydrolysis of the original phospholipids. This degradation can result from seed damage during storage and improper handling. List et al. (53) studied the factors promoting the formation of nonhydratable phospholipids in soybeans and showed that they are promoted by four interrelated factors: (1) moisture content of beans or akes, (2) phospholipase D activity, (3) heat applied to beans or akes prior to and during extraction, and (4) disruption of the cellular structure by cracking or aking. These results suggest that a nonhydratable-phosphatide formation can be minimized by control of the moisture of beans or akes entering the extraction process, inactivation of phospholipase D, and optimizing the temperature during conditioning of cracked beans or akes. Normal quality soybean oil from the conventional solvent extraction contains about 90% hydratable and 10% nonhydratable phospholipids. Phosphoric or citric acid can be used as a pretreatment to achieve more complete removal of nonhydratable phospholipids, but their presence in the gum will darken it and reduce its quality. The total phospholipid content in crude soybean oils ranges from 1.85% to 2.75% (19) and partially depends on the seed preparation and extraction methods employed. Use of an expander or the Alcon process to cook the akes prior to extraction will increase total phospholipids content in the crude oil and the phosphatidylcholine percentage in the gum (163).

606

SOYBEAN OIL

Degumming can be achieved in a batch or continuous fashion. In batch degumming, soft water at the same percentage as total phospholipid is added to oil heated to 70 C and mixed thoroughly for 3060 min, followed by settling or centrifuging. In continuous water degumming, heated oil is mixed with water by an in-line proportioning and mixing system and the mixture is held in a retention vessel for 1530 min before centrifugation. The phosphorus content is typically lowered to 12170 ppm (164). A well-degummed soybean oil should contain less than 50 ppm of phosphorus, which is well below the 200 ppm level specied in the National Oilseed Processors Association (165) trading rules for crude degummed soybean oil. Degumming for physical rening, as opposed to alkali rening of soybean oil, requires more complete removal of the phospholipids to prevent darkening during fatty acid distillation. For more complete phospholipid removal, several modied degumming methods can be employed (166, 167). Recently, polymeric ultraltration membranes were used for degumming crude soybean oil and removing phospholipids from the crude oil/hexane miscella (168). Crude soybean oil also can be de-acidied by methanol extraction of the free fatty acids and the extract separated into fatty acids and solvent by a membrane lter (169). A surfactant-aided membrane degumming also has been applied to crude soybean oil, and the degummed oil contained 2058 ppm of phosphorus (170). Supercritical carbon dioxide extraction was shown to be an effective means of degumming (171). In this process, soybean oil countercurrently contacted supercritical carbon dioxide at 55 MPa and 75 C. The phosphorus content of the oil was reduced from 620 ppm to less than 5 ppm. Ultrasonic degumming was also successfully used to reduce the gum content of soybean oil (172). 8.2. Neutralization Neutralization is also referred to as de-acidication and alkali or caustic rening. Neutralization is achieved by treating the soybean oil with aqueous alkaline solution (most commonly, sodium hydroxide) to neutralize the free fatty acids in a batch or continuous system. The soap formed in the reaction also adsorbs natural pigments, the gum and mucilaginous substances not removed by degumming. Natural settling or centrifugation is used to remove the soap. Crude soybean oil also can be netralized directly without degumming. When this is practiced, the oil commonly is pretreated with 3001000 ppm of 75% phosphoric acid to facilitate removal of phospholipids. The percentage of excess sodium hydroxide solution required for crude oil is higher than that for degummed oil (173). The quality changes, such as lipid oxidation and reduction of tocopherols and phytosteols during neutralization, are considerable compared with the other processing steps as shown by Wang and Johnson (174), and also as presented in Table 12. The further phospholipid removal (below 2 ppm phosphorus) also reduces the oxidative stability of soybean oil (175) due to the antioxidant property of these phospholipids. One of the new developments in neutralization is the use of silica-based adsorbent to remove the residual soap instead of using water washing. Water usage and

BASIC PROCESSING OPERATIONS

607

TABLE 12. Effect of processing on content of tocopherols, sterols, and squalene in soybean oil (25). Processing Step Crude Degummed Neutralized Bleached Deodorized Tocopherols ppm % Loss 1132 1116 997 863 726 1.4 11.9 23.8 35.9 Sterols Ppm % Loss 3870 3730 3010 3050 2620 3.6 22.2 21.2 32.3 Squalene ppm % Loss 143 142 140 137 89 0.7 2.1 4.2 37.8

waste generation is greatly reduced by this practice. Sodium silicate also was used as a mild neutralizing agent to rene specialty oils (176). Its agglomerating tendency allowed the removal of the soap by ltration, and its low alkalinity minimized saponication of neutral oil and loss of minor nutrients. Other adsorbents, such as magnesium silicate, also were shown to be effective in reducing free fatty acids, as well as reducing primary and secondary oxidation products in the treated oil (175, 177). Physical rening or steam rening is a process similar to steam deodorization. Steam distillation is typically used for oil with a high free-fatty acid content to reduce the rening loss, which would be signicant if caustic rening was used. Acid-aided degumming produces soybean oil with very low phosphorus content and makes the distillation of free fatty acids possible. Nevertheless, the relatively difcult task of removing sufcient phospholipids from soybean oil has prevented extensive use of this technique in the United States. Physical rening, however, has virtually replaced caustic rening of palm oil in Malaysia. 8.3. Bleaching Bleaching is a process designed not only to remove the oxidation-inducing pigments such as chlorophylls, but more importantly to decompose the peroxides produced by oxidation into lower molecular weight carbonyl compounds that can be removed by subsequent deodorization. Bleaching also removes other impurities such as soap and metal ions. In soybean oil rening, color reduction occurs at each step, nevertheless, the most signicant reduction of chlorophylls occurs in the bleaching step. Acid-activated bleaching clay is most effective in adsorbing chlorophylls and decomposing peroxides, and it is commonly used for soybean oil. The chlorophyll content in normal crude soybean oil (11.5 ppm) can be reduced by 25% by alkali rening, and bleaching with acid earth further reduced chlorophylls to 15 ppb (178) The subsequent hydrogenation and deodorization remove or degrade red and yellow pigments more than chlorophyll, so incomplete chlorophyll removal by bleaching will cause the rened oil to appear greenish. The rened and bleached oil is particularly susceptible to oxidation and is less stable than the crude, degummed, rened, or deodorized oils (178).

608

SOYBEAN OIL

The desired bleaching endpoint is typically zero peroxide, although a color specication is often used as an important measure. The amount of bleaching earth should be adjusted based on the quality of oil to be bleached, and it usually ranges from 0.3% to 0.6% for a typical soybean oil. Low contents of phosphorus (510 ppm P) and soap (1030 ppm) in the neutralized oil are essential to maximize the bleaching effect. Successful bleaching can be achieved by atmospheric batch bleaching, vacuum batch bleaching, or continuous vacuum bleaching at temperatures between 100 C and 120 C for 2030 min. More details of soybean oil bleaching are described by Erickson (179). Recently, silica-based synthetic materials have been used in bleaching. The natural bleaching earth, fullers earth, a hydrated aluminum silicate, mostly has been replaced by acid activated clays, which are sulfuric- or hydrochloric-acid-treated bentonites or montmorillonites. Manufacturers continuously improve the quality and develop new bleaching earths to meet the markets needs. Higher activity and lterability are the main focuses of such development. 8.4. Hydrogenation The high degree of unsaturation, particularly the relatively high content of linolenate, of soybean oil signicantly limits its food applications because of low oxidative stability. Hydrogenation is used to improve oxidative stability as well as to increase the melting temperature of soybean oil. A great proportion of soybean oil is hydrogenated to produce cooking oil, bakery/confectionery fats, and shortening. When oil is treated with hydrogen gas in the presence of a catalyst (typically nickel) and under appropriate agitation and temperature conditions, it becomes more saturated and forms a semisolid or plastic fat that is suitable for many food applications. Selectivity is a term used to describe the relative reaction rate of the fatty acids from the more unsaturated to the more saturated forms. Perfect selectivity would provide sequential elimination of linolenate, linoleate, and then oleate. To completely hydrogenate linolenate while minimizing changes in the other acyl groups, a high ratio of the reaction rates of linolenate to linoleate compared with linoleate to oleate is desirable. Generally, selectivity increases with temperature and catalyst concentration and with decreases in hydrogen pressure and agitation rate (180). The effect of pressure on hydrogenation selectivity of soybean oil was reported by List et al. (181), who found that the linoleate-containing triacylglycerols were reduced at a slower rates than the linolenate-containing triacylglycerols under selective condition. At higher pressures (500 psi), the reaction was truly nonselective; whereas at 50 psi, the reaction became selective. Impurities in soybean oil, such as phosphorus, oxidation products, carotene, and metal ions can poison the catalyst and cause slower hydrogenation (182). A particular limitation with nickel catalyst is its low selectivity for linolenate over linoleate, and copper-containing catalysts have greater selectivity for linolenate acid than the conventional nickel catalysts (183). The use of copper catalyst can produce soybean oil that has a low degree of hydrogenation (iodine value of 110115) but has less than

BASIC PROCESSING OPERATIONS

609

1% linolenate. However, copper catalysts are not as active as nickel catalysts; they are also easily poisoned (184). Furthermore, any trace of residual copper in the fully processed oil will promote lipid oxidation. The most common tests for degree of hydrogenation are congeal point and the iodine value as determined by refractive index. Refractive index is a valuable tool for iodine values above 95, but when the oil is further hydrogenated, refractive index becomes an inadequate measurement for melting prediction because increased amount of trans-isomers results in harder oil than the refractive index would indicate (185). For margarine or shortening, the solid fat index (SFI), as determined by dilatometry, or solid fat content (SFC), determined by nuclear magnetic resonance, is the most appropriate method to measure the consistency of the hydrogenated oil. These indices predict the workability and creaming ability at a particular temperature. Double-bond isomerization or trans-fatty acid formation is the most important side-reaction that occurs during hydrogenation, and it has a strong impact on the physical and possibly the nutritional properties of the products. Trans-double bonds are thermodynamically a more favorable conguration than their cis-counterpart; so trans-bonds are produced in signicant quantities if the hydrogenation does not go to completion. The trans-fatty acids have a much higher melting point than their cis-isomers, therefore a fat product with considerable trans-acyl groups will have an elevated melting point, which is desirable in shortening and margarine applications. A partially hydrogenated soybean oil can have at least 30 different one-, two-, and three-double-bond isomers that will result in more than 4000 different triacylglycerol molecules. This complexity allows the production of a great variety of oils, margarines, and shortenings that have a wide range of physical and functional properties. However, the established relationship between trans-fat consumption and health has prompted research to minimize trans-double formation in fats and oils. Hydrogenation of soybean oil may be carried out in a batch or a continuous system. In the United States, batch operations are typical. More comprehensive reviews on hydrogenation and formulation can be found in Erickson and Erickson (180), Hastert (186), and Kellens (187). 8.5. Deodorization Deodorization is usually the last step in conventional oil processing. It is a steamstripping process in which good quality steam (13% of oil) generated from de-aerated and properly treated feed water is injected into soybean oil under high temperature (252266  C) and high vacuum (<6 mm Hg) to decompose peroxides and vaporize the free fatty acids and odorous compounds. Deodorization relies on the large differences in volatility between the triacylglycerols and other undesirable components under certain conditions. The musty and earthy odor produced from bleaching and the hydrogenation odor and avor are effectively removed by deodorization. The free fatty acids, typically ranging from 0.1% to 0.5% in neutralized oil and 0.5% to 5% in oil to be physically rened, are also reduced to below 0.03%, a value used as an indicator for deodorization efciency. Zero peroxide

610

SOYBEAN OIL

value is another indicator for effective deodorization. Heat bleaching is achieved by holding the oil for 1560 min at high temperature to ensure considerable decomposition of carotenoid pigments. During the deodorization process, many desirable reactions take place, but some undesirable reactions, such as lipid hydrolysis, polymerization, and isomerization, also occur. Therefore, the deodorization temperature is carefully controlled to achieve optimum quality of the nished soybean oil product. The effect of rening condition on trans-fatty acid content in rened vegetable oils was investigated by Okamoto et al. (188). Trans-fatty acid contents of deodorized oils increased with prolonged exposure to high temperature, and trans-formation was higher in oils containing greater proportions of polyunsaturates. The isomerization rate of linolenate was 6.5- to 16.3-fold higher than that of linoleate in soybean oil. Kemeny et al. (189) studied kinetics of the formation of trans-linoleic acid and translinolenic acid in vegetable oils deodorized at temperatures from 204230 C for 286 h. Their data can give good estimates of the trans-level of rened oils for given deodorization conditions. Deodorization has also been modied to retain more nutrients and prevent other undesirable reactions. Mathematical models have been established describing the inuence of different process parameters such as time, temperature, steam rate, and pressure on tocopherol stripping, production of oxidized and polymeric triacylglycerols, and trans-fatty acid formation during physical rening of soybean oil (190). Tocopherol removal was mainly inuenced by processing temperature and steam rate, whereas oxidized and polymerized triacylglycerols were not signicantly affected by any of the investigated process parameters. There are three types of deodorization operations. The batch process is the least common because of its low efciency and inconsistent product quality. The semicontinuous and continuous deodorizers have improved processing efciency. There are several congurations of the continuous deodorizer, including the single-shell cylindrical vessel type, the vertically stacked-tray type, and the thinlm packed-column type. The thin-lm system provides excellent fatty acid stripping with minimum use of steam, but it does not achieve the desired heat bleaching or effective deodorization because of its relatively short retention time. A retention vessel held at high temperature has to be used after the column distillation to achieve bleaching (191). The overall oil quality change during rening of soybean oil was examined by Jung et al. (178), and their results are shown in Table 13. A study of oxidative
TABLE 13. Effect of Processing Steps on Quality of Soybean Oil (178). Rening Step Crude Degummed Rened Bleached Deodorized Phosphorus Iron (ppm) (ppm) 510 120 5 1 1 2.9 0.8 0.6 0.3 0.3 Chlorophyll (ppm) 0.30 not available 0.23 0.08 0.00 Peroxide Value Tocopherol Free Fatty (meq/kg) (ppm) Acid (%) 2.4 10.5 8.8 16.5 0.0 1670 1579 1546 1467 1138 0.74 0.36 0.02 0.03 0.02

ALTERNATIVE REFINING METHODS

611

stability of soybean oil at different stages of rening indicated that crude oil was the most stable and highly puried oil was the least stable (192). The inuence of the rening steps on the distribution of free and esteried phytosterols in soybean and other oils was reported by Verleyen et al (193). A signicant reduction in free sterols was found after neutralization. Deodorization removed free sterols and also promoted steryl ester formation when the oil was physically rened due to a heatpromoted esterication reaction between free sterols and free fatty acids. 8.6. Fractionation and Winterization Fractionation or winterization is a process in which the more saturated molecular species in the oil are solidied and removed by a low-temperature treatment, which increases the cold storage physical stability of the oil. Partially hydrogenated soybean oil with 110115 iodine value (IV) that is intended for use as salad and cooking oil should be fractionated. By doing so, the more saturated molecules and some high-melting trans-isomers are removed to produce clear oil that meets low-temperature storage requirements. The formation of large and easily lterable crystals and the removal of the crystallized fraction from the liquid oil can be challenging tasks. The temperature of the oil should be lowered slowly to prevent small crystal formation. Nucleation occurs when the oil is supercooled to a temperature that is much lower than the thermodynamic equilibrium temperature. Heterogeneous nucleation, i.e., the formation of nuclei on to foreign substances, typically takes place around dust particles or on the walls of the crystallizer. The crystal growth rate depends on the degree of supercooling and polymorphic form. In order to have continuous and uniform crystallization, an intense but nondestructive agitation is required. To produce salad oil with good cold stability, soybean oil is usually hydrogenated to an iodine value of 100110 (linolenate content of 23%) and winterized at 23 C. To produce a cooking and frying oil, hydrogenation to an iodine value less than 90 (linolenate content of less than 0.5%) is more desirable, and the stearine fraction obtained from winterization of such oil is a good shortening and margarine base. Crystal separation can be done by ltering, centrifuging, or decantating. More details about these systems are presented by Krishnamurthy and Kellens (194).

9. ALTERNATIVE REFINING METHODS Although oil extraction by mechanical pressing of soybeans accounts for a very small percentage of soybean processing, it is used by many farm cooperatives or family-owned on-farm operations in the United States, primarily for using protein meals as animal feed. There is an increasing use of extrusion-expelling technology to produce identity-preserved soybean oil and protein products for niche market. The advantages of small tonnage requirement, no ammable solvent used, low initial capital investment, and unique products have made this processing technology very appealing for many soybean growers and processors.

612

SOYBEAN OIL

Alternative techniques are being developed for rening soybean oil produced by mechanical means. Simple rening methods were explored to process extrudedexpelled (E-E) soybean oils with various fatty acid compositions (174, 177). E-E oils can be easily water degummed to very low phosphorus levels. Free fatty acid content was reduced to 0.04% by adsorption treatment with Magnesol1, a commercial magnesium silicate product from Dallas Group of America (Jeffersonville, IN). This material also adsorbed primary and secondary oil oxidation products. A mild steam deodorization as the last processing step produced goodquality soybean oil. This adsorption rening procedure was much milder than conventional rening, as indicated by little formation of primary and secondary lipid oxidation products and less loss of tocopherol during rening.

