14

Sunower Oil
Maria A. Grompone 1. HISTORICAL REVIEW Sunower (Helianthus annuus L.), one of the most ancient oilseed species in North America, belongs to the family Compositae (Asteraceae) and the genus Helianthus. Cultivation of sunower dates from times earlier than 3000 B.C., as indicated by archeological evidence obtained in sites once inhabited by the Hopi Indians, in the north of Arizona. According to other archaeological ndings and traditional tales, sunower was cultivated by indigenous people throughout central North America (from New Mexico to the Dakotas) and eastward (Pennsylvania and Ontario). It appears that sunower was domesticated in America even before corn was. Single-head plants were preferred by the indigenous people, who differentiated them from multiplehead plants growing wildly. Some tribes ate fruits directly, or ground into a meal that was baked in the form of bread. Other tribal practices included boiling of heads, and crushed roots, for the treatment of disease and bites. The oil extracted from seeds was used as body and hair ointment. Seeds, petals, and pollen were used in the preparation of facial and body makeup, and for dying cloth and utensils (12). Sunower was introduced into Europe by the Spanish explorers returning to the continent at the beginning of the 1500s A.D. The rst scientic review of American s Bautista Monardes (15081588), who plants was made by Sevillan doctor Nicola wrote Historia medicinal de las cosas que se traen de nuestras Indias Occidentales (A medical review of things brought from the West Indies, published in Seville in

Baileys Industrial Oil and Fat Products, Sixth Edition, Six Volume Set. Edited by Fereidoon Shahidi. Copyright # 2005 John Wiley & Sons, Inc.

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three volumes, in 1565, 1571, and 1574). It was in this study that sunower was rst mentioned. Monardes, who never traveled to America, described those plants that reached him and which he grew in a Botanic Garden designed for this purpose. He also gathered information that he obtained from navy captains, missionaries, and travelers. There is also a description of sunowercontemporaneous with the work of Monardesin a herbarium made by Rembert Dodoens in 1568. Even though this and other later herbaria attribute the origin of sunower to Peru and Central America, it is now believed to have originated in North America. Starting from Spain, sunower crops spread rapidly through France and Italy, and toward the north and east of Europe. In several regions, it was a source of smoking leaves, owers for consumption in salads, or for the manufacture of paint, edible, and medicinal seed, and cooking oil. But it was, perhaps, the beauty in the inorescence of sunowers that interested the rst growers, large and bright yellow, always facing the sun. Hence, the name of the genus, Helianthus, derived from the Greek helios meaning sun and anthos meaning ower; and its Spanish, English, French, and German words: girasol, sunower, tournesol and Sonnenblumen. It was not until the eighteenth century that sunower seeds were used as oilseed. According to records, the rst patent of oil extraction for industrial use was granted to Arthur Bunyan in 1716 in England, where reference is made to an English seed that could be pressed yielding sweet oil of great value for those interested in the manufacture of wool, paint, leather, and so on. Seeds of double- and single-head owers, known as sunowers, were indicated for oil extraction (2). In Russia, it was introduced by Peter I the Great, Czar between 1682 and 1725, who, having seen sunowers in the Netherlands, took seeds to Russia. It was in Russia where the most important development took place in the use of sunower as both food and oil source. The Russian Orthodox Church banned the consumption of several foods during Lent and Advent (periods of the religious calendar dedicated to fasting and penitence), including several sources of oil. As the ban did not include sunower seeds, they were adopted as an oil source. Rapidly, sunower spread through Russia, the earliest records of cultivation dating from 1770. The extraction of oil from sunower seeds was rst suggested in 1779, according to Russian Academy proceedings. The cultivated area increased rapidly as a result of the development of the sunower oil extraction industry, Russia being the worlds rst and largest sunower producer until current times. Once the value of the crop had been recognized, commercial production was started in 1880 over 150,000 hectares, a gure that reached one million hectares toward 1910. Pioneering and fundamental research work has been carried out in Russia since 1860 concerning the improvement of seed for oil content. Toward the end of the nineteenth century, improved Russian cultivars were introduced in the Balkans leading to the expansion of sunower crops. The crop did not reach northern Europe owing to the lack of cultivars adapted to cold climates. Sunower was the main Russian crop already at the beginning of the twentieth century. In 1912, scientist V. S. Pustovoit started research work in the elds of the Kuban region. Krasnodar was Russias experimental oilseed selection center, since

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1924. The Pustovoit All Union Research Institute was founded in 1932 and named after V. S. Pustovoit for his valuable contributions (Pustovoit was in charge of the Breeding Department until his death in 1972). Pustovoits work led to an improvement in the oil content and seed yield. The average oil content of a Russian cultivar was 330-g oil per kilogram seed in 1940, reaching values as high as 550 g per kilogram in strains developed by Pustovoit in 1965. Hybridization of sunower resulting from natural cross-breeding, performed in seed-producing elds with parents planted in alternating lines, led to major advances in research. It enabled improvements of yield in USSR cultivars and rapid disease control, as well as increases of oil content and other issues of agronomical interest. Most remarkable among these open-pollinated varieties was the Peredovik, named after the Russian agronomist. Two major events in the 1960s had a marked effect on the sunower industry worldwide: the introduction of USSR cultivars of high oil content, and the discovery of cytoplasmic male sterility and fertility-restoring genes. Male sterile sunowers were obtained in 1968 by Leclercq from the offspring of an interspecic hybrid between the cultivated sunower and wild sunower Helianthus petiolaris. The identication of fertility-restoring genes of several breeders led to hybrids of special characteristics. Open-pollinated cultivars were rapidly replaced by hybrids of higher yield, uniformity, and disease resistance. Currently, hybrid seeds are widely used for cheap and efcient production throughout the world (3). Sunower crops cultivated in North America are derived from seeds introduced by eastern European immigrants toward the end of the nineteenth century; hence, the name Russian Peanuts. Russian emigrants in the United States and Canada grew strains such as Giant or Mammoth Russian in gardens for the production of edible seeds. These served as a base for the development of improved cultivars for commercial production. The cultivated area in the United States reached 200,000 acres in 1968; most of which was destined to the production of seed for manufacture of food for human consumption, and to the bird meal market (4). An open-pollinated Russian-bred cultivar of high oil content (Peredovik variety, 40 45%) was introduced in the United States in 1966 (3). Commercial production of oilseed-type sunower was started with the Peredovik variety among other cultivars, and since 1966, several research programs in the United States have sought to improve sunower hybrids for oil yield. Around 1960, the USSR interrupted the supply of sunower oil to Europe, because of the high internal demand, including satellites, thus leaving an unattended sector in the European market, where consumption of tallow and butter were then indicated as causes of coronary disease. The high content of polyunsaturated fatty acids (PUFA) of sunower oil naturally interested many American and Canadian oil industries, with the consequent increase in sunower production in the late 1970s (1). Russian immigrants carrying sunower seeds introduced the crop into Argentina in the nineteenth century, for human consumption of seeds. Cultivation of the crop was performed at small-scale initially, and it was not until the world economic crisis of 1930 that it was rst sown intensively to supply the internal market, in

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replacement of imported oils. Around 1500 metric tons (MT) of sunower oil were produced in Argentina in 1930, a gure that reached 5000 MT in 1945. New, diseaseresistant varieties were developed as a result of the work of Experimental Stations of Argentinean National Institute of Agrarian Technology (INTA) and of private seed breeders. The appearance of hybrids characterized the Argentinean market in the period after 1975, although the rst hybrid had been launched in 1972. Almost 100% of the cultivated area is currently sown with hybrids. A higher seed and oil production capacity, together with the introduction of specialized upgraded technology, led to an increase in oil yield per hectare in Argentinean plantations. Seed yield levels increased from 0.73 tons per hectare in 19771978 2,200,000 hectares of sunower plantations producing 1,600,000 tons of seed to 1.38 tons per hectare in 1987-19882,117,000 hectares (2,915,000 tons) (1,2). 2. SUNFLOWER CROPS 2.1. General Characteristics The genus Helianthus comprises 68 known species divided into two major separate groups: the North American and the South American species. North American sunower species spread throughout the United States, reaching Canada and Mexico. Both groups do not seem to relate to each other; in South America, they appear to have originated by parallel evolution of the genus Viguiera (1). Sunower is a highly cross-pollinated crop. Wild sunowers have several owers or heads and depend on the work of insects for pollination. Wild sunowers are the genetic base of current commercial sunowers of a single ower or head per plant. Sunower is an annual crop. Plants reach 13 m in height. The head is composed of a large number of tiny owers that are tubular in shape (700 to 4000 single blossoms) forming a disk, those in the outer row having long strap-shaped corollas that form the rays of the composite ower. Plants have a large number of owers clustered in a capitulum, inorescence, or head. The back of the head is covered with small green bracts. Radial structures in the shape of petals are displayed over the bracts. These are known as ray owers, and they do not have a reproductive function other than serving as a signal for bees and other pollinizer insects. Toward the disk center, are a large number of complete tiny owers known as disk orets. Each of these owers is capable of bearing an achene or seed (a fruit from a strict botanical viewpoint). Those owers that form the rays are generally sterile, and although they have vestigial styles and stigmas, they do not possess anthers. Flowers yielding seed are complete, each with a tubular corolla and an anther. Sunower heads will follow the sun cycle until practically all owers comprising the head have been pollinated. After that, they remain in a xed position, facing eastward. Around 70 days are required from sowing to owering of the crop. Seeds reach maturity at 130 days and can be harvested 10 days later (45). Sunower grows in moderate climates (temperate to temperate-hot), especially in America, Europe, and China, predominantly at temperatures between 20 C and

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25 C, with an optimum temperature of 2728 C. It grows well in dry, sunny weather, in deep soils capable of supplying abundant water. The oil content of seeds is lower in regions of extreme heat. The crop has high resistance to temperature uctuations between night and day varying between 8 C and 34 C (1, 5). The highest yield in seed is achieved at temperatures between 18 C and 25 C through the period from formation to lling of the seed. Humidity conditions are critical during both 1520-day periods prior to and after owering. Improved lling of the seed takes place in periods without rain. Pollination is nearly all cross-type, i.e., from one ower to another. Crossing within one head is scarce. Insects, in particular bees, are the main fertilization agent (2). Climatic conditions in Argentina are ideal for cultivation of sunower in view of the varying degrees of inuence of the Atlantic Ocean. The buffering of thermal extremes between summer and winter (mean values in winter and summer of 8 C and 28 C), the circulation of east winds (allowing a rainfall range from 500 to 1100 mm annually), and the span of the period free of frost (over 6 months) are major climatic factors contributing to ensure the establishment and success of the cycle of sunower (6). In Argentina, the sunower is grown between latitudes 26 S (Chaco) and 39 S (southern Buenos Aires), over an area averaging 2.93 million hectares for 19902000 summer seasons. The cultivation environments include subtropical (northern Argentina) and temperate (central and southern) climate (7). Sunowers are ripe when the back of the head has turned from green to yellow and the bracts are turning brown. Harvest is done when the seed reaches commercial ripeness, that is, allowing time for the seed to dry from a 35% moisture content of heads at physiological maturity down to 11%. The harvest of seed-loaded, heavy fruits is advanced to prevent seeds falling off (2, 8). Drying agents such as magnesium chlorate may be used as an aid to advance harvesting. This practice readily reduces the moisture content of heads, stems, and leaves, but seeds retain most of their moisture. Articial drying of seeds is often necessary prior to storage. Seeds must be stored with moisture levels lower than 9.5% to avoid undesired enzymatic reactions. Some of these reactions start within 12 hours after harvesting for seeds with moisture higher than 20% (5). Seeding and harvesting periods obviously differ according to hemisphere of producer country. For Argentina and Uruguay, in the South Hemisphere, seeding is in October and harvesting between February and April, and in Australia, harvesting is between January and May. For countries in the Northern Hemisphere, such as ex-USSR, seeding is done in March and harvesting is between August and October; in the United States seeding is in April or May and harvesting is in September or October; in Spain and Italy, harvesting is in August (1, 5). 2.2. Yield of Sunower Crops Seed yield varies according to region. Maximum yield values in 1994 were obtained in Italy (2596 kg/ha), Greece (2577 kg/ha), and Austria (2544 kg/ha); minimum values were obtained in Tanzania (370 kg/ha). These values have been

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2000 1800 1600 Seed yield (kg/ha) 1400 1200 1000 800 600 400 200 0 1930 1940 1950 1960 1970 1980 1990 2000 world Argentina USA exUSSR

Figure 1. Evolution of seed yield (kg/ha) in the most important producer countries, as well as world average values (1, 5).

increased in the last years as a result of genetic improvements. Figure 1 shows the evolution of yield levels in major producer countries, as well as world average values (1, 5). 2.3. Structure of Sunower Seeds An achene, the seed of sunower, is pointed at the base and rounded at the top. Seed size ranges between 10 and 15 mm in length and between 4 and 12 mm in width, appearing to be four-sided in cross-section. The outer layer, the pericarp or hull, represents 1845% of the total achene weight. The white papery layer immediately beneath the pericarp, the testa or seedcoat, is made up of three parenchyma layers, the inner layer being spongy in texture. The endosperm comprises a single layer of cells rich in protein, rmly attached to the hull, and an embryo, commonly referred to as kernel. The embryo consists of two cotyledons attached to a protruding radicle (9). There are two basic types of sunower: (1) oilseed type and (2) nonoil type, the latter supplying the bird meal and confectionary markets. The rst hybrid oilseed types bore small black seeds with a thin hull (representing 2025% of total seed weight) with a 40% oil content. The non-oilseed type is somewhat different; it has a larger seed with a thicker black-and-white-striped hull (representing 40 45% of total seed weight), which is weakly attached to the kernel and can easily be removed. These seeds contain 30% of oil. The size of oil-type seeds varies according to cultivar and according to the seeds position in the head, those on the periphery being larger. Besides affecting the oil content, the position of seeds in the head inuences the fatty acid composition.

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ash 3%

oil 3%

protein 3%

N-free extract 31%

fiber 61%
Figure 2. Hull composition (1, 5, 11).

Internal seeds contain less oil than those in intermediate or external zones. The content of linoleic and palmitic acids increases, and the content of oleic acid decreases from the perimeter toward the ower head center (10). One thousand seeds of most currently used hybrids weigh from 30 to 80 g. Hull color ranges from completely white to black, with gray- or brown-striped intermediates. Both hull thickness and structure, as well as other seed characteristics, depend on variety and ambient growth conditions (9). The hull is mainly composed of brous substances, lignin and cellulosic materials in equal proportions. Kernels of oilseed-type sunower contain nearly all of the oil of seeds, besides proteinaceous substances and carbohydrates. The kernel represents 70% of the seed, with an oil content of approximately 55%, amounting to 40% with respect to the whole seed. The protein content ranges between 20% and 35%, amounting to up to 57% on a water-and-oil-free basis (1, 5, 11). A commonly occurring hull and kernel composition is shown in Figures 2 and 3, respectively, as well as of sunower meal in Figure 4. Data correspond to a fully dehulled meal, a condition difcult to obtain in practice (1, 5, 11). 2.4. The Inuence of Ambient Factors on Sunower Seed Oil The oil content of sunower seeds varies during the development of the seed: increasing from the fourteenth to the thirty-fth day after owering, when the seed is physiologically mature. The oil content remains steady after reaching maturity. Oil composition also changes during the formation and ripening stages of the seed. The linoleic acid content increases from the fourteenth day after owering while the oleic acid content decreases; also, saturated fatty acids decrease slightly (12).

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SUNFLOWER OIL

N-free extract 6% fiber 3%

ash 3%

protein 21%

oil 67%

Figure 3. Kernel (dehulled seed) composition (1, 5, 11).

Ambient factors, such as temperature and light, affect the oil composition of sunower seeds. Robertson and Russell (13) studied the effect of climatic conditions (temperature difference between night and day in Canada, Minnesota, and California) on the composition of sunower oil, nding that linoleic acid increased proportionally with increasing temperature difference. Robertson and Green (14) studied the effect of sowing time on oil content and composition. Eleven different hybrids
fiber 9%

N-free extract protein 63 % 19%

ash 8% oil 1%
Figure 4. Composition of fully dehulled meal (1, 5, 11).

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were used. Sowing was performed in February and August in Florida. The results show that the oleic acid content is lower (average: 19.4%) and that the linoleic acid content is higher (average: 68.4%) for seeds sown in August (lowest mean temperature from owering to maturity, 18 C). Seeds harvested in plantations sown at the beginning of April (highest mean temperature from owering to maturity, 27 C) have a lower content of linoleic acid (average: 36.3%) and a higher average content of oleic acid (54.6%). This indicates that adjustments in seeding time in Florida may lead to sunower oil of different compositions. Average temperature from owering to ripening appears to be a major factor affecting the fatty acid composition of sunower oil (15). The oleic/linoleic ratio was correlated with average temperature for different sunower plantations across Spain, average temperature being related not only to latitude, but also to other geographic factors that determine a microclimate of the crops. An increase in temperature resulted in a decrease in the linoleic acid content and an increase in the oleic acid content. The linoleic acid content ranged from 48.7% in seeds grown in warmer weather in the south of Spain to 70.2% for colder weather plantations. The addition of the contents of linoleic and oleic acids is not constant with temperature, the increase in oleic acid being greater than the decrease in linoleic acid, with a partial compensation by a reduction in the stearic acid content, suggesting the conversion of stearic acid to oleic acid. The above mechanism is related to the effect of temperature on the activity of desaturase enzymes converting oleic into linoleic acid. Research carried out with sunower crops grown in controlled temperature chambers 20/10 C (day/night) and 30/20 C (day/night) with equal light intensity and photoperiod, demonstrated a decrease in the linoleic/oleic ratio with increasing temperature (16). An increase in temperature also leads to a slight decrease in the stearic acid content. Similar results were obtained by authors in different countries, like France, Italy, Japan, the United States, Canada, and so on (17). This is because those enzymes involved in the sequence of steps leading to the formation of linoleic acid are alike in all higher plants; that is, all oilseed crops have a common enzyme base catalyzing the synthesis of fatty acids, producing varying amounts of 16:0, 18:0, 18:1, 18:2, and 18:3. Among a number of studies carried out in different regions worldwide, the composition of sunower seeds was determined for six different Argentinean regions (18). For the latitudes considered, according to region, mean ambient temperature during the development period of seed decreased from 28 C to 20 C southward. The linoleic acid content was found to decrease, and the oleic acid content increased with increasing temperature. A similar behavior was observed for sunower seeds grown in Japan (19). 2.5. Sunower Associations The International Sunower Association (ISA), with main ofces in Paris aims to enhance international cooperation toward the improvement of cultivation, growth, and technical and nutritional levels, besides promoting and facilitating close

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cooperation relations among researchers. ISA holds an International Conference on Sunower every four years. In addition, there is a national association in different countries. The U.S. National Sunower Association (NSA) with main ofces in Bismarck, North Dakota, promotes the production and trade of sunower products both at national and international levels. Founded in 1981, it currently has 20,000 members. The Australian Sunower Association was established in 1976; the membership of the ASA consists of growers, researchers, and personnel from all facets of the industry. The National Sunower Association of Canada (NSAC) was founded in 1996, with 105 members in 1999. The Argentinean Sunower Association (ASAGIR), created in 1980, hosted the Eleventh International Conference on Sunower in 1985.

