Effect of Extraction Method on the Oxidative Stability of Camelina Seed Oil Studied by Differential Scanning Calorimetry

Camelina seed is a new alternative omega‐3 source attracting growing interest. However, it is susceptible to oxidation due to its high omega‐3 content. The objective of this study was to improve the oxidative stability of the camelina seed oil at the extraction stage in order to eliminate or minimize the use of additive antioxidants. Camelina seed oil extracts were enriched in terms of natural antioxidants using ethanol‐modified supercritical carbon dioxide (SC‐CO₂) extraction. Oxidative stability of the camelina seed oils extracted by ethanol modified SC‐CO₂ was studied by differential scanning calorimeter (DSC), and compared with cold press, hexane, and SC‐CO₂ methods. Nonisothermal oxidation kinetics of the oils obtained by different extraction methods were studied by DSC at varying heating rates (2.5, 5, 10, and 15 ° C/min). Increasing ethanol level in the ethanol‐modified SC‐CO₂ increased the oxidative stability. Based on oxidation onset temperatures (T_on), SC‐CO₂ containing 10% ethanol yielded the most stable oil. Oxidative stability depended on the type and content of the polar fractions, namely, phenolic compounds and phospholipids. Phenolic compounds acted as natural antioxidants, whereas increased phospholipid contents decreased the stability. Study has shown that the oxidative stability of the oils can be improved at the extraction stage and this may eliminate the need for additive antioxidants.     

Effect of fruit ripeness and method of fruit drying on the extractability of avocado oil with hexane and supercritical carbon dioxide

BACKGROUND: Oil yield from avocado fruit may be influenced by fruit pre‐treatment and extraction method. Unripe and ripe avocado fruit pieces were deep‐frozen at ? 20 °C and either freeze‐dried or oven‐dried (80 °C). Oil yield from these samples was determined after extraction with hexane and supercritical carbon dioxide (SC‐CO₂). The fruit samples were examined using scanning electron microscopy before and after oil extraction. RESULTS: Average oil yield from ripe fruit (freeze‐dried and oven‐dried combined) was 72 g kg^?1 higher than from unripe fruit for SC‐CO₂ extracts and 61 g kg^?1 higher for hexane extracts. This may be due to enzymatic degradation of parenchyma cell walls during ripening, thus making the oil more available for extraction. Freeze‐dried samples had a mean oil yield 55 g kg^?1 greater than oven‐dried samples for SC‐CO₂ extracts and 31 g kg^?1 higher for hexane extracts. However, oil yields from ripe fruit (freeze‐dried and oven‐dried) subjected to hexane extraction were not significantly different. All hexane extracts combined had a mean oil yield 93 g kg^?1 higher than SC‐CO₂ extracts. CONCLUSION: SC‐CO₂ may be more selective and may create paths of least resistance through the plant material. Hexane, on the other hand, is less selective and permeates the whole plant material, leading to more complete extraction and higher oil yields under the experimental conditions. Copyright © 2007 Society of Chemical Industry     

Supercritical CO2 extraction of fatty oil from flaxseed and comparison with screw press expression and solvent extraction processes

Flax oil is commonly used in food due to high percentage of omega-3-fatty acid and omega-6-fatty acid. In the present work the flax seed was extracted using green solvent viz. supercritical CO₂ and compared with soxhlet and mechanical screw press methods. The chemical compositions of the oils were determined by CHNS analyser, GC-FID, GC/MS and ¹H NMR. The supercritical CO₂ process selectively extracted the fatty oils with high percentage of omega-3-fatty acid and omega-6-fatty acids. The chemical composition of screw press oil is close to that of supercritical CO₂ extracted oil, whereas the yield is nearly 27% less in comparison to the supercritical CO₂ method.     