10. COPRODUCTS AND UTILIZATION 10.1. Lecithin Soybean lecithin is the predominant source of food and pharmaceutical lecithin because of its availability and outstanding functionality. The composition of crude soy lecithin is shown in Table 14. As a result of the presence of a large amount of neutral oil, crude lecithin is usually de-oiled to improve its functionality. De-oiling is based on the solubility difference of neutral and polar lipids in acetone, in which the phospholipids are precipitated and separated. Alcohol fractionation of de-oiled lecithin can further separate lecithin into an alcohol-soluble fraction that is enriched with phosphatidylcholine and an alcohol-insoluble fraction enriched with phospha-

TABLE 14. Composition of Commercial Soy Lecithin in Comparison with Egg Lecithin, wt % (195). Compounds Phosphatidylcholine Phosphatidylethanolamine Phosphatidylinositol Phosphatidylserine Phosphatidic acid Lysophosphatidylcholine Lysophosphatidylethanolamine Phytoglycolipids Phytosterines Other phosphorus-containing lipids Sphingomyelin Carbohydrate Free fatty acids Mono-, diacylglycerols Water Triacylglycerols Soy Lecithin 1015 912 810 12 23 12 12 47 0.52.0 58 23 max 1 max 1 max 1.5 3540 Egg Lecithin 6570 913 24 24 23 max 1 Trace max 1.5 1015

COPRODUCTS AND UTILIZATION

613

TABLE 15. Typical Composition (%) of Commercially Rened Soy Lecithin Products (196). Lecithin Oil-Free Phosphatidylcholine Phosphatidylethanolamine Phosphatidylinositol and glycolipid Neutral oil Others Emulsion type favored 29 29 32 3 7 w/o or o/w Lecithin Alcohol-Soluble 60 30 2 4 4 o/w Lecithin Alcohol-Insoluble 4 29 55 4 8 w/o

tidylinositol. The phosphatidylcholine-enriched fraction is an excellent oil-in-water emulsier, and the phosphoinositol-enriched fraction is a good water-in-oil emulsier that is often used in the chocolate industry. The typical composition of de-oiled and fractionated lecithin products is shown in Table 15. Supercritical CO2 extraction also has been used to selectively extract phosphatidylcholine from de-oiled soybean lecithin (197). The effects of temperature, pressure, and amount of ethanol on phosphatidylcholine extraction were examined, and a high-purity product could be produced with optimized conditions. Lecithin recovered from solvent-extracted soybean oil had different phospholipid class compositions from those produced by mechanical pressing (198). The percentage of phosphatidylcholine was considerably higher in lecithin recovered from extruded-expelled oil than from solvent-extracted oil. The phosphatidylcholine- and phosphatidylinositol-enriched fractions produced by ethanol extraction of the crude lecithin also showed different functional properties (199). Soybean lecithins can be chemically altered to modify their emulsifying properties and improve their dispersibility in aqueous systems. Phospholipids may be hydrolyzed by acid, base, or enzyme to achieve better hydrophilic and emulsication properties. Hydroxylation of lecithin improves its oil-in-water emulsication property and water dispersibility. Acetylation creates improved uidity and emulsication, water dispersion properties, and heat stability (200). 10.2. Deodorizer Distillate Deodorizer distillate is the material collected from the steam distillation of oils. It is a mixture of free fatty acids (especially during physical rening) tocopherols, phytosterols and their esters, hydrocarbons, and lipid oxidation products. The quality and composition of deodorizer distillate depends on the feedstock oil composition and processing conditions. Tocopherols and sterols are the most valuable components that can be recovered from the distillate, and they are used in the nutrition supplement and pharmaceutical industries (201). Typical soybean deodorizer distillate contains about 33% unsaponiable matters, of which 11% is tocopherol and 18% sterol (202).

614

SOYBEAN OIL

Soybean tocopherols are the major source of natural fat-soluble antioxidants and Vitamin E. The Vitamin E activity of natural d-a-tocopherol is much greater that that of synthetic Vitamin E, which is a mixture of eight stereoisomers (203). Phytosterols are used as raw materials for over 75% of the worlds steroid production. The more recent application of phytosterol, phytostanol, and their fatty acid esters in margarine and table spreads is based on the blood cholesterol-lowering effect of these compounds (204, 205). The recent development of functional foods containing phytosterols has been reviewed by Hollingsworth (206) and Hicks and Moreau (207). The preparation of high-purity tocopherols and phytosterols involves steps such as molecular distillation, adduct formation, liquid-liquid extraction, supercritical uid extraction, saponication, and chromatography (175). The extraction of tocopherols from soybean oil deodorizer distillate by urea inclusion and saponication of free fatty acids resulted in good recovery of tocopherols (208). To improve the separation of sterols and tocopherols, Shimada et al. (209) used a lipase to esterify sterols with free fatty acids. Then the steryl esters and tocopherols were separated better by molecular distillation. Chang et al. (210) used supercritical uid CO2 extraction to recover tocopherols and sterols from soybean oil deodorizer distillate. A patent by Sumner et al. (211) advocated treatment of the distillate with methanol to converted free fatty acids and other fatty acid esters to methyl esters that can then be removed by a stripping operation. Then separation of sterols and tocopherols could be carried out by molecular distillation. 10.3. Soapstock Soap is recovered from alkaline neutralization of the crude or degummed soybean oil. Soap consists of water, free fatty acids, neutral oil, phospholipids, unsaponiable matter, proteins, and mucilaginous substances. Its composition depends on seed quality and oil extraction and rening conditions. Soapstock is the least valuable byproduct from oil processing, and it is generated at a rate of about 6% of the volume of crude soybean oil rened (212), amounting to as much as 0.8 million MT in the United States annually. The majority of the soap or acidulated soap is used as a feed ingredient contributing metabolizable energy. Soybean oil can be rened using potassium hydroxide and acidulated with sulfuric acid, followed by neutralization with ammonia rather than sodium hydroxide to produce a fertilizer (213). Soybean oil methyl esters can also be produced from soapstock (214218) for biodiesel applications.

11. FOOD AND BIOBASED PRODUCT USES OF SOYBEAN OIL 11.1. Distribution of Soybean Oil Utilization In 20012002, when 8.32 million MT (18,300 million pounds) of soybean oil was used in the United States, over 97% (8.09 million MT, 17,800 million pounds) was used for food, with the remainder used in nonfood products (219). Among the food

FOOD AND BIOBASED PRODUCT USES OF SOYBEAN

615

uses, about 48% (3.89 million MT, 8,570 million pounds) was for shortening, 43% (3.58 million MT, 7,897 million pounds) for cooking and salad oils, 7% (0.56 million MT, 1,237 million pounds) for margarine, and 1% (0.06 million MT, 125 million pounds) for other food uses. Soybean oil is used to produce about 95% of the total margarine and 83% of the total shortening consumed in the United States. Among the 0.24 million MT (519 million pounds) used in nonfood products, about 16% (0.04 million MT, 85 million pounds) was for resins and plastics, 12% (0.03 million MT, 60 million pounds) for paint and varnish, 13% (0.03 million MT, 68 million pounds) for fatty acids, and 59% (0.14 million MT, 306 million pounds) for a myriad of other inedible uses. The use of soybean oil in lubricants (220), oleochemicals (221), and bioplastics (222), and the production of methyl soyate for environmentally friendly solvents (223, 224) and for blending with diesel fuel to produce biodiesel (20% methyl soyate/80% diesel fuel) (225) are signicant parts of the soy oil used in nonfood applications (226). Usage of soybean oil to make biodiesel is likely to increase in future years because several new plants are planned for construction as a result of the recent Farm Bill of 2002 providing nancial incentives for producing biobiesel. Some states, notably Minnesota, have enacted legislation that provides biodiesel tax incentives. Biodiesel interests have become organized as the National Biodiesel Board (Jefferson City, MO) and the Renewable Fuels Association (Washington, DC), and exercise considerable political inuence. During 2002, 57 million liters (15 million gal) of biodiesel were produced in the United States (227), almost three times that which was produced in 2001. The usage of soybean oil in food products is similar to other oils, and these uses and products are discussed in more detail for all oils in other chapters of this edition. This chapter will focus on specics of soybean oil in those uses. The major products in which soybean oil is consumed are cooking and salad oils, frying oils and fats, baking shortenings, and margarine. Only minor amounts of soybean oil are used in vegetable dairy products and confectionery products. 11.2. Trading Rules for Crude and Rened Soybean Oils As the U.S. government does not have trading rules, the National Oilseed Processors Association (NOPA, Washington, D.C.) has established them, including quality specications, to facilitate trade and marketing of three types of oils: crude degummed, once-rened, and fully rened soybean oils (Table 16). These rules are also available on the Internet (228). Factors that impact grade of crude degummed and once-rened soybean oils are moisture and volatile matter content, ash point, free fatty acid content, smoke point, unsaponiable matter content, green color, phosphorus content, and rened bleached color. The ash point reects the presence of residual hexane, and the other factors reect expected rening loss. For fully rened soybean oils, the avor, cold test values, peroxide value, and AOM (Active Oxygen Method) are additional considerations that reect crystallization at low temperatures and stability to oxidation. Crude soybean oil is sold as degummed oil because the gums tend to spontaneously hydrate and settle out during

616

SOYBEAN OIL

TABLE 16. Trading Specications for Crude Degummed, Once-Rened and Fully Rened Soybean Oils (228). Factor Moisture and volatile matter and insoluble impurities (%) Flash point ( C) Free fatty acids (% as oleic) Crude Degummed 0.3 max.c Once-Reneda 0.10 max. (up to 0.15 with discount) 121 min. 0.10 max. (up to 0.15 with discount) 1.5 max. Fully Reneda 0.10 max.d (up to 0.15 with discount) 0.05 max. Methods of Analysisb Ca 2d-25 Ca 3a-46 Cc 9c-95 Ca 5a-40

121 min. 0.75 max. (up to 1.25 with discount) 1.5 max. Neg. 0.02 max. (up to 0.025 with discount)

Unsaponiable matter (%) Presence of sh and marine animal oils Phosphorus (%)

1.5 max.

Ca 6a-40 28.121 Ca 12-55

Rened bleached color (Lovibond) Green color Flavor Cold test (hr) Peroxide value (meg/kg) AOM Stability (hr to 35 PV)
a

3.5 Red max. None

20 Yellow, 2.0 Red, max. Bland 5.5 min. 2.0 max. 8 min.

Cc 8e-63 Cc 13b-45

Cc 11-53 Cd 8-53 Cd 12-57

The oil shall be clear and brilliant in appearance at 2129 C (7085 F) and free from settlings in this temperature range. b Analyses in accordance with the Ofcial and Tentative Methods of the American Oil Chemists Society except for presence of sh and marine animal oils in accordance with Association of Ofcial Analytical Chemists methods. c Includes insoluble impurities as determined by AOCS Method Ca 3-46. d Oil shall be free of settlings or foreign matter of any kind.

transportation and storage, which cause numerous handling problems. Once-rened soybean oil is seldom traded anymore because most buyers do their own rening or purchase fully rened oil. End-users typically have their own specications for fully rened soybean oil and use the NOPA values as bases for their more stringent specications (136). 11.3. Cooking and Salad Oils In most parts of the world, both cooking and salad oils from soybeans are rened to have bland taste and light color. For other oils, distinct avors and dark colors may be acceptable. Important distinctions between salad oils, cooking oils, and frying

FOOD AND BIOBASED PRODUCT USES OF SOYBEAN

617

oils, however, reect their differences in oxidative and thermal stabilities. Cooking and frying oils need to be more stable to oxidation than salad oil because of the higher temperatures to which cooking oils are exposed. Temperature stability is especially required in fats and oils used in deep-fat frying. Salad oils must be physically stable so that they do not crystalize at refrigerated temperatures. As soybean oil contains relatively great amounts of the polyunsaturates, notably unstable linoleate (61%) and linolenate (7.8%), partial hydrogenation is customary to make cooking or salad oils more stable to oxidation. Typical specications for different cooking and salad oils are shown in Table 17. Synthetic antioxidants, such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate (PG), ascorbyl palmitate, and tertiary-butylhydroquinone (TBHQ), are used in soybean cooking oils and frying fats (230). These antioxidants are typically added at 0.01% for one antioxidant and 0.02% total for two or more. Natural antioxidants, derived from sage, rosemary, and green tea, are increasingly popular because of consumer preferences for natural food ingredients (231). Salad oils differ from cooking oils in their tolerance to cold temperatures without crystallizing. Salad oils must not crystallize, cloud, or leave deposits of any kind when stored at refrigerator temperatures (4.4 C) and are dened as such. Soybean oil used as a salad oil should not cloud or produce any visible crystals and remain brilliant and clear for a minimum of 5.5 hr at 0 C. Fully rened soybean oil can be directly used as salad oil because it will normally meet this specication, whereas other oils, such as sunower and corn, must be dewaxed before they can meet typical salad oil specications. Soybean oil may be partially hydrogenated and then winterized to achieve greater oxidative stability and still not crystallize nor lose proper emulsion properties when refrigerated, although most of the soybean oil used in commercial dressings is not hydrogenated. New nutrition-oriented salad and cooking oils have been developed in recent years. LoSatSoy is an oil low in saturated fatty acids that was developed at Iowa State University, licensed to Pioneer Hybrid International (Johnston, IA), and commercialized as a salad or cooking oil. This specialty soybean oil has one-half the amount of saturated fatty acids in normal soybean oil (7% versus 15%); therefore, it is promoted as having improved nutritional and health benets. Other specialty soybean oils, low (<2% or <1%) in linolenate and with improved oxidative stabilities in salad and cooking oil applications, are comparable with typical soybean oil that is partially hydrogenated. Today, low-linolenic-acid soybean oil is an attractive alternative to hydrogenated oil that contains trans-fatty acids. Beginning in 2006, labeled food products must disclose both the grams of saturated fat and grams of trans-fat per serving (232). This is inducing food companies to eliminate or signicantly reduce trans-fatty acid contents of their products. All specialty soybean oils require identity-preserved soybean production, crushing, and rening systems. As nancial incentives are needed all along the production process to compensate for increased costs of identity preservation, specialty soybean oils command premium consumer prices and have been slow to impact soybean oil markets.

618

SOYBEAN OIL

TABLE 17. Trading Specications for Soybean Cooking and Salad Oils (229). Cooking and Salad Oil Rened, Fully, Fully, HWb Deodorized Reneda Reneda Soybean Fedd,e 0.06 max. NSPA 0.10 max. ASCSf 0.10 max. (0.14 with discount) 228 min. 0.05 max. 2.0 (2.6 with discount) Fedd 0.06 max. Ca 2d-25

Factor Source of specications Moisture and volatile matter (max) (%) Unsaponiable content (%) Flash point,  C Free fatty acids (wt%) as oleic Red color (Lovibond)

Analytical Methodc

0.05 max.g,h 4 max.

1.5 max. 0.05 max. 2.0 max.

0.05 max.g,h 2.0 max.

Ca 6a-40 Cc 9b-55 Ca 5a-40 Cc 8b-52 Cc 8e-63 Cc 13b-45 Cc 8b-52 Cc 8e-63 Cc 13b-45 Cd 8-53

Yellow color (Lovibond)

35 max.

20 max.

20 max.

20 max.

Peroxide value (meg/ kg) Fat stability by AOM methodi (a) Peroxide value after 8 hr (b) Peroxide value of 100 or less at indicated no. of hr Cold test (hr) Free from sediment and foreign matter of any kind Clear and brilliant at 2129 C Fish oil and marine animal oil test Iodine value Linolenic acid (wt%)

1.0 max.h

2.0 max.

0.5 max. (1.0 with discount)

1.0 max.h

15 min.h

35 max.

35 max.

25 min.h

Cd 1257 Cd 12-57

Yesj

Yes

Yes

Yesj

Ca 3-46

Yes

Yes Neg.

Yes

Yes 105115 3.0 max. by or 3.5 max. by 1

Cd 1-25 Cd 7-58 Cd 1-62 m

Odor and avor

FOOD AND BIOBASED PRODUCT USES OF SOYBEAN

619

TABLE 17. (Continued ) Additives n /preservative Permitted/required

a b

n, q

Typically a rened, bleached, and deodorized oil. Rened, bleached, partially hydrogenated, winterized, and deodorized, pure soybean oil. c Analyses in accordance with the Ofcial and Tentative Methods of the American Oil Chemists Society Champaign, Illinois, unless indicated otherwise. d Federal specications No. JJJ-S-30G dated March 24, 1978, issued by U.S. General Services Administration, Washington, D.C. e The salad oil may contain properly rened and deodorized cottonseed, corn, peanut, soybean, sesame, sunower, or safower vegetable oils or a mixture of these oils. Olive oil shall not be used. Edible vegetable oils not specied may also be used provided they are in accordance with good commercial practice. f Specications per announcement PV-501 dated June 17, 1976, issued by Agricultural Stabilization and Conservation Service, U.S. Department of Agriculture, Shawnee Mission, Kansas. g 0.05% will be acceptable if propyl gallate has been added as an antioxidant or as a component in an antioxidant. h Determination will be made within 7 days after packaging each lot. i Active oxygen method. j Exclusive of particles of resinous ux material from can manufacture. k Association of Ofcial Analytical Chemists Method No. 28.107. l The oil after heating shall be bland and free from beany, rancid, painty, musty, soapy, shy, metallic, and other undesirable or foreign avors and odors when tested by the method prescribed in footnote m within 7 days after packaging each lot. m Approximately 50 g of the nished product shall be placed in a clean 150-mL Pyrex glass beaker and heated to a temperature 177 3 C. The oil shall be examined for odor at this temperature, and for avor, each cooling to approximately 38 C. From Federal Specication JJJ-S-30G. n Heavy metal scavengers, antifoaming agents, and antioxidant materials may be added to improve the keeping quality and use performance of the oils. The ASCA specications also permit the addition of oxystearin. Such additives should be of a kind and at levels permitted in edible oil products under the federal Food, Drug, and Cosmetic Act and regulations promulgated thereunder. o Preservatives generally recognized as safe are permitted. p During the cooling stage of deodorization, 0.005% of citric acid or 0.006% of monoisopropyl citrate shall be added to the oil. q The packaging gas shall be of food-grade quality and may consist of pure nitrogen or a mixture of nitrogen and approximately 10% of carbon dioxide plus other inert gases in the atmosphere, but it shall contain no more than 0.005% oxygen. Maximum permissible oxygen content of the headspace gas within 15 min after the oil is packaged is 0.50% as measured at standard temperature and pressure. Measurement shall be made at time of packaging or within 15 min thereafter. For method of analysis, see Bulletin 916, issued in 1963 by American Dry Milk Institute, Chicago, IL.