3. CHEMICAL AND PHYSICAL PROPERTIES OF REGULAR SUNFLOWER OIL 3.1. Composition of Regular Sunower Oil Sunower oillike most vegetable oilsis composed mainly of triacylglycerols (9899%), and a small fraction of phospholipids, tocopherols, sterols, and waxes (all of the latter are commonly referred to as the unsaponiable fraction). Regular sunower oil is characterized by a high concentration of linoleic acid, followed by oleic acid. Saturated fatty acids (mainly palmitic acid and stearic acid) do not amount to more than 15% of the fatty acid content. Table 1 shows the variation range of major fatty acids in regular sunower oil (9, 20). Two facts regarding the composition of regular sunower oil are worth noting from the nutritional viewpoint: It provides an essential fatty acid (linoleic acid), and it has a low content of palmitic acid compared with other oils (palmitic acid is believed to increase LDL-C in blood). The reported composition of regular sunower oil has changed with adjustments of analytical methods and the samples considered. This is reected in the variation ranges approved successively by the Codex Alimentarius Comission. The values approved in 1981 and 1993 (21) are compiled in Table 2, as well as the current
3.1.1. Sunower Fatty Acids

TABLE 1. Variation Range for Major Fatty Acids (%) of Regular Sunower Oil (9, 20). Fatty Acid 16:0 18:0 18:1 18:2 18:3 AOCS (20) 58 2.57.0 1340 4074 <0.3 Merrien (9) 57 46 1525 6270 <0.2

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TABLE 2. Variation Range for Fatty Acids (%) of Regular Sunower Oil According to Standards Approved by the Codex Alimentarius Commission in Different Years. Fatty Acid 12:0 14:0 16:0 16:1 17:0 17:1 18:0 18:1 18:2 18:3 20:0 20:1 22:0 22:1 22:2 24:0 24:1 1981 <0.5 310 <1.0 1993 <0.2 5.67.6 <0.3 1999 ND0.1 ND0.2 5.07.6 ND0.3 ND0.2 ND0.1 2.76.5 14.039.4 48.374.0 ND0.3 0.10.5 ND0.3 0.31.5 ND0.3 ND0.3 ND0.5 ND

110 1465 2075 00.7 01.5 00.5 010 00.5 ND 00.5 <0.5

2.76.5 1439.4 48.374.0 00.2 0.20.4 00.2 0.51.3 00.2 00.3 0.20.3 ND

ND nondetectable, dened as 0.05%.

value of 1999 (Codex-Stan 210-1999). The Codex Alimentarius Commission (Codex) was established in 1962 by two United Nations organizations, the Food and Agriculture Organization (FAO) and the World Health Organization (WHO). Codex is the major international organization for encouraging fair international trade in food and protecting the health and economic interests of consumers. The Codex Committee on Fats and Oils (CCFO) was established to elaborate worldwide standards for fats and oils and their products. The Codex Alimentarius is thus taken as reference. According to the composition indicated by the Codex Alimentarius (Codex-Stan 210-1999), the saturated fatty acid content of regular sunower oil is lower than that in corn (maximum 22%), cottonseed (maximum 32%), peanut (maximum 28%), and soybean (maximum 20%) oils, and higher than the saturated content of safower (maximum 12%) and rapeseed (maximum 12%) oils. The linolenic acid content (18:3) of regular sunower oil is fairly low (always lower than 0.3%), giving the oil a good oxidative stability. The variation ranges of fatty acids in regular sunower oil have also changed in several countries. The Canola Council of Canada revised the table of composition of edible oils prepared in 1979, based on a study carried out by the POS Pilot Plant Corporation in Saskatoon, Saskatchewan, Canada. POS analyzed ten vegetable oils and three animal fats supplied by food processing and manufacturing enterprises of Canada and the United States, according to one issue of Canada Digest (22). Average regular sunower oil compositions are shown in Table 3 for Canada and the United States, as well as for Argentina (2, 23).

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TABLE 3. Average Composition (%) of Regular Sunower Oil for Canada/United States (normalized to 100%) and Argentina, Elaborated in Different Years (2, 22, 23). Fatty Acid saturated 18:1 18:2 Canada/U.S. 1979 (22) 11 20 69 Canada/U.S. 1994 (22) 12 16 71 Argentina 1981 (23) 8.7 24.0 66.0 Argentina 1998 (2) 10.1 26.8 62.2

3.1.2. Triacylglycerol Composition

Figure 5 shows the composition in major triacylglycerols (above 1%) of regular sunower oil [based on Prevot (17)]. As expected from its high linoleic acid content, the main triacylglycerol is trilinolein (36.3%), followed by oleo-dilinolein (29.1%); triolein being practically nonexistent (0.6%). Thus, the percentage of triacylglycerols (TAG) with four or more double bonds is higher than 80%. This TAG distribution is responsible for the low solidication point of regular sunower oil (16 C to 19 C), allowing, for example, storage of mayonnaise manufactured with regular sunower oil in a refrigerator without breakage of the emulsion (unlike the case of other oils such as peanut oil). Rossell et al. (24) analyzed the triacylglycerols of 20 regular sunower oil samples, regarding the total number of carbon atoms. The content of 54-carbon TAG was 75.179.5%. The composition of these triacylglycerols is OOO, SOL, OOL, SLL, OLL, and LLL. Grouping the data provided by Prevot (17) in the same manner, the 54-carbon TAG content would be 82.1%. Thus, the results of both works are to a large extent in agreement.

40 35 30 25 20 15 10 5 0 SOL POL OOL SLL Triacylglycerol PLL OLL LLL

Figure 5. Composition in major triacylglycerols (above 1%) of regular sunower oil [based on (17)]. (Key: P palmitic acid, S stearic acid, O oleic acid, L linoleic acid.)

Percentage

CHEMICAL AND PHYSICAL PROPERTIES OF REGULAR SUNFLOWER OIL

667

40 35

experimental
30

random
25 Percentage 20 15 10 5 0 SatOL OOL SatLL LLO LLL

Figure 6. Triacylglycerol composition of regular sunower oil as calculated from random distribution and experimentally determined (17). (Key: Sat saturated acid, O oleic acid, L linoleic acid.)

The 1,2,3-random hypotheses assumes that one pool of fatty acids is randomly distributed to all three positions of the glycerol molecules in an oil. The fatty acid compositions of the sn-1, sn-2, and sn-3-positions would thus be equivalent. Figure 6 shows the theoretical composition of regular sunower oil as calculated by the equations of random distribution. Calculation of the random distribution was based on the following composition: 11% saturated fatty acids (Sat), 20% oleic acid (O), and 69% linoleic acid (L). The TAG composition of a regular sunower oil determined experimentally is also shown; there is no indication of the overall fatty acid composition (17). Differences between both compositions are not great, in particular, taking into account the fact that the fatty acid composition may differ for the oils considered. Fatty acids are not randomly distributed in natural oils. Saturated fatty acids are almost exclusively concentrated in the sn-1,3 positions and are practically nonexistent in the sn-2 position (taxonomic pattern). Linoleic acid clearly has a higher occurrence in the sn-2 position. For example, out of a total 16.239.3% linoleic acid in peanut oil, the sn-2 position has 27.267.8%, clearly showing the concentration of linoleic acid in this position (24). Table 4 shows the fatty acid distribution in the sn-2 position with respect to the composition of the sn-1 and sn-3 positions (25) or with respect to the overall composition of the sunower oil samples analyzed (24). Occurrence of 18:2 is slightly higher in the sn-2 position than it would be if distributed in equal proportions among all three positions. The occurrence of linoleic acid is also slightly higher in the sn-2 position than in the sn-1,3 positions by a ratio of 1.27. As the content of linoleic acid is particularly high in regular sunower oil, the preferential distribution of linoleic acid is less apparent than for other vegetable oils. Saturated fatty

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TABLE 4. Distribution of Fatty Acids in the sn-2 Position with Respect to the sn-1 and sn-3 Positions (25) or with Respect to the Overall Sunower Oil Composition (24). lvarez-Ortega et al. (25) A 16:0 18:0 18:1 18:2 sn-1 sn-3 9.2 6.1 34.0 50.7 sn-2 0.5 0.4 34.7 64.2 Rossell et al. (24) overall 5.76.9 3.06.3 14.034.4 55.573.2 sn-2 0.20.4 0.10.3 12.131.3 66.287.4

acids have a tendency to concentrate in the sn-1 and sn-3 positions, hardly ever occurring in the sn-2 position. Oleic acid occurs equally among all three positions. However, differences are small, resulting in an apparent agreement between the TAG prole determined experimentally and the fatty acid distribution calculated on a supposed random distribution (as indicated in Figure 6).
3.1.3. Nonacylglycerol Components of Regular Sunower Oil 3.1.3.1. Phospholipids The phospholipid content of crude sunower oil ranges

between 0.5% and 1.2%. Oils extracted by solvent generally have a higher content of phosphlipids than those obtained by pressing. Major phospholipids are phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, and phosphatidic acid. Most are hydratable and may be removed from the crude oil through a water-degumming process (See Section 5.3.1.)
3.1.3.2. Tocopherols Tocopherols are heterocyclic compounds with a phenolic

group and a substituted side chain of branched hydrocarbon. Their high solubility in oil is caused by a long alkyl side chain. The Codex Alimentarius (Codex-Stan 210-1999) indicates levels of tocopherols and tocotrienols in crude regular sunower oil (mg/kg), compiled in Table 5.

TABLE 5. Levels of Tocopherols and Tocotrienols in Crude Regular Sunower Oil (ppm), According to the Codex-Stan 210-1999. Content (ppm) Alpha-tocopherol Beta-tocopherol Gamma-tocopherol Delta-tocopherol Alpha-tocotrienol Gamma-tocotrienol Delta-tocotrienol Total
ND nondetectable.

403935 ND45 ND34 ND7.0 ND ND ND 4401520

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The biological value of tocopherols differs according to isomer. Their importance as Vitamin E activity is the following: alpha > beta > gamma > delta. Vitamin E functions primarily as an antioxidant, especially in preventing oxidation and peroxidation of polyunsaturated fatty acid units of membrane phospholipid (within and on the plasma membrane of cells). The value of regular sunower oil as a source of Vitamin E is enhanced by a high content of alpha-tocopherol. Similar conclusions can be found in the literature for tocopherols of Argentinean sunower oil: 700 ppm of total tocopherols, 91% of which corresponds to alphatocopherol (2). Tocopherols also function as free radical scavengers. The alpha form has the highest Vitamin E activity, and gamma-tocopherol has the highest antioxidant activity. In one study, sunower tocopherols were added to stripped soybean oil, and soybean tocopherols were added to stripped sunower oil. The stability pattern of sunower oilgenerally less stable than soybean oilmimicked that of soybean oil. With the added sunower tocopherols, the stability pattern of soybean oil resembled that of sunower oil. The results suggest that gamma-tocopherol is a better antioxidant than the alpha isomer (26). Other authors, however, attribute a higher antioxidant activity to alpha-tocopherol. Disagreement with respect to the relative antioxidant activity of tocopherol homologs may be because of differences in the degree of unsaturation of the substrates used, the degree of oxidation achieved in the measurement, and the method of oxidation analysis. Figure 7 shows a comparison of maximum values for major tocopherols in crude regular sunower, peanut, soybean, corn, and cottonseed oils, according to the Codex Alimentarius (Codex-Stan 210-1999). Among these, regular sunower oil has the highest tocopherol level. In general, gamma-tocopherol is the most widely occurring isomer in vegetable oils.
4000 3500 total 3000 Content (ppm) 2500 2000 1500 1000 500 0 corn soybean sunflower peanut cottonseed gamma delta alpha

Figure 7. Maximum values of major tocopherols (ppm) of crude sunower, peanut, soybean, corn, and cottonseed oils, according to the Codex Alimentarius (Codex-Stan 210 -1999).

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SUNFLOWER OIL

TABLE 6. Levels of Desmethylsterols in Crude Regular Sunower Oil, as a Percentage of Total Sterols and Total Sterol Content (ppm), According to Codex-Stan 210-1999. Cholesterol (%) Brassicasterol (%) Campesterol (%) Stigmasterol (%) -sitosterol (%) -5-avenasterol (%) -7-stigmasterol (%) -7-avenasterol (%) Others (%) Total sterols (mg/kg) <0.7 ND0.2 7.412.9 7.011.5 56.265.0 ND6.9 7.024.0 3.16.5 ND5.3 24004600

ND nondetectable, dened as <0.05%.

3.1.3.3. Sterols Sterols are polycyclic alcohols derived from sterane. Sterols con-

stitute most of the unsaponiable fraction of an oil. The sterol prole is characteristic of each oil. The Codex Alimentarius (Codex-Stan 210-1999) indicates the total sterol content (ppm) and the percentages of each sterol type in regular sunower oil, as shown in Table 6. Among vegetable oils, regular sunower oil is characterized by a medium sterol content. According to the Codex Alimentarius (Codex-Stan 210-1999), the oils with the highest sterol content are rapeseed oil (low erucic acid), with 480011,300-ppm sterols; corn oil with 800022,100 ppm, and sesame oil with 450019,000 ppm. In regular sunower oil, the main component is b-sitosterol, followed by -7stigmasterol. The latter may be used as a tracer for detection of adulterations in sunower oil, as most vegetable oils (except safower oil) have fairly low amounts of -7-stigmasterol (less than 7%).
3.1.3.4. Other Components of the Unsaponiable Matter

The unsaponiable matter in a crude regular sunower oil is usually in the range of 0.51.5% (9, 17), or lower than 15 g/kg according to the Codex-Stan 210-1999. In addition to sterols (around 2.44.6 g/kg) and tocopherols and tocotrienols (0.41.5 g/kg), there are minor components of sunower oil. Aliphatic compounds and terpenoids occur naturally in oils. Of the terpenoid family, squalene is the most widely occurring compound. The occurrence of squalene in regular sunower oil is fairly low: 0.0080.019% (5) or 1520 mg/100 g (9). The aliphatic alcohol content is 100mg/100-g oil (9). Carotenoids and chlorophylls are the major lipochromes of vegetable oils. Crude regular sunower oil is not particularly rich in carotenoids (as palm oil is) or in chlorophylls (like rice bran, rapeseed, olive, and avocado oils). This gives crude regular sunower oil its light-amber color, turning to pale yellow upon the bleaching operation.

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3.2. Chemical Characteristics of Regular Sunower Oil The Codex Alimentarius (Codex-Stan 210-1999) indicates the characteristics of crude regular sunower oil: (1) saponication value 188194-mg KOH/g oil; (2) iodine value (calculated from the fatty acid composition) 118141. However, Merrien (9) reports an iodine value of 120134, and Bockisch (5) reports a value in the range of 110143 (Wijs method). 3.3. Physical Characteristics of Regular Sunower Oil
3.3.1. Refractive Index The refractive index is a characteristic property of fats and oils and may be used as a fast measurement of the advance of a hydrogenation operation. The Codex Alimentarius (Codex-Stan 210-1999) indicates a refractive index (nD) of regular sunower oil in the range of 1.4611.468 at 40 C; Merrien (9) reports the range 1.4741.476 at 20 C. 3.3.2. Density Determinations of the content of tanks or ow rates are usually

based on methods of volumetric dosing. These methods are used to facilitate equipment automation. However, mass determinations based on volume measurements will depend on the nature and temperature of an oil. The Codex Alimentarius (Codex-Stan 210-1999) indicates a relative density of regular sunower oil in the range of 0.9180.923 (20 C/water at 20 C). The values suggested by the Codex do not differ appreciably from the expected values for most vegetable oils. Figure 8 shows the temperature dependence of the density (g/mL) of an Indian edible sunower oil [based on Subrahmanyam et al. (27)].

0.96 0.95 0.94 Density (g/cc) 0.93 0.92 0.91 0.9 0.89 0.88 30

10

10

30 Temperature (C)

50

70

90

Figure 8. Temperature dependence of the density (g/cc) of an Indian edible sunower oil [based on (27)].

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SUNFLOWER OIL

60

50 Dynamic Viscosity (cP)

40

30

20

10

0 20 25 30 35 40 45 50 55 60 Temperature (C)

Figure 9. Temperature dependence of the dynamic viscosity (cP) of rened sunower oil [based on (28)].

