Tocopherol oil concentration in field-grown sunflower is accounted for by oil weight per seed

Tocopherols are natural antioxidants that increase the stability of fat-containing foods and perform important biological activities. Significant variations (389 to 1873 μg g oil⁻¹) in the total tocopherol concentration of sunflower seed oil have been reported. The main objectives of this work were to determine the influence of intercepted photosynthetically active radiation on tocopherol concentration during seed filling and to establish and validate relationships between tocopherol concentration in oil and other quality variables of the seed. Seven sunflower hybrids were grown under good water and nutritional conditions in two similar experiments carried out in two contrasting environments. Treatments were applied to modify the amount of radiation intercepted per plant during seed filling in order to obtain a range in oil yield per plant and its components. Greater per plant intercepted radiation decreased the tocopherol concentration in oil. Tocopherol concentration decreased when oil weight per seed increased. Tocopherol concentration stabilized for oil weight per seed higher than 23 mg oil seed⁻¹. This exponential relationship accounted for 73% of the variability in tocopherol concentration (507 to 1203 μg g oil⁻¹) despite differences in hull type, locations, hybrids, and radiation treatments. The proposed relationship acceptably predicted independent results. Crop management techniques could lead to seeds with greater concentrations of tocopherols.     

EFFECT OF SOME PHYSICAL AND CHEMICAL PROPERTIES OF OILSEEDS ON DRYING KINETICS PARAMETERS

Physical and chemical characteristics of Argentine varieties of high oleic, confectionery and oil-type sunflower seeds, soybean and rapeseed were studied in relation to drying kinetics. Page equation provided the best fit to the data. A significant difference was found in half time response between soybean and the other oilseeds. Diffusivity was positively correlated with the size of the seed (r²=0·969) and negatively (r²=0·876) with the true density independently of the oil content. Half time response tended to increase with oil content according to the grain structure. Lower true density, equivalent diameter and oil seed content were detected in high oleic sunflower varieties with respect to the traditional ones, although a similar behaviour respect drying kinetics was observed. Confectionery sunflower showed the largest size but high diffusivity and low drying rate was obtained. Rapeseed drying behaviour was similar to sunflower varieties with low oil content and high true density.     

EFFECT OF SOME PHYSICAL AND CHEMICAL PROPERTIES OF OILSEEDS ON DRYING KINETICS PARAMETERS

ABSTRACT

Physical and chemical characteristics of Argentine varieties of high oleic, confectionery and oil-type sunflower seeds, soybean and rapeseed were studied in relation to drying kinetics. Page equation provided the best fit to the data. A significant difference was found in half time response between soybean and the other oilseeds. Diffusivity was positively correlated with the size of the seed (r²=0·969) and negatively (r²=0·876) with the true density independently of the oil content. Half time response tended to increase with oil content according to the grain structure. Lower true density, equivalent diameter and oil seed content were detected in high oleic sunflower varieties with respect to the traditional ones, although a similar behaviour respect drying kinetics was observed. Confectionery sunflower showed the largest size but high diffusivity and low drying rate was obtained. Rapeseed drying behaviour was similar to sunflower varieties with low oil content and high true density.     

Determination of seed oil content and fatty acid composition in sunflower through the analysis of intact seeds, husked seeds, meal and oil by near-infrared reflectance spectroscopy

A methodological study was conducted to test the potential of near-infrared reflectance spectroscopy (NIRS) to estimate the oil content and fatty acid composition of sunflower seeds. A set of 387 intact-seed samples, each from a single plant, were scanned by NIRS, and 120 of them were selected and further scanned as husked seed, meal, and oil. All samples were analyzed for oil content (nuclear magnetic resonance) and fatty acid composition (gas chromatography), and calibration equations for oil content and individual fatty acids (C_16:0, C_16:1, C_18:0, C_18:1, and C_18:2) were developed for intact seed, husked seed, meal, and oil. For intact seed, the performance of the calibration equations was evaluated through both cross- and external validation, while cross-validation was used in the rest. The results showed that NIRS is a reliable and accurate technique to estimate these traits in sunflower oil (validation r ² ranged from 0.97 to 0.99), meal (r ² from 0.92 to 0.98), and husked seeds (r ² from 0.90 to 0.97). According to these results, there is no need to grind the seeds to scan the meal; similarly accurate results are obtained by analyzing husked seeds. The analysis of intact seeds was less accurate (r ² from 0.76 to 0.85), although it is reliable enough to use for pre-screening purposes to identify variants with significantly different fatty acid compositions from standard phenotypes. Screening of intact sunflower seeds by NIRS represents a rapid, simple, and cost-effective alternative that may be of great utility for users who need to analyze a large number of samples.     