改良的DPPH与ABTS自由基法评价不同葡萄籽油抗氧化能力

本研究采用改良的1,1-二苯基-2-三硝基苯肼(1,1-diphenyl-2-picryhydrazyl,DPPH)法和2,2'-联氮双-(3-乙基苯并噻唑林-6-磺酸)二胺盐[2,2'-azinobis(3-ethylbenzothi azoline-6-sulfonic acid)ammonium salt,ABTS]法测定不同方法提取葡萄籽油极性部分、非极性部分及全油的抗氧化能力,测定不同葡萄籽油多酚含量,研究多酚与葡萄籽油极性部分抗氧化能力的相关性。热榨毛油与溶剂法毛油在经过精炼后多酚含量和抗氧化能力显著降低;在溶剂法精炼油、热榨法精炼油、低温压榨油、超临界CO_2萃取葡萄籽油中,低温压榨油极性部分清除DPPH与ABTS自由基的能力最强,低温压榨油的多酚含量最高,超临界CO_2萃取葡萄籽油非极性部分与低温压榨油全油的DPPH与ABTS自由基清除能力最强;各不同葡萄籽油总酚含量与极性部分DPPH和ABTS自由基的清除能力具有显著的正相关性。     

Impact of Roasting on the Chemical Composition and Oxidative Stability of Perilla Oil

Abstract: The impact of roasting was observed with regard to certain changes in the chemical components and oxidative stability of oil expelled from the roasted perilla seeds. The roasting times were established differently at each roasting temperature of 180, 200, and 220 °C. Trans fatty acids in perilla oil were detected, and the level detected increased as the roasting time increased. Moreover, the roasting of perilla seed led to an increase of 4 tocopherols, α‐, β‐, γ‐, and δ‐tocopherol, as well as phosphorus in the oil. The oxidative stability of the oils obtained after roasting increased during 60 d of storage at 60 °C. The rate of decrease of tocopherol in the oil from unroasted perilla seed was faster than that of the tocopherol in the oils from roasted perilla seeds during storage. Practical Application: The results reported in present research provide useful information that the producers of perilla oil could apply for their processing.     

LIFE CYCLE ASSESSMENT OF SOYBEAN OIL PRODUCTION

A life cycle assessment (LCA) case study was conducted on the processing of soybeans to soybean oil. Three stages of soybean oil processing are studied in detail: preprocessing, extraction and separation, and postprocessing. For extraction, hexane (current industrial process) and supercritical CO₂ (research and development [R & D ] laboratory‐scale process) methods are compared in detail. The initial life cycle comparison found that the laboratory‐scale CO₂ system was not as good in life cycle impacts as the hexane system. However, reasonable engineering improvements typical of scale‐up practices would make the CO₂ technology better than hexane and eliminate the hexane emissions. Utilization of membrane techniques to separate the small molecular CO₂ from the soybean oil hydrocarbon appears to be a much better R & D direction for development. This article illustrates the ability to use life cycle as an aid to R & D to select more advantageous directions for process improvement.     

不同方法制备的美藤果油品质研究

对美藤果成分进行了分析,并对乙醚萃取、超临界CO_2萃取以及压榨制备的美藤果油的品质进行研究。结果表明:美藤果全籽粗脂肪含量为32.88%,美藤果仁粗脂肪含量为51.86%,美藤果仁中粗蛋白质含量为23.23%;3种方法制备的美藤果油皂化值、碘值以及脂肪酸组成和含量并无明显的差异,均含有较高的不饱和脂肪酸(92%),且以亚麻酸和亚油酸为主;美藤果油中生育酚主要为γ-生育酚和δ-生育酚;超临界CO_2萃取和乙醚萃取的美藤果油中甾醇和生育酚含量稍高于压榨美藤果油,其中超临界CO_2萃取的美藤果油中生育酚含量较高,乙醚萃取的美藤果油中游离态甾醇和酯态甾醇含量较高。     

Distribution of microbes in supercritical CO2 extraction of sea buckthorn (Hippopha? rhamnoides) oils