3.3.3. Viscosity The viscosity of an oil is a fundamental parameter when pump-

ing is required. The viscosity of a vegetable oil will depend on the fatty acid composition. Oils with hydroxylated fatty acids (like castor oil and lesquerelle oil) have a particularly high viscosity. Figure 9 shows the temperature dependence of the dynamic viscosity (cP) of rened sunower oil. The curve corresponding to the crude oil is along the same curve [based on Abramovic and Klofutar (28)].
3.3.4. Specic Heat and Combustion Heat The specic heat of sunower oil

at constant pressure is 2.197 J/kg  C (29). The energy content or combustion heat of an oil is a major parameter when used as an energy source. The gross heat contents of all vegetable oils are fairly close to each other. Ali and Hanna (30) report a gross heat content of regular sunower oil of 39,575 kJ/kg, and Bhattacharyya and Reddy (31) a value of 39,486 kJ/kg.
3.3.5. Smoke Point, Flash Point, and Fire Point

The smoke point, ash point, and re point of an oil are relevant parameters in deep-fat frying processes. The fatty acid composition of the oil is not relevant (unless the oil has short-chain fatty acids, as is the case of butter or coconut oil). The most important effect is generally that of free fatty acids (FFA) in the oil. The following values have been reported for fully rened sunower oil (with 0.10% free fatty acids): smoke point 209 C; ash point 316 C; re point 341 C (5). The ash point is also an important parameter when considering the possibility of using an oil as an alternative diesel fuel in ignition engines. The ash points of all vegetable oils are far above that of diesel fuel, reecting the nonvolatile nature

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of vegetable oils. Ali and Hanna (30) report a value of 274 C for the ash point of regular sunower oil.
3.3.6. Melting Characteristics

The cloud point is the temperature at which solids rst become visible when an oil is cooled. The pour point is the temperature at which the amount of solids out of solution is sufcient to gel the liquid; thus, it is the lowest temperature at which the oil is uid. The above parameters are relevant when pumping oils at low temperatures or for their use as alternative diesel fuel in ignition engines. The cloud points and pour points of the vegetable oils are higher than for diesel fuel. Widely varying values have been reported in the literature for regular sunower oil. For example, Bockisch (5) reports a cloud point of 10 C (and a solidication point in the range 16 to 18 C). Ali and Hanna (30) report a cloud point of 7.2 C and a pour point of 15.0 C. Differences between reported cloud points are possibly caused by a varying degree of winterization of the oils considered.
3.3.6.1. Cloud Point and Pour Point 3.3.6.2. Thermal Behavior of Regular Sunower Oil Crude regular sunower oil

is a liquid at room temperature. The rened oil resists refrigerator temperatures without the appearance of turbidity. These characteristics make it suitable as salad oil. The thermal behavior of an oil may be determined within wide temperature ranges through methods of nuclear magnetic resonance (NMR) or through differential scanning calorimetry (DSC). Both methods allow the evaluation of indices related to the solid content as a function of temperature.

Power

Sunflower oil Soybean oil

-60

-40

-20

20

40

Temperature (C)
Figure 10. Thermograms of a rened sunower oil and of a rened soybean oil (32).

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SUNFLOWER OIL

100

80

Sunflower oil
60

Soybean oil
SFI 40

20

0 -60 -40 -20 Temperature (C) 0 20 40

Figure 11. Solid fat content (SFI) of a rened regular sunower oil and a rened soybean oil (32).

The thermogram of an oil determined by DSC allows the study of thermal behavior, and the evaluation of the solid percentage from the area of peaks. This information is characteristic of the fatty material considered. The thermograms of a rened regular sunower oil and a rened soybean oil (32) are compared in Figure 10. It is clear that melting of sunower oil is practically complete above 15 C. Soybean oil, however, has a second, smaller peak between 5 C and 5 C, which corresponds to a higher content of saturated fatty acids. Figure 11 shows the solid content as a function of temperature for both oils, as determined by partial integration of peaks in the above thermograms (32).

4. SUNFLOWER SEED OF MODIFIED FATTY ACID COMPOSITION Until two decades ago, the fatty acid composition of vegetable oils was closely related with their origin. The fatty acid prole of sunower oil was thus dened within natural variation ranges. Current practices, however, are widely based on the production of oilseed of modied fatty acid composition. Several methods have been developed to this end. The genetic diversity of wild sunower allowed researchers to obtain a number of varieties of dened characteristics. The North Central Regional Plant Introduction Station (Iowa), which gathers dozens of species, has distributed materials to researchers and companies interested in either the study or use of these materials. The sunower germplasm collection of the U.S. Department of Agriculture (USDA) is the largest and most complete collection worldwide, including wild materials from 48 U.S. states, as well as samples from Canada and Mexico. The

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program of the U.S. Department of Agriculture/Agricultural Research Service (USDA/ARS) evaluates wild material according to oil content and composition. Most breeding programs are aimed at the development of hybrids, although other projects are for the improvement of open-pollinated varieties and synthetic cultivars. In view of the improvements in yield, disease resistance, uniformity, and self-compatibility achieved in some modications, open-pollinated varieties have been replaced by hybrids. Varieties have been produced with increased oil content of seeds and/or improvements in oil composition. Inbreeding has been used since 1920 for the improvement of sunower, the most common method consisting in the self-pollination of those phenotypically desirable plants within the existing cultivars. The progeny of the best plants are sown in the following season, and the selection procedure is continued among the resulting progeny. A variation of recurrent selection, the method of reserves, developed by Pustovoit in the USSR, consists of the evaluation of progeny and subsequent crosspollination among superior progenies. In order to obtain hybrid seeds, self-pollination and pollination by a sibling plant must be avoided. It is sought to develop a female parental line accepting pollen from other lines (cross-pollination), without reproduction of its own line. This can be achieved directly through emasculation, i.e., elimination of the pollenbearing organ, usually at the expense of large labor requirements. Other methods can be used to induce male sterility. Modications in the characteristics of sunower are obtained through crosses to recombine genes from two sexually compatible parents. Both for self pollination and for controlled crosses, it is important that heads be isolated before owering to avoid natural cross-pollination. Emasculation of the female parent is used for the production of articial hybrids. Acid-induced male sterile plants pollinated without emasculation are also used. These hybrids were produced by natural crossing in seed production elds (breeding nursery), with the two parents planted in alternating groups of rows. The rst hybrid cultivars were introduced in Canada for commercial production in 1946 (4). Cytoplasmic male sterility of sunower was discovered in 1958, whereby one factor in the cell cytoplasm leads to the male-sterility in all plants of the second generation. However, as a result of the pollination of fertile ordinary lines, plants will still bear some fertile progeny. Patrice Leclercq, in France, in 1969, reported on cytoplasmic male sterility obtained in the progeny of a cross of Helianthus petiolaris Nutt and Helianthus annuus. In 1970, fertility restorer lines were found. Two years later, hybrid seeds produced by this system were made available to farmers. In 1976, 80% of the U.S. sunower harvest had been produced on hybrid seed. The production of single crosses or three-way hybrids using cytoplasmic male sterility and nuclear fertility restorer system is widely used. Genic male sterility was used for the production of hybrid seeds in the early 1970s in France and Romania. The rst hybrids produced in this way were introduced in the United States in 1972 (4). Various genetically different types of cultivar are commercially available. In open-pollination varieties, each individual is genetically different from another

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among the population. This results in a high level of adaptation to different environment conditions on the one hand, but it may also cause handling difculties because of the lack of phenotypical uniformity. Open-pollination varieties may be recovered yearly by the producer, the regular purchase of new seed being necessary only for maintenance of purity and type. Commercial hybrid cultivars include single and three-way hybrids. The former type is produced by crossing two lines, resulting in genetically identical individuals; the latter are developed by crossing a single hybrid with a homozygote line. Seed must be procured yearly by the producer in both cases. The production of high-quality hybrid seeds does not only depend on the use of parental lines of superior class, but also on the degree of isolation of the cultivation eld from other sunower plantations, including wild varieties. The isolation conditions cannot be accurately established, in view of the role of insects as pollination agent, and the long viability period of pollen; yet, recommendations have been made. Genetic variation occurring naturally within crop species is scarce. Additional genetic modication strategies are required to generate variants of a certain fatty acid prole. Such variants may be included in crossing programs for the development of cutivars or strains of interest. Modications in the fatty acid prole of an oil may be achieved through techniques of mutagenesis, Stable genetic mutations may be induced by use of chemical mutagens, such as ethyl methyl sulfonate. This procedure was used in the USSR to develop sunower seeds of improved oleic acid content. 4.1. Modication of the Saturated Fatty Acid Content The consumption of fat of high saturated fatty acid content has been associated with increased risk of coronary heart disease. Traditional sunower oil contains around 1112% saturated fatty acids, a considerably low value among vegetable oils. Canola oil has 7% and safower oil less than 10% of saturated fatty acids, both being strong competitors of the edible oil market. Since 1992, the National Sunower Association (NSA) has supported a cultivation program developed by researchers of the USDA/ARS for a reduction of the saturated content of sunower oil. New germplasm stocks with reduced content of palmitic and stearic acids were made available. They were developed through continuous selection starting from a sunower accession collected in Egypt around 1950. Several private companies have also carried out investigations aiming at obtaining hybrids of low saturated fatty acid content (6% or lower). Cultivators of Pioneer Hi-Bred International Incorporation managed to reduce the stearic acid content to 1.5% for commercial products. SVO Enterprises and Triumph Seed Company developed research lines aiming at reducing the saturated quantity in high-oleic sunower oil (3334). With a view to nding new industrial uses of vegetable oils, the saturated fatty acid content may also be increased. Three high stearic acid sunower mutants, having as much as 28%, 15%, and 14% of stearic acid in the seed lipids have been

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biochemically characterized (35). An increased solid content of the oil could be obtained in the oil without requiring hydrogenation, although such an increase may not meet nutritional standpoints. 4.2. High-Oleic Sunower The typical sunower oil composition is 6672% linoleic acid, 12% saturated acids (palmitic and stearic), 1620% oleic acid, and less than 1% a-linolenic acid. An increase in low-density lipoprotein cholesterol (LDL-C) and a decrease of highdensity lipoprotein cholesterol (HDL-C) are believed risk factors of coronary heart disease (CHD). Diets rich in saturated fat increase plasma total and LDL-C. Traditional high-linoleic sunower oil has always been regarded as healthy because of its high content of polyunsaturated fatty acids (PUFA) and relatively low content in saturated fatty acids. The substitution of saturated fatty acids by PUFA in a diet leads to a reduction of total cholesterol and LDL-C. It has been suggested that a high intake of polyunsaturated fatty acids leads to a decrease of HDL-C. Some authors have proved this theory based on rather unrealistic high PUFA in the diet (PUFA/MUFA > 3). Others have found statistically nonsignicant decrease values for HDL-C in more realistic high PUFA diets. An increased intake of monounsaturated fatty acids (MUFA) also leads to a decrease in total cholesterol and of LDL-C levels without reducing HDLC even with fairly high MUFA intake values. As oleic acid is more stable against oxidation than linoleic acid, consumption of MUFA has further advantages over PUFA. It is recommended to avoid foods containing peroxidized lipids, as these might be initiators of pathologic processes. In view of the considerations above, new genetic strategies were started toward a high-oleic sunower oil (HOSO). There is also controversy over the importance of MUFA over PUFA from the metabolic viewpoint. Great emphasis is placed on the distinction between the n-3 PUFA and those of the n-6 family. An increased intake of n-3 and a reduced intake of n-6 are recommended in light of the competitive metabolism of both families of fatty acids. As linoleic acid is a n-6 parent, a reduction of its intake favors the n-3/n-6 ratio; on the other hand, it is also an essential fatty acid. High-oleic sunower oil, with very low PUFA levels, may well suit the requirements of processors, but it does not support the work of nutritionists who recommend n-6/n-3 ratios within the range 5 to 10. In addition, HOSO does not represent an increased intake of family n-3 fatty acids as recommended by nutritionists, the linolenic acid content being very low for all types of sunower oil. K. I. Soldatov, in Russia, developed high-oleic sunower seeds through the treatment of normal seed with a chemical mutagen (dimethyl sulfate). Through programs of selected breeding, a number of plants containing seed with as much as 8090% oleic acid were obtained. L. N. Kharachenko, also in Russia, studied the standard Peredovik progeny and the Pervenets progenyobtained from treatment of seeds of the former variety with a chemical mutagen. It seems that modications in the seed genotype of high-oleic Pervenets are responsible for an irreversible blockage of the desaturating enzyme system. G. N. Fick developed progenies of

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cultivar Pervenets in plantations in the United States, Argentina, and Chile and incorporated the dominant genes into hybrids that were suitable for commercial production. High-oleic seeds were rst grown commercially in the United States in 1984 (3637). The Lubrizol Corporation obtained U.S. patents (granted to Sigco and inventor Gerhardt N. Fick) for sunower seeds and oils of oleic acid content of 80% or higher and linoleic/oleic ratios lower than 0.09Patent 4,627,192 for seed granted on December 9, 1986, and Patent 4,743,402 for oils granted on May 10, 1988. SVO Enterprises, a division of Agrigenetics Company, which is a part of The Lubrizol Corporation, has produced high-oleic sunower oil trademarked under the name Trisun in the United States (3334, 38). High-oleic sunower oil is sold in Australia under the name Sunolaa registered trademark of Meadow Lea Foods. The seed variety was bred by Australian farmers through traditional selective breeding techniques. The rst Sunola crop was developed in Queensland. The oils fatty acid composition is 85% monounsaturated, 8% polyunsaturated, and 7% saturated. The composition of oil extracted from Sunola seed in the rst stages of ripening resembles that of regular sunower varieties. Only when the synthesis of oil has actually started (some three weeks after owering) does the oleic acid content start to increase considerably and the linoleic content start to decrease rapidly (39). A further approach to modied sunower oils was made by the Agriculture Canada Research Station in Saskatoon (Saskatchewan) from two different types of dwarf early-ripening sunower trademarked under the name Sunola (Western Grower Seed Corp. was created for commercialization and further improvement of Sunola). One of these types was regular high-linoleic Sunola, which was rst produced commercially in 1993. The hybrid was specially developed for farmers in regions of the west of Canada where cultivation of sunower was nonexistent because of a short growing season. The fatty acid composition of this oil is 72 74% linoleic acid (owing to the colder growth conditions), 14% oleic acid, and 12% saturated acids. The other hybrid is high-oleic Sunola sunower, whose production started in 1995. The ripening time of high-oleic Sunola is about 100 days (three weeks shorter than for most sunower crops). The fatty acid composition is 87% oleic acid, 5% linoleic acid, and 78% total saturated acids. Seeds of this type are smaller than regular sunower seeds, the hull being slightly lighter and bearing a narrow stripe (3334, 40). As both Sunola crops are special, care must be taken against contamination with traditional sunower or canola. However, this is rarely the case, as Sunola is grown in northern areas of the United States, where regular sunower is not grown and in areas of southern Canada that are too hot and dry for the development of canola crops. It is worth noting that the name Sunola for modied oils is used in Australia for high-oleic sunower oil, whereas, in Canada, it is a registered trademark of two oils of different composition: one of higher linoleic acid content than traditional sunower and another of high-oleic type. Care must be taken that this should not lead to confusion. Canadian Western Grower Seed Corporation has also developed

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TABLE 7. Fatty Acid Composition (%) of High-Oleic Sunower Oil (37, 41, 43). Fatty Acid 16:0 18:0 18:1 18:2 Vermeersch (41) 3 5 83 9 Krawczyk (43) 6.7 80.0 12.0 Purdy (37) 2.74.2 3.45.0 80.586.7 4.08.5

lines of Sunola with higher oleic acid content to be introduced in the cosmetics market. One of these has as much as 88% oleic acid. Purdy (37) reported on the fatty acid composition and other analytical characteristics of high-oleic sunower oil of the Pervenets variety cultivated in three regions of the United States. The oil content of seeds ranged between 43.3% and 47.9% (dry basis), the hull accounting for 2433% of total seed weight. Table 7 shows the fatty acid composition of high-oleic sunower oil (37, 41 43). Table 8 shows the chemical and physical characteristics of crude high-oleic sunower oil according to the Proposed Draft Amendment to the Codex Standard for Named Vegetable Oils (Alinorm 01/17). The Active Oxygen Method (AOM) value for rened oil extracted from seed of high-oleic Pervenets variety is 5156 hours, compared with 13 hours for regular oils (37). In another study, Purdy (36) extracted oil from high-oleic Pervenets seed and from high-linoleic seed. The saturated fatty acid content of these oils varies only slightly (811%); the main variation occurs in the oleic/linoleic ratio. Table 9 shows AOM values for rened sunower oils as a

TABLE 8. Chemical and Physical Characteristics of Crude High-Oleic Sunower Oil (Codex Alimentarius, Alinorm 01/17). Relative density (25 C/water at 20 C) Refractive index (ND 25 C) Saponication value (mg KOH/g oil) Iodine value Unsaponiable matter (g/kg) 0.9090.915 1.4671.471 182194 7890 <15

TABLE 9. AOM Time (hr) for Rened Sunower Oils of Different Oleic Acid Content [based on (36)]. Oleic Acid 26 % 51 % 79 % 83 % 89 % (regular) (regular) (high-oleic) (high-oleic) (high-oleic) AOM (hr) 11 18 38 60 100

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TABLE 10. Fatty Acid and Triacylglycerol Composition (%) of Regular Sunower Oil and of High-Oleic Sunower Oil [based on (25)]. Regular Oil Fatty Acid: 16:0 18:0 18:1 18:2 Triacylglycerol: sn-1 sn-3 16:0 18:0 18:1 18:2 sn-2 16:0 18:0 18:1 18:2 % 6.8 5.0 31.4 55.4 % 9.2 6.1 34.0 50.7 0.5 0.4 34.7 64.2 High-Oleic Oil % 5.3 3.8 88.3 1.4 % 5.1 5.8 87.4 1.6 0.3 98.6 1.1

function of the oleic acid content. Data presented show that the oxidative stability of this oil is enhanced considerably with an increase in the oleic acid content. Table 10 shows the triacylglycerol composition of high-oleic oil (derived from Pervenets) and of regular sunower oil, with practically no occurrence of saturated fatty acids in the sn-2 position for either oil (25). Although the content of oleic acid is high in both high-oleic sunower oil and olive oil, there is a higher content of saturated acids in olive oil. Their MUFA contents are similar, but the composition of triacylglycerols differs widely (Table 11). Whereas the triacyglycerol OOO (O oleic) is the main species in both oils, HOSO has a higher content, olive oil, in contrast, having a higher proportion of POO (P palmitic). Further differences are in the fatty acids occupying those positions other than sn-2, which is occupied by oleic acid in both oils. In addition, HOSO has a higher proportion of linoleic acid in position sn-2, whereas olive oil has more alinolenic acid (44) Another major difference between olive oil and HOSO is a most distinct avor of olive oil that characterizes it from HOSO and other oils. Extra virgin olive oil,
TABLE 11. Composition in Major Triacylglycerols (%) of Olive Oil and High-Oleic Sunower Oil (HOSO) [Based on (44)]. Major Triacylglycerols (%) POO OOO OLL
O oleic, P palmitic, L linoleic.