A lipidomic approach for profiling and distinguishing seed oils of Hibiscus manihot L., flaxseed,and oil sunflower

As important oil crops in Inner Mongolia, sunflower, and flaxseed had distinct lipid profiles in seeds. As an emerging cash crop, Hibiscus manihot L. has strong potential market competitiveness. In this study, the lipidome, fatty acid composition and quality characteristics of flaxseed, H. manihot L., and sunflower seed oils were analyzed and compared. A total of 270 distinct lipids were identified and analyzed with an emerging detection approach—lipidomics, which illustrated the tremendous difference among the samples. triacylglycerol, diacylglycerol and polar lipids were the most abundant lipids in all samples. H. manihot L. seeds contained higher saturated and monounsaturated fatty acids and lower polyunsaturated fatty acids. H. manihot L. seed oil had the longest oxidative stability index time, high content of vitamin E and total phenolics, while flaxseed oil embodied the lowest oxidative stability. The peroxide value and acid value of the three oils were within the allowable range of Chinese national standards.     

Storage of sunflower‐seeds: variation on the wax content of the oil

Storage conditions of oil seeds before industrial extraction might influence the quality of the crude oil. The objective of this work was to study the influence of sunflower seed storage conditions (temperature and time) on the quality of the resulting oil in terms of its wax content and composition. Sunflower seeds were stored under different conditions, 10, 21 and 37 °C, in sealed recipients. Extractions of the seeds with hexane were made to obtain the oil at different storage times. The amount of oil extracted (25–40%) showed no significant differences with storage conditions. Wax content of the samples was determined with two different methods (laser polarized turbidimetry and microscopy), and results showed that wax concentration increased with storage conditions (time and temperature). Composition of wax components, determined using capillary gas chromatography, during storage was approximately constant for C₃₅–C₃₉ and showed significant differences for C₄₀–C₄₈ components. Waxes with high carbon number cause more turbidity than waxes with low carbon number, due to their higher melting point, resulting in a low‐quality crude oil and therefore in variations in processing conditions during the oil refining. According to the data showed in this study, seed storage at low temperatures during short periods of time may be the more adequate conditions to obtain high‐quality oil.     

Virgin sunflower oil

Sunflower oil is the second most important virgin oil in Europe but, from the nutritional point of view, the assessment of this oil has become increasingly poorer over the last few years because of the high amount of linoleic acid in traditional sunflower seeds. Today sunflower oil with a high oleic acid content is coming more into the focus of interest since the fatty acid composition is more comparable to rapeseed and olive oil. Another important aspect is that the high content of oleic acid results in a high oxidative stability, making this oil interesting for a wide range of applications. A special challenge is the production of high‐quality tasty virgin sunflower oil because, in contrast to other raw materials, about 30% of sunflower seeds consist of hulls that are covered by waxes. During oil processing these waxes are co‐extracted with the oil, resulting in undesired turbidity of the oil on storage. Pressing of the raw material is done in a screw press or expeller and results in residue fat contents between 7 and 15% depending on the pressing conditions. We discuss two possibilities to avoid or to remove waxes by dehulling of the seeds or winterisation of the resulting oil. Dehulling is carried out by an impact dehuller with removal of the hulls by airflow and gravity. Removal of hulls before pressing improves the sensory quality of the oil because it results in products with a mild sunflower seed‐like nutty taste, while oils from whole seeds often have a woody and bitter taste. In addition, the development of heat during pressing is reduced if dehulled seeds are used for oil production. Conventional sunflower seeds are processed mainly in big oil mills, whereas in small and medium‐sized facilities organic raw material is in use.     