 The distribution of vegetative microbial cells and their spores in a supercritical CO₂ extraction process was studied. The seed and flesh/skin fractions of the press residue of sea buckthorn berries (Hippopha? rhamnoides) from a juice factory were used as raw materials. A pilot-scale extraction plant was operated at 30 MPa at temperatures of 40 and 60°C. The number of yeasts, moulds and bacteria in the pulp/skin fraction, in the extraction residues, in the extracted oils as well as in the water phases separated from the extracted oils was estimated by the spread plate technique. The microbial content of the flesh/skin material was increased in some extractions by the addition of bacterial spores. In general, the extraction process led to a decrease in the bacterial count of the extracted material, whereas no microbial growth was detected in the oils extracted or in the water phases separated from them. Neither yeasts nor moulds were found in any samples after the extraction process. The microbial status of seed oil and flesh/skin oil obtained by industrial-scale CO₂ extraction at 40°C and at 30 MPa before and after gelatine encapsulation remained unchanged. This proves that supercritical CO₂ can be used to manufacture edible oil products free of living micro-organisms and their spores. Received: 14 May 1996     

Tocol Composition and Supercritical Carbon Dioxide Extraction of Lipids from Barley Pearling Flour

Samples of whole grain and 35% pearling flour of 20 different barley varieties grown in Alberta were analyzed for their lipid contents. Total lipid contents of whole grains were within 1.9% to 3.0% (w/w), whereas those of the 35% pearling flour were 4.3% to 7.9%. Lipids of 35% pearling flour fraction of Tercel barley were extracted using supercritical carbon dioxide (SC‐CO₂) at different pressures (24, 45, and 58 MPa) and temperatures (40 and 60 °C) for 3 h. Lipid recoveries of 73% to 97% were achieved using SC‐CO₂ extraction under different operational conditions. Tocol contents and compositions of whole grain, 35% pearling flour, and SC‐CO₂ extracts were analyzed using HPLC. Tocol content of the whole grain was 53.8 to 124.9 μg/g and that of the pearling flour was 195 to 363 μg/g of flour. The hulless barley varieties were higher in tocols, with waxy, double waxy and Tercel varieties having the highest levels (P < 0.05). The ratios of total tocotrienols to total tocopherols varied within 1.6 to 3.9 range. Tocol concentrations of SC‐CO₂ extract fractions varied from 1171 to 4391 μg/g extract depending on the operational conditions. Barley oil is a good natural source of different tocol isomers rich in tocotrienols.     

Distribution of microbes in supercritical CO2 extraction of sea buckthorn (Hippophaë rhamnoides) oils

The distribution of vegetative microbial cells and their spores in a supercritical CO₂ extraction process was studied. The seed and flesh/skin fractions of the press residue of sea buckthorn berries (Hippophaë rhamnoides) from a juice factory were used as raw materials. A pilot-scale extraction plant was operated at 30?MPa at temperatures of 40 and 60°C. The number of yeasts, moulds and bacteria in the pulp/skin fraction, in the extraction residues, in the extracted oils as well as in the water phases separated from the extracted oils was estimated by the spread plate technique. The microbial content of the flesh/skin material was increased in some extractions by the addition of bacterial spores. In general, the extraction process led to a decrease in the bacterial count of the extracted material, whereas no microbial growth was detected in the oils extracted or in the water phases separated from them. Neither yeasts nor moulds were found in any samples after the extraction process. The microbial status of seed oil and flesh/skin oil obtained by industrial-scale CO₂ extraction at 40°C and at 30?MPa before and after gelatine encapsulation remained unchanged. This proves that supercritical CO₂ can be used to manufacture edible oil products free of living micro-organisms and their spores.     