11.4. Frying Oils and Fats In addition to its use as a common household cooking oil, soybean oil is used widely in home and commercial deep-fat frying procedures. The popularity of fried foods among U.S. consumers has created a large market for stable frying oils and for fast-food establishments. Typical untreated cooking and salad oils, including soybean oil, are not suitable for frying applications because they oxidize too quickly. Thus, the oils must be altered to make them stable to the frying treatment. Heat treatments, such as commercial and household frying, accelerate autoxidation. The heat itself causes oxidation and breakdown of the fat. In addition, when

620

SOYBEAN OIL

fats are heated in the presence of moisture, as often is the case in food applications, fatty acids are released via hydrolysis of the ester linkages (233). The free fatty acids, in turn, can accelerate oxidation of the oil. Decomposition and condensation of hydroperoxides also produces a multitude of nonvolatile monomeric products, including di- and tri-oxygenated esters, and dimeric and polymeric materials, especially at elevated temperature. Many of these dimers and polymers are known to be rich sources of volatile carbonyl compounds and decrease the avor and oxidative stability of soybean oil (234). These high-molecular-weight materials also can produce a series of physical and chemical changes to the oil and food products, including increased viscosity, polarity, free-fatty acid content, development of dark color, and an increased tendency of the oil to foam (233). A typical soybean oil shortening is generally hydrogenated to enhance its stability, making it suitable for frying procedures. In addition, polydimethylsiloxane is routinely added at a level of 0.022 ppm as an antifoaming agent, which greatly extends the frying life of soybean oil (235). The antioxidants mentioned in the subsection on Cooking and Salad Oils provide oil stability prior to frying and can enhance the oxidative stability of the fried food. Even though most antioxidants are volatile at frying temperatures, with their concentration decreasing during frying, some antioxidant is transferred to and retained in the food (carry through), thus providing antioxidant protection in the food during storage. In tests, heated palm olein with no frying lost 70% of its original BHT and 60% of the original BHA after 8 hr (236). TBHQ being the highest molecular weight (lowest volatility) of the typical antioxidnts, provides the greatest carry-through benet (237). Extensive hydrogenation produces aked fats or shortening-like products for frying applications, which offer convenience in lling fryers and excellent frying stability. Unfortunately, the process of hydrogenation creates trans-fatty acids as byproducts of the reaction As noted elsewhere in this chapter, recent concerns about the presence of trans-fatty acids in our diets, and the subsequent new labeling requirements for trans-fatty acids (232), have prompted food manufacturers and oil producers to explore alternative treatments to create soybean oil that is stable to frying. One procedure to increase stability without creating trans-fatty acids involves adding a small amount of a fully hydrogenated oil (hardstock) to a typical soybean oil. The blended oil is then interesteried to create a stable frying oil without trans-fatty acids. In a recent study, the low-linolenate soybean oil noted in the subsection on Cooking and Salad Oils, when blended with 5% of a soybean oil hardstock, was as stable as a traditional trans-fat-containing soybean oil that had been stabilized for deep-fat frying, while still retaining excellent avor characteristics (238). Another approach to enhance frying stability of soybean oils is to increase the oleate concentration in the soybean oil created by the plant, either through traditional plant breeding or biotechnological methods. The resulting oil, however, when used in frying, creates a fried food with a stale, waxy-like avor that lacks the desirable avor components typical of a fried food (239, 240).

FOOD AND BIOBASED PRODUCT USES OF SOYBEAN

621

11.5. Mayonnaise and Salad Dressing In the United States, mayonnaise, salad dressing, and French dressing are dened by Standards of Identity issued by the U.S. Food and Drug Administration (FDA; Code of Federal Regulations, Section 21, 169.140) (241). The Food, Drug and Cosmetic Act of 1930 and later revisions and amendments were promulgated to prevent adulteration and misrepresentation of certain food products by establishing Standards of Identity. Mayonnaise is dened as a semisolid food prepared with not less than 65% vegetable oil, and egg yolk and vinegar. Most mayonnaise in the United States, however, contains 7582% oil, to get the proper texture (242). Soybean oil is usually used in mayonnaise but winterized cottonseed, corn, and canola and hydrogenated soybean oil also can be used. Mayonnaise is an oil-in-water emulsion with oil droplets measuring 12 mm in diameter. The higher the oil content, the more tightly the oil droplets are packed in the continuous water phase and thus, the greater the viscosity and rigidity. Mayonnaise production is partly an art because of the difculty of producing an oil-in-water emulsion in which the dispersed phase has seven times more volume than the continuous phase. The protein in the egg yolk solids is the only emulsier allowed and processing conditions play critical roles in achieving high-quality and high-stability mayonnaise. Salad dressings are also oil-in-water emulsions and were developed as alternatives to mayonnaise. The Standard of Identity (21 CFR, 1699.150) requires that salad dressings contain not less than 30% vegetable oil (but most contain 3550% oil), vinegar, !4% egg yolk, and starch. For texture and viscosity, salad dressings rely on starch, in contrast to mayonnaise, which depends on greater oil content. The oils used in salad dressings are selected using the same criteria for mayonnaise. The qualities of mayonnaise and salad dressing are determined by the physical and oxidative stability of its lipid components. Phase separation or emulsion breakdown is caused by mechanical shock, agitation, extreme temperatures, or fat crystallization. Oxidation of vegetable oil and egg lipid also can occur. As the quality of oil plays a major role in the avor stability of these products, only the best quality salad oil should be used. It is particularly important to use salad oils with long cloud point times (high cold test hours). If fat crystals form during storage at refrigerated temperatures, the emulsion will break and the product will become unsightly with visible free oil. Crystal inhibitors, such as oxystearine, lecithin, and polyglycerol esters, are allowed to prevent crystallization and emulsion breakdown. Although mayonnaise and salad dressings are spoonable products due to their high viscosity, French dressing is a pourable oil-in-water dressing. French dressing must contain !35% oil as dened by a Standard of Identity (21 CFR, 169.115). Egg products are optional. Other dressings, such as Thousand Island, are not subject to Standards of Identity, and any ingredients can be used. Pourable dressings can be in two different nished forms; emulsion or two phases depending on whether the product is homogenized. The oil used in these products is predominantly soybean salad oil in the United States. In Canada and Europe, other salad oils are often used, depending on the availability and costs of those vegetable oils in each specic region.

622

SOYBEAN OIL

As the oil contents of mayonnaise, salad dressings, and French dressing are high, it is important to prepare them from salad oils that taste bland and are relatively stable to oxidation. Peroxide values of the oil should be <2 meq/kg. Even early stages of oxidation can be detected in mayonnaise and salad dressings as grassy and beany avors. Packaging with an inert headspace is important to prevent oxidation during distribution, retailing, and consumer storage. Storage under refrigeration is important once the package is opened and the headspace gas becomes replaced with air. 11.6. Margarine Margarine was rst produced in 1869 by the French chemist Hippolyte Megge Mouries. During the Franco-Prussian War, he was awarded a prize and patent for his invention of a butter substitute. It was not until the 1940s, however, that margarine became widely used. Until then, the powerful dairy industry in the United States prevented the sale of colored margarine in many states, and consumers did not readily accept white table margarine. Today, more than twice as much margarine is consumed as butter per capita in the United States, and margarine is no longer considered a cheap imitation of butter. Unlike butter, margarine can be formulated from a variety of fats and oils to give a variety of physical and functional properties, which are needed in many food applications today. In the United States, margarine or oleomargarine is also controlled by an FDA Standard of Identity (21 CFR, 166.110), requiring at least 80% fat. Soybean oil is predominantly used in the United States, followed by cottonseed and corn oils. The other 20% of the margarine formulation may be made up of water and other optional ingredients, including milk products, soy protein isolate, salt, selected emulsiers (up to 0.5%), mold inhibitors, antioxidants, color additives, avorings, and acidulants. Margarine is a water-in-oil emulsion. The traditional retail form of margarine is stick margarine, but margarine is now also marketed as pourable and soft tub products. Margarine may also be sold as a whipped product in which air or an inert gas is incorporated. Still other margarinelike forms, including polyunsaturated and low-fat spreads, have been developed to satisfy consumer demands for improved convenience and reduced saturated fat and calories. In addition to the traditional use as a table food, margarine is also widely used in baking applications such as in cookies and as roll-in fats for puff and Danish pastries. A signicant recent consumer trend is increased demand for margarine-like spreads that are not controlled by a Standard of Identity and that contain much less fat. Most spreads contain 4060% fat with 40% fat spreads being more popular in Europe and 60% in the United States. During the past 15 years, however, very low-fat spreads containing less than 20% fat have been introduced. As a result of these trends, there are signicantly fewer 80%-fat margarine products available in the United States today than in the previous decades. Stabilizing these high levels of aqueous phases in such a small amount of fat as the continuous phase requires special equipment to generate the necessary shear and higher amounts of emulsiers.

FOOD AND BIOBASED PRODUCT USES OF SOYBEAN

623

Moustafa (243) reports that the aqueous droplets must no longer be spherical but rather polyhedral when loading levels of the aqueous phase exceed 74%. Margarine processing includes blending the fats separately from the aqueous phase ingredients and water, dispersing and emulsifying the aqueous phase within the fat phase, chilling to solidify the fats, pin working the solidied mass, resting, forming, and packaging. The ingredients are emulsied before being fed into a swept-surface heat exchanger for crystallizing. The mass emerging from the cooling tubes is partially solidied, and it is further crystallized in the working unit. The texture of the product is further modied in the resting tube before the margarine is packaged. Margarine and shortening have fat crystal networks in which liquid oil is entrained. As a result, they exhibit a yield stress that must be exceeded before the product begins to ow as a viscous uid. The yield stress is related to spreadability. The rheological properties of margarine have been discussed by Segura et al. (244). In North America, margarines may be composed of blends of hydrogenated soybean oil and palm oil, partially hydrogenated soybean oil and cottonseed oil, liquid soybean oil and partially hydrogenated soybean oil, liquid corn oil and hydrogenated corn oil, or simply hydrogenated soybean oil. Most oil blends contain high levels of soybean oil to keep costs competitive. Table 18 shows some typical compositions and properties of margarine. The most important functional properties of margarines and spreads are spreadability and hardness, oiliness, and melting characteristics. These properties relate to fat level, proportion of solid fat, fat melting point, and crystal form. Diverse textures and functionalities can be achieved by varying the extent of hydrogenation. Consistency and emulsion stability depend on the amount and type of crystallized fat. Spreadability and hardness can be predicted by the solid fat index and penetration measurements. A cone penetrometer is typically used to determine margarine hardness (245). Typical margarines should be spreadable at refrigeration temperatures, remain semisolid at ambient temperatures, and melt at less than body temperature. Oil-off refers to the separation of liquid fat when the fat crystals no longer form a network able to hold the liquid oil.

TABLE 18. Compositions and Properties of Hydrogenated and Interesteried Soybean Margarine Oils (187). Melting Point 10 C 21.1 C 33.3 C ( C) 28.6 15.6 7.1 1.7 4.3 8.0 18.9 8.8 4.5 1.3 2.2 3.5 5.3 1.3 2.0 0.2 0.9 2.2 46 46 46 40 46 47 Trans IV (%) (calc) 31.0 23.2 12.9 1.7 2.1 1.6 92.1 108.0 121.8 123.8 116.6 109.4

Soybean Oil Hydrogenated Hydrogenated Hydrogenated Interesteried Interesteried Interesteried

Type Stick margarine Tub margarine Tub margarine 90:10a 85:15a 80:20a

624

SOYBEAN OIL

Fats exhibit polymorphism in which they can exist in different crystalline forms depending on how the triacylglycerols pack in the crystal and a, b0 , and b polymorphs are known. The preferred polymorphic form for margarine is b0 , which gives a smooth, pleasing mouthfeel and proper spreadability. Despite hydrogenated soybean oils tendency to form b crystals, it is used in over 90% of all margarines and table spreads in the United States. The less heterogeneous the fatty acid composition of the hydrogenated fats, the more it is b tending. Hydrogenated fats richer in trans-isomers are less b tending and tend to produce margarines with smoother textures. Blending small amounts of b0 -tending base fats (palm and cottonseed oils) or different soybean base oils increase fatty acid heterogeneity favoring b0 crystal stability. Blending unmodied oils with oils that have been hydrogenated to various degrees allows the production of margarines with desirable texture. The greater the number of base stocks available, the greater the exibility to produce a wide range of products and the higher the tolerance to processing conditions. Different procedures for designing good margarine from various base stocks were evaluated by Cho et al. (246). Base oils for margarine must be hydrogenated to achieve the desired solid-fat content with the consequential isomerization of some fatty acids. The new regulations requiring reporting of trans-fats content on labels may dissuade some consumers from using traditional margarine. Emken (247) reported that some traditional margarines may have as much as 21% trans-fatty acids while Kellens (187) found as much as 31%, and DSouza et al. (248) reported that the high-melting acylglycerols contained in hydrogenated base stocks used for formulating North American margarines have 33.145.0% trans-fatty acid content in stick margarine and 22.4 30.1% trans-fatty acid content in soft margarine. Trans-acyl groups contribute to the rmness of margarine. A recent comprehensive review concluded that consuming more than 4% of total calories as trans-fatty acids may raise plasma lipid levels (249) and may cause heart disease (250, 251). Some companies are producing low-trans- or zero trans-margarines by random (252) or directed interesterication of mixtures of unhydrogenated and fully hydrogenated soybean oils and other fats (253). To produce these products, a liquid oil and completely hydrogenated hardstock are interesteried, so that proper plasticity can be obtained. Oils that contain considerable amounts of palmitic acid favorably inuence crystallization and polymorphic form of the interesteried fat blends (254). Chemical interesterication is conveniently achieved by using alkali metal methylates as a catalyst. Microbial lipases are also used as biocatalysts in enzymatic interesterication. In contrast to the chemical process, the enzymatic process can be more selective if an enzyme with positional specicity is used, but this reaction is usually much slower and more sensitive to reaction conditions. Recent developments in lipase-catalyzed interesterication have resulted in new industrial applications of this process (255). Nevertheless, the high costs of enzymes and process equipment may limit widespread adoption of this process. In developing trans-free fat, various methods for laboratory-scale, pilot plant, and commercial batch reaction were described by Erickson (256). List et al.

FOOD AND BIOBASED PRODUCT USES OF SOYBEAN

625

TABLE 19. Example of Combined Hydrogenation, Interesterication, and Fractionation to Produce Low Trans-Margarine Fat (187). Solid Fat Content (%, at  C) Iodine Value Soybean oil (SBO) feedstock Fully hydrogenated SBO (FHSBO) Blending SBO and FHSBO (60:40) Random interesterication of SBO and FHSBO (60:40) Fractionation of the interesteried oil Soft fraction Hard fraction 134 1 81 81 Melting Point ( C) 7 71 63 53 10 0 95 44 38 20 94 42 33 30 94 39 20 40 93 35 11

91 63

24 58

25 60

1 58

0 45

0 32

(252) developed a zero-trans margarine by interesterifying 80% rened, bleached, and deodorized (RBD) soybean oil with 20% fully hydrogenated soybean oil. The resulting product has a solid fat index comparable with that of conventional products. The randomly interesteried low- [zero-] trans-soybean margarines crystallize in the more favorable b0 crystal form (252) but tend to crystallize slowly after chilling and result in a product that is harder than desired (257). Addition of 20% liquid soybean oil to the interesteried oil yielded a softer, more desirable product. Table 19 presents a typical example of the combined use of hydrogenation, interesterication, and fractionation to produce low-trans fats with physical properties comparable with partially hydrogenated soybean oil with high trans content. Alternatively, recent research has focused on soybeans bred for high contents of saturated fatty acids, some with as much as $43% saturates, 23% palmitate, and 20% stearate compared with the normal $15 % saturates, 11% palmitate, and 4% stearate. Soybeans only produce cis-fatty acids and, thus, there are no sources of trans-fatty acids in the blends. List et al. (258, 259) showed that soybean oil from soybeans bred to produce 3040% saturates was not sufciently solid to make good margarine, but soybean oil with elevated saturated fatty acid contents (1738%) could be blended with high-melting oils, such as palm oil, interesteried palm oil, interesteried palm and soybean oils, and cottonseed and soybean hardstocks, to make a good margarine. Kok et al. (260) used blends (50:50) of traditional soybean oil and oil from soybeans bred to produce oil high in saturated fat ($43% saturates, 23% palmitate, 20% stearate). The blend was then interesteried to produce oil that was made into soft tub margarines. The small differences in sensory properties observed in comparisons with other tub margarines indicated the interesteried product should be quite acceptable to most consumers. List et al. (259) also report randomly interesterifying (randomizing) neat soybean oil high in saturated fatty acids (10% palmitate, 18% stearate) gave good margarine without graininess (SFI values of 58 at 10 C, 23 at 21.1 C, and 12 at 33.3 C).