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

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

Wax composition of sunflower seed oils

Waxes are natural components of sunflower oils, consisting mainly of esters of FA with fatty alcohols, that are partially removed in the winterization process during oil refining. The wax composition of sunflower seed as well as the influence of processing on the oil wax concentration was studied using capillary GLC. Sunflower oils obtained by solvent extraction from whole seed, dehulled seed, and seed hulls were analyzed and compared with commercial crude and refined oils. The main components of crude sunflower oil waxes were esters having carbon atom numbers between 36 and 48, with a high concentration in the C₄₀−C₄₂ fraction. Extracted oils showed higher concentrations of waxes than those obtained by pressing, especially in the higher M.W. fraction, but the wax content was not affected significantly by water degumming. The hull contribution to the sunflower oil wax content was higher than 40 wt%, resulting in 75 wt % in the crystallized fraction. The oil wax content could be reduced appreciably by hexane washing or partial dehulling of the seed. Waxes in dewaxed and refined sunflower oils were mainly constituted by esters containing fewer than 42 carbon atoms, indicating that these were mostly soluble and remained in the oil after processing.     

An analysis scheme for estimation of crude oil quality

A seed analysis scheme was designed to rapidly estimate the quality of extracted oil. Factors of crude oil quality evaluated were: free fatty acids, oxidative status (Totox value), color, and phosphatides (soybean) or wax (sunflower). Soybean and sunflower seeds subjected to extended storage at varying moisture contents were sampled at incremental time periods to yield fifty storage-damaged samples of each oilseed. Oil was extracted from 50-g lots of each sample and analyzed for the crude oil quality factors according to standard methods. Alternative instrumental and chemical analyses of the quality factors were correlated with the standard methods. Hexanal content, measured by headspace-gas Chromatographie analysis of the ground full-fat meal, was correlated to the oxidative status. Crude oils recovered by rapid extraction, using sonication, and desolventation were monitored by spectrophotometry for color correlation. Free fatty acid content was determined by titration methods and monitored by spectrophotometry. Modified turbidimetric methods estimated the phosphatides (soybean) or wax (sunflower seed) contents. The analysis scheme provides for the rapid estimation of oil quality as impacted by various pre- and post-harvest events that cause deterioration of oilseeds. The mention of firm names or trade products does not imply that they arc endorsed or recommended over other firms or similar products not mentioned.     

Nondestructive determination of fatty acid composition of husked sunflower (Helianthus annua L.) seeds by near-infrared spectroscopy

Determination of the fatty acid composition of sunflower (Helianthus annua L.) seeds by near-infrared (NIR) spectroscopy was examined. Sunflower seeds were husked (removed from their hulls by a husking machine or manually with a knife). NIR spectra of these seeds were scanned from 1100 to 2500 nm at 2-nm intervals in a whole-grain cell with a wideangle moving drawer for machine-husked seeds or in a single-grain cup for a manually husked single-grain seed. The extracted oils from machine-husked seeds also were scanned by sandwiching them between a pair of slide glasses to create a thin layer and by placing them on a syrup cup. For extracted oil, the absorption band around 1720 nm filled out to the shorter wavelength region in the NIR second-derivative spectra as the percentage of the linoleic acid moiety increased, because linoleic acid absorbs in this region. On the other hand, for husked seeds and for a single-grain seed, as the percentage of linoleic acid increased, the trough at 1724 nm where oleic and saturated acids absorb decreased in the second-derivative NIR spectra. Determination of the fatty acid composition of sunflower seeds could be carried out successfully according to the NIR spectral pattern for both extracted oil (r=−0.989) and kernel seed (r=−0.993). This is important, especially for a manually husked single-grain seed (r=−0.971), because it can still be germinated after such nondestructive analysis.     

A twin-screw extruder for oil extraction: I. Direct expression of oleic sunflower seeds

Lipids are traditionally removed from seeds by mechanical crushing and solvent extraction. During the mechanical crushing process the oilseed is cleaned, cracked, flaked, and cooked before entering a mechanical screw press. Seventy-five percent of the oil of sunflower seeds can be extracted by crushing, and the fatty cake then contains about 15% of oil. The oil levels remaining in the cake can be reduced to less than 2% by solvent extraction. However, the crude oil has to be refined as it contains many impurities and approximately 600 ppm phosphorus. A new process, in which sunflower seeds are pressed in a twin-screw extruder, is examined here. The screw profile was first optimized. Oleic sunflower seeds were crushed and 80% of the oil was removed. The resultant oil was of good quality, with acid numbers below 2 mg KOH/g of oil and total phosphorus contents of about 100 ppm. The influence of pressing temperature and of fresh seed moisture content was determined. High pressing temperature and low moisture content improved oil extraction. The quality of the meal was examined through the solubilization of its proteins in alkaline water at 50°C. The fatty meal proteins remained quite soluble, and therefore one can assume that they were still relatively close to their native conformation. The pressing of oleaginous material in a twin-screw extruder provides a new option to traditional processes. Presented as an oral communication at the 2nd American Oil Chemists’ Society Europe Symposium, October 1–4, 1998, at Cagliari, Italy.     

