Optimization of activated carbon‐based decontamination of fish oil by response surface methodology

The effect of activated carbon (AC) adsorption on the reduction of persistent organic pollutants (POP) in fish oil was studied based on response surface methodology at a 5‐g/kg AC inclusion level. Pretreatment of the oil by alkali refining and bleaching increased the POP levels. The tested process variables (contact time and temperature) affected the AC adsorption rate and significant first‐ and second‐order response models could be established. Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) showed a very rapid adsorption behavior and the concentration and toxic equivalent (TEQ) level could be reduced by 99%. Adsorption of dioxin‐like polychlorinated biphenyls (DL‐PCB) was less effective and depended on ortho substitution, i.e. non‐ortho PCB were adsorbed more effectively than mono‐ortho PCB with a maximum of 87 and 21% reduction, respectively, corresponding to a DL‐PCB‐TEQ reduction of 73%. A common optimum for both PCDD/F and DL‐PCB adsorption could not be identified. AC treatment had no effect on the level of polybrominated diphenyl ether flame retardants. The differences in adsorption patterns may be explained based on molecular conformation. No change in oil quality could be observed based on oxidation parameters. Compliance with present PCDD/F and DL‐PCB legislation levels in fish oil can be achieved based on AC adsorption.     

Influence of interesterification on the oxidative stability of marine oil triacylglycerols

To understand the relationship between triacylglycerol structure of marine oils and their oxidative stability, peroxide values and absorbed oxygen levels of whale, sardine, cod liver and skipjack oils, interesterified by lipase and NaOCH₃, were compared with those of native oils during storage at 40°C. Triacylglycerol structures of marine oils were characterized by high-performance liquid chromatography and differential scanning calorimetry analyses. Enzymatically interesterified fish oils were more stable than native oils because the level of highly unsaturated triacylglycerols was decreased. However, the oxidative stability of interesterified whale oil was more susceptible to oxidation than the native oil.     

Oxidative stability and acceptability of camelina oil blended with selected fish oils

The effects of blending camelina oil with a number of fish oils on oxidative stability and fishy odour were evaluated. Camelina oil was found to be more stable than tuna oil, ‘omega‐3’ fish oil and salmon oil as indicated by predominantly lower ρ‐anisidine (AV), thiobarbituric acid reactive substances (TBARS) and conjugated triene levels (CT) during storage at 60 °C for 20 days (p < 0.05). Peroxide values (PV) were similar for all oils until Day 13 when values for camelina oil were higher. Values for blends of the fish oils (50, 25, 15, 5%) with camelina oil were generally between those of their respective bulk oils indicating a dilution effect. Camelina oil had a similar odour score (p < 0.05) to sunflower oil (9.2 and 9.6, respectively) indicating, as expected, an absence of fishy odours. In comparison, the fish oils had lower scores of 6.1 to 6.6 (p < 0.05) indicating mild to moderate fishy odours. Odour scores were improved at the 25% fish oil levels (p < 0.05) and were not different to camelina oil at the 15 or 5% levels (p < 0.05). Practical applications: Camelina oil is a potentially important functional food ingredient providing beneficial n‐3 PUFA. Oil extracted from Camelina sativa seeds contains greater than 50% polyunsaturated fatty acids of which 35‐40% is α‐linolenic acid (C18:3ω3, ALA), an essential omega‐3 fatty acid 1 . While EPA and DHA from fish oils are more potent nutritionally, they are less stable than ALA. This work evaluated innovative blends of fish oil with camelina oil for stability and acceptability. The results demonstrate that there is potential for use of blends of camelina oil with fish oils in food products, as the results show some benefits in terms of reduction of fishy odours. Such information could be valuable in relation to formulation of food products containing high levels of n‐3 PUFA from both plant and fish sources.     