Olive Oil 30.5 49.9 0.3

HOSO 12.1 65.1 3.1

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TABLE 12. Sterol Composition (as Percentage of Total Sterols) of High-oleic Sunower Oil (According to Codex Alimentarius, Alinorm 01/17) and Olive Oil (20). Sterol Composition Campesterol (%) Stigmasterol (%) b-Sitosterol (%) 5-Avenasterol (%) 7- Stigmasterol (%) 7-Avenasterol (%) Others (%) Total sterols (mg/kg) High-Oleic Sunower Oil (Codex) 5.013.0 4.513.0 42.070 1.56.9 6.524.0 ND9.0 3.59.5 17005200 Olive Oil (20) 4.0 <4.0 75.0 414 0.5

ND nondetectable, dened as <0.05%.

being the preference of so many gourmets worldwide, is considered the nest choice oil. The similarity in the fatty acid composition of HOSO and olive oil may lead to cases of adulteration or fraud, in view of the price difference between the two oils. These adulterations may be difcult to detect through conventional analytical methods. The nature of an oil can be traced through a study of its sterol composition. The sterol composition of both oils is compared in Table 12. Clearly, for HOSO, b-sitosterol is the sterol with the highest occurrence (4270% of total sterols), followed by 7-stigmasterol (6.524%), campesterol (513%), and stigmasterol (4.5 13%). Although there are differences in the sterol composition of both oils, they are not large enough to enable easy analysis. Several studies have been aimed at the detection of a fraudulent addition of vegetable oils to olive oil. In particular, different analytical methods can be applied to determine blends of regular and high-oleic sunower oil with olive oil. The minimum sunower oil detection level depends on the analytical method used. For example, a minimum detectable level of 0.7% of regular or high-oleic sunower oil may be achieved through methods of sterol analysis, and analysis of the fatty acids will not enable detection of additions below 20% (45). High-oleic sunower oil is widely used as salad oil and cooking oil, because of its composition, light avor. A high content of oleic acid provides enhanced oxidative stability in frying processes. In addition, it does not require partial hydrogenation for an increase in product shelf-life, with the additional nutritional advantages. The effect of trans-fatty acids generated as byproducts of hydrogenation processes on the plasma lipoprotein prole is as adverse as that of saturated fatty acids, both increasing the concentration of LDL-C and reducing that of HDL-C (44). High-oleic sunower oil is sprayed on cereals, crackers, and cookies to retain freshness and crispness. It is also used in the manufacture of non-dairy creamers, snack foods, and frozen desserts. Special properties of oleic acid make high-oleic sunower oil a choice ingredient for cosmetic formulations. The AOM value of

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Florasun-90 (of International Flora Technologies Ltd.) is higher than 90 hoursa high value compared with less than 40 hours for high-oleic rapeseed oil and about 20 for sesame oil. Research has indicated that the oil is not skin-irritating or sensitizing. It may be used in suntanning products and cosmetics with a high content of natural lipids, such as bath oils, massaging oils, skin-care products, lipstick, and cosmetic cream bases (33, 34). High-oleic sunower oil is currently used in the manufacture of a lubricant for lianthe, is commercialized by diesel and gas motors. The product, denominated He the Tecnol Society (France). It is composed of 7080% high-oleic sunower oil and lianthe is a formulation type 5W40, with a high viscosity 2030% additives. He index and high uidity at ignition (41). 4.3. Mid-Oleic Sunower The production of high-oleic sunower oil with 80% or higher oleic acid content was protected under patents. However, the patent holder agreed to license breeding material for the development of mid-oleic sunower seed. In July 1995, the NSA decided to redirect efforts toward an increase in oleic acid. It was established that mid-oleic sunower should contain 65% oleic acid, no higher than 10% saturated acids, and the rest being linoleic acid, a balance that, according to research, provides in-process functionality in frying. Breeding a mid-oleic sunower requires at least one oleic parent. The USDA/ ARS Northern Crop Science Laboratory in Fargo, North Dakota, provided private companies with crossing lines of mid-oleic sunower. Hybrid seeds were developed by traditional crossing methods; no hybrids of transgenic sunower were used. The mid-oleic concentration appears to be controlled by a partially dominant major gene and one or more dominant minor modier genes (46, 47). In a market accustomed to HOSO and traditional high-linoleic sunower, the name NuSun seemed suitable and was trademarked by the NSA. Seed and other companies using the name NuSun in their commercial products should have authorization of the NSA. NuSun contains less than 10% saturated, 5075% monounsaturated, and 3032% polyunsaturated fatty acids, with less than 1% linolenic acid (46). Harvests of NuSun were rst commercialized in 1999. In 2000, Procter & Gamble chose NuSun for the manufacture of Pringles chips in North America, part of Europe, and Asia, nding a low rate of formation of polar compounds as compared with other oils, an important factor for extending product shelf-life (46, 48). Figure 12 shows the fatty acid composition (%) of regular, mid-oleic, and higholeic sunower oils according to the Proposed Draft Amendments to the Standard for Named Vegetable Oils (Report of the Eighteenth Session of the Codex Committee on Fats and Oils, London, 2003). Table 13 shows the composition in major triacylglycerols of mid-oleic sunower oil, compared with the composition of regular sunower oil (49). Clearly, there is a difference in the unsaturated triacylglycerol composition of both oils: mid-oleic sunower oil has a higher content of OOO, and regular sunower oil is richer in LLL and LLO (the addition of both contents amounting to 60.3%).

SUNFLOWER SEED OF MODIFIED FATTY ACID COMPOSITION

683

100 90 80 70 60 Percentage 50 40 30 20 10 0 minimum maximum minimum maximum minimum maximum 18:1 18:2 16:0 18:0

regular

mid-oleic

high-oleic

Figure 12. Fatty acid composition (%) for regular, mid-oleic, and high-oleic sunower oil (based on the Proposed Draft Amendments to the Standard for Named Vegetable Oils Committee on Fats and Oils, 2003).

Figure 13 shows the composition in major triacylglycerols of mid-oleic sunower oil (49), as compared with the calculated composition from a random distribution. The triacylglycerol distribution does not t the random model, the main differences being in the levels of OOL and OOO, the main triacylglycerols. In contrast, as shown in Figure 6, the fatty acid distribution in regular sunower oil TAG differs only slightly from the random distribution. Table 14 shows the chemical and physical characteristics of crude mid-oleic sunower oil according to the Proposed

TABLE 13. Composition in Major Triacylglycerides (%) of Mid-Oleic Sunower Oil, as Compared with the Composition of Regular Sunower Oil [Based on (49)]. Triacylglycerols LLL LLO LLP LOO LLS LOP OOO LOS POO SOO Mid-Oleic 11.5 12.1 4.1 8.3 2.7 2.6 40.2 1.6 5.7 5.4 Regular 32.4 27.9 10.7 6.7 7.4 4.8 1.7 2.2 0.6 0.4

L linoleic, O oleic, P palmitic, S stearic.

684
45 40 35 30 Percentage 25 20 15 10 5 0

SUNFLOWER OIL

experimental random

SatOL

SatLL

Sat OO

OOL

LLO

LLL

OOO

Figure 13. Triacylglycerol composition of mid-oleic sunower oil as calculated from random distribution and experimentally determined (49). (Key: Sat saturated acid, O oleic acid, L linoleic acid.)

Draft Amendments to the Standard for Named Vegetable Oils (Report of the Eighteenth Session of the Codex Committee on Fats and Oils, London, 2003). Table 15 shows the sterol composition of mid-oleic sunower oil according to the Proposed Draft Amendments to the Standard for Named Vegetable Oils (Report of the Eighteenth Session of the Codex Committee on Fats and Oils, London, 2003). Clearly, b-sitosterol is the sterol with the highest occurrence (5658% of total sterols), followed by campesterol (9.19.6%) and stigmasterol (9.09.3%). b-sitosterol is the main sterol in all three types of sunower oil (regular, mid-oleic, and high-oleic). 4.4. Semi-Dwarf and Dwarf Sunower The search for sunower varieties of dened characteristics was also aimed at a reduction of plant size and adaptation to other climates. Short-stature cultivars in
TABLE 14. Chemical and Physical Characteristics of Crude Mid-oleic Sunower Oil (According to the Proposed Draft Amendments to the Standard for Named Vegetable Oils, 2003). Relative density (25 C/water at 20 C) Refractive index (ND 25 C) Saponication value (mg KOH/ g oil) Iodine value Unsaponiable matter (g/kg) 0.9140.916 1.4611.471 190191 94122 <15

EXTRACTION AND PROCESSING OF SUNFLOWER OIL

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TABLE 15. Sterol Composition (as Percentage of Total Sterols) of Mid-Oleic Sunower Oil (According to the Proposed Draft Amendments to the Standard for Named Vegetable Oils, 2003). Sterol Composition Campesterol Stigmasterol b-Sitosterol 5-Avenasterol 7- Stigmasterol 7-Avenasterol Others Mid-Oleic Sunower Oil (%) 9.19.6 9.09.3 5658 4.85.3 7.77.9 4.34.4 5.45.8

sunower are classied as semi-dwarf (typical 1.20 m to 1.50 m high) and dwarf (typical 0.80 m to 1.20 m high) types. Dwarf cultivars were developed more recently and include dwarf hybrids and dwarf open-pollinated cultivars. Two types of hybrid denominated Sunola and Sunwheat were developed in Canada to address the handling problems caused by traditional hybrids, requiring special machinery adapted only to the long growing season areas in southeastern Saskatchewan. These new hybrids are 2535% shorter than regular sunower (hence the denomination miniature or dwarf), allowing use of the same machinery as is used for cereal or canola production. Both early maturing types offer producers in short-growing-season areas the opportunity to diversify rotations. Sunola is a miniature type of sunower developed by the Agriculture Canada Research Station in Saskatoon as a sowing alternative for areas where growth of traditional sunower is not viable. It is the result of persistent selection of openpollinated varieties. Plant height is small (6090 cm), and heads are 813 cm in diameter. Ripening time is 99103 daysthree weeks shorter than for most sunower varieties. Sunola has a high oil content (similar to that of the best hybrids) and a higher content of linoleic acid (7274%) than any other commercial sunower. Sunwheat is a dwarf hybrid of sunower, having leaves and heads of similar size to other hybrids, but short (96120 cm). Ripening time is 100110 days, and the oil content is slightly lower than that of Sunola. It is appropriate for cultivation in barren areas and has a higher resistance to extreme-heat summer periods.

5. EXTRACTION AND PROCESSING OF SUNFLOWER OIL The procedures used for the extraction and processing of sunower oil are broadly the same as for other seed oils. Focus will be made on those operations or details specic of the production of sunower oil. Sunower oil is usually extracted through pressing of seed and later extraction by solvent. The crude oil is usually subjected to traditional rening stages. Otherwise, cold-pressed sunower oil is currently valued as a new extra virgin oil.

686

SUNFLOWER OIL

Sunflower seed

Cleaning

Drying

Storage

Cracking

Hull

Dehulling

Cracking

Conditioning

Pre-treated seed to oil extraction

Figure 14. Preparatory treatment of sunower seed for extraction.

5.1. Preparation of Sunower Seeds for Extraction Figure 14 shows normal stages in the preparation of sunower seed. Once harvested, sunower seeds are cleaned, dried, and stored. Seeds must be dehulled prior to pressing and oil extraction stages. Depending on processing plant, seeds may be cracked before the dehulling stage to reduce seed size and help remove the hull. Kernels may be further broken and subjected to two conditioning stages: cooking and aking. Thermal conditioning or cooking is directed to an adjustment of the moisture content (generally to 34.5%) and the temperature (generally 100 C) of meats. The last stage in the preparation of seed is the conversion of the cracked, dehulled, and conditioned meat into a ake. As these stages are common to a number of oilseeds, only those aspects specic of sunower seeds are considered, namely, in the drying and dehulling stages.

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5.1.1. Drying of Sunower Seeds The moisture content of sunower seed

must be reduced to around 89% prior to storage. Different authors indicate slightly varying levels: 15% (50), 910% (51), 8.5% (52), and 10.5% (5). In order to prevent losses caused by unfavorable climatic conditions, seeds are usually harvested with moisture contents above the recommended levels for storage. When seed moisture is higher than the recommended value, enormous spoilage of the seeds by microbiological attack is possible. Fungi may also grow explosively over the surface of seeds, with the consequent increase in temperature caused by biological activity. Such temperature increase leads to ideal life conditions for thermophilic bacteria; their metabolism contributes further to a temperature increase. Enzyme and mold activity reduces the quality and the yield of the extracted oil. Seed moisture is normally expressed as weight percentage of the whole seed. As water is insoluble in seed lipids, the moisture content is concentrated in the nonfatty parts of the seed. The water content calculated on a nonfatty basis is dened as critical moisture. The critical moisture of sunower seeds is 16%, although a maximum 15% is recommended for storage. As the content of nonfatty materials in sunower seeds decreases as the oil content increases, the moisture content corresponding to one critical moisture value is inversely related to the oil content, as shown in Table 16 [based on Muller (50)]. For critical moisture levels above 15%, the rate of respiration of seeds increases. Respiration is accompanied by an exothermic transformation of organic substances of seeds, creating conditions that may lead to spontaneous combustion (50). Drying of seed may be performed at room temperature with no additional equipment, or with hot-air dryer. The rst stage of drying consists of the removal of external moisture from the fresh seeds. Internal water diffuses outward, evaporating in the external part of seeds. After a certain time, seeds reach a hygroscopic equilibrium state at which the moisture content remains constant. The equilibrium depends on ambient temperature and relative humidity of the surrounding air. Figure 15 is a representation of these values for different temperatures: 10 C, 25 C, and 40 C [based on Mazza and Jayas (51)]. The equilibrium moisture of seeds is modied upon dehulling. Equilibrium moisture values for undehulled sunower seeds, hulls, and kernels are compared as a function of the relative humidity of the surrounding air at 25 C (Figure 16). The initial moisture content of all seeds was 5% (dry basis). Those samples stored at a relative humidity below 33% reached the equilibrium by desorption, and those at a relative humidity above 33% reached the equilibrium by adsorption (51).
TABLE 16. Critical Moisture of Sunower Seeds with Different Oil and Moisture Content [Based on (50)]. Oil Content (%) 35 40 45 48 Nonfat Content (%) 65 60 55 52 Moisture (%) 9.75 9.00 8.25 7.80 Critical Moisture (%) 15 15 15 15

688
25 equilibrium moisture content (%)

SUNFLOWER OIL

20

10C 25C

15

40C

10

0 0 20 40 relative humidity (%) 60 80 100

Figure 15. Equilibrium moisture (%) of sunower seed with hull as a function of air relative humidity (%) for three temperatures [based on (51)].

5.1.2. Dehulling of Sunower Seeds With approximately 30% of hull, sun-

ower seeds must be dehulled prior to processing. The high wax content of hulls, which would otherwise be transferred to the oil during extraction, is one major reason for dehulling. The wax content of an oil extracted from undehulled seed is approximately ve times higher than for oils extracted from dehulled seed. However, a small fraction of hull (less than 15%) is left with the seed for easy percolation during the process of extraction by solvent. Seed moisture is usually reduced to values below 8% for hulls to turn more brittle and be easily removed.
30 equilibrium moisture content (%) 25 20

seeds kernels hulls

15 10 5 0 0 20 40 60 80 100 relative humidity (%)

Figure 16. Equilibrium moisture (%) of sunower seeds with hull, hulls, and kernels as a function of air relative humidity (%) at 25 C [based on (51)].

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689

Genetic improvements of sunower seeds have been aimed at increasing oil content, but also leading to a decrease in the amount of hull. The seed pericarp is thinner and more rmly attached to the kernel in improved varieties. The hullability of improved seeds, i.e., the ease with which hulls can be cracked and removed from the seed, is lower than that of seeds with hull of higher thickness. Dehulling consists of mechanical removal of the pericarp (hull) of seeds. The most widely used method consists of colliding of seeds at high speed against a hard surface by centrifugal effect, leading to the cracking of seeds. Loose hull bits are separated from partially dehulled seed. In addition to the size and shape of seeds, the moisture content is a most relevant parameter in the dehulling process. A decrease in moisture content facilitates hull removal, the effect being greater for hybrids of higher oil content. However, a decrease in moisture also leads to an increase in the amount and composition of nes. Therefore, it is necessary to determine the optimum value of seed moisture for maximum hullability and a reduction in the amount of nes. 5.2. Sunower Oil Extraction Partially dehulled sunower seed is generally used for oil extraction, with 8% moisture and 10% residual hull content, approximately. The process employs mechanical pressing followed by hexane extraction. Figure 17 represents a diagram of the unit operations involved.

Pre-treated seed

Hot pressing

Pressed oil

Expander

Solvent extraction

Extracted oil

Desolventization Pelleting

CRUDE SUNFLOWER OIL

SUNFLOWER MEAL

Figure 17. Production of crude sunower oil.