Performance of sunflower oil with high levels of oleic and palmitic acids during industrial frying of almonds,peanuts, and sunflower seeds

High-oleic, high-palmitic sunflower oil (HOHPSO) is a seed oil from a new mutant sunflower line characterized by increased levels of both oleic acid (>50%) and palmitic acid (>25%) and a high oxidative stability. In this study, its performance at frying temperature was compared with that of palm olein in thermoxidative assays (4 h, 180°C). Also, industrial discontinuous frying of almonds, peanuts, and sunflower seeds (200 kg of each product) was carried out to define both the performance of HOHPSO and the main changes undergone by the foods. The evaluation of polar compounds and their distribution in the main groups, i.e., polymers, oxidized monomers, and DAG, as well as changes in tocopherols and oxidative stability, demonstrated the excellent behavior of HOHPSO during thermoxidation and frying. The increase in polar compounds and the loss of tocopherols and stability were much lower for HOHPSO than for palm olein under identical heating conditions. Only 1.3% polar compounds were formed during industrial discontiuous frying for 4 h and the oil stability increased, probably due to the formation of antioxidant compounds. As for the foods, the FA composition of the surface oil was clearly different from that corresponding to the internal oil, the former denoting the presence of HOHPSO in high concentration, particularly in fried sunflower seeds. Changes in oil stability of the foods attributable to the frying process clearly demonstrate the interest in using a highly stable oil such as HOHPSO to protect the surface against oxidation during food storage.     

Determination of tocopherols and phytosterols in sunflower seeds by NIR spectrometry

The objective of this work was to develop a near‐infrared reflectance spectrometry (NIRS) calibration estimating the tocopherol and phytosterol contents in sunflower seeds. Approximately 1000 samples of grinded sunflower kernels were scanned by NIRS at 2‐nm intervals from 400 to 2500 nm. For each sample, standard measurements of tocopherol and phytosterol contents were performed. The total tocopherol content was obtained by high‐performance liquid chromatography coupled with a fluorescence detector, while the total phytosterol content was assessed by gas chromatography. For tocopherol, the calibration data set ranged from 175 to 1005 mg/kg oil (mean value around 510 ± 140 mg/kg oil), whereas for the phytosterol content, the calibration data set ranged from 180 to 470 mg/100 g oil (mean value of 320 ± 50 mg/100 g oil). The NIRS calibration showed a relatively good correlation (R² = 0.64) between predicted by NIRS and real values for the total tocopherol content but a poor correlation for the total phytosterol content (R² = 0.27). These results indicate that NIRS could be useful to classify samples with high and low tocopherol content. In contrast, the estimation of phytosterol contents by NIRS needs further investigation. Moreover, in this study, calibration was obtained by a modified partial least‐squares method; the use of other mathematical treatments can be suitable, particularly for total phytosterol content estimation.     

Chemical characterization of oils and meals from wild sunflower (<Emphasis Type="Italic">helianthus petiolaris</Emphasis> nutt)

Chemical characterizations of oils and meals from the wild sunflower species Helianthus petiolaris Nutt and their comparison with those from cultivated sunflower (H. annuus) were performed. Seeds from indigenous populations of H. petiolaris were harvested in Argentina in different years. The analytical parameters studied were as follows: (i) FA profile, PV, p-anisidine value, oxidative stability, phosphorus and phospholipid content, tocopherols, polar compounds, and waxes in the extracted oils; and (ii) moisture, ash, crude fiber, metals, sugars, urease activity, starch, protein, available lysine, neutral detergent fiber, acid detergent fiber, lignin, gross energy, and amino acid content in the residual meals. The products from wild sunflower seed, which yielded 27–30% oil by solvent extraction, showed some characteristics similar to the commercial products. Nevertheless, the oil had lower quality and stability owing to the high unsaturation levels and lower concentrations of antioxidant components, and the meal had a lower protein content. The phospholipid content was significantly lower than in industrial crude sunflower oils. Most of the important parameters in the meal such as available lysine, gross energy, and digestibility compared favorably with those for cultivated sunflower meals. The results showed the potential for using these meals for animal feed.     