FA composition of the oil extracted from farmed atlantic salmon (Salmo salar L.) viscera

The FA composition of visceral oil extracted from farmed Atlantic salmon (Salmo salar L.) viscera was studied. Seventeen FA were identified in the extracted visceral oil, and the major FA were 18∶1n9, 16∶0, 16∶1n7, 20∶5n3 (EPA), 14∶0, and 22∶6n3 (DHA). The percentages of saturated, monounsaturated, and polyunsaturated FA in the total FA were 31.7, 36.0, and 32.2%, respectively. Compared with other fish oils, oil from farmed Atlantic salmon had much higher EPA (1.64 g/100 g) and DHA (1.47 g/100 g) contents. The FA profile of the salmon visceral oil was similar to that of the salmon fillet. Thus, the salmon visceral oil could be a replacement for the oil obtained from edible salmon fillet and used in functional foods or feeds requiring a high level of omega-3 FA. Furthermore, producing visceral oil is also beneficial to salmon fish industry by adding value back to the processing waste.     

Separation of EPA and DHA in fish oil by lipase-catalyzed esterification with glycerol

The objective of this study was to investigate the use of lipases as catalysts for separating EPA and DHA in fish oil by kinetic resolution based on their FA selectivity. Esterification of FFA from various types of fish oils with glycerol by immobilized Rhizomucor miehei lipase under water-deficient, solvent-free conditions resulted in a highly efficient separation of EPA and DHA. Reactions were conducted at 40°C with a 10% dosage of the lipase preparation under vacuum to remove the coproduced water, thus rapidly shifting the reaction toward the products. The bulk of the FA, together with EPA, were converted into acylglycerols, whereas DHA remained in the residual FFA. As an example, when FFA from tuna oil comprising 5% EPA and 25% DHA were esterified with glycerol, 90% conversion into acylglycerols was obtained after 48 h. The residual FFA contained 78% DHA and only 3% EPA, in 79% DHA recovery. EPA recovery in the acylglycerol fraction was 91%. The type of fish oil and extent of conversion were highly important parameters in controlling the degree of concentration.     

Oxidative flavour deterioration of fish oil enriched milk

The oxidative deterioration of milk emulsions supplemented with 1.5 wt‐% fish oil was investigated by sensory evaluation and by determining the peroxide value and volatile oxidation products after cold storage. Two types of milk emulsions were produced, one with a highly unsaturated tuna oil (38 wt‐% of n‐3 fatty acids) and one with cod liver oil (26 wt‐% of n‐3 fatty acids). The effect of added calcium disodium ethylenediaminetetraacetate (EDTA) on oxidation was also investigated. Emulsions based on cod liver oil with a slightly elevated peroxide value (1.5 meq/kg) oxidised significantly faster than the tuna oil emulsions, having a lower initial peroxide value (0.1 meq/kg). In the tuna oil emulsions the fishy off‐flavour could not be detected throughout the storage period. Addition of 5—50 ppm EDTA significantly reduced the development of volatile oxidation products in the cod liver oil emulsions, indicating that metal chelation with EDTA could inhibit the decomposition of lipid hydroperoxides in these emulsions. This study showed that an oxidatively stable milk emulsion containing highly polyunsaturated tuna fish oil could be prepared without significant fishy off‐flavour development upon storage, provided that the initial peroxide value was sufficiently low.     

Chemical composition and physicochemical and hydrogenation characteristics of high-palmitic acid solin (low-linolenic acid flaxseed) oil

The physicochemical characteristics and FA compositions were determined for refined-bleached-deodorized (RBD) high-palmitic acid solin (HPS) oil, RBD solin oil, and degummed linseed oil. The predominant FA in HPS oil were palmitic (16.6%), palmitoleic (1.4%), stearic (2.5%), oleic (11.3%), linoleic (63.7%), and linolenic (3.4%). HPS oil was substantially higher in palmitic acid than either solin oil or linseed oil, and similar to solin oil in linolenic acid content. HPS, solin, and linseed oils exhibited similar sterol and tocopherol profiles. The physicochemical characteristics of the three oils (iodine value, saponification value, m.p., density, specific gravity, viscosity, PV, FFA content, color) reflected their FA profiles and degree of refinement. During hydrogenation of HPS oil, the proportion of saturated FA (palmitic and stearic) increased, and that of unsaturated FA (oleic, linoleic, and linolenic) decreased as the iodine value declined. This resulted in an inverse linear relationship between m.p. and iodine value. Hydrogenation also generated trans FA. The proportion of trans FA was inversely related to iodine value in partially hydrogenated samples. Fully hydrogenated HPS oil (i.e., HPS stearine, iodine value <5) was devoid of trans FA.     