Original article: Extraction of lipid from scallop (Patinopecten yessoensis) viscera by enzyme‐assisted solvent and supercritical carbon dioxide methods

In the present study, lipid was extracted from scallop (Patinopecten yessoensis) viscera by using the enzyme‐assisted solvent method and the supercritical carbon dioxide (SC‐CO₂) method. Soxhlet extraction with ethyl ether produced a yield of 23.7 ± 0.6 g of lipid 100 g^?1 of dry matter. Enzyme‐assisted solvent extraction allowed recovering 60.6 ± 1.5% of P. yessoensis viscera lipid from the samples treated with papain, whereas a lipid recovery rate of 78.3 ± 0.6% was achieved by SC‐CO₂ extraction. The lipid extracted was divided into the unsaponifiable fraction (sterol) and the saponifiable fraction (fatty acid) and analysed by gas chromatography mass spectrometry. Results indicated that the fatty acid composition and sterol composition for lipids extracted by different methods were slightly different. Eicosapentaenoic acid and docosahexaenoic acid were dominant polyunsaturated fatty acids accounting for 35–40% of the total fatty acid.     

Comparative evaluation of the composition of vegetable essential and fixed oils obtained by supercritical extraction and conventional techniques: a chemometric approach

We compared by a chemometric approach the composition of essential (EO) and fixed (FO) oils previously obtained from several vegetable matrices by supercritical CO₂ extraction (CO₂-SFE) and conventional techniques (n-hexane in a Soxhlet apparatus and hydrodistillation). A multivariate approach, by determining the principal components analysis (PCA) applied to data of FO fatty acids and EO volatile compounds, generally indicated that the vegetable oils extracted with CO₂-SFE tightly clustered with those obtained by conventional methods. The graphical distances calculated in the PCA plots between the score of each SFE oil and the corresponding conventional oil revealed that the CO₂-SFE FO and EO profiles were quite similar to conventional oils, with the additional benefit of not having unwanted traces of solvent. SFE FO were more similar to conventional oils than SFE EO (mean values of calculated graphical distances were 0.83 and 1.46 for FO and EO, respectively). Our results strongly corroborate the role of CO₂-SFE as a suitable, environmentally safe and efficient method alternative to the traditional ones for the extraction of natural vegetable oils for food and pharmaceutical applications.     

Effect of supercritical CO2 extraction process parameters on oil yield and pigment content from by‐product hemp cake

This research gives an insight into the possibility of exploiting the one of the food industry's by‐products – pressed hemp cake. The complete recovery of oil from pressed hemp cake was achieved. Residual oil that remained in cake after pressing was extracted with supercritical CO₂ by applying different process parameters. Optimal extraction conditions were determined using response surface methodology. Total pigment contents of the oils obtained were determined. Extraction pressure had the most significant influence on yield and pigment content of extracted hemp cake oil. Depending on the pressure, the chlorophyll a content ranged from 101.11 to 378.28 mg kg^?1 and chlorophyll b from 65.14 to 189.78 mg kg^?1, while total carotene content was in the range from 33.58 to 132.67 mg kg^?1. The remaining oil in pressed hemp cake after supercritical CO₂ extraction was determined to be 0.56 ± 0.08% and the defatted cake was rich in proteins and fibre.     

Singlet Oxygen‐Related Photooxidative Stability and Antioxidant Changes of Diacylglycerol‐Rich Oil Derived from Mixture of Olive and Perilla Oil

Abstract: This study investigated the oxidative stability and antioxidants changes in diacylglycerol (DAG)‐rich oil under singlet oxygen. DAG‐rich oil was derived from triacylglycerol (TAG) oil of extra virgin olive and perilla oil mixture by hydrolysis and re‐esterification using lipases. The oxidation of oils was performed at 25 °C for 48 h under singlet oxygen produced with chlorophyll b under light, and was evaluated by headspace oxygen consumption and peroxide value (POV). The oxidation of DAG‐rich oil was higher and faster in the co‐presence of light and chlorophyll than in their single presence. DAG‐rich oil was more oxidation‐susceptible than TAG oil. There was no significant change in fatty acid and lipid subclass compositions in DAG‐rich oil during the photooxidation. Tocopherols were degraded, whereas polyphenols weren't during phootooxidation of DAG‐rich oil. The oxidation of DAG‐rich oil was well‐correlated with tocopherol contents, not with polyphenol contents, indicating that tocopherols were effective antioxidants in the singlet oxygen‐related phootooxidation of DAG‐rich oil. The results suggested that the oxidative stability of DAG‐rich oil under singlet oxygen be improved by a precise control through retention of tocopherols. Practical Application: The results of this study can be applied to the utilization of diacylglycerol oils to the area of functional edible oils with good oxidative stability.     