Tocopherols,Tocotrienols and Carotenoids in Kernel Oils Recovered from 15 Apricot (<Emphasis Type="Italic">Prunus armeniaca</Emphasis> L.) Genotypes

We studied the content of tocopherols, tocotrienols and carotenoids in oil extracted from the kernels of 15 apricot (Prunus armeniaca L.) genotypes and the associated oil yield of the studied samples. The oil yield in apricot kernels was in a wide range of 27.2–61.4% (w/w) dry weight basis. For each class of studied compounds (tocochromanols and carotenoids), a three-fold difference was found between the lowest and the highest content (78.8–258.5 and 0.15–0.53 mg/100 g of oil, respectively). γ-Tocopherol accounted for 91–94% of total tocochromanols detected in all tested samples. Lutein, zeaxanthin, β-cryptoxanthin and β-carotene were the main compounds among the eight different carotenoids detected in apricot kernel oils; they comprised 76–94% of the total carotenoids content, and compositions were characteristic for specific genotypes. The oil yield and content of lipophilic antioxidants in apricot kernel oils were significantly affected by the genotype. The oil yield was negatively correlated with the total amount of tocochromanols (r = ?0.910) and carotenoids (r = ?0.704) in apricot kernel oils.     

Phospholipid molecular profiles in the seed kernel from different sunflower (Helianthus annuus) mutants

Phospholipids are essential components of plant cell membranes whose acyl composition appears to be influenced by oil composition in the sunflower. In the current study, we have determined the diacylglycerol profile of the main phospholipids using phospholipase C degradation and separation of the diacylglycerols by HPLC and GLC. The main polar lipid molecular species were defined in different classes of sunflower kernel: PC, PE, and PI. The proportions of each were determined at different stages of development in order to define the point at which the mutations carried by each sunflower line affected the phospholipid composition of the seeds. The results indicated that modifications to intraplastidial de novo FA synthesis affected the seed phospholipid profile during the whole period of the seed formation, including accumulation and maturation, whereas the influence of mutations in the endoplasmic reticulum desaturases were more readily detected at later stages of development. These results are discussed in terms of the pathways involved in glycerolipid synthesis and phospholipid conversion in sunflower seeds.     

Tocopherol—An intrinsic component of sunflower seed oil bodies

Oil bodies were removed from mature sunflower through wet grinding followed by filtration then centrifugation and recovered as the buoyant fraction. Washing this fraction with buffer (water-washed oil bodies, WWOB) or 9 M urea (urea-washed oil bodies, UWOB) resulted in the removal of extraneous proteins. SDS-PAGE of the proteins still associated with the oil body fraction after washing indicated that this effect was particularly dramatic with urea washing. Thirty-eight percent of the total seed tocopherol was recovered in WWOB after only one cycle of oil body recovery. The total phenolic content (TPC) of differentially washed sunflower seed oil bodies was used as a marker for the nonspecific association of phenolic compounds to oil bodies. This value decreased with increased removal of proteins from oil bodies, whereas the converse was true for tocopherol values, which increased from 214 mg total tocopherol kg⁻¹ WWOB [dry wt basis (dwb)] to 392 mg total tocopherol kg⁻¹ UWOB (dwb). The ratio of the four tocopherol isomers remained constant in the seed and oil body preparations (α:β:γ:δ approximately 94∶5∶0.5∶0.5). This work provides evidence that an intrinsic population of tocopherol molecules exists in the oil bodies of mature sunflower seeds.     

Supercritical fluid extraction in sunflower seed technology

Sunflower (Helianthus annuus L.) seed represents an important source for edible oil and its protein fraction is also recognised as valuable for human consumption when suitably purified from polyphenols, which negatively affect colour and nutritional value. On this basis, a main research has been developed, with the aim of testing the technical feasibility of a supercritical fluid extraction (SFE) process involving a preliminary supercritical CO₂ (SC‐CO₂) extraction of oil from sunflower de‐hulled seeds, followed by the removal of polyphenols from de‐fatted meal by means of ethanol coupled with SC‐CO₂. The paper reports the experimental protocol followed, together with the kinetics of the extractions, knowledge of which allows the optimisation of working parameters and the determination of process yields.