690

SUNFLOWER OIL

Extraction of sunower oil is generally carried out in two stages. The rst stage consists of mechanical extraction using screw-presses (expellers). The meal obtained in the pressing stage, containing 1520% of oil, is subjected to extraction by solvent (normally hexane). The solvent must then be eliminated from both meal and oil. Oils obtained through pressing are of better quality than those obtained by solvent extraction. However, both are blended before storage. Pressed oils are sometimes commercialized separately from solvent extracted oils. The solventextracted meal is obtained as a byproduct of this stage. 5.3. Treatment of Crude Oil Figure 18 shows a diagram of alkali rening and physical (steam) rening of sunower oil. The traditional method, alkali rening, involves degumming, neutralization with alkali, bleaching, dewaxing, and deodorization. A pre-dewaxing stage may be performed after neutralization to reduce the wax content to 100150 ppm, in addition to a stage of winterization after bleaching for removal of the remaining waxes. Physical rening includes the following stages: degumming, bleaching, dewaxing, and deodorization. Also for physical rening, a combined stage of predewaxing and degumming makes post-dewaxing easier and less costly.

Crude sunflower oil

Degumming Predewaxing

Alkali refining or neutralization Predewaxing Bleaching

Bleaching

Dewaxing

Dewaxing

Deodorization/ Deacidification

Deodorization

FULLY REFINED SUNFLOWER OIL

Figure 18. Rening of crude sunower oil.

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691

Sunower oil contains moderate quantities of carothenoids and xanthophylls, but it does not contain chlorophylls. It may be easily bleached with less than 1% bleaching earth. In physical rening, bleaching is carried out for the removal of phosphatides and metals in addition to colored materials. The rening of crude sunower oil is performed along the same stage sequence as for other oilseeds. Inclusions of a degumming stage and a dewaxing stage are both worth considering separately in detail. Details of physical rening of sunower oil are also given below.
5.3.1. Degumming Major phosphoacylglycerols of sunower oil are phosphati-

dylcholine (PC), phosphatidylethanolamine (PE), phosphatidylinositol (PI), and phosphatidic acid (PA). The phospholipid content of solvent-extracted oils is higher than that of hot-pressed oils. Cold-pressed oils contain hardly any phospholipids. Most of the phospholipids in sunower oil are hydratable and may be removed by water degumming. Figure 19 shows a comparison of the variation in the phospholipid content of two crude sunower oils, obtained by pressing and by solvent extraction, respectively, and a degummed sunower oil (53). Nonhydratable phospholipids (mainly Ca and Mg salts of PA and lysoPA, glycerophosphates, and inorganic phosphates) remain in the oil after water degumming. As a result, a degummed oil may have a signicantly higher percentage of PA and a lower percentage of other phospholipids (particularly PC) than the original crude oilPC being almost fully hydratable and PA is nonhydratable when complexed with Ca or Mg, PC and PI hydrating considerably faster than
1.4 1.2 Phospholipid content (%) 1 0.8 0.6 0.4 0.2 0 pressed extracted degummed

minimum maximum

Figure 19. Minimum and maximum values of the total phospholipid content in two crude sunower oils, obtained by pressing and by solvent extraction respectively, and in a degummed oil [based on (53)].

692
100 90 80 70 Percentage 60 50 40 30 20 10 0

SUNFLOWER OIL

pressed extracted degummed

PE (min) PE (max) PA (min) PA (max) PI (min)

PI (max) PC (min) PC (max)

Figure 20. Minimum and maximum values of the content of each phospholipid in two crude sunower oils, obtained by pressing and by solvent extraction respectively, and in a degummed oil [based on (53)].

PE and PA (54). Figure 20 shows a comparison of the variation range of each phospholipid in two crude sunower oils, obtained by pressing and by solvent extraction, respectively, and a degummed sunower oil (53). The hydratability of these compounds may be increased with the addition of either phosphoric or citric acid, leading to a more efcient degumming process. Nonhydratable phospholipids may also be removed by enzymatic treatment through special biochemical reactions, such as enzyme-catalyzed hydrolytic cleavage of the phospholipid molecules (53). Smiles et al. (55) studied the effectiveness of six different degumming reagents for crude sunower oil: water, citric acid, phosphoric acid, oxalic acid, acetic anhydride, and maleic anhydride. All reagents were signicantly more effective than water in removing phospholipids, with maleic anhydride and oxalic acid removing 95% and 90% of total phosphorous, respectively. No signicant changes were found in the composition of the phospholipids remaining in the oil. Pan et al. (56) studied the inuence of different operation variables (temperature, contact time, type and concentration of degumming reagent, pH, calcium and magnesium content) on both water and acid degumming efciency for sunower oil. All degumming solutions (phosphoric acid, citric acid, and a 50:50 blend of both solutions) had a 2.5% concentration. Optimum degumming conditions with phosphoric acid were 6070 C and addition of 10% of its solution. Optimum degumming conditions with citric acid were 70 C and addition of 10% of its solution, whereas for the blend of both reagents, treatment at 60 C and 8% of the blend was optimum.
5.3.2. Dewaxing Winterization is achieved by cooling an oil with the consequent

crystallization of high melting point fractions (waxes and/or triacylglycerols).

EXTRACTION AND PROCESSING OF SUNFLOWER OIL

693

These are responsible for the appearance of turbidity in some edible oils during storage at low temperature or even at room temperature. Winterization of sunower oil is usually referred to as dewaxing. Improved techniques have emerged in recent years with the appearance of seed varieties of high oil and additional wax contents. As the improvements in oil yield (higher than 40% for these seeds) have been obtained at the expense of a reduction in hull thickness, the concentration of seed protection substances (waxes) in the hull has also been increased. The concentration of wax in hulls of improved hybrids may be as high as 34%, compared with 1% in hulls of the traditional seeds. Around 83% of the wax content is in the seed hull, 17% in the seedcoat and traces are in the seed. In order to facilitate oil extraction, either through pressing or by solvent extraction, it is necessary to leave a certain amount of hulls in the seed. The wax content is thus considerably higher in these oils than in oils of traditional seed varieties. Crude sunower oils may contain 20003000 ppm of wax, depending on the seed type and the oil extraction method employed.
5.3.2.1. Cold Stability of Rened Sunower Oil

Sunower oil waxes are fatty alcohol esters of fatty acids. Their melting point is around 75 C, and their solubility in the oil is low, leading to the appearance of turbidity in the rened oil with decreasing temperature. An oils cold stability is usually assessed by means of the cold test (method AOCS Cc 7-25). Oils passing the cold test will remain clearwithout the appearance of turbidityafter 5.5 hours permanence at 0 C. The solubility of waxes in sunower oil is shown in Figure 21 as a function of
14 12 Wax solubility (ppm) 10 8 6 4 2 0 0 2 4 6 8 10 12 14 16 18 20 22 Temperature (C)

Figure 21. Solubility of sunower oil waxes (ppm) as a function of temperature ( C) [based on (57)].

694
10 9 Turbidity appearance (days) 8 7 6 5 4 3 2 1 0

SUNFLOWER OIL

10

20 30 40 wax content (ppm)

50

60

70

80

Figure 22. Time required for turbidity appearance in a sunower oil stored at 0 C as a function of the wax content [based on (58, 59)].

temperature [based on Bloch (57)]. The solubility of waxes is extremely low (in the order of 0.1 ppm) at 0 C and increases to 12 ppm at 20 C. It is possible that oils that are clear at room temperature may develop some cloudiness if stored in a refrigerator. Another problem concerning rened sunower oil is that the wax precipitate may appear several days upon elaboration, even for oils successfully passing quality control checks carried out by means of the cold test. The precipitate, although not affecting the nutritional or organoleptic properties of the oil, will be considered as an impurity by the consumer and should be avoided for oils commercialized in transparent bottles. Consequently, other factors than the wax content inuence the time required for the appearance of turbidity. Figure 22 shows the time required for turbidity appearance in sunower oil stored at 0 C as a function of the wax content. All oils passed the cold test, i.e., remained clear after 5.5 hours at 0 C, except the sample containing 80 ppm of wax (58, 59). Turbidity develops in an oil containing 6 ppm of wax after 10 days, that is, a longer time period than that considered by the cold test. The phenomenon of turbidity appearance in sunower oil is complex. The time necessary for turbidity appearance for a given wax content depends on the tempering temperature. Both the time necessary for the appearance of turbidity at temperatures above 0 C and the minimum concentration causing turbidity may be expected to increase with temperature. However, the wax crystallization rate is reported to be the highest at 13 C, i.e., the time necessary for the appearance of visible turbidity in an oil is the shortest at this temperature (58, 59). In view of the above difculties,

EXTRACTION AND PROCESSING OF SUNFLOWER OIL

695

25

cold pressed
20

hot pressed hexane extracted

Percentage

15

10

0 36 37 40 41 42 44 46 48 Wax (carbon number)

Figure 23. Inuence of type of extraction on wax composition in sunower oils [based on (53)].

several analytical methods have been developed for predicting the appearance of turbidity (6062) or for determining the wax content in sunower oil (53, 63, 64).
5.3.2.2. Content and Composition of Sunower Oil Wax Both the wax content

and composition of sunower oil depend on the method of oil extraction. According to work carried out by Carelli et al. (53) with sunower oils extracted from the same seed lot, the crude industrial oil obtained by hexane extraction contained 1073 ppm, the crude industrial oil obtained by hot pressing contained 947 ppm, and the coldpressed oil obtained in the laboratory had 771 ppm of wax. That is, the oil extracted by hexane had the highest wax content, the hot-pressed oil having a higher content than the cold-pressed oil. Figure 23 shows the composition of wax esters according to total number of carbons, for the oils obtained by the three above methods. Waxes in the cold-pressed oil were composed predominantly of esters below 42 carbons. Both hot-extracted oils had a similar wax prole. Wax extractability appears to depend largely on temperature, in particular for those waxes containing over 42 carbons, where reductions of 70% can be achieved. Degumming did not lead to any signicant reduction in the wax content for either type of industrial oil. In short, the content and composition of sunower waxes are affected by the extraction method, although degumming does not have a signicant effect on the total wax content. Carelli et al. (53) studied the wax content of crude sunower oil (995 ppm) and of three commercially rened edible oils (366624 ppm), nding a high degree of dependence of the wax content on the rening process conditions. The wax composition in the crude oil and in one of the rened oils is shown in Figure 24. Waxes remaining after rening are richer in 40 and 41 carbon esters (less rich in esters of

696
40 35 30 Percentage 25 20 15 10 5 0

SUNFLOWER OIL

crude oil refined oil

36

37

40

41

42

44

46

48

WAX (carbon number)

Figure 24. Wax composition in a crude oil and in a commercial rened oil [based on (53)].

over 42 carbons) than the original waxes, indicating a clear tendency of waxes of higher molecular weight (higher melting point) to crystallize during rening; i.e., the cooling stage produces a fractionation of the waxes. Figure 25 shows the composition of waxes precipitating in the dewaxing process of sunower oil [based on
40 35 30 Percentage 25 20 15 10 5 0 42 44 46 Wax (carbon number)
Figure 25. Composition of precipitated waxes in the dewaxing process of sunower oil [based on (53)].

48

>48

EXTRACTION AND PROCESSING OF SUNFLOWER OIL

697

50 45 40 35 Percentage 30 25 20 15 10 5 0 16:0 18:0 18:1 18:2 19:0 20:0 22:0 24:0 26:0 28:0 30:0 Fatty acid (carbon number)
Figure 26. Fatty acid composition of sunower wax (53, 65).

Carelli et al. (53) Liu et al. (65)

Carelli et al. (53)]. The predominance of esters of higher number of carbons (over 44) is clear, in accordance with the above. Because the composition of the wax remaining in an oil differs markedly from that precipitating from it, care must be taken against differences in the sunower wax prole as reported in the literature. The fatty acid composition and the fatty alcohol composition of sunower wax (53, 65) are compared in Figures 26 and 27.
35 30 25 Percentage 20 15 10 5 0 16 18 19 20 22 24 26 Fatty alcohol (carbon number) 28 30 32

Carelli et al. (53) Liu et al. (65)

Figure 27. Fatty alcohol composition of sunower wax (53, 65).

698

SUNFLOWER OIL

It is worth noting that Liu et al. (65) studied the wax removed from an oil that had been stored at 0 C for 1 week, allowing enough time for crystallization and fractionation to take place. The wax contained preferentially esters of a higher number of carbons. Carelli et al. (53) extracted quantitatively all the waxes contained in a crude sunower oil.
5.3.2.3. Sunower Dewaxing Procedures Several methods are used for wax

removal. Most widespread are those associated to the rening process, whereas cold degumming and superdegumming, both related to the treatment of crude oils, are scarcely used (57, 66). Cold neutralization was developed for high-capacity plants and for the processing of oils of high wax content. The crude oil is neutralized at a low temperature, and the wax is removed simultaneously with the soapstock. The processed oil is of good quality, although losses may be considerable, especially with oils containing over 1.5% free fatty acids. Water dewaxing is the latest method of sunower oil dewaxing. As the crystallization process of waxes is inhibited or delayed by the phosphatides in the oil, dewaxing is carried out after full degumming has been completed. The process of dewaxing through hot neutralization followed by cold washing has gradually replaced the traditional methods. After conventional hot neutralization is performed, and the soapstock removed, the oil is cooled to 68 C and left to settle for 810 hours. A small percentage of soda (NaOH) is added; time is allowed for maturation; it is heated to 2025 C and centrifuged. One nal ltration step must be performed on the cold oil to remove the remaining waxes. Cold ltration may be performed before or after deodorization. Oil from the bleacher or the deodorizer is cooled to 1215 C, and after settling for 12 hours, it is cold-ltrated with the addition of lter aid (perlite or diatoma) to prevent clogging caused by the wax.
5.3.3. Physical Rening

The success of the physical rening stage depends largely on the pretreatment of crude oil. Among other compounds, phosphatides must be efciently removed. The elimination of nonhydratable phosphatides (NHP), mainly Ca and Mg salts of phosphatidic acid and lysophosphatidic acid, poses one major difculty to the pretreatment of oil for physical rening. NHP may be removed from the oil with the addition of an acid, generally phosphoric or citric acid, or complexation agents for Ca/Mg (preventing the precipitation of insoluble salts). Treatment with these acids is the basis for several oil pretreatment processes prior to physical rening. The content and ratio of NHP in an oil differs signicantly depending on the method applied (Table 17). The NHP content is lower in extracted and mixed oils (67). The NHP content of sunower oil is low, and degumming may readily be accomplished. Dimic et al. (67) studied a simplied process for pretreatment of sunower oil with the application of multiple acid degumming stages. Part of the unsaponiable matter (such as tocopherols, sterols, and sterolesters) is distilled together with the free fatty acids during deodorization/deacidication, as

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699

TABLE 17. Content of Total Phosphatides (TP) and Nonhydratable Phosphatides (NHP) of Crude Sunower Oil [Based on (67)]. Pressed Oil TP (g/100 g oil) NHP (g/100 g oil) NHP*100/TP 0.24 0.14 59% Extracted Oil 1.32 0.04 3% Mixed Oil 0.70 0.09 13%

well as volatile oxidation byproducts, and avor components. Ideally, natural oil components should remain in the oil in the highest possible amount. As much as 85% of tocopherols remain in a nished oil upon physical rening operations carried out at temperatures below 240 C. Sunower oil processing byproducts depend on the kind of rening, whether chemical or physical. The so-called deodistillate of chemical rening of sunower oil can be used as feedstock for obtaining tocopherols and sterols. The tocopherol composition of sunower oil (over 90% alpha-tocopherol and only a low proportion of the beta and gamma isomers) makes deodistillates of great value for industrial Vitamin E production. Increased importance has been placed on vegetal sterols because they were found to reduce the risk of cardiovascular disease. As a result, the demand for tocopherols and sterols was increased as food additives. Deodistillate originated in physical rening, diluted in free fatty acids, is not an attractive feedstock for Vitamin E and sterol producers. Deodistillate originated in chemical rening of sunower oil may contain 57% of total tocopherols, compared with only 12% for deodistillate of physical rening (68).
5.3.4. Deodorization There are no major differences between deodorization

procedures for sunower oil and other vegetable oils. The loss of tocopherols in the oil is worth noting for sunower oil, though. The average tocopherol content of sunower oil is medium (4401520 ppm, according to Codex-Stan 210-1999), nearly all of which is alpha-tocopherol (403935 ppm). Table 18 shows the reduction in the tocopherol content upon deodorization of sunower oil (69). Tocopherols may be recovered from the distillate of deodorization.

TABLE 18. Total Tocopherol Content (ppm) of Sunower Oil in Different Rening Stages [Based on (69)]. Rening Stage Crude Neutralized Bleached Dewaxed Deodorized Tocopherols (ppm) 823 815 843 903 510

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5.4. Cold-Pressed Sunower Oil Virgin oils currently available on the market are not restricted to virgin olive oil but include other oils obtained by cold pressing of seed. These oils are appreciated highly by consumers in view of their nutritional characteristics and avor (particularly those organoleptic notes that are lost in rened oils). The consumer appreciates the natural characteristics of these oils, as they are not subjected to chemical treatment. A relatively new market has developed for these oils in the U.K., Germany, France, Italy, and Switzerland, among other markets. Sunower oil is manufactured and commercialized as cold-pressed or rst cold-pressed oil. Cold-pressed sunower oil is obtained through mechanical pressing at a low temperature (3035 C, for example). It has a clear appearance, an agreeable goldenyellow color, and a typical light avor. The visible spectrum of this oil indicates a low content of chlorophylls and carotenoids, characteristic of unbleached oils. It may be stored in dark containers at room temperature for 1 year without the appearance of turbiditycharacteristic of sunower oil extracted with solvent from undehulled seed. A high tocopherol content constitutes a natural protection against oxidation, to a higher extent than antioxidants added to commercial oils (70). De Panlis et al. (71, 72) also analyzed regular cold-pressed sunower oils manufactured by different European countries. Relatively high acidity values were found for these oils (0.651.59 %), characteristic of virgin oils (unrened).