紫苏不同部位精油成分及体外抗氧化能力的比较研究

采用同时蒸馏萃取法提取紫苏不同部位(叶、花蕾、梗和籽)精油,利用气相色谱-质谱法对精油成分进行分析,并比较不同部位精油体外抗氧化能力。结果表明：紫苏叶精油得率相对最高,达到8.21‰。从紫苏叶、花蕾、梗和籽精油中依次鉴定出40、53、29和26种组分,分别占各自精油总量的99.85%、99.25%、96.73%和97.51%。不同部位精油成分和相对含量差异显著,共有组分仅5种,分别是2-己酰呋喃、4-(2-甲基环己烯)-2-丁烯醛、石竹烯、芳樟醇和石竹素,其中相对含量最高的组分均是2-己酰呋喃。紫苏不同部位精油均具有一定的抗氧化能力,紫苏叶精油清除DPPH自由基的能力较强,紫苏籽精油清除羟自由基的能力较强。     

Evaluating two kinds of centrifuged virgin oils arising from continuous olive processing

Oils extracted from olive pastes by the direct centrifugation mode were compared with the homologous oils produced by the indirect centrifugation (after percolation) mode. The former were characterised by: (i) higher contents of total phenols, o‐diphenols, hydroxytyrosol, hydroxytyrosol‐aglycons, total volatiles, trans‐2‐hexanal and other pleasant volatiles, total tocopherols, total sterols and waxes; (ii) lower contents of triterpene dialcohols, aliphatic and triterpene alcohols, chlorophylls and pheophytins; (iii) lower values of integral colour index; (iv) higher values of turbidity, campesterol/stigmasterol ratio, 1,2‐diglycerides/1,3‐diglycerides ratio, oxidative stability and overall quality indices; and (v) higher sensory score. Stigmastadienes and trans‐isomer C₁₈ fatty acids were always not detected. The average oil outputs of the two centrifugation extraction procedures were comparable, as confirmed by similar overall oil amounts found in the by‐products. © 2000 Society of Chemical Industry     

Physicochemical properties of Kalahari melon seed oil following extractions using solvent and aqueous enzymatic methods

The physico‐chemical properties of oil from Kalahari melon seed were determined following extraction with petroleum ether and aqueous‐enzymatic methods. Two different enzymes Flavourzyme 1000 L and Neutrase 0.8 L were separately used during aqueous‐enzymatic method. The free fatty acid, peroxide, iodine and the saponification values of the oils extracted using the methods were found to be significantly (P < 0.05) different. The melting point of the oils extracted was in the range of ?18.7 °C to ?17.5 °C and no significant (P > 0.05) difference between the oil obtained from solvent and aqueous‐enzymatic extractions was observed. Enzyme‐extracted oil tended to be light‐coloured and more yellow in colour compared with solvent‐extracted oil. The predominant fatty acids in the extracted oils were linoleic acid (62.2–63.1%), with some oleic (16.8–17.1%), palmitic (11.4–12.4%), stearic (7.5–8.1%), linolenic (0.7–1.2%) and eicosenoic (0.3%). Phenolic acids in enzyme‐extracted oils were comparable to the solvent‐extracted oil. The oils extracted with these two methods were differed in the composition of their phytosterol and tocopherol contents, but no significant (P > 0.05) difference between the two enzyme‐extracted oils was observed.     