Steaming,boiling after pre-frying,and stir-frying influence the fatty acid profiles and oxidative stability of soybean oil blended with docosahexaenoic acid algal oil

The objective of this study was to improve the content of docosahexaenoic acid (DHA) and obtain the blended oils used for different cooking methods (steaming, boiling, and stir-frying) by blending 0%–15% DHA algal oil into soybean oil. It was shown that the addition of DHA algal oil increased saturated fatty acid (SFA) (1.57%) but decreased monounsaturated fatty acid (MUFA) (0.76%) and polyunsaturated fatty acid (PUFA) (0.68%). Various cooking methods significantly changed the fatty acid (FA) compositions. Steaming is a more effective way to prevent DHA loss and the production of trans-fatty acid than boiling and stir-frying. Besides, a positive result from free fatty acid (FFA) and peroxide value also demonstrated that steaming was a better way to protect oils. Overall, the soybean oil blended with 3% DHA algal oil with better oxidative stability and could be recommended for daily application by steaming.     

Analysis of regioisomers of triacylglycerols of northern currant seed oil by tandem mass spectrometry

Currant oils have special health properties due to their moderate contents of α‐linolenic, γ‐linolenic and stearidonic acids. The distribution of fatty acids (FA) in the triacylglycerols (TAG) may affect the beneficial effects. Seed oils of wild northern red currant (NRC) (Ribes spicatum L.) from Northern Finland and of wild alpine currant (AC) (R. alpinum L.) from the South‐West coast of Finland were investigated. The purified TAG were analysed by tandem mass spectrometry by applying the ammonia negative ion chemical ionisation – collision‐induced dissociation method. Molecular weight fractions rich in C18:3 FA and C18:4 FA were investigated. Of the total oil, the molecular weight species 54:7 (ACN:DB), 54:8 and 54:9 were more abundant in NRC than in AC, being 21.0%, 15.8%, 7.4% and 16.2%, 11.2%, 4.8%, respectively (p <0.05). The species 52:6 was more abundant in AC (3.1%) than in NRC (2.6%) (p <0.05). The preferential order of FA to be in the sn‐2 position in both berries was typically C18:1 > C18:2 > C18:4 > C18:3. No difference was observed between relative locations of C16:0 FA and C18:3 FA in either of the oils. Within the TAG consisting of FA combinations C18:3/C18:3/C18:1 (54:7), C18:1 was more preferentially in the sn‐2 position (p <0.05) in AC (93.2%) than in NRC (74.6%), and in the case of C18:3, the preference was vice versa. Within the molecular weight species 54:9, FA combination C18:4/C18:3/C18:2, linoleic acid preferentially occupied the secondary position (p <0.005) in both berries, and the proportion of the TAG regioisomer pair sn‐C18:3‐C18:4‐C18:2 + sn‐C18:2‐C18:4‐C18:3 was more abundant (30.2%) in NRC than in AC (15.3%). Within the TAG species 52:6, proportions of all the existing combinations, C16:0/C18:3/C18:3, C16:0/C18:4/C18:2 and C16:1/C18:3/C18:2, varied between the two berry species (p <0.005).     

Quality differences between pre‐pressed and solvent extracted rapeseed oil

Most seed oils are obtained by pre‐pressing the crushed seeds followed by solvent extraction of oil from the press cake. The prepressed oil will contain no solvent residues, and is moreover expected to contain more nutritionally valuable compounds, which can in turn enhance the oxidative stability of the oil. However, reports on differences between extracted and pressed oils are scarce. Therefore, in this study, for a case study on rapeseed oil, the composition and quality were systematically compared between pre‐pressed and solvent extracted oil. In the extracted oil, solvent residues and a clear sensory difference were detected, which disappeared almost completely during refining. The crude oils had a high content in free fatty acids and in primary and secondary oxidation products, which were higher in the extracted than in the pressed oil. However, surprisingly, also the content of minor compounds was slightly higher in the extracted oil than in the pressed oil. This can be explained by a selective extraction of those compounds into the solvent. During refining, a difference between pressed and extracted oils still existed but was less pronounced. The slight difference in antioxidants content might explain the higher oxidative stability of extracted over pressed oils. Practical applications : Traditionally, high yields of vegetable oils are obtained by pre‐pressing the seeds, followed by solvent extraction of the residual oil from the press cake. The solvent extraction leads to higher oil yields, but is expected to affect the composition and quality of the oil, and has moreover negative environmental impacts. In this study, the solvent extracted oil contained slightly higher levels of tocopherols and phytosterols, and had slightly higher oxidative stability, which are desirable quality aspects. In contrast, the solvent extracted oil contained also higher levels of undesirable phospholipids, as well as solvent residues, which were, however, removed during degumming and deodorization, respectively. These results suggest that the final quality of refined pre‐pressed and solvent extracted oils is comparable from nutritional and safety point of view. A choice for pressing instead of solvent extraction will, therefore, rather be driven by sustainability concerns than by nutritional aspects.     