6. HYDROGENATION OF REGULAR SUNFLOWER OIL Regular sunower oil contains hardly any linolenic acid, a factor contributing to a high oxidative stability. Light hydrogenation processes (low temperature) are therefore unnecessary to increase the stability of sunower oil, as is the case for soybean and rapeseed oilaiming at the elimination of linolenic acid, while avoiding the formation of considerable amounts of trans-isomers. Sunower oil is hydrogenated in producer countries for use in the manufacture of shortenings and margarines. It is a good raw material for the production of hydrogenated fat of relatively at melting curve, with melting point in the range of 3236 C. The behavior of sunower oil in the hydrogenation process is similar to that of soybean oil, and it does not require particularly special or different reaction conditions. It does not contain compounds that may interfere with the reaction, as is the case for rapeseed oil. Mention will be made here only of those aspects that are specic to sunower oil, without treatment of the general conditions valid for hydrogenation of any vegetable oil. Process control parameters are the refractive index, melting point, iodine value, and solid fat index. Topallar et al. (73) studied the density and viscosity of hydrogenated regular sunower oil of iodine value up to 82.4. The density of hydrogenated sunower oil is slightly higher than that of its nonhydrogenated counterpart, varying linearly with temperature. At a given temperature, oil viscosity was found to double upon hydrogenation.

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701

45 40 35 trans fatty acids (%) 30 25 20 15 10 5 0 120 C 150 C 180 C

0.03% 0.05% 0.10%

Figure 28. Content of trans-isomers in a hydrogenated regular sunower oil at different temperatures (120 C, 150 C, and 180 C) with varying amounts of a nickel catalyst at 20% on silica (0.03%, 0.05%, and 0.10% nickel in the oil) [based on (74)].

Around 40% of trans-isomers are formed in the traditional hydrogenation process. Figure 28 shows the amount of trans-isomers formed as a function of hydrogenation temperature (120, 150, and 180 C) and the amount of nickel catalyst at 20% on silica (0.03, 0.05, and 0.10% nickel in the oil), for reactions taking place in the laboratory at a pressure of 3 atm and an agitation rate of 1500 rpm (74). Hydrogenation of vegetable oils at a low temperature (105120 C) with a high hydrogen concentration on the catalyst results in a minimum amount of trans-isoacid formation. Medium-temperature hydrogenation (150 C) may be unselective, and high-temperature hydrogenation (180 C) generates the highest content of trans-isomers, a value near equilibrium. Sunower oil shows the expected behavior, with a minimum of trans-isomers corresponding to the lowest temperature and the least amount of catalyst, and a maximum at the highest temperature and the highest amount of catalyst. Variations of the hydrogen pressure and the amount of catalyst, keeping temperature at a constant 180 C and the rate of agitation at 750 rpm, did not result in signicant modication in the trans-content. Figure 29 shows this effect (74). The traditional hydrogenation process generates a high proportion of transisomers. Having considerably higher melting points than their cis-isomers, transisomers contribute to a large extent to an enhancement of product thermal behavior and plasticity. On the other hand, from the nutritional viewpoint, it is recommended to avoid intake of trans-isomers; thus, ways have been sought to reduce their content in margarines. One widely used procedure consists full hydrogenation of the oil and later interesterication with nonhydrogenated oil. A new method consists hydrogenation with solvent under supercritical conditions, leading to a reduction

702
50 45 40 trans fatty acids (%) 35 30 25 20 15 10 5 0

SUNFLOWER OIL

3 atm 5 atm

0.03%

0.05%

0.10%

Figure 29. Content of trans-isomers in a hydrogenated regular sunower oil at different pressures (3 and 5 atm) and with different amounts of nickel catalyst at 20% on silica (0.03%, 0.05%, and 0.10% nickel in the oil) [based on (74)].

in the trans-content below 5%. The rate of hydrogenation is some 1000 times greater owing to an increased transfer of hydrogen toward the catalyst and the lack of blockage of pores in the catalyst produced by stagnant oil (74). Catalytic transfer hydrogenation (CTH) is one method currently being developed. This method differs from traditional hydrogenation with molecular hydrogen in the use of a hydrogen donor (for example, sodium formate solution) in a catalytic transfer reduction reaction. Naglic et al. (75) used this procedure to hydrogenate regular sunower oil, among other vegetable oils. Hydrogenated sunower oil may suffer from disadvantages for use in the manufacture of margarine spreads. The appearance of sandiness in these products during storage is because of a strong tendency of partially hydrogenated sunower oil to form b crystals. Under rapid cooling conditions, as used in the manufacture of margarines, the a phase is the rst to form, followed by its rapid transformation into phase b. This is the desirable crystalline form, because, under certain conditions, it tends to form a ne three-dimensional network capable of immobilizing a large amount of liquid oil. From a thermodynamic viewpoint, phase b is the stable form of hydrogenated sunower oil. Thus, the solid state transformation of b0 into b always takes place, leading to the formation of a coarse, sandy texture detected during storage but not during product elaboration. The transformation of b0 to b is slow. The time required for full transformation depends on temperature and crystallization rate of the manufacturing process, as well as storage temperature of the margarine (7679). Various procedures have been proposed to solve the problem of graininess of margarines manufactured with hydrogenated sunower oil. The hydrogenated oil

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may be mixed with partially hydrogenated cottonseed oil with the consequent increase of fatty acids of over 16 carbons. Cottonseed oil, crystallizing at a higher temperature than hydrogenated sunower oil, induces and stabilizes b0 crystallization in the rest of the fatty material (76). Food emulsiers provide another solution to the problem. Addition of saturated and unsaturated fatty acid monoacylglycerols, acting as modiers of the crystalline structure, aids in preventing the undesired phenomenon. Also, the addition of 0.3% of sorbitan tristearate inhibits the transition from b0 to b in a margarine. The same is observed for sucrose polyesters (80).

7. STORAGE AND DETERIORATION OF SUNFLOWER OIL Several general factors affect the oxidative stability of sunower oilas well as most vegetable oilsduring storage. One of these factors is the degree of unsaturation, i.e., the relative content of oleic and linoleic acids. Product shelf-life is affected by manufacturing conditions such as the type of extraction process (pressing, with solvent, with supercritical uids), degree of purication (crude, rened, deodorized, etc.), addition of antioxidants, and type of packaging (container material, incorporation of inert atmosphere, etc.). Other major factors inuencing the oxidative stability are the particular storage conditions: time, temperature, and light, among others.

7.1. Composition of the Rened Oil Sunower oil extracted from different types of hybrid may have different compositions. It is expected that the degree of unsaturation will inuence the oxidative stability of sunower oil markedly. AOM time measurements were used to determine the inuence of oleic/linoleic ratio on the oxidative stability of sunower oil (36). Oil samples extracted (rened and deodorized) from three progenies of cultivar Pervenets were analyzed, as well as other oil samples from different regions of the United States. The oleic acid content thus ranged from 18% to 89%, and the linoleic acid content decreased from 69% to 1%; the saturated fatty acid content was nearly constant. AOM values increased from 11 hours for the oil containing the least amount of oleic acid to 100 hours for that with the oleic acid highest content. These results show the importance of monounsaturated fatty acid content on the oxidative stability of sunower oil. Inherent stability of an oil may be calculated from the oil composition and the relative rates of oxidation of oleic (dened as 1), linoleic (evaluated as 10), and linolenic (evaluated as 25) acids. The higher this value, the more unstable or susceptible to oxidation an oil is. Values of 6.8 and 1.9 are obtained for regular and high-oleic sunower oils, respectively, taking into account their standard compositions. The inherent stability of olive oil, calculated as 1.5, is slightly lower than that of high-oleic sunower oil, whereas even lower values are obtained for saturated fatty materials like tallow (0.86), palm kernel (0.27), and coconut (0.24). The

704

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inherent stability of high-oleic sunower oil is 3.5 times higher than that of highlinoleic sunower, and higher than the values for most vegetable oils (81). 7.2. Storage Conditions Three major factors inuence the storage conditions of oils: temperature, light, and the presence of dissolved oxygen. The combined effect of temperature and light exposure on the stability of a rened commercial high-linoleic sunower oil was studied (82). Oil bottled in PET (polyethylene terphthalate)the head space being lled with nitrogenwas stored at three different temperatures (35, 45, and 60 C), both in a dark chamber and with 12-hour lighting per day (18-W uorescent tube). Lighting conditions were chosen considering bottles packed in cardboard boxes (darkness), or displayed on supermarket shelvesexposed to articial lighting. The criterion for establishing oil deterioration was the rejection of an oil sample by a panel of trained consumers. The corresponding shelf-lives were estimated for the three temperatures (35, 45, and 60 C). These values were used to extrapolate shelf-life at 20 C (taken as room temperature). Storage temperature was found to have a marked inuence on oil deterioration, even when bottled under inert nitrogen atmosphere. For example, an oil stored in the absence of light at 45 C is rejected by consumers after 102 days, compared with 1140 days estimated for oils stored at 20 C. Estimated shelf-lives for those samples stored under conditions of darkness were considerably higher than for the corresponding samples exposed to light. Estimated shelf-life at 20 C was 281 days for oil exposed to light and around 1140 days for oil stored in dark chambers. This value is higher than the 2 years generally established by manufacturers as useful life period of this kind of oil. Exposure to light must be avoided to extend the life-span of sunower oil, and it must be bottled in containers that prevent the passage of light. PET bottles do not prove efcacious light lters in preventing oil deterioration. Other researchers (83) have studied the effect of light exposure on regular sunower oil (iodine value 132) and on partially hydrogenated sunower oil (iodine value 82). Oil samples were stored in containers of glass, PET, and glass covered by tin, and were exposed directly to solar radiation at atmospheric conditions for 30 days (no indication is given of either temperature or exposure time). As expected for each type of container, the increase in the peroxide value was higher for the nonhydrogenated oil than it was for its hydrogenated counterpart. A rapid increase of the peroxide value was reported for those samples stored in glass containers, whereas an intermediate value (yet high) was for PET containers, with practically no deterioration of those samples in metal-covered containers. These results are in accordance with the work of other authors (82). Values denoting oxidative deterioration increase gradually during the shelf-life of an oil. Determinations of induction times in rapid-aging tests also reect the oxidative stability of commercial rened oils. Grompone et al. (84) studied the stability of commercial regular sunower oils. The oil samples were stored at ambient conditions in their original PET bottles for a one-year period. The OSI induction time

STORAGE AND DETERIORATION OF SUNFLOWER OIL

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at 110 C was found to decrease from 4.6 hours (at the time of purchase of the oil) to 3.3 hours (one year later). A similar behavior was observed for two rened oils produced by the same manufacturer over a one-year time difference. The OSI times of both oils were determined simultaneously: 3.9 hours for the oil procured that year and 3.2 for the sample procured in a previous year (85).

7.3. Presence of Free Fatty Acids The pro-oxidant effect of free fatty acids in vegetable oils is widely known. To determine their inuence (86), pure oleic acid was added (up to 3%) to a high-oleic sunower oil extracted by cold-pressing. The effect intensity was found to be directly related with the concentration of free fatty acids.

7.4. Addition of Antioxidants The effectiveness of antioxidants depends on the type of fatty material; tests are, therefore, required for each case. Stabilization studies have been reported, for example, of rened high-linoleic sunower oil with the addition of three antioxidants and blends of them (87). Butylated hydroxytoluene (BHT), propyl gallate (PG), and tert-butylhydroxyquinone (TBHQ) were evaluated as antioxidants through determinations of induction time by Rancimat method at 98 C and the changes in the properties (acidity, peroxide value, anisidine value, polar compounds content) of the oil samples during storage in glass jars without lid, in the dark, at constant temperature: 30 days at 47 C and 30 C and 10 days at 67 C. The stability of oils containing TBHQ and PG, measured by Rancimat induction time, increased rapidly with increasing antioxidant concentration. An induction time of 12.7 hours for the original oil was increased to 25.7 hours with the addition of 50 ppm of TBHQ and to as much as 42.2 hours with the addition of 200 ppm. PG had a lesser stabilizing effect, with induction times of 18.8 hours at 50 ppm and 32.3 hours at 200 ppm. BHT had a slight stabilizing effect with practically no modication of induction time: increasing only to 14.2 hours at 200 ppm. Thus, TBHQ proved 1.7 times more effective than PG and 22 times more effective than BHT. No cooperative interaction (synergism) was observed between antioxidants through Rancimat method. Different results were obtained with respect to the effectiveness of antioxidants for oil stored at 47 C in the dark. Effectiveness was evaluated as the time required for a sample to reach a peroxide value of 10 meq/kg, as estimated from curves of peroxide value as a function of storage time. The estimated effectiveness of TBHQ was approximately 9.6 times higher than that of GP and 51 times higher than for BHT. According to these results, the relative antioxidant effectiveness of BHT increased with decreasing temperature, and it decreased for GP. The Rancimat method underrated the stability of those samples containing BHT, perhaps because of volatilization of antioxidants during Rancimat testing. The relative activity of

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antioxidants depends on both temperature and the conditions of the method used to measure such activity. Independent of the method and test conditions employed, TBHQ proved to be the most effective of all three antioxidants, followed by PG, and BHT had little antioxidant effect on the sunower oil studied. Further research should focus on evaluation of antioxidant effectiveness through methods of oxidative experimentation in conditions similar to those of storage. 7.5. Effect of Heating and Microwaves Vegetable oils exposed to high temperature undergo rapid deterioration, as can be evidenced both through chemical and sensory analysis. For example, a rened highlinoleic sunower oil kept at 60 C for one hour showed changes in its ultraviolet absorption spectrum, with the appearance of a peak at 234 nm corresponding to the formation of conjugated dienes generated in the oxidation of linoleic acid. Another peak was observed at 268 nm for oil kept at 180 C for 1 hour, corresponding to oxidation byproducts, especially ethylene diketones (84). The development of rancidity in sunower oil is accelerated with increased temperature, the process being even more complex in microwave cooking. To determine the inuence of combined factors (88), both a regular sunower oil and a high-oleic sunower oil were exposed to different heating conditions: (1) microwave heating at approximately 170 C for 120 min; (2) conventional electric heating at 180 C for 120 min; (3) exposure to microwave radiation for 120 min at temperatures lower than 40 C. Greater degrees of alteration were found for both oil types when microwave-heated than if heated in a conventional oven, and exposure to microwaves without heating did not produce signicant alteration. Hence, the increase in temperature was found to be the main deterioration factor for both oil types. 7.6. Crude Sunower Oil Crude sunower oils are produced via mechanical pressing or through extraction with hexane, followed by water degumming. Most oils are stored for relatively long periods prior to rening operations. Cold-pressed crude oils, of superior edible quality, are commercialized as such. Whether unrened or cold-pressed, the oil may be subject to temperature uctuations. The inuence of composition, storage temperature (30, 47, and 67 C), and oxygen concentration (open and stoppered bottles containing different amounts of oil, and under nitrogen atmosphere) was studied for degummed crude sunower oils obtained by pressing and by hexane extraction (89, 90). The oil obtained by solvent extraction had a lower rate of oxidation than the cold-pressed oil, although initially at a more advanced step of deterioration. Although all oils had equal amounts of unsaturated fatty acids and the same concentration of natural tocopherols, the solvent-extracted oil had a higher concentration of phosphorous related with the phospholipid content. It appears that differences in oxidative stability may be attributed

USES OF SUNFLOWER OIL

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to the phospholipid concentration, having synergic activity and a metal scavenger capacity. OSI induction times were determined at 110 C for three virgin high-linoleic sunower oils, corresponding to three different manufacturers (85). These OSI times, ranging between 3.8 and 4.7 hours, were equal to or higher than the value obtained for a rened sunower oil of the same fabrication year (3.9 hours), yet lower than the value for a virgin olive oil (8 hours). Virgin oils, which are not subjected to physical or chemical processes, retain their natural antioxidants, a fact that might explain the high oxidative stability of these oils. 7.7. Sunower Oil Extracted by Supercritical Fluids Although several studies have been made on the extraction of oil from seed by supercritical uids, few are about sunower oil (91). Reports on supercritical carbon dioxide (SC-CO2) over a wide range of pressure (2070 Mpa) and temperature (4080 C) show a maximum solubility of sunower oil in supercritical CO2 at 80 C and 70 Mpa, conditions similar to those obtained for other seed oils. Over 90% of the oil content of seed can be removed under these conditions (92). One disadvantage of oils obtained by this method is their low oxidative stability (91). To determine the causes of such instability, one study was made of sunower oil extracted with SC-CO2, nding that, although the composition and organoleptic properties of these oils were similar to those of hexane-extracted oils, their oxidative deterioration rate was higher (93). The results of this study suggest that the instability of oils extracted with SC-CO2 may be attributed to the oxygen contained in the supercritical uid, the tocopherols in the oil being inefcient in preventing oxidation. Thus, the oxidative stability of sunower oil decreased when re-extracted with SC-CO2. Improvements may be obtained with the addition of traces of ascorbic acid. 8. USES OF SUNFLOWER OIL 8.1. Food Products
8.1.1. Regular Sunower Oil In view of its light avor, relatively high oxida-

tive stability, and light golden-yellow color, sunower oil nds many applications both in domestic and industrial levels. In countries where sunower oil is a common oil, it is used mainly as a salad oil and as a cooking oil. Industrial applications of sunower oil include use as frying oil, as well as in the manufacture of mayonnaise and oil-based dressings.
8.1.2. High-oleic Sunower Oil Formulations A high oxidative stability is

required by non-dairy coffee creamer formulas for an extended shelf-life without refrigeration. Both high-oleic sunower oil and monoacylglycerols obtained from it prove stable products for use in this kind of creamer. The oil may also be used in uid margarine, uid spreads, dressings, and so on.