Temperature Dependence of Autoxidation of Perilla Oil and Tocopherol Degradation

Abstract: Temperature dependence of the autoxidation of perilla oil and tocopherol degradation was studied with corn oil as a reference. The oils were oxidized in the dark at 20, 40, 60, and 80 °C. Oil oxidation was determined by peroxide and conjugated dienoic acid values. Tocopherols in the oils were quantified by HPLC. The oxidation of both oils increased with oxidation time and temperature. Induction periods for oil autoxidation decreased with temperature, and were longer in corn oil than in perilla oil, indicating higher sensitivity of perilla oil to oxidation. However, time lag for tocopherol degradation was longer in perilla oil, indicating higher stability of tocopherols in perilla oil than in corn oil. Activation energies for oil autoxidation and tocopherol degradation were higher in perilla oil (23.9 to 24.2, 9.8 kcal/mol, respectively) than in corn oil (12.5 to 15.8, 8.8 kcal/mol, respectively) indicating higher temperature-dependence in perilla oil. Higher stability of tocopherols in perilla oil was highly related with polyphenols. The study suggests that more careful temperature control is required to decrease the autoxidation of perilla oil than that of corn oil, and polyphenols contributed to the oxidative stability of perilla oil by protecting tocopherols from degradation, especially at the early stage of oil autoxidation.     

Supercritical carbon dioxide extraction of oil and α‐tocopherol from almond seeds

The objective of this study was to extract oil and tocopherols from almond seeds using supercritical carbon dioxide and to compare this extraction with a traditional solvent method. Oil and tocopherol extraction rates were determined as functions of the pressure (350–550 bar), temperature (35–50 °C) and CO₂ flow rate (10–30 kg h⁻¹), using a 10‐l vessel. The effects of matrix particle size on extraction yield were also studied and it was demonstrated that extraction yield is greatly influenced by particle size. Maximum recovery was obtained in the first 2–3 h of extraction at a pressure of 420 bar, a temperature of 50 °C and a flow rate of 30 kg h⁻¹ CO₂. These results suggest that the elevated initial oil and tochopherol solubility is related to the increased proportion of fatty acids in the initial extract. The results were compared with those obtained when hexane/methanol was used as a solvent. Copyright © 2005 Society of Chemical Industry     

Optimisation of biological and physical parameters for lycopene supercritical CO2 extraction from ordinary and high‐pigment tomato cultivars

BACKGROUND: Lycopene is used for several industrial applications. Supercritical CO₂ (SC‐CO₂) extraction from red‐ripe tomato fruits is an excellent technique to replace the use of harmful solvents. In this study, starting from red‐ripe tomatoes of ordinary and high‐lycopene cultivars, the effect of different agronomical and technical aspects on lycopene content, stability and yield was evaluated throughout the production process from fresh tomatoes to the final SC‐CO₂‐extracted oleoresin containing lycopene. RESULTS: Red‐ripe tomato cultivars differed in their lycopene content. Irrigation excess or deficit caused an increase in the amount of lycopene in the fruits. Fresh tomatoes were processed into a lyophilised matrix suitable for SC‐CO₂ extraction, which could be stored for more than 6 months at ? 20 °C without lycopene loss. Under the optimal extraction conditions, efficiencies of up to 80% were achieved, but the recovery of lycopene in the extracted oleoresin was very low (～24%). Co‐extraction of the tomato matrix mixed with a lipid co‐matrix allowed the recovery of ～90% of lycopene in the oleoresin. Using the high‐lycopene cultivars, the yield of total extracted lycopene increased by ～60% with respect to the ordinary cultivars. Lipids and other biologically active molecules were present in the oleoresin. CONCLUSION: A method for extracting, from a tomato matrix, a natural and solvent‐free oleoresin containing lycopene dissolved in a highly unsaturated vegetable oil has been described. The oleoresin represents an excellent product for testing on cancer and cardiovascular disease prevention. Copyright © 2010 Society of Chemical Industry