626

SOYBEAN OIL

11.7. Shortenings Shortenings are fats of vegetable or animal origin used in baking, but the term shortening also has been accepted as a term to describe semisolid fats for frying and cooking. Just as in margarine, the solid fat exists as a tight network of small crystals, which trap liquid oil. Plastic shortenings differ from margarine in that shortening is not an emulsion; it is all lipid material and may contain emulsiers. Prior to the development of hydrogenation, lard and tallow were the principle shortening fats, but these fats lack the diversity of texture and functionality required for many products. Today, most shortenings contain at least some soybean oil, largely because it is the least expensive oil that can confer adequate functionality. Shortening is available in many forms: plastic and semisolid (cubed, sheeted, and printed), pourable uid (with suspended solids), encapsulated powder, and aked. Most plastic shortenings are produced by blending oils with hydrogenated fats and often emulsiers and solidifying or crystallizing and plasticizing the blend. The shortening is packaged and tempered by holding it in a quiescent state for several days at 30 C. During solidication, 1025% air is often incorporated to improve the color and texture. Pourable and uid shortenings are produced by blending appropriate oils and emulsiers. They are crystallized by cooling the uid mass and stirring the suspended crystals for 46 hr at precise temperatures so that large crystals do not develop, and the uid becomes stabilized. Shortenings are added to baked goods to shorten or tenderize them by interrupting the gluten structure. Shortenings improve mouthfeel and eating qualities, add lubricity, improve dough-handling properties, contribute avor and structure, and promote desirable crumb grain and texture (261). Shortening and tenderizing effects are especially important in cakes, piecrusts, pastries, cookies, and crackers. Generally, solid fat indices that change little with temperature are desired for most shortening applications. Table 20 shows plasticity and melting properties of different commercial shortenings. Typical shortening levels are 25% in bread, 525% in cake, 2030% in sweet goods, 3040% in puff pastry, and 2035% in piecrusts. Many plastic shortenings are packaged in 50-lb polyethylene-lined boxes, primarily for use in retail bakeries, e.g., in grocery stores. These are difcult to handle in large, automated wholesale bakeries. Sometimes, 190-kg drums are used, but are still difcult to manage and use in the bakery where large amounts are needed. Pourable and pumpable uid shortenings were developed to avoid these problems and are based on soybean oil. However, liquid oils do not cream and aerate well. The addition of small amounts of hardfats, known as stearine, and various emulsiers can impart good functional properties to the liquid shortening. Although adequate quality bread and rolls can be produced without shortening by using the sponge-and-dough or straight-dough methods, the inclusion of shortening increases volume by as much as 25% compared with breads with no shortening. This volume increase often is referred to as oven spring, and it reduces rmness throughout the products storage life. The largest volume of bread is made by the continuous-mixing method in the United States and shortening is critical to good quality bread manufactured when using this method. Shortening

TABLE 20. Typical Compositions and Properties of Baking Shortenings. Solid Fat Index Melting Point 10 C 21.1 C 26.7 C 33.3 C 37.8 C ( C) 2630 2327 2429 1822 1619 1418 1620 1518 1215 1215 912 9.513 912 4648 4850 4447

Type Cookie and pie dough shortening Cake and icing shortening Yeast-raised sweet goods Fluid cake shortening

Composition Partially hydrogenated soybean and palm oils (unemulsied) Partially hydrogenated soybean and cottonseed oils (mono and diglycerides) Partially hydrogenated soybean and palm oils (mono and diglycerides) Partially hydrogenated soybean oil (mono and diglycerides, triglycerol monostearate, sodium stearoyl 2lactylate) Partially hydrogenated soybean and palm oils (mono and diglycerides, polysorbate 60) Partially hydrogenated soybean and palm oils (unemulsied) Partially hydrogenated soybean and palm oils (mono and diglycerides) Partially hydrogenated soybean oil (mono and diglycerides) Partially hydrogenated soybean oil (mono and diglycerides, sodium stearoyl 2-lactylate, ethoxylated mono and diglycerides)

High volume cream lling and icing Biscuit shortening Roll-in margarine for yeast-raised sweet goods Fluid bread shortening Fluid bread shortening

2528 2530 2530

1922

1821 1620 1519

1417 7.5 11.5 69

1114

4749 4447 4142

628

SOYBEAN OIL

delays starch gelatinization and allows the dough to expand more before the structure is set. Maximum loaf volume, which is a desirable trait in the United States, is achieved with 6% of emulsied shortening, based on our weight, but, in practice, 35% is normally used. Hardfats in bread shortenings are important in reducing collapse of the loafs sidewall. At least 4% hydrogenated lard stearine is desired in many bread shortenings. Rened, bleached, and deodorized soybean oil is used in most commercial white pan breads. Bread shortenings should crystallize in the b form. The base fat of a typical plastic bread shortening is comprised of 90% partially hydrogenated soybean oil (70 IV) and 10% lard stearine (<5 IV); whereas the base fat of a typical uid bread shortening is comprised of 95% partially hydrogenated soybean oil (95 IV) and 5% lard stearine. Mono-and diglycerols, are added to reduce staling rate and more functional emulsiers, such as sodium steroyl-2-lactylate or ethoxylated or succinylated mono-and diglycerols, are added as dough conditioners to impart greater mixing tolerance to enable the bread to withstand abuse without loss of loaf volume (262). Using emulsied shortening in layer cakes, cake doughnuts, and mufns increases volume and reduces air cell size and produces a ne internal grain. Creaming is dened as the mixing of the shortening over wheat our particles and incorporating of air nuclei into the fat. The air nuclei can become sites for gas bubble formation, which is important in cakemaking. The large number of minute air bubbles incorporated into shortening improves the leavening in baked goods. For the shortening used in cakes and icings, small ($1 mm) needle-like b0 crystals are preferred to the larger (515 mm) b crystals because the b0 shortenings appear smooth, provide good aeration, and have better creaming properties (263). Typically, partially hydrogenated soybean oil is blended with cottonseed or palm oil hardstock to obtain b0 crystals. Most cake shortenings contain mono- and diglycerides to decrease the size of entrained air cells during creaming, to produce ner air cells and grain in the cake crumb, and obtain a larger volume per unit weight of batter (specic volume). To achieve proper aeration of uid cake shortenings, however, partially hydrogenated soybean oil with b-tending soybean hardstock is balanced with a-tending emulsiers, which are typically mono- and di-glycerides and glyceryl-lacto fatty esters. Generally, plastic baking shortenings should be rm and plastic, but not brittle or too soft and oily. Hardfat is added to soybean oil to achieve proper texture, plasticity, and creaming properties. Plastic shortenings should be soft and plastic at low temperatures and still remain semisolid at body temperature. Soybean oil is excellent for preparing hydrogenated base stocks from which a wide array of shortenings is made. Up to 50% soybean hardfats are blended with partially hydrogenated soybean oil in some shortenings. Soybean hardfats, however, crystallize in the b polymorph unless blended with an equal or greater amount of b0 hardfat, such as hydrogenated palm or cottonseed oil. Partial hydrogenation of the base soybean oil improves the oxidative stability of the shortening. The amount of hardstock is varied to achieve the desired texture for the specic product application. Various kinds of baked goods need varied shortening functionalities and

OXIDATIVE QUALITY OF SOYBEAN OIL

629

plasticities to produce optimum quality. Plasticity is controlled by achieving the proper solid fat content or solid fat index. Typical plastic shortenings should have a relatively at solid fat index, with solids content in the range of 15% to 30% over the temperature range of 15 C to 32 C (264). One means of getting these properties is blending 10% hardstock from two sources to get the proper crystal structure with 90% partially hydrogenated soybean oil (IV 6580). 11.8. Confectionery and Imitation Dairy Products, and Low-Calorie Fat Substitutes Very little soybean oil is used to manufacture the hard butters used in confectionery products or imitation dairy products. For imitation chocolate, enrobing fats, coffee whiteners, whipped toppings, imitation cheese, frozen desserts, and lled milk, coconut and palm kernel oils are preferred because of their sharp melting points. It is important in these applications to have very low solids at body temperature to prevent a waxy mouthfeel. A few fractionated specialty blends of hydrogenated soybean oil and hydrogenated cottonseed oils (265) or soybean oil that has been hydrogenated by using sulfur-treated nickel catalysts to achieve high selectivity (266) occasionally may be used. These fats, however, are also high in trans-fatty acids (>40%) and new trans-fat labeling requirements discourage their use. The advantages of imitation dairy and chocolate products are improved functionality compared with natural products. Thus, freeze-thaw stability in whipped toppings and melting properties can be customized for specic applications (267). As a result of widespread concern about weight control, the production of lipid materials with reduced or zero calories has been of special interest recently. The lipid-based fat replacers are esters that resist enzymatic hydrolysis, are poorly absorbed, have relatively low-energy content, or have different modes of metabolism. Many of these materials can be made from soybean oil or contain soybean oil fatty acids. Sucrose polyester or other synthetic esters and diacylglycerol oils are examples of these low-calorie fat substitutes (268274). 12. OXIDATIVE QUALITY OF SOYBEAN OIL The oxidative stability of soybean oil is affected by its composition, handling of beans prior to extraction, processing conditions, and additives. Important compositional factors in soybean oil stability include its fatty acid composition and the presence of free fatty acids, phospholipids, natural antioxidants, and pigments (275). Important handling and processing factors include excessive bean moisture, damage, and temperature; exposure to oxygen; contamination by pro-oxidant metals; and exposure to light (276). 12.1. Flavor Reversion Soybean oil has poor oxidative stability, which is a major problem for the soybean industry. Crude soybean oil has a characteristic green-beany avor, which is

630

SOYBEAN OIL

eliminated during rening, bleaching, and deodorization, to produce a bland-tasting, light-colored oil. During storage, however, rened soybean oil develops a characteristic avor that often is called reversion avor (277). Prior to the 1940s, some believed that soybean oil reverted to its unrened avor after being rened and deodorized. Soybean oil was considered extremely light sensitive, and it was believed to revert if one carried the freshly deodorized oil past the light of a north window. This reversion was not considered an oxidative phenomenon (278). Actually, the term reversion is a misnomer, because (1) soybean oil does not revert to its original crude-oil avor, (2) the effect of light is real but was greatly exaggerated, and (3) the off-avor development is indeed an oxidative reaction (278). Procedures available for following oxidation prior to the 1940s involved an iodometric titration to obtain a peroxide value, but this method was too insensitive to measure the low degree of oxidation that could be detected in soybean oil by sensory examination. With the support of more sensitive methods, we now know that upon oxidation, soybean oil develops beany and grassy avors at the early stages (i.e., peroxide value 10 or below), rancidity at higher levels of oxidation (peroxide value of 10 or more), and shy or painty avors at the more advanced stages. These avor deterioration characteristics are common to all unsaturated oils containing signicant amounts of linolenate (279). It is now widely accepted that avor deterioration of soybean oil is an oxidative phenomenon, and that linolenate is the most important precursor of avor reversion of soybean oil. The technology to handle soybean oils off-avor was discovered by an interesting set of circumstances. Near the end of World War II, Warren Goss, who was commissioned to learn the secrets of the German oilseed industry, found that a Dr. Tassusky and his daughter Ilona had patented a process involving multiple washes of crude soybean oil with water or sodium silicate solution and the addition of 0.01% citric acid to the deodorizer (278). This process worked, not because of the washings, but because of the addition of citric acid. Now we know that trace metals accelerate avor deterioration and that treatment with citric acid or other metal deactivators is a practical and effective means of improving avor stability (274). 12.2. Studies on Oil Oxidation Extensive work has been done to clarify the mechanism of oil oxidation. It is a freeradical chain reaction catalyzed by light, heat, and metals, in which molecular oxygen reacts with unsaturated fatty acids to produce hydroperoxides. (280). An important factor in initiating the oxidation of unsaturated fats is by exposure to light in the presence of oxygen and a sensitizer. The activation of ordinary triplet oxygen in this way forms singlet oxygen, which reacts readily with unsaturated fatty acids (281). Oxygen is quite soluble in soybean oils (282), which frequently contain natural photosensitizers, such as chlorophylls or pheophytins. Singlet oxygen readily reacts with the double bonds of unsaturated fatty acids; for example, singlet oxygen reacts with methyl linoleate at a rate of at least 1500 times faster than normal triplet oxygen (282). Once oxidation is initiated by singlet oxygen, the hydroperoxides

OXIDATIVE QUALITY OF SOYBEAN OIL

631

that result can decompose to yield free radicals, and the reaction mode quickly becomes autocatalytic in the presence of triplet oxygen. A study by Carlsson et al. (283) found that the photo-oxidation of various unsaturated vegetable oils was not retarded by known free-radical scavengers, but was retarded by compounds known to quench singlet oxygen. Furthermore, the degree of retardation apparently paralleled the singlet oxygen-quenching ability of these compounds. Commonly, the fatty acids in food lipids are exposed to heat during oil processing and food manufacture. Once peroxides are formed, they can decompose and generate free radicals, and the rate of peroxide decomposition increases with temperature. Such reactions are of extreme importance to both consumers and processors, because of their avor signicance, and under frying conditions they can affect the physical, nutritional, and toxological properties of the fried food. Enzymes native to plants and animals can initiate oxidation reactions. The most important and best known of these enzymes is lipoxygenase (linoleate:oxygen oxidoreductase, E.C. 1.13.11.12) (LOX) (284, 285). Enzymatic oxidations in plant systems are mediated by lipoxygenases that use molecular oxygen to catalyze the oxidation of lipids containing a cis, cis-1,4-pentadiene moiety, such as linoleate and linolenate. The reaction leads to the formation of hydroperoxides, giving the same isomers as those formed during autoxidation of linoleate and linolenate. Soybeans are a rich source of lipoxygenase isozymes known as LOX-1, LOX-2, and LOX-3, and their activity is associated with the development of off-avors, especially green-beany avors, in soybean products (285). Monohydroperoxides are the primary products of lipid oxidation. A variety of hydroperoxides with positional and geometrical isomers are formed depending on the position and number of double bonds of the unsaturated fatty acids and the oxidation mechanism. A number of reviews have been published on the composition of isomeric hydroperoxides formed from oxidation of oleate, linoleate, and linolenate (286, 287291). The hydroperoxides formed are odorless, but they are relatively unstable and are the precursors of a variety of volatile and nonvolatile scission products that are important to the oxidized avor. Secondary volatile scission products from primary hydroperoxide decomposition include aldehydes, alkanes, alkenes, alkynes, alcohols, and hydrocarbons. There are considerable differences, however, in the avor signicance of these volatile compounds. When estimating the impact of volatile oxidation products on avor, it is necessary to know not only their relative concentration, but also their relative threshold values. One way of evaluating avor impact is to divide the concentration by the threshold concentration, although the relative avor impact may change with absolute concentration (292). Also, interactions among avor compounds in the olfactory response may be important. The relative volatility also may play a role if a compound must be in the gas phase to reach the olfactory organ. Lee et al. (293) created equations to relate the avor impact of individual volatiles, dispersed in an oil-water emulsion, to a specic concentration of 2-heptanone (Table 21). By this method, in a fresh and oxidized soybean oil, nonanal contributed the greatest individual effect on the avor intensity, followed by trans, trans- and trans,

632

SOYBEAN OIL

TABLE 21. Concentrations (ppb in emulsion) of 2-Heptanone Perceived to Have the Same Flavor Intensity as the Components Isolated from Commercial Soybean Oil Oxidized at 35 C Under Fluorescent Light for up to 11 Days (293). Day 0 4 7 11 0.21 0.27 0.27 0.80 2.57 12.35 5.37 1.58 1.41 17.09 3.54 20.80 5.14 76.58 none none 148.0 0.46 0.27 0.18 0.44 4.67 15.50 16.02 1.86 3.98 29.30 4.51 34.27 8.07 108.18 none none 227.8 1.14 0.34 0.24 0.37 6.21 17.47 28.55 2.43 8.74 42.66 5.26 45.10 10.82 113.70 15.62 25.09 323.8 1.00 0.35 0.35 1.24 6.42 16.19 38.86 2.47 12.60 48.05 5.52 48.18 12.09 101.90 26.24 43.30 364.8

Component 1-Penten-3-one Pentanal t-2-pentenal Toluene Hexanal Heptanal t-2-Heptenal 1-Octen-3-one 1-Octen-3-ol t,c-2,4-Heptadienal 2-Pentylfuran t,t-2,4-Heptadienal 2-Octenal Nonanal t,c-2,4-Decadienal t,t-2,4-Decadienal Total

cis-2,4-heptadienal, and 2-heptenal. Hexanal produced a large GC peak, but its effect on avor intensity was relatively small. More recently, Kao et al. (294) suggested that particles formed in the oral cavity could transport entrained triacylglycerols to the olfactory epithelium, allowing the triacylglycerols themselves to impart avor, thus implying that compounds in oxidized soybean oil do not need to be volatile to contribute to avor. They noted that the nutty avor of fresh soybean oil could only be observed when the lips were parted or the tongue drawn away from the palate, both being conditions that generated particles. Liu and Hammond (295) did further work to support the hypothesis that oral particles strongly inuence avor perception of ketones typically found in oxidized soybean oils and of avor compounds in other foods. Numerous studies have shown that the off-avor intensity of soybean oil is correlated with its concentration of linolenate. Although the concentrations of both linoleate and linolenate, which can reach 6065% in typical soybean oil, undoubtedly contribute to soybean oils instability, it is not clear why the much smaller amount of linolenate has such a strong effect on soybean oil avor. Linolenate is expected to oxidize about twice as fast as linoleate, but there is seven to eight times more linoleate than linolenate in typical soybean oil. The avor compounds produced by linolenate do not seem to have much lower thresholds than those produced from linoleate. Possibly avor interactions in olfaction may account for these effects.