Composition of organic and conventionally produced sunflower seed oil

The aim of the present study was to highlight the main differences between seed oils produced from conventionally cultivated crops and organically cultivated ones and processed using mild extraction procedures. The composition and the nutritional and health aspects of both types of sunflower seed oils were compared and were analytically tested to determine the macroscopic differences in proximate composition, the main differences in the minor components, the main quality parameters, the in vitro antioxidant activity, and the presence of trans-ethylene steroisomers in FA. No significant trends were found in the oil samples for TAG and FA composition, but remarkable differences were found in the composition of minor components and in the main chemical and analytical quality properties. The organically grown samples had a higher total antioxidant activity compared with the conventional samples. Trans FA were found only in the conventional oils.     

The conjugation and epoxidation of fish oil

Wilkinson's catalyst [RhCl(PPh₃)₃] has been used to conjugate fish oils in high yields under very mild reaction conditions. A catalyst load of 0.35 mol% of RhCl(PPh₃)₃, 0.43 mol% of (o-CH₃C₆H₄)₃P, and 0.87 mol% of SnCl₂·2H₂O in ethanol solvent at 60°C for 2 d produces 82% conjugated Norway fish oil affords 90% conjugated fish oil in 93% yield. The Sharpless epoxidation procedure has also been employed to epoxidize fish oils. Using 0.34 mol% of CH₃ReO₃, 8.15 mol% of pyridine, and 1.03 equivalents of aq. 30% hydrogen peroxide in methylene chloride solvent at 25°C for 6 h, the Norway fish oil ethyl ester can be 100% epoxidized in an 86% yield. The Capelin fish oil gives 100% epoxidized fish oil in a 72% yield. Decreasing the amounts of CH₃ReO₃ and pyridine used in the reaction results in partially epoxidized fish oils.     

Dioxin,Dioxin–Like PCBs and Indicator PCBs in Some Medicinal Plants Irrigated with Wastewater in Ismailia,Egypt

Wastewater is often leaden with various contaminants that may accumulate in soils and can under some conditions enter the agricultural food chain. Concentrations of PCDD/Fs, DL-PCBs and NDL-PCBs have been determined using GC/HRMS in three of the commonly used medicinal plant (henna, rosemary, and moghat) grown on raw wastewater. In the case of henna and rosemary plants, all wastewater irrigated samples showed higher content of the studied contaminants than freshwater irrigated samples, while moghat samples, whether irrigated with freshwater or wastewater, had more or less the same content of the studied contaminants. Concentrations in plant samples ranged between 0.00004 and 0.865 pg WHO TEQ/g wet w for PCDDs, and between 0.03 and 1.86 pg WHO TEQ/g wet w for the PCDFs. Levels of PCB TEQ ranged from 0.005 to 0.76 pg/g wet w. In descending order, rosemary, henna, and moghat had the highest concentrations of total TEQ (PCDD/Fs + DL-PCBs). The congeners pattern in henna and rosemary samples was generally characterized by the dominance of PCDFs with a significant contribution from the lower (mono- to tri-) PCDFs. In moghat samples the profile was dominated by PCDDs, with OCDD contributing 100% to PCDDs. PCBs contribution to the total TEQ was on average 25%, 7% and 2% in rosemary, moghat and henna respectively. For NDL-PCBs, the sum concentration of 17 PCBs congeners increased from 2.65 to 4.13 ng/kg wet w in henna, and from 4.64 to 7.16 ng/ kg wet w in rosemary due to the irrigation with wastewater. Congener PCB 28 was the main contributor (60%) to sum 6 indicators in all samples, followed by PCB 52 (18%) and PCB 101 (6%).     