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8.1.3. Margarines Owing to the strong tendency of hydrogenated sunower oil

to crystallize in the b form, precautions must be taken to avoid the problem of sandiness. The addition of crystal-modifying agents delays the transformation from unstable a phase to b phase, or stabilizes the intermediate meta-stable b0 phase. For optimum creaminess conditions, it is generally recommended to add 515% of b0 -crystallizing hydrogenated oils to formulations of margarines and of some shortenings (2). There are studies in the literature (76) about margarine formulations with blends of partially hydrogenated cottonseed oil, partially hydrogenated sunower oil, and nonhydrogenated sunower oil. Hydrogenated cottonseed oil, having a strong tendency to crystallize in the b0 form, has a favorable inuence in the blend with sunower oil. There has been controversy over the consumption of foods rich in trans-isomers. As partially hydrogenated oils contain high amounts of trans-components, alternative processes have been sought that do not lead to the formation of trans-isomers as byproducts. One such alternative is total hydrogenation of an oil (which does not form trans-isomers) and later blending with liquid nonhydrogenated oil. The oxidative stability of the blend is determined by the instability of the nonhydrogenated oil. High-oleic sunower oil appears a most appropriate ingredient in view of its low content in polyunsaturated fatty acids. Products of this kind are produced by some manufacturing companies. Soft nonhydrogenated margarines containing high-oleic sunower oil and other oils are available. Parmalat Canada, for example, produces a soft nonhydrogenated margarine trademarked under the name Olivina, containing a blend of rened olive oil, high-oleic and regular sunower oil, and canola oil, as well as palm, and palmkernel oils (94). Another alternative for increasing oxidative stability while improving margarine texture consists in the interesterication of hydrogenated and nonhydrogenated oils. As an example, an outstanding increase of crystals in the b0 form was observed upon interesterication of a blend of sunower oil and fully hydrogenated soybean oil with a strong tendency to crystallize in the b form. This procedure leads to bases for zero-trans-margarines of optimum texture (95).
8.1.4. Interesteried Tallow with Regular Sunower Oil Countries rich in

livestock resources produce large amounts of tallow as a byproduct of the slaughter industry. Tallow is used in the manufacture of food, mainly bakery products and cookies. Among other reasons, a high hardness texture, and a melting point above the mouth temperature, make foods manufactured with tallow of lower quality. Interesterication of tallow with vegetable oils is an alternative for an improvement in the behavior of tallow. Studies have been published on chemical interesterication of tallow with regular sunower oil (9698). Changes in the proportion of sunower oil in blends with tallow produce little modication of the solid content or the melting point. However, important modications take place in the thermal properties of these blends when they are subjected to a process of chemical interesterication. In addition, modications occur in the crystalline structure. Solid beef tallowcomposed

USES OF SUNFLOWER OIL

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of large spherulites responsible for a sandy mouthfeelmay be interesteried with sunower oil into a liquid blend (at process temperature), which solidies in the form of tiny crystals, giving the solid product enhanced consistency and texture. Lipase catalysis constitutes an alternative to the method of interesterication using chemical catalysts. Products of different physical properties may be obtained, according to lipase specicity (99,100).
8.1.5. Frying with Regular and Modied Sunower Oil Deep-fat frying, a

common cooking procedure, may be performed in a continuous or discontinuous manner. In repeated discontinuous fryingeither in the home or in restaurants the oil remains hot for long time periods, in contact with the surrounding air, with occasional cooking. The process is carried out with a relatively low rate of fresh-oil supply (turnover). In continuous frying, generally performed in industrial facilities for processing of fried and prefried foods, turnover is high because of the large amount of oil removed by products during continuous cooking. Contact of the oil with oxygen is limited in this case by the steam protection barrier generated in the cooking process. The deterioration of deep-frying oil depends on a large number of factors, including frying frequency (discontinuous or continuous), turnover, the time the oil is hot, and type of oil. Oil decomposition products absorbed by fried foods together with the frying oil during the cooking process affect not only the sensory and nutritional quality of these foods but also their shelf-life. They include polar compounds, triacylglycerol polymers and dimers, diacylglycerols, peroxides, volatile compounds, and so on. Storage time and characteristics depend on the type of product. Crisps, for instance, are generally stored at room temperature, whereas prefried french fries are stored in a freezer. Frozen prefried foods are prepared before ingestion. Deep-fat frying is a most common cooking method for the manufacture of prefried foods. These foods are thus subjected to two different frying processes and a stage in a freezer prior to nal cooking and consumption. Several studies have been performed to evaluate the oxidative resistance of sunower oils when used in frying processes.
8.1.5.1. Regular Sunower Oil High-linoleic sunower oil is of customary use

for frying in strong producer countries, as is the case of Argentina and Uruguay. In contrast, consumption and cooking use of olive oil has decreased in traditional consumer countries mainly because of price reasons. In Spain, the consumption of olive oil dropped from 55 g/capita/day in 1964 to 25 g/capita/day in 1987. Olive oil has been replaced by seed oils, especially sunower oil (101, 102). Although several studies have been performed to determine the characteristics of regular sunower oil for use in frying, few were focused on the in situ stability of an oil contained in fried foods. In one study, french fries fried in high-linoleic sunower oil and crushed to different sizes, were subjected to fast-aging in OSI equipment at 110 C and the induction period was determined (84). The values obtained differed from those for pure sunower oil. This method is a more realistic

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representation of the deterioration phenomenon, as it enables the study of an oils oxidative stability in the intact food matrix. Recent publications are based on the simulation of frying operations without the addition of food (103, 104). Others consider the process with the addition of food, generally french fries. The deterioration of sunower oil was determined in the frying oil during discontinuous frying processes (101, 105), or continuous processes with different rates of turnover (106, 107), as well as in the oil extracted from fried foods (101, 108, 109). Other studies are on the deterioration of a sunower oil absorbed in foods during storage in normal or fast-aging conditions. Results show that regular sunower oil rarely reaches a critical value of 25% of polar compounds in continuous frying processes with frequent turnover, indicating the suitability of sunower oil for this use. However, use of this oil is recommended only for frying of crisp-type foods with short commercialization periods, ensuring their consumption before detectable levels of deterioration of the absorbed oil are reached (109).
8.1.5.2. High-Oleic Sunower Oil Studies on the use of high-oleic sunower oil

in frying processes have similar characteristics to those performed on regular sunower oil, and generally they include a comparison of both types (104, 109119). Several reports have been published on oil deterioration in deep-fat frying processes carried out in intermittent manner (102, 114, 119) or continuously (110, 114, 119). Some studies simulate the frying process (in the absence of food) using Rancimat equipment without air bubbling at 180 C (104), or simply study oils heated in convection oven and on a hot plate (113). Other studies are on oil extracted from fried foods, generally potato crisps and french fries (111), and on the deterioration of oils contained in fried foods during storage in normal and fast-aging conditions (109, 112, 115, 116, 119). rquez-Ruiz et al. (119) compared regular and high-oleic sunower oils in Ma continuous and discontinuous potato frying processes. Oil deterioration was monitored in the fryer as well as in the absorbed oil, during the time of cooking and during 30 days storage at 60 C. Several conclusions may be reached: (1) high-oleic sunower oil deteriorated to a lesser extent than regular sunower oil, in either continuous or discontinuous frying; (2) products fried in high-oleic sunower oil and stored at 60 C were more stable than those fried in regular sunower oil; (3) antioxidant protection was essential for fried products requiring storage prior to their consumption. High-oleic sunower oil is the most appropriate type for industrial frying, as determined through customary deterioration indices and sensory evaluation of nal fried products. Both high-oleic and regular sunower oils are feasible alternatives for processing of prefried products stored in freezer; i.e., no sensory differences were found in frozen precooked french fries stored for 19 months at 18 C, shelf-life for this kind of product being normally 2 years. However, for crisps stored under ambient conditions, those fried in regular sunower oil had developed detectable levels of rancidity after 4 months, the process evolution being both more rapid and intense. Despite the above difference, the legal commercialization period for

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crisps is usually 3 months, making both oils suitable for manufacture of this kind of product. Studies have been made on the effect of additions of dimethyl polysiloxane (DMPS; 2 mg/kg) on frying oil performance and the storage of fried potato as crisps or french fries (109114). DMPS is an antifoaming silicone forming a monolayer over the oil surface, protecting against oxidation by air contact. The addition of DMPS is inefcient for both regular and high-oleic sunower oil in continuous frying, but it is useful in discontinuous frying where the oil surface is exposed to the atmosphere for extended time periods.
8.1.5.3. Mid-Oleic Sunower Oil With the relatively recent appearance of mid-

oleic sunower oil, researchers have shown an interest in its use in frying processes. Abidi and Warner (120) used the three types of sunower oil (regular, high, and mid-oleic) in the preparation of french fries, potato crisps, and fresh white corn tortilla chips. However, no general conclusions may be drawn regarding inherent stability as there is no indication of antioxidant type and concentration in the different oils. Kleingartner and Warner (48) summarized several studies performed with midoleic sunower oil in frying. Mid-oleic sunower oil was used successfully by several potato chip manufacturing enterprises. In July 2000, Procter & Gamble announced it would use mid-oleic sunower oil in the production of Pringles potato chips. The U.S. Department of Agricultures National Center for Agricultural Utilization Research in Peoria also carried out performance evaluations in processes of frying of tortilla chips and of french-fried potatoes. Oxidative stability was evaluated through the appearance of polar compounds during intermittent frying and through avor evolution during storage. Three years research showed that midoleic sunower oil was of higher frying quality than other nonhydrogenated oils (soybean, canola, corn, and cottonseed). Pan-frying is a popular frying method at home and in many restaurants. The panfry stabilities of two oils with similar iodine valuesmid-oleic sunower oil (NuSun) and a commercial canola oilwere compared (121). Both oils have similar pan-fry stabilities, with few signicant differences in the physicochemical properties during the heating process. 8.2. Industrial Products
8.2.1. Biodiesel The importance of biodiesel as a partial or total substitute for

petroleum-based fuels has increased in the last two decades. Already in the 1980s, studies had been made in the United States for the use of vegetable oils (mustard, canola, corn, soybean, peanut) as fuel, sunower being the preferred oil. The North Dakota State University, Agriculture Engineering Department, conducted a project to determine the effects of sunower oil used in diesel engines. The Iowa State University, College of Agriculture, also conducted studies on the use of sunower oil as fuel. Several short studies were carried out with a tractor by the USDA-SEA-AR Subtropical Texas Area unit in Weslaco (Texas). Other studies

712

SUNFLOWER OIL

were made outside the United States; for example, sunower oil was tested on a range of diesel engines in South Africa. The use of vegetable oils as a substitute for petroleum-based diesel has been replaced by use of their methyl or ethyl esters. These are produced in several countries for use in ignition engines, especially blended with petroleum diesel. Having a high population density and serious pollution problems, the development of biodiesel has been stimulated in European countries. A large number of diesel vehicles constitute a potential market for biodiesel production. In Germany, the rst commercial plant was built in 1995 with a capacity of 60,000 ton/year. In 2001, Germany produced some 500,000 ton of biodiesel. Production of methyl ester biodiesel in Italy was 200,000 ton in 2001. In France, several plants currently operate, especially for rapeseed methyl ester production, with a total biodiesel production over 300,000 ton in 2001. Rapeseed and sunower biodiesels are also produced commercially in Austria. Sunower oil, either regular or high oleic, may be used in biocarburants in the form of methyl esters. These products were already in use in Italy in 1998, pure or in blends. In Austria, high-oleic sunower was used as carburant for tractors. The French oilseed sector launched an experimental program for the incorporation of methyl esters of traditional sunower in fuels, instead of rapeseed esters, as certain regions of southern France are not suitable for rapeseed cultivation (41). Experiences with sunower-based biodiesel were carried out in Spain, Greece, and Portugal, among others. The optimization of biodiesel production by transesterication of sunower oil was studied (122). The best combination of process parameters was found to be three stoichiometric doses of methanol, 0.28% w/w of KOH, and 70 C temperature. Several reports have been published on the properties of biodiesel manufactured with different fatty materials and on their performance in compression ignition engines, including information about sunower oil and its esters (30, 31, 41, 123). Table 19 shows major properties of sunower oil and its methyl esters. The physicochemical characteristics of these esters meet the norm specications of different countries, even with improvements of some properties, such as the cetane number. Although the production of methyl esters is the easiest alternative, the production of ethyl esters from ethanol obtained from renewable starch sources, e.g., corn, poses a more interesting challenge. However, the production of ethyl esters through
TABLE 19. Properties of Sunower Oil-Based Biodiesel (30, 41, 123). Regular Oil (30) Cetane number Energy content Cloud point ( C) Flash point ( C) Density (kg/l) 37 39,575 kJ/kg 7.2 183 0.9161 Methyl Esters of Regular Oil (41) 54 39,687 MJ/kg 1 180 0.8866 Methyl Esters of Methyl Esters of Regular Oil (123) High-Oleic Oil (41) 49 33.5 MJ/l 1 274 0.860 55 39,733 MJ/kg 4 185 0.8821

WORLD PRODUCTION AND DISTRIBUTION OF SUNFLOWER OIL

713

basic catalysis is difcult to achieve because of the formation of stable emulsions. Studies have been conducted with a view to nding solutions to the problems associated with the production of ethyl esters of sunower oil (124), opening new alternatives for its use as biodiesel.
8.2.2. Lubricants Mineral-based lubricants lead the lubricant market. However,

with the advancement of the need for biodegradable products, vegetable oils have become popular, because of they are also better lubricants. The fatty acid composition of vegetable oils, however, is one major disadvantage. Oils rich in saturated fatty acids have poor low-temperature ow properties, and those rich in polyunsaturated fatty acids are of low oxidative resistance. Vegetable oils rich in monounsaturated fatty acids have optimum oxidative stability and low-temperature properties (125). In view of the higher oxidative stability of high-oleic sunower oil, it is used as diesel and gasoline engine lubricant. In France, for example, a product is commercialized containing 70 80% of high-oleic sunower oil and 20 30% other additives. Several studies have been aimed at the production of polyol esters (propyl glycol, pentaerytritol, trimethylpropane) from high-oleic sunower oil (41).
8.2.3. Vegetable Oil-Based Printing Inks

Lithography and letterpress processes require paste inks. Printing inks that are conventionally used in these applications are multicomponent systems comprising a pigment, a hydrocarbon and/or alkyd resin, a hydrocarbon solvent, and optional additives. Vegetable oil-based nonpetroleum inks have been formulated for various specialized applications. These ink formulations cost even less than petroleum oil-based ink formulations. Sunower oil is used for the manufacture of vegetable oil-based inks (126).

8.2.4. Other Applications Containing around 70% linoleic acid, sunower oil is

a semidrying oil. Insofar as economically feasible, sunower oil may replace soybean oil in the manufacture of resins for paint and press-ink formulations. Through epoxidation of sunower oil, PVC stabilizers may be obtained, and dimerization would yield products that could be used for lubricant manufacture (41). Epoxides have received increased attention in view of their interest both as endproducts and as chemical intermediates. Epoxidized oilsmainly high-oleic sunower oiland their ester derivatives have found important applications as plasticizers and additives for polyvinyl chloride (PVC). Epoxidized esters produced from high-oleic sunower methyl esters have hydroxyl values of 0, oxirane values of 5.2/ 4.5, and iodine values of 1.7/1.5 (127)

9. WORLD PRODUCTION AND DISTRIBUTION OF SUNFLOWER OIL The world production of sunower seed has grown steadily since 1950, at a lower rate toward the last several years. Figure 30 shows the evolution since 1935 (5, 128,

714
30

SUNFLOWER OIL

Sunflower Seed Production (MMT)

25

20

15

10

0 1930

1940

1950

1960

1970

1980

1990

2000

2010

Figure 30. World production of sunower seed in million of metric tons (MMT) (5, 128, 129).

129). World production of sunower seed in 2000 2001 was of 23.3 MMT, 8.9 MMT of sunower oil and 10.2 MMT of sunower meal. World production of sunower seed (7%) was third in the world production of oilseeds in 2001 2002, after soybean (57%) and canola seeds (11%). Production of soybean being by far the largest, sunower seed production does not amount to much of the world total oilseed production (129). The evolution of the sunower oil production (MMT) in the last few years is shown in Figure 31 by country/region [based on Gunstone (129)]. The world
9 Sunflower seed production (MMT) 8 7 6 5 4 3 23 2 1 0 96-97 97-98 98-99 99-00 00-01 22 21 28 27 26 25 24 Total sunflower seed production (MMT)

EU-15 Central Europe Ex.USSR Argentina total

Figure 31. Evolution of sunower seed production (MMT) by country/region in the last years compared with total world production [based on (129)].

WORLD PRODUCTION AND DISTRIBUTION OF SUNFLOWER OIL

715

others 22% soybean 31%

sunflower 8%

canola 14% palm 25%

Figure 32. Distribution of world production of vegetable oils in 20012002 [based on (129)].

production of sunower oil has changed (in both distribution and amount) in the last decade because of economic and political reasons, such as the facts occurred in exUSSR and Central Europe. In Argentina, the largest world producer of sunower oil until 1999, the substitution of sunower by more protable crops since that year resulted in a drop in sunower seed production, making ex-USSR the largest world producer (in this year, the production of sunower seeds in ex-USSR also increased markedly). In 2000/2001, EU-15 became the second largest producer. In view of the amounts produced in Argentina, the decline in sunower oil production in this country was reected in the total world production. Sunower oil production is determined by the production of sunower seed. Sunower oil is fourth in importance among vegetable oils (including oils extracted from fruits, as is the case of palm oil), as shown in Figure 32. World production of sunower oil is around 9 million metric tons, amounting to 8% of the total vegetable oil production [based on Gunstone (129)]. Despite its fourth position in the world production of vegetable oils, the participation of sunower oil is fairly low. Figure 33 shows the evolution of the world production of sunower oil in the last several years, compared with the total fat and oil world production (128, 130, 131); including the projected value for 20082012, according to the literature (132). The trend in sunower oil production is for a steady value (declining slightly), and the total fat and oil production tends to increase considerably. Figure 34 shows the evolution of the sunower oil production (MMT) by country/region in the last years, compared with the total sunower oil production [based on Gunstone (129131)]. The leading position in the producer market varies according to period, with fairly similar amounts for the European Union and Argentina (major producer countries), except for a sharp drop in Argentina in 20002001 as a result of the decrease in seed production (showed in Figure 31). As for exUSSR, it became the worlds largest producer country as of 19992000. The

716
14

SUNFLOWER OIL

140

sunflower oil
12 sunflower oil production (MMT) 10 8 6 4 2 0 93/94 94/95 95/96 96/97 97/98 98/99 99/00 00/01 01/02 02/03 08/12

total

120 total fats and oils (MMT) 100 80 60 40 20 0

Figure 33. World production of sunower oil (MMT) in the last years, compared with the total fat and oil production (MMT) (Key: Solid box real production. Open box estimated production (128, 130132).

participation of sunower oil in the world trade has declined in the last years, as shown in Figures 31 and 33. Soybeans have a strong participation in the world supply of oilseeds. The supply being oriented mainly to the production of meals rich in protein, an oversupply of soybean oil is commercialized at a lower relative price, a fact that is reected in the general composition of the vegetable oil trade.
3 Sunflower oil production (MMT) 2.5 2 1.5 1 0.5 0 96-97 97-98 98-99 99-00 00-01 9.8 9.6 9.4 9.2 9 8.8 8.6 8.4 8.2 8 7.8 Total sunflower oil production (MMT)

EU-15

Ex.USSR

Central Europe

Argentina

total

Figure 34. Sunower oil production (MMT) by country/region, compared with total world production of sunower oil [based on (129131)].