OXIDATIVE QUALITY OF SOYBEAN OIL

633

12.3. Control/Stabilization Measures Selective hydrogenation to lower the concentrations of linolenate or linolenate and linoleate has been practiced to improve the oxidative stability of soybean oil. The linolenate concentration of soybean oil also can be altered by mutation breeding and genetic engineering (296). Autoxidation can be inhibited or retarded by adding low concentrations of chainbreaking antioxidants that interfere with either chain propagation or initiation (286). Chain-breaking antioxidants include phenolic and aromatic compounds hindered with bulky alkyl substituents. Common synthetic chain-breaking antioxidants used in food lipids include butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), tert-butylhydroquinone (TBHQ), and propyl gallate (PG). This class of antioxidants react with peroxy free radicals to terminate reaction chains. The antioxidant radical (A) formed in Equation 5 should be relatively stable and unable to initiate or propagate the oxidation chain reaction. ROO AH ! ROOH A 5

The phenolic antioxidants achieve stability by forming resonance hybrids (Figure 10) (297). A radical intermediate, such as semiquinone, can undergo a variety of reactions, including dismutation, to form a stable quinone and can regenerate the original hydroquinone (Figure 11). However, these antioxidants generally lose their efciency at elevated temperatures, and they are most effective during the induction period. Once the antioxidant is consumed, oxidation accelerates (297). Preventive antioxidants reduce the rate of the chain initiation. The most important initiation suppressors are metal deactivators that chelate metal ions. Metal deactivators used for stabilizing edible fat and lipid-containing foods include citric, phosphoric, tartaric acids, and phospholipids. Peroxide destroyers also are preventive

OH ROO + OH ROOH +

OH

OH

Figure 10. The formation of resonance hybrids by phenolic antioxidants.

O + OH

OH +

OH

OH

Figure 11. This dismutation of a semiquinone radical intermediate.

634

SOYBEAN OIL

antioxidants; for example, the sulfur compounds, phosphates, and phosphines reduce hydroperoxides to more stable alcohols (286). Ultraviolet light deactivators can prevent oxidation by absorbing irradiation without the formation of radicals. Examples include pigments such as carbon black, phenyl salicylate, and a-hydroxybenzophenone. A signicant synergistic antioxidative effect can be achieved when chain-breaking and preventive antioxidants are used together, because they suppress both initiation and propagation. The synergistic effect of common antioxidants in combination with metal inactivators in foods has been known for some time (33). Loliger (298) showed that the tertiary antioxidant system of Vitamin E, Vitamin C, and phospholipids provided the best protection against oxidative degradation when compared with the two antioxidants used alone or in combination. Light deterioration is also an important factor in the storage stability of soybean oils. Rening and bleaching remove not only natural photosensitizers, but also singlet oxygen quenchers such as carotenoids. The restoration of the removed carotenoids may protect lipids effectively against singlet oxygen deterioration, but the resulting yellow coloration may be objectionable to consumers. Another approach to protecting stored oils from light is the use of a package or container that absorbs the light necessary for photosensitization or that prevents light from reaching the oil. Avoiding metal contamination is also very important, as metals such as copper and iron are strong pro-oxidants for soybean oil. Copper or iron-containing alloys, except stainless steel, should never be used for equipment involved in direct contact with soybean oil. Soybean oil may be stored in containers made from carbon steel that is coated on the interior with an epoxy or polyurethane lacquer, in stainless steel, or in berglass-reinforced polyester. Displacement of oxygen in container headspaces by nitrogen or carbon dioxide to 2% has been shown to reduce oxidation effectively in vegetable oil (299). Therefore, nitrogen or other inert gas protection should be considered whenever the oil is to be stored for an extended period or held in the hot, liquid state. 12.4. Evaluation of Finished Oil Quality Regardless of the ofcial specications for soybean oil and its products, the ultimate proof of the pudding is in the eating; that is, sensory evaluation of the odors and avors of soybean oil and its products is the ultimate method to assess oil quality and stability. Sensory evaluation cannot be replaced fully by any chemical or instrumental analysis, although some methods can correlate fairly well with sensory results. Sensory evaluation of oils usually is done by a panel of experts or a trained panel, and often the method recommended by the American Oil Chemists Society (300) is used. During the evaluation, the panel is asked to score the overall avor quality, as well as the intensity of many individual off-avors. Although chemical and physical tests are more reproducible and less time consuming than sensory evaluations, oxidative rancidity and off-avor evaluation of soybean oils are best done by sensory tests. Correlations established between sensory evaluation scores and

OXIDATIVE QUALITY OF SOYBEAN OIL

635

various chemical tests, however, can be used to predict the sensory quality of nished oil products. Peroxide value, expressed as milliequivalents of peroxide per kilogram of oil, measures the primary oxidation products of oilsthe hydroperoxides. The peroxide value has shown a particularly good correlation with sensory avor scores of soybean oil, and its use during storage is quite common. The peroxide value is an index to the oxidative state of an oil. Soybean oil is considered fresh with a peroxide value <1.0 mEq/kg, to have low oxidation with 1.05.0 mEq/kg, to have moderate oxidation at 5.010.0 mEq/kg, to have high oxidation at >10.0 mEq/kg, and to have poor avor quality at >20 mEq/kg (6). Several methods (300303) can be used to measure the peroxide value of an oil depending on the specic circumstance. One of the rst steps in the oxidation of polyunsaturated fatty acids is a shift in the position of double bonds, resulting in the formation of conjugated hydroperoxides. The conjugated structure absorbs strongly at a wavelength of 232234 nm. The conjugated diene value (300) is expressed as the percentage of conjugated dienoic acid in the oil and is an indication of initial or primary oxidation products. Conjugated diene value can be used as a comparative method only when the oils have the same initial fatty acid composition, because the greater the amount of polyenoates in an oil, the greater the potential rise in the conjugated diene value. As a result, this method should be used as a relative measurement of oxidation in an oil only if the fatty acid composition is known (303). As aldehydes and some ketones have long been identied as oxidation and breakdown products of fats, their determination also has been common in soybean oil quality control. The p-anisidine value (300) measures light absorbance of aldehydes, primarily 2-alkenals, and 2,4-dienals at 350 nm. However, this measure is not entirely specic, because the color intensity developed depends not only on the concentration but also on the structure of the aldehyde. Therefore, the results are comparable only within oils of similar type and treatment (304). Free fatty acid (305), polar compounds (300), viscosity, and color analyses are often performed to determine the degree of abuse that oils receive during heating or frying. They are important indicators of frying oil quality, because these components affect the quality of the fried food. The free fatty acid increase during frying indicates released from triacylglyceride ester linkages via hydrolysis (233). Thus, it is an important marker for oil quality. Abused frying oil should be discarded if it contains >27% total polar compounds, according to a German standard of frying oil quality (306). Changes in viscosity and color of the frying oil also are used as indicators of the extent of frying oil degradation. There are many other methods for measuring lipid oxidation and quality by chemical means. Among the best-known procedures are the thiobarbituric acid (TBA) test, carbonyl value, and headspace oxygen analysis. These methods have been reviewed and discussed elsewhere (287, 307). The volatile carbonyl compounds formed during oxidation of fats and oils are major contributors to off-avor development. Therefore, there have been signicant efforts at identifying and quantifying these compounds. It is difcult to analyze these compounds in fats and oils for several reasons. First, it is difcult to remove

636

SOYBEAN OIL

them quantitatively from the fats and oils. Second, widespread contamination by carbonyls in solvents, glassware, and other laboratory materials may cause artifacts. Finally, hundreds of volatile compounds may be formed in fats and oils during oxidation causing difculties in the interpretation. Today, the use of efcient gas chromatography (GC) columns and proper means of identication has made reliable volatile compound analysis become possible. Three basic GC procedures are generally employed (300), including static headspace, dynamic headspace, and direct injection. Static headspace involves equilibration of gases from the area above a liquid sample; a set volume of the headspace gas from the sample is then injected directly into the GC for separation and quantication. The dynamic headspace method, also known as purge and trap, employs a sorbent, such as Tenax GC, Chromosorb, or Porapak Q, to collect volatile compounds that are swept from a heated sample with an inert gas such as helium or nitrogen. After trapping, the sorbent may be extracted with solvent, or transferred directly to the GC inlet port. In direct injection, an oil sample may be injected directly into the port of the GC through a silanized glass wool plug. Each of these methods has their own advantages and disadvantages (287). Recently, the method of gas chromatographic solid-phase microextraction (GCSPME) has been developed (308310). This method uses bers coated with various polymers to extract volatile compounds from a food system. The method can be used in solid, liquid, and gaseous systems. It is fairly easy to evaluate volatile compounds by this analysis and to maintain consistent conditions. Evans et al. (311) and Scholz and Ptak (312) used GC analysis of n-pentane as a measurement of rancidity of vegetable oils. Dupuy et al. (313, 314) determined the volatile carbonyl compounds from soybean oil using a modied gas chromatographic inlet tube and found good correlations between the volatile prole analysis and sensory scores. The Flavor Quality and Stability Committee of the AOCS evaluated GC volatile proling as a standard method of avor evaluation (275). As a result, they wrote two Recommended Practices, entitled Volatiles in Fats and Oils by Gas-Liquid Chromatography Cg 4-94, 1997 (300) and Correlation of Oil Volatiles with Flavor Scores of Edible Oils AOCS method Cg 1-83, 1997 (300). These AOCS methods were validated in an AOCS collaborative study on sensory and volatile analyses, in which three methods of volatile compound analyses were compared with sensory analyses by using the AOCS avor scales (315). Despite agreement on the usefulness of these methods, the committee stressed that only humans can measure avor, thus these volatile GC methods measured features such as oxidative stability and compound breakdownnot sensory perceptions per se. Not surprisingly, heat treatment, such as commercial and household frying, accelerates autoxidation. In addition to undergoing autoxidation, when fats are heated in the presence of moisture, as often is the case in food applications, fatty acids are released via hydrolysis of the ester linkages (233). The free fatty acids can accelerate oxidation of the oil. During heat treatment, the formation of dimeric and cyclic compounds seems to be the predominant thermolytic reaction of unsaturated fatty acids. In the presence of oxygen during heat treatment, however, oxidative

OXIDATIVE QUALITY OF SOYBEAN OIL

637

polymerization also can occur (233). Obviously, temperature, heating time, availability of oxygen, etc. can largely inuence the extent to which these thermal and oxidative polymerization reactions occur. Decomposition and condensation of hydroperoxides also produces a multitude of nonvolatile monomeric products, including di- and tri-oxygenated esters, and dimeric and polymeric materials, especially at elevated temperature. Many of these dimers and polymers are known to be rich sources of volatile carbonyl compounds and to decrease the avor and oxidative stability of soybean oil (316). These highmolecular-weight materials also can produce a series of physical and chemical changes to the oil and food products, including increased viscosity, polarity, free acid content, development of dark color, and an increased tendency of the oil to foam (233). 12.5. Storage and Handling Production of good quality soybean oil requires close control from harvesting of the soybeans, during bean storage, during and after oil processing, through consumption of the nished oil products to guard against oxidative, enzymatic, and microbiological deterioration. Good processing measures include careful control of rening temperature, vacuum bleaching, and inert gas blanketing. Heat accelerates the reaction of atmospheric oxygen with edible oils, therefore, localized overheating is detrimental to nal oil quality. After processing, soybean oil should be stored at as low a temperature as possible and practical, and with protection from light. Vacuum conditions are very important during bleaching, because oxidation can readily occur by exposure of a large surface area to air at elevated temperatures. During storage, a package containing the maximum amount of oil is preferable, because oxygen availability is lower with a lower headspace-to-oil ratio. Peroxide formation also is a linear function of surface-to-volume ratio (275). According to List (317), in eld storage tanks, the oil is also subjected to conditions that cause development of sizable temperature gradients that can produce considerable internal oil movement. Such movement would be expected to increase the quantity of oil available at the surface and to accelerate oxygen diffusion. Therefore, soybean oil stored in lled tanks should be at as low a temperature as possible to avoid such conditions. 12.6. Special Processing for Off-Specication Oil Oils from eld-, frost-, moisture-, and storage-damaged beans usually have higher levels of free fatty acids and iron, lower levels of phosphorous, darker colors, and poorer avor and oxidative stability in the nished products than do oils from undamaged beans. Such beans are difcult to process, and standard processing methods usually do not produce nished oils that can meet soybean oil specications for trading or domestic consumption. The National Soybean Processors Association (318) trading rules specify that prime crude oils, after rening and bleaching by an ofcial method (300), must

638

SOYBEAN OIL

meet a Lovibond color level of 6.0. Frost-damaged oils often will not meet this requirement. Oils from frost-damaged beans tend to have an undesirable green color in the crude oils caused by compounds related to, but not identical to, chlorophyll (includes pheophytin) or some of its derivatives, according to Stern and Grossman (319). When bleaching such oils, acid-activated clays are more efcient than neutral clays and increased amounts of bleaching earth make the removal of the green color more effective. According to Stern and Grossman (319), pretreatment with charcoal (0.41.0%) at 90 C or treatment of a cold hexane-oil mixture with charcoal is effective in partly removing the green pigment. When charcoal pretreatment is combined with additional treatment from sugars and activated bleaching clays, complete removal of green pigments is possible. Hydrogenation can also be used to remove green color from soybean oil. According to Beal et al. (175), a green oil (IV 132) hydrogenated to IV 110 in the presence of 1% copper chromate catalyst was no longer green after cooling and ltration. However, the use of copper chromate is not a common practice. When soybeans are exposed to rain or humid weather in the eld, the beans tend to sprout and decay, and the oil from these beans develops a dark-brown color and chalky texture (312). Drought stress affects protein and oil content of soybeans but seldom damages oil quality signicantly. According to List (317), off-specication oils from eld-, frost-, heat-, and moisture-damaged soybeans result in high rening losses during processing, poor rened-bleached color, and lowered avor and oxidative stability. High rening losses may be partly overcome by use of phosphoric acid or acetic anhydride degumming. Color problems of oils from damaged beans may be alleviated, in part, by use of acidic bleaching earths, increased amounts of bleaching earths, and higher bleaching temperatures. Overall, however, the best practice for producing high-quality oil is to segregate the bad beans and not include them in the processing. 13. DIETARY FATTY ACIDS AND THEIR HEALTH EFFECTS 13.1. Cholesterol and Heart Disease Heart disease is still the number one cause of death for both men and women in the United States. High-blood-cholesterol levels increase the risk of getting heart disease (319), so, generally, serum (blood) cholesterol is measured to determine a persons risk of developing heart disease. Although some cholesterol is essential in forming the bodys cell membranes and synthesizing hormones and bile acids, too much cholesterol is associated with heart disease. The fat eaten can affect the blood-cholesterol level. In addition to monitoring total blood cholesterol, the ratio of high-density lipoproteins (HDL) to low-density lipoproteins (LDL) of the blood also is important in predicting heart disease. As cholesterol, a waxy substance, does not mix with water, it needs help circulating through blood, which is mostly water. Lipoproteins transport cholesterol throughout the body. Low-density lipoproteins carry cholesterol from the liver to the body and leave deposits on artery walls. High-density lipoproteins carry cholesterol back to the liver for

DIETARY FATTY ACIDS AND THEIR HEALTH EFFECTS

639

elimination. If the ratio of low/high-density lipoproteins becomes too large, it is likely that more cholesterol will be deposited in the arteries than is removed. So the low/high-density lipoprotein ratio also may be used to predict a persons chances of developing heart disease. A ratio greater than 3 can indicate above average risk. The most important dietary inuences on blood cholesterol levels are saturated fat, total fat, and dietary cholesterol. 13.2. Saturated Fat and Health Effects Saturated fat has more impact on raising blood cholesterol levels than anything else in the diet. The most effective way to reduce the blood cholesterol level is to reduce the amount of saturated fat in the diet. Animal products are a major source of saturated fat in the average American diet. A very few vegetable oils, including coconut, palm kernel, and palm oils, are rich in saturated fat. Other vegetable oils, including soybean oil, can become saturated by hydrogenation. Consumption of too much saturated fat has been associated with the development of heart disease, some cancers, and other health problems. As soybean oil is the major edible oil consumed in the United States, lowering its saturated fat could help reduce heart disease in this country, even though its total saturated fatty acid composition is only about 15% to 16%. As noted, the major saturates in soybean oil are palmitate and stearate. Palmitate is responsible for about 70% of the total saturated fat in soybean oil. Substitution of palmitate for carbohydrates or monounsaturates in the diet increased levels of serum low-density lipoproteins and total cholesterol (320). Stearate has been found to be relatively neutral in its effects on blood lipids, and some researchers (321, 322) showed that dietary stearate actually lowered serum lowdensity lipoproteins and total cholesterol levels; thus, many people recommend that this saturate not be included in the category of hypercholesterolemic acyl groups. It was for these reasons that Iowa State University scientists developed LoSatSoyTM, a soybean oil with half the saturated fat of conventional soybean oil, with reduction of palmitate to <$3%. 13.3. Unsaturated Fat and Health Effects Unsaturated fats, classied as either monounsaturated or polyunsaturated, can help lower the cholesterol levels in blood when substituted for saturated fats. Sources of monounsaturated fat include nuts, olive oil, and canola oil. Sources of polyunsaturated fat include corn, safower, sesame, soybean, and sunower oils. Soybean oil contains about 21% of the monounsaturate oleate. Studies have shown that the oxidation rate of oleate is much slower than that of the polyunsaturates, linoleate and linolenate, which oxidize quickly and are the major contributors to the poor stability of soybean oil (287, 323). A diet high in monounsaturates may help to reduce elevated levels of total plasma cholesterol without reducing the highdensity lipoprotein-cholesterol level (324). Therefore, high-oleate soybean oil is not only more stable than conventional soybean oil (275), but also has enhanced nutritive value.