A multivariate study of the relationship between fatty acids and volatile flavor components in olive and walnut oils

The relationships between FA and the volatile profiles of olive and walnut oils from Argentina were studied using GC and solid-phase microextraction coupled with GC-MS. The major volatiles were aldehydes and hydrocarbons, produced mainly through the oxidative pathways. n-Pentane, nonanal, and 2,4-decadienal were predominant in walnut oils, whereas nonanal, 2-decenal, and 2-undecenal were the most abundant components in olive oils. A multivariate analysis applied to the chemical data emphasized the differences between the oils and allowed us to see a pattern of covariation among the FA and the volatile compounds. The main differences between walnut and olive oils were the presence of larger amounts of short-chain (C₅–C₆) saturated hydrocarbons and aldehydes in the former and the greater quantities of medium-chain (C₇–C₁₁) compounds in olive oil. This can be explained by their different origins, mainly from the linoleic acid in walnut oil or almost exclusively from the oleic acid in olive oil.     

Cyclic FA monomers in high-oleic acid sunflower oil and extra virgin olive oil used in repeated frying of fresh potatoes

The measurement of FA profile, polar material, oligomers, oxidized triacylglycerols (OTG), total polyphenols, and cyclic FA monomers (CFAM) was used to evaluate the alteration of a high-oleic sunflower oil (HOSO) and an extra virgin olive oil (EVOO) used in 75 domestic fryings of fresh potatoes with frequent replenishment (FR) of unused oil. CFAM were absent in the unused EVOO but appeared in small amounts in the unused HOSO. Although polar material, oligomers, OTG, and CTAM contents increased and linoleic acid and polyphenols content decreased in both oils during repeated frying, the changes produced should be considered small and related to the use of very stable oils and FR. Throughout the 75 fryings, the total CFAM concentration was higher in HOSO than in EVOO. OTG increased more quickly in EVOO, whereas oligomers increased more quickly in HOSO. Polar material and oligomer content appear significantly correlated (r=0.9678 and r=0.9739, respectively; for both, P<0.001) with the CFAM content. A 25% polar material and 12% oligomer content would correspond to about 1 mg·kg⁻¹ oil of CFAM. Data suggest that both oils, particularly EVOO, perform very well in frying, with a low production of oligomers, polar materials, and CFAM.     

A method of concentration estimation of trienes,tetraenes, and pentaenes in evening primrose oil

There is no simple method available to estimate the concentration of conjugated fatty acids (CFA) with more than two double bonds in plant oils, because there are no commercially available complete sets of CFAs standards needed for such analysis. This paper presents such a method based on the absorption and fluorescence spectra of available CFAs standards and a computer program calculation. Using this method, the concentrations of the α‐eleostearic acid (conjugated trienoic acid (ELA) 8.8 × 10^?4 mol/L) and cis‐parinaric acid (conjugated tetraenoic acid (PnA) 3.5 × 10^?5 mol/L) in evening primrose oil were estimated. The accuracy of the calculation method is around 10%. Practical applications: This is the first report about the existence of CFAs in evening primrose oil. The described method estimates the total concentration of trienes, tetraenes, and pentaenes in evening primrose oils without using HPLC or other analytical methods. These CFAs are important from a health point of view. They are not synthesized by the human body. Therefore, plant oils containing these fatty acids (FA) are very valuable. Knowledge about the concentrations can be utilized to prepare a mixture of the plant oils with a favourable n‐3 to n‐6 FAs ratio and in addition containing CFAs.     

Determination of polyphenols,tocopherols, and antioxidant capacity in virgin argan oil (Argania spinosa,Skeels)

This study establishes data on polyphenols, tocopherols, and antioxidant capacity (AC) of virgin argan oil. A total of 22 samples from Morocco were analyzed. Total polyphenol content ranged between 6.07 and 152.04 mg GAE/kg. Total tocopherols varied between 427.0 and 654.0 mg/kg, being γ‐tocopherol the major fraction (84.68%); α‐, β‐, and δ‐tocopherols represent 7.75, 0.33, and 7.29%, respectively. No influence of oil extraction method on total tocopherols was observed. The AC of argan virgin oils determined by the ABTS method in n‐hexane oils dilution ranged between 14.16 and 28.02 mmol Trolox/kg, and by the ABTS, DPPH, and FRAP methods in methanolic oil extracts between 2.31–14.15, 0.19–0.87, and 0.62–2.32 mmol Trolox/kg, respectively. A high correlation was found between ABTS and DPPH methods applied to a methanolic oil extract. Virgin argan oil presents a higher polyphenol and tocopherol content, and total AC than other edible vegetable oils.     