WORLD PRODUCTION AND DISTRIBUTION OF SUNFLOWER OIL

717

Others 15% Turkey 5% United States 4% Central Europe 8%

EU-15 23%

Argentina 18%

exUSSR 27%

Figure 35. Participation by country/region in the world production of sunower oil in 20012002 (based on (129131)].

Figure 35 shows the participation (%) by country/region in the world production of sunower oil in 20002001 [based on Gunstone (129131)]. The largest world producer was ex-USSR for that period (27%), followed by the European Union (23%), and Argentina (18%). The production of sunower oil may supply either the internal or external market of a region or country. The world exports distribution does not follow the same pattern as the distribution of production. The participation in sunower oil exports is shown by country/region in Figure 36 for 20002001 [based on Gunstone (129131)].
Others 17% EU-15 7%

Central Europe 4%

exUSSR 22%

Argentina 50%
Figure 36. Participation by country/region in world exports of sunower oil in 20012002 [based on (129131)].

718

SUNFLOWER OIL

For that period, the main exporter was Argentina (50%), with a participation twice as large as ex-USSR (22%) in exports, whereas the latter was the largest producer in the same period. The above gures show how a large proportion of the Argentinean production (1.18 MMT) nds its way into the external market (out of a total 1.60 MMT produced). Most of it is exported as bulk crude oil and as bottled rened oil in a lesser proportion. The amount of sunower oil produced by ex-USSR (2.40 MMT) was far larger than the exported amount (0.53 MMT), showing a large consumption (1.87 MMT) in this country of the produced oil. It is exported primarily as processed oil, mainly to the Middle East countries (Algeria, Egypt, Turkey, etc.) for later processing, demand for this type of oil being scarce in the European market. Figure 37 shows the participation by country/region in world imports of sunower oil for 20002001 [based on Gunstone (129131)]. A comparison of Figures 35 and 37 shows that major importer countries are generally not strong producers of sunower oil. In the European Union, exports of sunower oil (0.16 MMT) were balanced by imports (0.17 MMT), whereas it was a net importer of sunower seed for processing (1.94 MMT). Likewise, Central Europe exported the same amount of sunower oil (0.10 MMT) as it imported (0.13 MMT), but it was an exporter of sunower seed (0.39 MMT). These relationships of the international European market are reected in the characteristics of the internal market. A number of vegetable oils are available for consumption in the European Union, unlike the case of Argentina. Production of canola oilthe main oilis closely followed by sunower, soybean, palm, and olive oils, with regional variations. Olive oil is more important in the south of Europe (Greece, Italy, Spain, and Portugal), amounting to 36% of the total vegetable oil consumption, sunower oil also being important.

India 19%

Algeria 10% Others 59%

EU-15 7% Central Europe 5%

Figure 37. Participation in sunower oil imports by country/region in 20012002 [based on (129131)].)

SUNFLOWER OIL EXTRACTION AND PROCESSING BY-PRODUCTS

719

Consumption in the north of Europe is more varied: the market is supplied by regional oilseeds (especially canola), with sufcient sunower production in France. Soybean, sunower, canola, and palm oils together constitute nearly 80% of total vegetable oils in northern Europe (133). In 20002001, Argentina produced 1.60 MMT of sunower oil and exported 1.18 MMT (of that oil), with 0.42 MMT disappearance, 75% of which was destined for direct consumption, whereas the rest was used in the manufacture of margarine and mayonnaise. An analysis of internal demand by oil type in Argentina shows sunower oil with 70% of the trade, followed by soybean (26%), and low volumes of corn and olive oils. Use of sunower oil is widespread in this region. Sunower oil, as well as canola oil, is produced annually for sale of the oil primarily, unlike the case of soybean oil, mainly related to the demand for its meal. Sunower oil accounts for 80% of the seed price, being six to seven times higher than the price of meal pellets. The price of sunower seed is determined by the price of the extracted oil.

10. SUNFLOWER OIL EXTRACTION AND PROCESSING BY-PRODUCTS Two coproducts are originated in the sunower-seed oil extraction process: meal and hulls. Sodium soapstock is obtained as a byproduct of alkali rening of the oil, and it may contain phosphatides, depending on process type. Sunower lecithin is obtained by treatment of the oil. Less important byproducts are waxes, tocopherols, and so on. 10.1. Soapstock Sodium soapstock obtained from alkali rening of sunower oil may be used as an ingredient in animal feed meals in view of its high caloric value, in addition to being a good phosphorous source in the case of soapstock containing phosphatides. Use of soapstock is local because of transportation costs and ready fermentation, resulting from a high water content. Dehydration is often carried out prior to transportation, storage, and incorporation of soapstock into other meals. Sodium soapstock may also be subjected to treatment with mineral acids, freeing the constituent fatty acids upon decomposition of the soaps. The product thus obtained, having a very low water content, is called acid oil. Storage and transportation requirements are the same as for crude oil. Both acid oil and the free fatty acids obtained in the physical rening may be incorporated in the manufacture of soap. In view of its high linoleic acid content (in particular when originating in the rening of regular sunower oil), soapstock does not make a fatty material of good properties for the manufacture of toilet soap. To this end, it is blended in relatively low proportions with other more appropriate fatty materials. It is used in cattle producer countries also producing sunower oil as a means to reduce the titer of beef tallow or of the beef tallow/coconut oil blend.

720

SUNFLOWER OIL

A high titer is one problem of beef tallow in Argentina and Uruguay, for example: 45.4 C mean value, although it may be as high as 48 C (134, 135). Sunower oil, having a titer of 1620 C, may be added to this blend to obtain appropriate values for soap manufacture, generally considered around 42 C. 10.2. Sunower Lecithin Responding to the recommendations of food and nutrition scientists, studies have been made of new phosphoacylglyerols (phosphatides or phospholipid) sources. Oilseeds and cereals are important sources of phospholipids. The phospholipid (lecithin) content of crude sunower oil ranges from 0.5% to 1.2% (53, 136 138). Oils extracted by solvent generally have a higher phospholipid content than those obtained by pressing. Major phosphoacylglyerols of sunower oil are PC, PE, PI, and PA. Most are hydratable and may be removed from the crude oil through a water degumming process. Most published research is into the content and composition of unremoved phospholipids in sunower oil after different degumming processes. Little research has been done, however, of the separated lecithins. Some conclusions may still be reached about efciency of production method, as well as the possible composition of these lecithins from the composition of the phospholipids remaining in the oil. The fact that the phospholipid composition of sunower depends on the oil extraction method and the degumming treatment used to remove them explains the differences in the reported compositions in the literature. Phospholipid compositions of sunower oil are shown by type in Table 20 (136, 139141). The overall fatty acid composition also varies widely for the same reason. Cherry and Kramer (140) report composition ranges of 11.131.9% of palmitic acid, 3.07.9% stearic acid, 13.317.3% oleic acid, and 42.868.7% linoleic acid. Sunower lecithin is not produced in considerable amounts worldwide. This is mainly because of the low lecithin content of crude sunower oil as compared with 2.9% for soybean, 1.9% for canola, 2.4% for cottonseed, and 2.02.7% for corn oil (normalized at 70% of insolubles in acetone). Lecithin removal from sunower oil may be justied in strong sunower producer countries. It may be used as a food additive in view of its high phosphatidylcholine and essential fatty acid content. Upon rening and fractioning stages, the quality of sunower lecithin may be improved for the manufacture of food products and cosmetics.

TABLE 20. Phosphoacylglycerol Composition (%) of Sunower Oil (136, 139141). PC (%) Cherry/Kramer (140) Morrison (136) Carelli et al. (141) Chapman (139) PE (%) PI (%) 3.721.4; 24.036.6 26.0 2021 27.9 PA (%) 2.2 1215 2.2

12.726.8; 42.264.2 9.929.4; 46.6 52.0 19.7 4448 2021 48.7 21.2

SUNFLOWER OIL EXTRACTION AND PROCESSING BY-PRODUCTS

721

et al. (142) report on studies carried out in Hungary (where sunower oil Hollo represents 80% of the total vegetable oil production) about possible uses of sunower lecithin. It may be added to sunower meal by 2.5% or it may be dried, representing an increase to 5570% in the phospholipid content, prior to blending with animal feed meals. Used in swine feed meals, it leads to an increase of body weight and a shortened fattening period. It is also useful for an adjustment of the energetic level of poultry feed meals, and it replaces the addition of synthetic choline chloride, in view of the high natural choline content of sunower lecithin. It is also used in the food industry as emulsier, and as a viscosity reducer agent in the manufacture of chocolates. 10.3. Sunower Meal The remaining material from the pressing stage (expeller) of sunower seed usually contains 1012% of oil. Sunower meal is obtained as a byproduct of solvent extraction from this material. In order to facilitate handling and transportation, the meal is often compacted through pressure and temperature treatment, into the shape of sunower pellets. Sunower pellets are the fourth important oleaginous raw material used in animal feeds, after soybean, cottonseed, and canola pellets. Production of sunower pellets in Argentina, the main world producer and exporter, is around 1,900,000 tons annually, 8085% of which is exported to the Rotterdam market mainly, and the remaining 300,000 tons are destined to the local market (143). The evolution of the world production of sunower meal (MMT/year) in the last years (harvests in 1996/1997 through 2000/2001) is indicated in Figure 38,
20 18 16 14 MMT/year 12 10 8 6 4 2 0 96-97 97-98 98-99 99-00 00-01 06-10 16-20

Figure 38. World production of sunower meal (MMT/year). (Key: Solid box actual production. Open box estimated production) [based on (129)].

722

SUNFLOWER OIL

Others 26%

EU-15 26%

Central Europe 9% Argentina 16% Ex-USSR 23%

Figure 39. Production of sunower meal by major countries/regions in 20012002 [based on (129)].

including the estimated projection for the ve-year periods 2006/2010 and 2016/ 2020 [based on Gunstone (129)]. Figure 39 is a representation of the production of sunower meal (MMT/year) by major countries/regions involved. Argentina is the largest world producer (16% of the world production), although certain regionsas a group of countriesrepresent larger productions. Exports are usually from Argentina (68%) and ex-USSR (19%), and most of them reach the EU-15 (66%). Soybean meal leads the world market of oleaginous meals, sunower meal representing only 6% (129). The sunower oil extraction industry produces three kinds of meal: meal produced from undehulled seeds, containing around 28% of protein and 2528% ber; meal of partially dehulled seed, containing 3537% protein and 18% ber; and meal obtained through a two-step dehulling process of seed, containing 4042% protein and 1214% ber. The meal composition thus depends on the efciency of the dehulling process of sunower seeds. The oil content of sunower meals ranges between 1.5% and 2.5%, depending on oil extraction efciency and raw material (3, 144 146). Undehulled sunowerseed meals cannot match soybean meals in the meal market, their use being limited to ruminant feeds. In addition, sunower hulls contain a large amount of raw ber (6065%) of practically no nutritional value, so that they are almost exclusively used as ruminant feed. The amino acid composition of sunower meal is generally balanced. The energy content of sunower meal compares favorably with other oilseed meals. The energy value of a sunower meal increases with increasing residual oil content and a reduction of the ber content. Sunower meal is also valuable as a calcium and phosphorous source and a good source of hydrosoluble B complex vitamins,

SUNFLOWER OIL EXTRACTION AND PROCESSING BY-PRODUCTS

723

mainly nicotinic acid, thiamine, pantothenic acid, riboavin, and biotin (146). Sunower meal also contains chlorogenic acid, a polyphenolic compound. For meals extracted in the conventional manner under alkaline conditions, chlorogenic acid reacts with a certain protein fraction, giving the product a dark green color. Several methods have been proposed for the production of protein concentrates obtained from sunower meal through extraction or inactivation of chlorogenic acid (3, 146). Compared with soybean, cottonseed, and peanut meals, dehulled sunowerseed meals are substantially less rich in lysine, although richer in methionine and cystine. Sunower proteins are therefore a good complement for soybean meals when both are blended in animal feeds. Supplementation with lysine must generally be performed for sunower meals to be used alone as swine and poultry feeds (145). Sunower meal (blended with wheat our) can be used for human nutrition. Despite their dark color, sunower protein concentrates are of excellent digestibility. A method was proposed (147) for obtaining sunower protein concentrates from defatted wholemeal sunower our, through extraction of these proteins with a basic solution. The process yields a concentrate of 71% protein (dry basis), rich in glutamic and aspartic acids. The supernatant liquid, rich in potassium and phosphorous, can be used as agricultural fertilizer. 10.4. Hulls Hulls are obtained as a byproduct of sunower seed processing for oil extraction. The amount of hull represents around 2228% of seed weight. Hulls may be separated either prior to or upon extraction of the oil. They may also remain in the meal, making a wholemeal product. Hulls contain around 4% of crude protein, 5% of lipidic matter (including waxes, hydrocarbons, fatty acids, sterols, and triterpenic acid), 50% carbohydrates (mainly cellulose and lignin), 26% reducing sugars (mainly xylose), and 2% ash. The high ber content (6065%) and the low protein and energy content of hulls reduce their nutritional value; they are used as roughage in certain animal feeds (146). Hulls may be used as ruminant feed when nely milled and blended with other ingredients, composing the nondigestible part of the meal in view of the high content in cellulose and lignin. They may be used for an additional volume of concentrated meals and to absorb liquids such as molasses. Owing to the high content of nondigestible ber, the nutritional value of hulls as feed for farm animals is extremely low, so that they are used as livestock or poultry litter. Sunower hulls are also used as fuel, with a caloric power of 19.2 MJ/kg, and the caloric power of hull and meal is 23.6 MJ/kg, constituting an improved fuel. Hull burning is an alternative to the use of more expensive fuels in some countries. The resulting ashes are rich in potassium and may be used as fertilizers (146). Sunower hulls may also be pressed and shaped into replace logs, including wood residues. In view of their high content in reducing sugars, sunower hulls can be used for the production of ethyl alcohol and furfural. Other minor uses include building or insulation board.

724

SUNFLOWER OIL

10.5. Waxes Sunower seed oil waxes are fatty alcohol esters of fatty acids. The fatty acids are in the range of 14 to 30 carbons, with a predominance of linoleic (44.0%), oleic (18.6%), behenic (9.7%), and palmitic (9.8%) acids. The fatty alcohols have chain-lengths in the range 16 32 carbons, with a predominance of octadecanol (23.1%), nonadecanol (18.4%), and tetracosanol (11.9%). This fatty acid and alcohol prole leads to esters of 36 to 48 carbons, with a predominance of 41 carbons (14.3%), 48 carbons (13.9%), 36 carbons (13.0%), 40 carbons (11.5%), 46 carbons (11.2%), and 37 carbons (9.2%). Other authors report sunower waxes to contain fatty acids with 1630 carbons (highest occurrence of 20 and 22) and fatty alcohols in the range of 2032 carbons (highest occurrence of 24 and 26). The saponication value of these waxes is 8590 and the iodine value of 812. The melting point is 7080 C. They behave as nonpolar lipophilic compounds at temperatures below 40 C, and at higher temperatures, they adopt a crystalline state of weak hydrophilic character (53, 57, 64). These waxes are located mainly in the hull of sunower seeds (1.53%). The concentration will depend on the hybrid or seed variety, as well as on origin and storage factors. They are incorporated in the oil during oil extraction operations. The quantity of extracted wax will depend on the degree of dehulling of seeds, the extraction method (pressing or extraction by solvent), and the temperature and technology used. The wax content of crude sunower oil is usually in the range 0.020.35%, although it may reach values as high as 1%; the wax content of rened sunower oil can be as high as 60 ppm (53, 64). Sunower waxes have been used successfully as ingredient in livestock feeds, mixed with grain, silage, and so on.
4000 3500 3000

total gamma

alpha delta

Content (ppm)

2500 2000 1500 1000 500 0 corn soybean sunflower peanut cottonseed

Figure 40. Typical tocopherol levels in deodorizer distillate obtained from crude oils [based on (148)].

REFERENCES

725

10.6. Tocopherols A low percentage of tocopherols is lost during operations of oil neutralization, bleaching, and deodorization of sunower oil. The tocopherols lost during deodorization may be recovered together other volatile compounds, from the deodorizer distillate. The distillate obtained from sunower oil is also a good source of phytosterols. Figure 40 shows typical tocopherol levels in deodorizer distillate obtained from crude oils [based on Walsh et al. (148)]. The distillate obtained from sunower oil may be sold to pharmaceutical companies for tocopherol and sterol isolation. Tocopherols may be used as natural antioxidants or may be converted to vitamin E by methylating the heterocyclic ring. The interest in phytosterols is caused by the high potential of some of them to inhibit intestinal cholesterol absorption.

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