640

SOYBEAN OIL

In both clinical trials and population studies, polyunsaturated fats in the diet have been shown to actively lower serum cholesterol levels. Soybean oil is considered to have good nutritive value mainly because of its high concentration of essential polyunsaturates. As noted previously, it contains about 55% linoleate and 8% linolenate, both recognized as essential fatty acids. Ingestion of approximately 12% of daily calories as linoleate is widely accepted as the amount needed to meet the essential fatty acid requirement of rodent species and humans (325). The physiological effects of linoleate have been well characterized. Various deciency symptoms include depressed growth, scaly dermatoses, increased skin permeability, fatty liver, kidney damage, and impaired reproduction. The 8% linolenate of soybean oil, makes it not only an excellent source of essential fatty acids, but also a member of the n-3 fatty acid group (the third carbon atom from the terminal end of the hydrocarbon chain is involved in a double bond). A number of health benets have been associated with the consumption of foods or oils that contain n-3 fatty acids. These associations originally derived from epidemiological studies of Eskimos who consumed high levels of n-3 fatty acid from seals and coldwater sh (326). Compared with Danish counterparts, these Eskimos were found to have a low incidence of heart disease and immune system diseases, although a somewhat higher level of hemorrhagic stroke. Still today, large-scale epidemiological studies suggest that individuals at risk for CHD benet from the consumption of plant- and marine-derived n-3 fatty acids (327). 13.4. Trans-Fatty Acids and Their Health Effects The process of catalytic hydrogenation of vegetable oils was discovered in 1897 to reduce the polyunsaturates and to improve avor stability, versatility, and performance of vegetable oils in salad dressings, during cooking, in deep-fat-frying, and for the manufacture of margarines, shortenings, and other baking and snack food applications (328). A side reaction that occurs during hydrogenation is the formation of positional and geometrical isomers of the unsaturated sites that are left unsaturated. Formation of trans-isomers is rapid and extensive (320). Although hydrogenation can improve soybean oil oxidative stability and performance versatility, the presence of the trans-fatty acids may make hydrogenated oils nutritionally undesirable. In particular, the role of partially hydrogenated soybean oil in nutrition has been under scrutiny because of the health concerns over the presence of transacyl groups in our diets (329); however, the biological signicance of these transacyl groups is unclear. The formation of trans-acyl groups in vegetable oils also can occur, to a small extent, during deodorization (330, 331) and during frying (332, 333). The 9-cis,12-trans-linoleate is present in most vegetable shortenings in much greater quantities than the 9-trans,12-trans-linoleic acid (334). In heated vegetable oils, the isomers just mentioned have been reported, plus trans-, cis-isomers of linolenate (330, 332, 335). Trans-isomers are essential fatty acid antagonists, especially when the linoleate and linolenate are limited in the diet. For example, the cis, cis, trans-isomer of 18:3 is elongated and desaturated to form n-3 trans-isomers of 20:5n-3 and 22:6n-3 in rats (336); isomers that also have

REFERENCES

641

been found in human platelets (337). The 9-cis,12-trans-linoleic acid can be converted to 20:4n-6 containing a trans-double bond. Unfortunately, this trans-isomer of 20:4n-6 inhibited the formation of prostaglandins from all-cis-20:4n-6 (338). Mensink and Katan (250) reported that a diet high in trans-acyl groups raised total and low/high-density lipoprotein cholesterol ratio compared with a diet high in cisacyl groups may be more cholesterolemic than saturates (339), and were linked to an increased risk of breast cancer development (340). The estimated trans-acyl group intake by typical U.S. consumers is 11.127.6 g/ person/day (341). A comprehensive review concluded that trans-acyl groups consumed at 4.0% or more of total calories may raise plasma lipid levels (342). As a result of health concerns over the presence of trans-acyl groups in our diet, modifying fatty acid composition of soybean oil to improve its oxidative and avor stability in ways similar to that obtained by hydrogenation, but without transformation, has become an objective of plant breeders. 13.5. Total Fat and Its Health Effects Excessive intake of any fat is not healthy. According to Klurfeld and Kritchevsky (342), the enhancement of tumor growth by dietary fat may result, in part, from the caloric contribution of this nutrient. Signicant reduction of tumor incidence with consumption of 25% less energy was seen consistently in rat tumor systems induced by chemicals. Currently, most American children get about 34% of their calories from fat (318). It is recommended, however, that healthy childrens intake of fat average no more than 30% of calories. Experts also suggest lowering childrens saturated fat intake to less than 10% of calories. Similar recommendations have been made for adults (343).

REFERENCES
1. Economic Research Service of United States Department of Agriculture. (October, 2002). Oil Crop Situation and Outlook Yearbook. Available: http://usda.mannlib. cornell.edu/reports/erssor/eld/ocs-bby/ocs2002.pdf. 2. 2004 Soya & Oilseed Bluebook, Soyatech, Inc., Bar Harbor, Maine, 2003. 3. T. J. Brumm and C. R. Hurburgh, Jr., Quality of the 2002 Soybean Crop from the United States, Report to the American Soybean Association. 4. D. M. Maestrl, J. M. Mariles, and C. A. Guzman, Grassas Aceites, 49, 395399 (1998). 5. C. R. Hurburgh, Jr., J. Amer. Oil Chem. Soc., 71, 14251427 (1994). 6. D. M. Maestri, D. O. Labuckas, J. M. Meriles, A. L. Lamarque, J. A. Zygadlo, and C. A. Guzman, J. Sci. Food Agric., 77, 494498 (1998). 7. R. F. Wilson, Agro-Food Industry Hi-Tech., 12(6), 1722 (2002). 8. R. F. Wilson, Lipid Technol., 11, 107110 (2000). 9. J. A. Hoeck, W. R. Fehr, P. A. Murphy, and G. A. Welke, Crop Sci., 40, 4851 (2000). 10. J.-S. Choi, T.-W. Kwon, and J.-S. Kim, Food Biotechnol., 5, 167169 (1996).

642

SOYBEAN OIL

11. C. Tsukamoto, S. Shimada, K. Igita, S. Kudou, M. Kokubun, K. Okubo, and K. Kitamura, J. Agric. Food Chem., 43, 11841192 (1995). 12. T. Wang, Phospholipid fatty acid composition of modied soybeans and the effect of saturated fatty acid content on seed performance, Ph.D. Dissertation, Iowa State University, Ames, Iowa, 1998. 13. T. Gutnger and A. Letan, Lipids, 9, 658663 (1974). 14. M. Bastic, L. J. Bastic, J. A. Javanovic, and G. Spiteller, J. Amer. Oil Chem. Soc., 55, 886891 (1978). 15. J. D. Weete and R. C. Manley, J. Ala. Acad. Sci., 50, 3546 (1979). 16. T. L. Mounts, S. L. Abidi, and K. A. Rennick, J. Amer. Oil Chem. Soc., 73, 581586 (1996). 17. J. L. Weihrauch and J. M. Gardner, J. Amer. Diet. Assoc., 73, 39 47 (1978). 18. C. D. Evans, G. R. List, R. E. Beal, and L. T. Black, J. Amer. Oil Chem. Soc., 51, 444448 (1974). 19. G. R. List, A. J. Heakin, C. D. Evans, L. T. Black, and T. L. Mounts, J. Amer. Oil Chem. Soc., 55, 521522 (1978). 20. G. O. Almonor, G. P. Fenner, and R. F. Wilson, J. Amer. Oil Chem. Soc., 75, 591596 (1998). 21. C. Vlahakis and J. Hazebroek, J. Amer. Oil Chem. Soc., 77, 4953 (2000). 22. K. L. McCord, W. R. Fehr, T. Wang, G. A. Welke, S. R. Cianzio, and S. R. Schnebly, Crop Sci., 44, 772776 (2004). 23. S.-N. Ko, C.-J. Kim, H. Kim, C.-T. Kim, S.-H. Chung, B.-S. Tae, and I.-H. Kim, J. Amer. Oil Chem. Soc., 80, 585589 (2003). 24. L. H. Wiedermann, J. Amer. Oil Chem. Soc., 58, 159166 (1981). 25. S. Ramamurthi, A. R. McCurdy, and R. T. Tyler, in S. S. Koseoglu, K. C. Rhee, and R. F. Wilson, eds., Proc. World Conf. Oilseed Edible Oils Process, vol. 1, AOCS Press, Champaign, Illinois, 1998, pp. 130134. 26. Yearbook and Trading Rules, National Oilseed Processors Association, Washington, D.C., 1993. 27. H. Klein, Ernahrung/Nutrition, 23, 452460 (1999). 28. D. M. Maestri, D. O. Labuckas, C. A. Guzman, and L. M. Glorda, Grasas Aceites, 49, 450453 (1998). 29. J. Siebrecht and J. Hazebroek, J. Amer. Oil Chem. Soc., 74, 989998 (1997). 30. X. Wu, E. G. Hammond, P. J. White, and W. Fehr, J. Amer. Oil Chem. Soc., 74, 1099 1103 (1997). 31. F. G. Sietz, Fette Scifen Anstrichm., 67, 411412 (1965). 32. M. Wesolowski, Food Sci.Technol., 95, 377383 (1993). 33. X. Ndzana, W. R. Fehr, G. A. Welke, E. G. Hammond, D. N. Duvick, and S. R. Cianzio, Crop Sci., 34, 646649 (1994). 34. S. R. Schnebly, W. R. Fehr, G. A. Welke, E. G. Hammond, and D. N. Duvick, Crop Sci., 36, 14621466 (1996). 35. G. L. Graef, L. A. Miller, W. R. Fehr, and E. G. Hammond, J. Amer. Oil Chem. Soc., 62, 773775 (1985). 36. T. Wang, E. G. Hammond, and W. R. Fehr, J. Amer. Oil Chem. Soc., 78, 11391144 (2001).

REFERENCES

643

37. A. J. Kinney, J. Food Lipids, 3, 273292 (1996). 38. W. R. Fehr and E. G. Hammond (to Iowa State University Research Foundation), U.S. Patent 5,534,425, July 9, 1996. 39. R. F. Wilson, J. W. Burton, V. R. Pantalone, and R. E. Dewey, Lipid Biotechnology, Marcel Dekker, New York, 2002, pp. 95113. 40. T. F. Horejsi, W. R. Fehr, G. A. Welke, D. N. Duvick, E. G. Hammond, and S. R. Cianzio, Crop Sci., 34, 331334 (1994). 41. R. B. Hartmann, W. R. Fehr, G. A. Welke, E. G. Hammond, D. N. Duvick, and S. R. Cianzio, Crop Sci., 36, 14661470 (1996). 42. T. Wang, T. Harp, E. G. Hammond, J. S. Burris, and W. R. Fehr, Seed Sci. Res., 11, 9397 (2001). 43. W. R. Fehr, J. C. Thorne, and E. G. Hammond, Crop Sci., 11, 211213 (1971). 44. G. Ishikawa, H. Hasegawa, Y. Takagi, and T. Tanisaka, Plant Breeding, 120, 417423 (2001). 45. T. K. Harp and E. G. Hammond, Lipids, 33, 209216 (1998). 46. T. Wang, unpublished results, September 2003. 47. C. Litcheld, Analysis of Triglycerides, Academic Press, New York, 1972, pp. 233264. 48. W. E., Neff, G. R. List, and W. C. Byrdwell, J. Liq. Chromatogr. Related. Technol., 22, 16491662 (1999). 49. W. E. Neff and W. C. Byrdwell, J. Amer. Oil Chem. Soc., 72, 11851191 (1995). 50. T. Wang, E. G. Hammond, and W. R. Fehr, J. Amer. Oil Chem. Soc., 74, 15871594 (1997). 51. T. Wang, E. G. Hammond, J. L. Cornette, and W. R. Fehr, J. Amer. Oil Chem. Soc., 76, 13131321 (1999). 52. T. L. Mounts and A. M. Nash, J. Amer. Oil Chem. Soc., 67, 757760 (1990). 53. G. R. List, T. L. Mounts, and A. C. Lanser, J. Amer. Oil Chem. Soc., 69, 443446 (1992). 54. E. Gutierrez, Method Development for Sphingolipid Quantication in Soybeans and Soy Products, M. S. Thesis, Iowa State University, Ames, Iowa 2003. 55. V. Piironen, T. Koivu, O. Tammisalo, and P. Mattila, Food Chem., 59, 473480 (1997). 56. T. Yamagami, M. Aoyama, T. Tsutsumi, S. Tokairin, H. Ehara, T. Maruyama, and I. Niiya, Yukagakkaishi, 48, 12711274 (1999). 57. T. Yamagami, M. Aoyama, T. Tsutsumi, S. Tokairin, H. Ehara, T. Maruyama, and I. Niiya, Chem. Abstr., 132, 77768 (2000). 58. T. Koivu, V. Piironen, A.-M. Lampi, and P. Mattila, J. Food Chem., 64, 411414 (1999). 59. R. F. Wilson, J. W. Burton, W. P. Novitzky, and R. E. Dewey, J. Oleo Sci., 50, 353358 (2001). 60. K. Warner, P. Orr, and M. Glynn, J. Amer. Oil Chem. Soc., 74, 347356 (1997). 61. H. Guth and W. Grosch, Fat Sci. Technol., 93, 249255 (1991). 62. J.-W. Kao, X. Wu, E. G. Hammond, and P. J. White, J. Amer. Oil Chem. Soc., 75, 831 835 (1998). 63. J. deD. Alvarado, Grasas Aceites, 46, 264269 (1995). 64. J. deD. Alvarado, Chem. Abstr., 124, 200581 (1996).

644

SOYBEAN OIL

65. V. V. Kravchenko, A. K. Pugach, and V. Z. Geller, Izv. Vysshikh, Uchebnykh, Zavedenii, Pishchevaya Tekhnol., 1987, 7981 (1987). 66. V. V. Kravchenko, A. K. Pugach, and V. Z. Geller, Chem. Abstr., 108, 54638 (1987). 67. H. Noureddini, B. C. Teoh, and L. D. Clements, J. Amer. Oil Chem. Soc., 69, 11841188 (1992). 68. Y. Tochitani and M. Fujimoto, Netsu Bussei, 15, 230236 (2001). 69. Y. Ali, M. A. Hanna, and S. L. Cuppett, J. Amer. Oil Chem. Soc., 72, 15571564 (1995). 70. R. Sh. Kuliev, F. R. Shirinov, and F. A. Kuliev, Chem. Technol. Fuels Oils., 35, 235237 (1999). 71. H. Koseki, Y. Natsume, and Y. Iwata, J. Fire Sci., 19, 3144 (2001). 72. E. W. Washburn, ed. International Critical Tables, vol. 5, McGraw-Hill, New York, 1929, pp. 162169. 73. K. S. Miller, B. E. Farkas, and R. P. Singh, J. Food Process. Preservation., 18, 461472 (1994). 74. E. S. Perry, W. H. Weber, and B. F. Daubert, J. Amer. Chem. Soc., 71, 37203726 (1949). 75. A. Tekin and E. G. Hammond, J. Amer. Oil Chem. Soc., 75, 737740 (1998). 76. S. B. Detwiler, Jr. and K. S. Markley, Oil & Soap, 17, 3940 (1940). 77. K. Yokota and M. Tachimori, Kogyo Kagaku Zasshi, 40 (Suppl. binding) 426429 (1937). 78. K. Yokota and M. Tachimori, Chem. Abstr., 32, 13680 (1937). 79. J. D. Halvorsen, W. C. Mammel, Jr., and L. D. Clements, J. Amer. Oil Chem. Soc., 70, 875880 (1993). 80. C. M. Rodenbush, F. H. Hsieh, and D. S. Viswanath, J. Amer. Oil Chem. Soc., 76, 1415 1419 (1999). 81. H. F. Johnstone and I. H. Spoor, Ind. Eng. Chem., 32, 832835 (1940). 82. F. C. Magne and E. L. Skau, Ind. Eng. Chem., 37, 10971102 (1945). 83. L. K. Arnold and L. J. Breuklander, Iowa Acad. Sci., 57, 157160 (1950). 84. F. C. Magne, E. J. Hughes, and E. L. Skau, J. Amer. Oil Chem. Soc., 27, 552555 (1950). 85. P. E. Clark, C. R. Waldeland, and R. P. Cross, J. Ind. Eng. Chem., 38, 350353 (1946). 86. T. Kasprzycka-Guttman and D. Odzeniak, Thermochimica Acta, 191, 4145 (1991). 87. T. Wang and J. L. Briggs, J. Amer. Oil Chem. Soc., 79, 831836 (2002). 88. N. A. Morad, A. A. Mustafa Kamal, F. Panau, and T. W. Yew, J. Amer. Oil Chem. Soc., 77, 10011105 (2000). 89. Y. Hagura and K. Suzuki, Nippon Shokuhin Kagaku Kogaku Kaishi, 49, 272276 (2002). 90. Y. Hagura and K. Suzuki, Chem. Abstr., 138, 38393 (2003). 91. V. Chiof, Chim. Provinciali, 12, 123136 (1961). 92. G. J. Arissen, Verfkroniek, 6, 911 (1996). 93. D. B. Dahlberg, S. M. Lee, S. J. Wenger, and J. A. Vargo, Applied Spectroscopy, 51, 11181124 (1997). 94. I. Boyaci, A. Tekin, M. Cizmeci, and I. Javidpour, J. Food Lipids, 9, 175183 (2002). 95. J. A. Ibemesi and I. O. Igwe, J. Amer. Oil Chem. Soc., 68, 147152 (1991). 96. S. Z. Erhan, S. Asaduauskas, and A. Adhvaryu, J. Amer. Oil Chem. Soc., 79, 11571161 (2002). 97. E. G. Hammond and W. O. Lundberg, J. Amer. Oil Chem. Soc., 31, 427432 (1954).