Über Schadstoffe in Fettfischzubereitungen

Harmful Substances in Fatty Fish Preparations The occurrence of harmful substances in fish and fish preparations is outlined. These discussions include mercury, DDT and PCB. Harmful substances can be removed from fish oils by intensive processing. It is also shown that oxidative changes in fish oils might indicate the occurrence of harmful substances. Relationships between the age as well as length of the fishes and their mercury content are discussed. Examples are given which show that it is unnecessary to examine younger fishes and preparations obtained therefrom for harmful substances. Large and heavy old fishes should be sorted out immediately after hauling and processed separately to yield oils that can be freed from harmful substances after refining and hardening. Mechanical separation of fish oil from fatty fish preparations generally leads to alteration in the distribution of harmful substances. The use of strongly contaminated fatty fish parts can be improved by mechanical separation of fish oil and conversion to corresponding products. Conversion factors correlating processed fish to fresh fish are given for different varieties of fish treated in different manner.     

Nitrogen bubble refining of sunflower oil in shallow pools

High-temperature steam deodorization of sunflower oil results in the formation of unwanted by-products, such as trans isomers and polymers, and partial destruction of vitamins. There is an urgent need to develop a process that replaces steam with an inert gas such as nitrogen. The use of nitrogen bubble sparging at low temperatures has recently been reported as a technique to strip volatiles from edible oils. In this study, a hypothesis was proposed that nitrogen bubbles sparged at temperatures of 25 to 150°C are able to remove odoriferous, surface-active, or volatile contaminants from shallow pools of sunflower oil. Analysis of the composition of sunflower oil that had been sparged at 3 mbar pressure showed that both the odor and peroxide content of the oil were considerably reduced to values that are commercially acceptable. Odor improvement occurred at temperatures between 100 and 150°C, while the peroxide content reduction was achieved at a temperature of 150°C. There were no significant improvements in the free fatty acid concentration or color.     

Effect of natural antioxidants in virgin olive oil on oxidative stability of refined,bleached, and deodorized olive oil

The factors influencing the oxidative stability of different commercial olive oils were evaluated. Comparisons were made of (i) the oxidative stability of commercial olive oils with that of a refined, bleached, and deodorized (RBD) olive oil, and (ii) the antioxidant activity of a mixture of phenolic compounds extracted from virgin olive oil with that of pure compounds andα-tocopherol added to RBD olive oil. The progress of oxidation at 60°C was followed by measuring both the formation (peroxide value, PV) and the decomposition (hexanal and volatiles) of hydroperoxides. The trends in antioxidant activity were different according to whether PV or hexanal were measured. Although the virgin olive oils contained higher levels of phenolic compounds than did the refined and RBD oils, their oxidative stability was significantly decreased by their high initial PV. Phenolic compounds extracted from virgin olive oils increased the oxidative stability of RBD olive oil. On the basis of PV, the phenol extract had the best antioxidant activity at 50 ppm, as gallic acid equivalents, but on the basis of hexanal formation, better antioxidant activity was observed at 100 and 200 ppm.α-Tocopherol behaved as a prooxidant at high concentrations (>250 ppm) on the basis of PV, but was more effective than the other antioxidants in inhibiting hexanal formation in RBD olive oil.o-Diphenols (caffeic acid) and, to a lesser extent, substitutedo-diphenols (ferulic and vanillic acids), showed better antioxidant activity than monophenols (p- ando-coumaric), based on both PV and hexanal formation. This study emphasizes the need to measure at least two oxidation parameters to better evaluate antioxidants and the oxidative stability of olive oils. The antioxidant effectiveness of phenolic compounds in virgin olive oils can be significantly diminished in oils if their initial PV are too high.