REFERENCES

645

98. 99. 100. 101. 102. 103. 104. 105. 106. 107. 108. 109. 110. 111. 112. 113. 114. 115. 116. 117. 118. 119. 120. 121. 122. 123. 124. 125. 126. 127. 128. 129. 130. 131.

K. R. Majors and R. T. Milner, Oil & Soap, 16, 228231 (1939). Y. Maruta and K. Tenurama, Kogyo Kagaku Zasshi, 40 (Suppl), 299 (1937). Y. Maruta and K. Tenurama, Chem. Abstr., 31, 65303 (1937). J. R. Daer, J. Amer. Oil Chem. Soc., 52, 425426 (1975). C. F. Cole, G. M. Hill, and A. J. Adams, J. Amer. Oil Chem. Soc., 71, 13391342 (1994). Y. H. Chu, J. Amer. Oil Chem. Soc., 68, 379384 (1991). C. Inoue, Y. Hagura, M. Ishikawa, and K. Suzuki, J. Food Sci., 67, 11261129 (2002). N. Tomoto and K. Kusano, Yukagaku, 16, 108113 (1967). N. Tomoto and K. Kusano, Chem. Abstr., 66, 106141 (1967). M. Loncin, Fette Seifen Anstrichm., 57, 413415 (1955). A. S. Smith and F. J. Wechter, J. Amer. Oil Chem. Soc., 27, 381383 (1950). A. S. Smith, J. Amer. Oil Chem. Soc., 28, 360361 (1951). A. S. Smith, J. Amer. Oil Chem. Soc., 28, 356359 (1951). K. Kusano, Yukagaku, 8, 814 (1959). K. Kusano, Chem. Abstr., 54, 2002060 (1960). A. I. Anikin, G. N. Danilova, and V. V. Klyuchkin, Izvestiaya Vysshikh Ucbebnykh, Zavedenii Pishchevaya Tekhnologiya, 4345 (1987). A. I. Anikin, G. N. Danilova, and V. V. Klyuchkin, Chem. Abstr., 108, 54636 (1988). C. Aberhard and Z. Spekuljak, Revista Facultad Ingenieria Quimica, 48, 712 (1988). C. Aberhard and Z. Spekuljak, Chem. Abstr., 112, 156952 (1990). W. H. Dickhart, Amer. J. Pharm., 104, 284 (1932). G.-C. Yen, C. H. Shao, C. J. Chen, and P. D. Duh, Food Sci. Technol., 30, 648652 (1997). B. Kowalski, Thermochimica Acta, 173, 117127 (1990). V. Barquin, Tecnicas Laboratorio, 11, 345349 (1987). M. Wakakura, Kenkyu Hokoku-Kanagawa-ken Kogyo Shikensho, 55, 7677 (1984). M. Wakakura, Chem. Abstr., 103, 217718 (1985). Federal Grain Inspection Service, Federal Grain Inspection Handbook, Washington, D.C., 1990. U.S. Department of Agriculture. Available: http://www.usda.gov/gipsa/referencelibrary/brochures/soyinsepction.pfd. T. J. Brumm and C. R. Hurburgh, J. Amer. Oil Chem. Soc., 67, 302307 (1990). University of Illinois, Urbana-Champaign, Illinois. Available: http://www.stratsoy.uiuc. edu/epv/. T. L. Mounts, G. R. List, and A. J. Heakin, J. Amer. Oil Chem. Soc., 56, 883885 (1979). G. R. List C. D. Evans, K. Warner, R. E. Beal, W. F. Kwiolek, L. T. Black, and K. J. Moulton, J. Amer. Oil Chem. Soc., 54, 814 (1977). C. R. Hurburgh, T. J. Brumm, J. M. Quin, and R. A. Hartwig, J. Amer. Oil Chem. Soc., 67, 966973 (1990). E. G. Hammond, L. A. Johnson, and P. A. Murphy, in C. Wrigley, C. Walker, and H. Corke, eds., Encyclopaedia of Grain Sciences, Academic Press, London, 2003. P. Golbitz, 2003 Soya & Oilseed Bluebook, Soyatech, Inc., Bar Harbor, Maine, 2003.

646

SOYBEAN OIL

132. D. Erickson, ed., Handbook of Soybean Processing and Utilization, AOCS Press, Champaign, Illinois, 1995. 133. L. A. Johnson, in P. J. Wan and W. Farr, eds., Introduction to Fats and Oils, AOCS Press, Champaign, Illinois, 2000, pp. 108135. 134. L. A. Johnson, in C. Akoh and D. Min., eds., Food Lipids, 2nd ed., Marcel Dekker, New York, 2002, pp. 223273. 135. T. J. Brumm, C. R. Hurburgh, and L. A. Johnson, J. Amer. Oil Chem. Soc., 67, 750756 (1990). 136. J. M. Guinn, American Soybean Association, St. Louis, MO. (2002). Available: http:// www.asasoya.org/Import/Guinn_Quality_Standards_Trading_Rules2002.htm. 137. L. A. Johnson and E. W. Lusas, J. Amer. Oil Chem. Soc., 60, 181A193A (1983). 138. R. J. Hron, J. Amer. Oil Chem. Soc., 59, 674A684A (1982). 139. P. J. Wan and P. J. Wakelyn, eds., Technology and Solvents for Extracting Oilseeds and Nonpetroleum Oils, AOCS Press, Champaign, Illinois, 1997. 140. R. D. Good, Oil Mill Gaz., 75(3), 1417 (1970). 141. F. McDonald, Oil Mill Gaz., 84(12), 25 (1980). 142. M. A. Williams, Oil Mill Gaz., 91(5), 2429 (1986). 143. M. A. Williams, INFORM, 6(3), 289293 (1995). 144. E. W. Lusas and L. R. Watkins, J. Amer. Oil Chem. Soc., 65, 11071114 (1988). 145. National Oilseed Processors Association, Washington, D.C. (2002). Available: http:// www.asasoya.org/Import/Guinn_Quality_Standards_Trading_Rules2002.htm. 146. A. I. Nelson, W. B. Wijeratne, S. W. Yeh, T. M. Wei, and L. S. Wei, J. Amer. Oil Chem. Soc., 64, 13411347 (1987). 147. N. W. Said, INFORM, 9(2), 139144 (1997). 148. T. Wang, L. A. Johnson, and W. Wijeratne, in N. T. Dunford and H. B. Dunford, eds., Nutritionally Enhanced Edible Oil Processing, AOCS Press, Champaign, Illinois, 2004, p. 219238. 149. T. Wang and L. A. Johnson, J. Amer. Oil Chem. Soc., 78, 311318 (2001). 150. T. Wang and L. A. Johnson, in Proceedings of 2003 International Conference on Environmental Systems, Vancouver, British Columbia, Canada, 2003. 151. L. A. Johnson, D. J. Myers, and D. J. Burden, INFORM, 3, 282290 (1992). 152. L. A. Johnson, D. J. Myers, and D. J. Burden, INFORM, 3, 429444 (1992). 153. J. C. Endres, Soy Protein Products: Characteristics, Nutritional Aspects, and Utilization. AOCS Press, Champaign, Illinois, 2001. 154. C. T. Egger and R. E. Olson (assigned to Grain Processing Corporation, Muscatine, Iowa), U.S. Patent 3,849,391, November 19, 1974. 155. C. Y. Wang and L. A. Johnson, J. Amer. Oil Chem. Soc., 78, 189195 (2001). 156. P. A. Howard, M. Campbell, and D. T. Zollinger (assigned to Central Soya Co., Ft. Wayne, Indiana), U.S. Patent Re. 32,725, August 2, 1988. 157. S. Wu, P. A. Murphy, L. A. Johnson, A. R. Fratzke, and M. A. Reuber, J. Amer. Oil Chem. Soc., 76, 285293 (1999). 158. S. Wu, P. A. Murphy, L. A. Johnson, M. A. Fratzke, and M. A. Reuber, J. Agric. Food Chem., 48, 27022708 (2000). 159. K. H. Lee, H. S. Ryu, and K. C. Rhee, J. Amer. Oil Chem. Soc., 80, 8590 (2003).

REFERENCES

647

160. National Archives and Records Administration, Federal Register, 64, (206), 57699 57733 (1999). 161. Food and Drug Administration. Available: http://vm.cfsan.fda.gov/%7Elrd/fr991026.html. 162. M. Kock, J. Amer. Oil Chem. Soc., 60, 198202 (1983). 163. C. D. Evans, P. M. Cooney, C. R. Scholeld, and H. J. Dutton, J. Amer. Oil Chem. Soc., 31, 295297 (1954). 164. G. R. List, C. D. Evans, L. T. Black, and T. L. Mounts, J. Amer. Oil Chem. Soc., 55, 275 276 (1978). 165. Yearbook and Trading Rules (19931994), National Oilseed Processors Association, Washington, D.C., p. 86. 166. J. C. Seger and R. L. K. M. van de Sande, in D. R. Erickson, ed., World Conference Proceedings Edible Fats and Oils Processing: Basic Principles and Modern Practices, AOCS Press, Champaign, Illinois, 1990, pp. 8893. 167. A. J. Dijkstra, in T. A. Applewhite, ed., Proceedings of the World Conference on Oilseed Technology and Utilization, AOCS Press, Champaign, Illinois, 1992, pp. 138151. 168. C. Pagliero, N. Ochoa, J. Marchese, and M. Mattea, J. Amer. Oil Chem. Soc., 78, 793 796 (2001). 169. L. P. Raman, M. Cheryan, and N. Rajagopalan, J. Amer. Oil Chem. Soc., 73, 219224 (1996). 170. S. Subramanian, M. Nakajima, A. Yasui, H. Nabetani, T. Kimura, and T. Maekawa, J. Amer. Oil Chem. Soc., 76, 12471253 (1999). 171. G. R. List, J. W. King, J. H. Johnson, K. Warner, and T. L. Mounts, J. Amer. Oil Chem. Soc., 70, 473476 (1993). 172. K. J. Moulton and T. L. Mounts, J. Amer. Oil Chem. Soc., 67, 3338 (1990). 173. D. R. Erickson, in D. R. Erickson, ed., Practical Handbook of Soybean Processing and Utilization, AOCS Press, Champaign, Illinois, 1995, pp. 184202. 174. T. Wang and L. A. Johnson, J. Amer. Oil Chem. Soc., 78, 461466 (2001). 175. R. E. Beal, E. G. Lancaster, and O. L. Brekke, J. Amer. Oil Chem. Soc., 33, 619624 (1956). 176. E. Hernandez, Abstracts: 92nd AOCS Annual Meetings and Expo, Minneapolis, 2001, p. S98. 177. T. Wang and L. A. Johnson, J. Amer. Oil Chem. Soc., 78, 809815 (2001). 178. M. Y. Jung, S. H. Yoon, and D. B. Min, J. Amer. Oil Chem. Soc., 66, 118120 (1989). 179. D. R. Erickson, in D. R. Erickson, ed., Practical Handbook of Soybean Processing and Utilization, AOCS Press, Champaign, Illinois, 1995, pp. 203217. 180. D. R. Erickson and M. D. Erickson, in D. R. Erickson, ed., Practical Handbook of Soybean Processing and Utilization, AOCS Press, Champaign, Illinois, 1995, pp. 218 238. 181. G. R. List, W. E. Neff, R. L. Holliday, J. W. King, and R. Holser, J. Amer. Oil Chem. Soc., 77, 311314 (2000). 182. Y. Chu and L. Lin, J. Amer. Oil Chem. Soc., 69, 880883 (1992). 183. K. J. Moulton, R. E. Beal, and E. L. Grifn, J. Amer. Oil Chem. Soc., 50, 450454 (1973). 184. S. Koritala, J. Amer. Oil Chem. Soc., 54, 267268 (1977). 185. T. L. Mounts, in D. R. Erickson, E. H. Pryde, O. L. Brekke, T. L. Mounts, and R. A. Falb, eds., Handbook of Soybean Oil Processing and Utilization, AOCS Press, Champaign, Illinois, 1980, pp. 131144.

648

SOYBEAN OIL

186. R. C. Hastert, in Y. H. Hui, ed., Baileys Industrial Oil and Fat Products, vol. 4: Edible Oil and Fat Products: Processing Technology, 5th ed., John Wiley & Sons, Inc., New York, 1996, pp. 213300. 187. M. Kellens, in W. Hamm and R. J. Hamilton, eds., Edible Oil Processing, Shefeld Academic Press, Shefed, U.K., 2000, pp. 129173. 188. T. Okamoto, T. Tsutsumi, S. Tokairin, H. Ehara, T. Maruyama, I. Niiya, and M. Sugano, Jpn. Inst. Oil & Fat, 48, 877883 (1999). 189. Z. Kemeny, K. Recseg, G. Henon, K. Kovari, and F. Zwobada, J. Amer. Oil Chem. Soc., 78, 973979 (2001). 190. W. F. De Greyt, M. J. Kellens, and A. D. Huyghebaert, Fett/Lipid, 101, 428432 (1999). 191. W. De Greyt and M. Kellens, in W. Hamm and R. J. Hamilton, eds., Edible Oil Processing, Shefeld Academic Press, Shefed, U.K., 2000, pp. 79128. 192. T. W. Kwon, H. E. Snyder, and H. G. Brown, J. Amer. Oil Chem. Soc., 61, 18431846 (1984). 193. T. Verleyen, U. Sosinska, S. Ioannidou, R. Verhe, K. Dewettinck, A. Huyghebaert, and W. De Greyt, J. Amer. Oil Chem. Soc., 79, 947953 (2002). 194. R. Krishnamurthy and M. Kellens, in Y. H. Hui, ed., Baileys Industrial Oil and Fat Products, vol. 3: Edible Oil and Fat Products: Products and Application Technology, 5th ed., John Wiley & Sons, Inc., New York, 1996, pp. 193223. 195. A. Wendel, in M. Howe-Grant, ed., Kirk-Othmer Encyclopedia of Chemical Technology, vol. 15, 4th ed., John Wiley & Sons, New York, 1995, pp. 192210. 196. O. L. Brekke, in D. R. Erickson, E. H. Pryde, O. L. Brekke, T. L. Mounts, and R. A. Falb, eds., Handbook of Soy Oil Processing and Utilization, AOCS Press, Champaign, Illinois, 1980, pp. 7188. 197. L. Teberikler, S. Koseoglu, and A. Akgerman, J. Amer. Oil Chem. Soc., 78, 115119 (2001). 198. Y. Z. Wu and T. Wang, J. Amer. Oil Chem. Soc., 80, 127132 (2003). 199. Y. Wu and T. Wang, J. Amer. Oil Chem. Soc., 80, 319326 (2003). 200. G. R. List, in B. F. Szuhai, ed., Lecithins: Source, Manufacture & Uses, AOCS Press, Champaign, Illinois, 1989, pp. 145161. 201. M. D. Pickard, T. J. Jones, and R. T. Tyler, in Y. H. Hui, ed., Baileys Industrial Oil and Fat Products, vol. 4: Edible Oil and Fat Products: Processing Technology, 5th ed., John Wiley & Sons, Inc., New York, 1996, pp. 603630. 202. R. L. Winters, in D. R. Erickson, ed., Proceedings: World Conference Edible Fats and Oils Processing, Basic Principles and Modern Practices, AOCS Press, Champaign, Illinois, 1990, pp. 402405. 203. J. P. Clark and S. S. Frandsen, in S. S. Koseoglu, K. C. Rhee, and R. F. Wilson, eds., Proc. World Conf. Oilseed Edible Oils Process, vol. 1, AOCS Press, Champaign, Illinois, 1998, pp. 135138. 204. M. R. Law, Western Journal of Medicine, 173, 43 47 (2000). 205. L. Normen, P. Dutta, A. Lia, and H. Andersson, Amer. J. Clin. Nutr., 71, 908913 (2000). 206. P. Hollingsworth, Food Tech., 55, 5962 (2001). 207. K. B. Hicks and R. A. Moreau, Food Techol., 55, 6367 (2001). 208. H. Wu, X. Weng, O. Qiu, and L. Li, Shanghai Daxue Xuebao-Ziran Kexueban, 7, 331 333 (2001).

REFERENCES

649

209. Y. Shimada, S. Nakai, M. Suenaga, A. Sugihara, M. Kitano, and Y. Tominaga, J. Amer. Oil Chem. Soc., 77, 10091013 (2000). 210. C. J. Chang, Y. Chang, H. Lee, J. Lin, and P. Yang, Ind. Eng. Chem. Res., 39, 45214525 (2000). 211. C. E. Sumner, Jr., S. D. Barnicki, and M. D. Dol (to Eastman Chemical Co.), U.S. Patent 5,424,457, June 12, 1995. 212. P. Golbitz, Soya & Oilseed Blue Book, Soyatech, Inc., Bar Harbor, Maine, 2000. 213. R. S. Daniels, Can. Patent 1,256,449, June 27, 1989. 214. R. Stern, G. Hillion, P. Gateau, and J. C. Guibet, in A. R. Baldwin, ed., Proceeding: World Conference on Emerging Technologies in the Fats and Oils Industry, AOCS Press, Champaign, Illinois, 1986, pp. 420422. 215. H. N. Basu, and M. E. Norris (to Agricultural Utilization Research Institute), U.S. Patent 5,525,126, June 11, 1996. 216. M. J. Haas and K. M. Scott, J. Amer. Oil Chem. Soc., 73, 13931401 (1996). 217. M. J. Haas, S. Bloomer, and K. Scott, J. Amer. Oil Chem. Soc., 77, 373379 (2000). 218. M. J. Hass, K. M. Scott, P. J. Michalski, and S. Runyon (to Runyon Industries), U.S. Patent 2,003,158,074, August 21, 2003. 219. P. Golbitz, 2004 Soya & Oilseed Bluebook, Soyatech, Inc., Bar Harbor, Maine, 2004. 220. D. R. Kodali, INFORM, 14, 121123 (2003). 221. H. Eierdanz, in T. Applewhite, ed., Proceedings of the World Conference on Oilseed Technology and Utilization, AOCS Press, Champaign, Illinois, 1992, pp. 221223. 222. L. Crandall, INFORM, 13, 626631 (2002). 223. Annonymous, Oils and Fats, 17(6), 1819 (2001). 224. F. Sliney, INFORM, 12, 1018 (2001). 225. G. Knothe, INFORM, 13, 900903 (2001). 226. R. Ohlson, in T. Applewhite, ed., Proceedings of the World Conference on Oilseed Technology and Utilization, AOCS Press, Champaign, Illinois, 1992, pp. 221223. 227. American Soybean Association, St. Louis, MO. (2003). http://www.soystats.com/2003/ page_24.htm. 228. Yearbook and Trading Rules 20032004, National Oilseed Processors Association, Washington, D.C., 2003. 229. E. F. Sipos and B. F. Szuhaj, in Y. H. Hui, ed., Baileys Industrial Oil and Fat Products, vol. 2, 5th ed., John Willey & Sons, Inc., New York, 1996, pp. 497601. 230. E. R. Sherwin, J. Amer. Oil Chem. Soc., 53, 430436 (1976). 231. Q. Chen, H. Shi, and C. Ho, J. Amer. Oil Chem. Soc., 69, 9991002 (1992). 232. National Archives and Records Administration, Federal Register, 68, (133), (2003). Available: http://fda.gov/OHRMS/DOCKETS/98fr/03 17525.htm. 233. W. W. Nawar, in D. B. Min and T. H. Smouse, eds., Flavor Chemistry of Fats and Oils, AOCS Press, Champaign, Illinois, 1985, pp. 3960. 234. G. Paquette and D. B. Kupranycz, Can. Inst. Food Sci. Technol. J., 18, 197206 (1985). 235. I. P. Freeman, F. B. Padley, and W. L. Sheppard, J. Amer. Oil Chem. Soc., 50, 101103 (1973). 236. M. A. Augustin and S. K. Berry, J. Amer. Oil. Chem. Soc., 60, 15201523 (1983).

650

SOYBEAN OIL

237. M. H. Gordon and L. Kourimska, Food Chem., 52, 175 (1994). 238. P. J. White, C. P. Su, and M. Gupta, in American Oil Chemists Society annual meeting abstract book, pp. 4546 (2003). 239. K. Warner and S. Knowlton, J. Amer. Oil Chem. Soc., 74, 13171322 (1997). 240. C. P. Su and P. J. White, in American Oil Chemists Society annual meeting abstract book, p. 132 (2003). 241. Code of Federal Regulations, Food and Drug Administration, Washington, D.C. 242. H. J. Basset, Cereal Foods World, 24(1), 79, 24, 25, 29, 30 (1979). 243. A. Moustafa, in D. Erickson, ed., Practical Handbook of Soybean Processing and Utilization, AOCS Press, Champaign, Illinois, 1995, pp. 339362. 244. J. A. Segura, M. L. Herra, and M. C. Anon, J. Amer. Oil Chem. Soc., 72, 375378 (1995). 245. A. J. Haighton, J. Amer. Oil Chem. Soc., 36, 345348 (1959). 246. F. Cho, J. M. deMan, and O. B. Allen, J. Food Lipids, 1, 2552 (1993). 247. E. A. Emken, Ann. Rev. Nutr., 4, 339376 (1984). 248. V. DSouza, L. deMan, and J. M. deMan, J. Amer. Oil Chem. Soc., 68, 153162 (1991). 249. R. Wood, in C. K. Chow, ed., Fatty Acids in Foods and Their Health Implications, Marcell Dekker, New York, 1992, pp. 663688. 250. R. P. Mensink and M. B. Katan, N. Engl. J. Med., 323, 439445 (1990). 251. H. B. Hu, M. J. Stampfer, J. E. Manson, E. Rimm, G. A. Colditz, B. A. Rosner, C. H. Hennekens, and C. W. Willet, N. Engl. J. Med., 337, 14911499 (1997). 252. G. R. List, E. A. Emken, W. F. Kwolek, T. D. Simpson, and H. J. Dutton, J. Amer. Oil Chem. Soc., 54, 408413 (1997). 253. H. H. Hustedt, J. Amer. Oil Chem. Soc., 53, 390392 (1976). 254. M. A. M. Zeitoun, W. E. Neff, G. R. List, and T. L. Mounts, J. Amer. Oil Chem. Soc., 70, 467471 (1993). 255. C. Hoy and X. Xu, in F. D. Gunstone, ed., Structured and Modied Lipids, Marcel Dekker, Inc., New York, 2001, pp. 209239. 256. M. D. Erickson, in D. R. Erickson, ed., Practical Handbook of Soybean Processing and Utilization, AOCS Press, Champaign, Illinois, 1995, pp. 277296. 257. G. R. List, T. Pelloso, F. Orthoefer, M. Chrysam, and T. L. Mounts, J. Amer. Oil Chem. Soc., 72, 383384 (1995). 258. G. R. List, T. L. Mounts, F. Orthoefer, and W. E. Neff, J. Amer. Oil Chem. Soc., 73, 729 732 (1996). 259. G. R. List, T. Pelloso, F. Orthoefer, K. Warner, and W. E. Neff, J. Amer. Oil Chem. Soc., 78, 103104 (2001). 260. L. L. Kok, W. R. Fehr, E. G. Hammond, and P. J. White, J. Amer. Oil Chem. Soc., 76, 11751181 (1999). 261. C. E. Stauffer, Fats and Oils, Eagan Press, American Association of Cereal Chemists, St. Paul, Minnesota, 1996. 262. W. M. Smith, Bakers Dig., 53(8), 810 (1979). 263. H. Birnbaum, Bakers Dig., 52(2), 2836 (1978). 264. A. E. Thomas, J. Amer. Oil Chem. Soc., 55, 830833 (1978). 265. F. R. Paulicka, J. Amer. Oil Chem. Soc., 53, 421424 (1976).

REFERENCES

651

266. R. D. OBrien, in D. Erickson, ed., Practical Handbook of Soybean Processing and Utilization, AOCS Press, Champaign, Illinois, 1995, pp. 363379. 267. J. H. Hetrick, J. Amer. Oil Chem. Soc., 46, 58A, 60A, 62A (1969). 268. S. A. Schlicker and C. Regan, Topics Clin. Nutr., 6, 5060 (1990). 269. T. Nagao and T. Teramoto, Rinsho Eiyo, 99, 414418 (2001). 270. M. G. Soni, H. Kimura, and G. A. Burdock, Food Chem. Toxicol., 39, 317329 (2001). 271. N. Matsuo and I. Tokimitsu, INFORM, 12, 10981102 (2001). 272. T. Yasukawa and K. Yasunaga, J. Oleo Sci., 50, 427432 (2001). 273. C. Watkins, INFORM, 14, 70 (2003). 274. Anonymous, Oils and Fats, 17(1), 1819 (2001). 275. C. Su, Fatty Acid Composition of Oils, Their Oxidative, Flavor, and Heat Stabilities and the Resultant Quality in Foods, Ph. D. Dissertation, Parks Library, Iowa State University, Ames, Iowa, (2003). 276. Y. H. Hui, in Y. H. Hui, ed., Baileys Industrial Oil & Fat Products, vol. 2, 5th ed., John Wiley & Sons, Inc., New York, 1996, pp. 497601. 277. T. H. Smouse, J. Amer. Oil Chem. Soc., 56, 747A750A (1979). 278. H. J. Dutton, in K. Warner and N. A. M. Eskin, eds., Methods to Assess Quality and Stability of Oils and Fat-Containing Foods, American Oil Chemists Society, Champaign, Illinois, 1995, pp. 116. 279. E. N. Frankel, in D. R. Erickson, E. H. Pryde, O. L. Brekke, T. L. Mounts, and R. A. Falb, eds., Handbook of Soy Oil Processing and Utilization, AOCS Press, Champaign, Illinois, 1980, pp. 229244. 280. E. H. Farmer, G. F. Bloomeld, A. Sundralingam, and D. A. Sutton, Trans Faraday Soc., 38, 348356 (1942). 281. M. B. Korycka-Dahl and T. Richardson, CRC Critical Reviews in Food Science and Nutrition, 10, 209241 (1978). 282. P. J. Ke and R. G. Ackman, J. Amer. Oil Chem. Soc., 50, 429435 (1973). 283. D. J. Carlsson, T. Suprunchuk, and D. M. Wiles, J. Amer. Oil Chem. Soc., 53, 656660 (1976). 284. J. M. deMan, in C. K. Chow, ed., Fatty Acids in Foods and Their Health Implications, Marcel Dekker, Inc., New York, 1992, pp. 1746. 285. R. J. Hsieh, in C.-T. Ho and T. G. Hartman, eds., Lipids in Food Flavors, ACS Symposium Series 558, American Chemical Society, Washington, D.C., 1994, pp. 3048. 286. E. N. Frankel, Prog. Lipid Res., 19, 122 (1980). 287. P. J. White, in R. D. OBrien, W. E. Farr, and P. J. Wan, eds, Fats and Oils Technology, 2nd ed., AOCS Press, Champaign, Illinois, 2000, pp. 341353. 288. H. W. Gardner, in H. W.-S. Chan, ed., Autoxidation of Unsaturated Lipids, Academic Press, Inc., London, 1987, pp. 5194. 289. E. N. Frankel, in D. B. Min and T. H. Smouse, eds., Flavor Chemistry of Fats and Oils, AOCS Press, Champaign, Illinois, 1985, pp. 137. 290. E. N. Frankel, Prog. Lipid Res., 22, 133 (1982). 291. E. N. Frankel, Prog. Lipid Res., 23, 197221 (1985). 292. M. D. Dixon and E. G. Hammond, J. Amer. Oil Chem. Soc., 61, 14521456 (1984).

652

SOYBEAN OIL

293. I. Lee, S. H. Fatemi, E. G. Hammond, and P. J. White, J. Amer. Oil Chem. Soc., 72, 539 546 (1995). 294. J.-L. Kao, E. G. Hammond, and P. J. White, J. Amer. Oil Chem. Soc., 75, 1103 (1998). 295. L. Liu, and E. G. Hammond, J. Food Quality, 23, 521 (2000). 296. K. Liu, Inform, 10, 868878 (1999). 297. M. H. Gordon, in B. J. F. Hudson, ed., Food Antioxidants, Elsevier Applied Science, New York, 1990, pp. 1318. 298. J. Loliger, in D. B. Min and T. H. Smouse, eds., Flavor Chemistry of Lipid Foods, AOCS Press, Champaign, Illinois, 1985, pp. 303325. 299. S. J. Bishov, A. S. Henick, J. W. Giffee, I. T. Nil, P. A. Prell, and M. Wolf, J. Food Sci., 36, 532535 (1971). 300. D. Firestone, ed., Ofcial Methods and Recommended Practices of the American Oil Chemists Society, 4th ed., AOCS Press, Champaign, Illinois, 1993. 301. D. L. Hamm, E. G. Hammond, V. Parvanah, and H. E. Snyder, J. Amer. Oil Chem. Soc., 42, 920922 (1965). 302. C. Paqout, ed., Standard Methods for the Analysis of Oils, Fats and Derivatives, 7th ed., Pergamon Press, New York, 1987. 303. G. Yildiz, R. L. Wehling, and S. L. Cuppett, J. Amer. Oil Chem. Soc., 80, 103107 (2003). 304. P. J. White, in K. Warner and N. A. M. Eskin, eds., Methods to Assess Quality and Stability of Oils and Fat-Containing Foods, AOCS Press, Champaign, Illinois, 1995, pp. 159178. 305. I. H. Rukunudin, P. J. White, C. J. Bern, and T. B. Bailey, J. Amer. Oil Chem. Soc., 75, 563568 (1998). 306. G. Billek, G. Guhr, and J. Waibel, J. Amer. Oil Chem. Soc., 55, 728732 (1978). 307. J. I. Gray, J. Amer. Oil Chem. Soc., 55, 539546 (1978). 308. J. Pawliszyn, in J. Pawliszyn, ed., Solid Phase Microextraction: Theory and Practice, Wiley-VCH, Inc., New York, 1997, pp. 97140. 309. H. H. Jelen, M. Obuchowska, R. Zawirska-Wojtasiak, and E. Wasowicz, J. Agric. Food Chem., 48, 23602367 (2000). 310. D. D. Roberts, P. Pollien, and C. Milo, J. Agric. Food Chem., 48, 24302437 (2000). 311. C. D. Evans, G. R. List, R. L. Hoffman, and H. A. Moser, J. Amer. Oil Chem. Soc., 46, 501504 (1969). 312. R. G. Scholz and L. R. Ptak, J. Amer. Oil Chem. Soc., 43, 596599 (1966). 313. H. P. Dupuy, S. P., Fore, and L. A. Goldblatt, J. Amer. Oil Chem. Soc., 50, 340342 (1973). 314. H. P. Dupuy, E. T., Rayner, and J. I. Wadsworth, J. Amer. Oil Chem. Soc., 53, 628631 (1976). 315. K. Warner and T. J. Nelsen, J. Amer. Oil Chem. Soc., 73, 157166 (1996). 316. G. Paquette and D. B. Kupranycz, Can. Inst. Food Sci. Technol. J., 18, 197206 (1985). 317. G. R. List, in D. R. Erickson, E. H. Pryde, O. L. Brekke, T. L. Mounts, and R. A. Falb, eds., Handbook of Soy Oil Processing and Utilization, AOCS Press, Champaign, Illinois, 1980, pp. 267354.

REFERENCES

653

318. Iowa State University Extension. (2003). Available: http://www.extension.iastate.edu/ Publications/4H956.pdf. 319. K. G. Stern, and Grossman H. S., (to H. Sobotka), U.S. Pat. 2,842,577 (1958). 320. J. M. DeMan, in C. K. Chow, ed., Fatty Acids in Foods and Their Health Implications, Marcel Dekker, Inc., New York, 1992, pp. 1746. 321. A. Bonanome and S. M. Grundy, N. Engl. J. Med., 318, 12441248 (1988). 322. S. M. Grundy and M. A. Denke, J. Lipid Res., 31, 11491172 (1990). 323. S. H. Fatemi and E. G. Hammond, Lipids, 15, 379385 (1980). 324. S. M. Grundy, L. Florentin, D. Nix, and M. F. Whelan, Amer. J. Clin. Nutr., 47, 965969 (1988). 325. R. T. Holman, S. B. Johnson, and P. L. Ogburn, Proc. Natl. Acad. Sci. USA, 88, 4835 4839 (1991). 326. W. E. M. Lands, in Fish and Human Health, Academic Press, Inc., Orlando, Florida, 1986. 327. P. M. Kris-Etherton, W. S. Harris, and L. J. Appel, Circulation, 106, 27472757 (2002). 328. J. M. King and P. J. White, in L. Jackson, ed., Impact of Processing on Food Safety, Kluwer Academic/Plenum Publishers, New York, 1999, pp. 5165. 329. K. Almendingen, O. Jordal, P. Kierulf, B. Sandstad, and J. I. Pedersen, J. Lipid Res., 36, 13701384 (1995). 330. R. L. Wolff, J. Amer. Oil Chem. Soc., 69, 106110 (1992). 331. R. L. Wolff, J. Amer. Oil Chem. Soc., 70, 219224 (1993). 332. J.-L. Sebedio, A. Grandgiard, C. Septier, and J. Prevost, Rev. Francas Corps Gras, 34, 1518 (1987). 333. R. L. Wolff, J. Amer. Oil Chem. Soc., 70, 425430 (1993). 334. K. Almendingen, O. Jordal, P. Kierulf, B. Sandstad, and J. I. Pedersen, J. Lipid Res., 36, 13701384 (1995). 335. A. Grandgirard and F. Juilliard, Rev. Francais Corps Gras, 34, 213219 (1987). 336. A. Grandgirard, A. Piconneaux, J. L. Sebedio, S. F. OKeefe, E. Semon, and J. L. Lequere, Lipids, 24, 799804 (1989). 337. J. M. Chardigny, J. L. Sebedio, and A. Granddirard, in A. Sinclair and R. Gibson, eds., Essential Fatty Acids and Eicosanoids, AOCS Press, Champaign, Illinois, 1992, pp. 148152. 338. L. Bretillon, J. M. Chardigny, J. P. Noel, and J. L. Sebedio, J. Lipid Res., 39, 22282236 (1998). 339. J. R. Judd, B. A. Clevidence, R. A. Muesing, J. Wittes, M. E. Sunkin, and J. J. Podczasy, Amer. J. Clin. Nutr., 59, 861868 (1994). 340. L. Kohlmeier and M. Mendez, Proc. Nutri. Soc., 56, 369383 (1997). 341. M. G. Enig, S. Atal, M. Keeney, and J. Sampugna, J. Amer. College Nutr., 9, 471486 (1990). 342. D. M. Klurfeld and Kritchevsky, INFORM, 3, 515516 (1992). 343. U.S. Department of Agriculture and U.S. Department of Health and Human Services, Nutrition and Your Health: Dietary Guidelines for Americans, 3rd ed., Home and Garden Bulletin No. 232, Washington D.C., 1990.