Ascorbyl palmitate, gamma-tocopherol, and EDTA affect lipid oxidation in fish oil enriched salad dressing differently

The aim of the study was to investigate the ability of gamma-tocopherol, ethylenediaminetetraacetate (EDTA), and ascorbyl palmitate to protect fish oil enriched salad dressing against oxidation during a 6 week storage period at room temperature. The lipid-soluble gamma-tocopherol (220 and 880 microg g-1 of fish oil) reduced lipid oxidation during storage by partly retarding the formation of lipid hydroperoxides (PV) and by decreasing the concentrations of individual volatile oxidation products by 34-39 and 42-66%, respectively. EDTA (10 and 50 microg g-1 of dressing) was the most efficient single antioxidant, and overall peroxide values and volatiles were reduced by approximately 70 and 77-86%, respectively. Conversely, prooxidant effects were observed with a high concentration of ascorbyl palmitate (300 microg g-1 of fish oil), whereas a low concentration was slightly antioxidative (50 microg/g of fish oil). Finally, a combination of all three antioxidants completely inhibited oxidation during storage, indicating that the prooxidant effects of ascorbyl palmitate were reverted or overshadowed by EDTA and gamma-tocopherol.     

Homogenization conditions affect the oxidative stability of fish oil enriched milk emulsions: lipid oxidation

In this study fish oil was incorporated into commercial homogenized milk using different homogenization temperatures and pressures. The main aim was to understand the significance of homogenization temperature and pressure on the oxidative stability of the resulting milks. Increasing homogenization temperature from 50 to 72 degrees C decreased droplet size only slightly, whereas a pressure increase from 5 to 22.5 MPa decreased droplet size significantly. Surprisingly, emulsions having small droplets, and therefore large interfacial area, were less oxidized than emulsions having bigger droplets. Emulsions with similar droplet size distributions, but resulting from different homogenization conditions, had significantly different oxidative stabilities, indicating that properties of significance to oxidation other than droplet size itself were affected by the different treatments. In general, homogenization at 72 degrees C appeared to induce protective effects against oxidation as compared to homogenization at 50 degrees C. The results thus indicated that the actual composition of the oil-water interface is more important than total surface area itself.     

Lipid oxidation in fish oil enriched mayonnaise: calcium disodium ethylenediaminetetraacetate, but not gallic acid, strongly inhibited oxidative deterioration

The antioxidative effects of gallic acid, EDTA, and extra emulsifier Panodan DATEM TR in mayonnaise enriched with 16% fish oil were investigated. EDTA reduced the formation of free radicals, lipid hydroperoxides, volatiles, and fishy and rancid off-flavors. The antioxidative effect of EDTA was attributed to its ability to chelate free metal ions and iron from egg yolk located at the oil-water interface. Gallic acid reduced the levels of both free radicals and lipid hydroperoxides but promoted slightly the oxidative flavor deterioration in mayonnaise and influenced the profile of volatiles. Gallic acid may therefore promote the decomposition of lipid hydroperoxides to volatile oxidation products. Addition of extra emulsifier reduced the lipid hydroperoxide levels but did not influence the level of free radicals or the oxidative flavor deterioration in mayonnaisse; however, it appeared to alter the profile of volatiles. The effect of the emulsifier on the physical structure and rheological properties depended on the presence of antioxidants.     

Chemical and olfactometric characterization of volatile flavor compounds in a fish oil enriched milk emulsion

Development of objectionable fishy off-flavors is an obstacle in the development of fish oil enriched foods. Only little is known about the sensory impact of specific volatile fish oil oxidation products in food emulsions. This study examined the volatiles profiles of fish oil enriched milk during cold storage (2 degrees C) for 14 days by dynamic headspace sampling followed by gas chromatography-mass spectrometry analyses. Different volatiles (n = 60) comprising alkenals, alkadienals, alkatrienals, and vinyl ketones were identified in the fish oil enriched milk. The potent odorants identified by gas chromatography-olfactometry were 1-penten-3-one, (Z)-4-heptenal, 1-octen-3-one, (Z)-1,5-octadien-3-one, (E,E)-2,4-heptadienal, and (E,Z)-2,6-nonadienal, but despite their potency, none of the separated volatiles imparted a fishy or metallic odor. Two isomers, (E,Z,Z) and (E,E,Z) of 2,4,7-decatrienal were identified in fish oil enriched milk emulsions with peroxide values 0.8 and 3.4 meq/kg, respectively. To our knowledge, this is the first report on appearance of these decatrienals in food emulsions having a relatively low peroxide value.     

Homogenization conditions affect the oxidative stability of fish oil enriched milk emulsions: oxidation linked to changes in protein composition at the oil-water interface

Fish oil was incorporated into milk under different homogenization temperatures (50 and 72 degrees C) and pressures (5, 15, and 22.5 MPa). Subsequently, the oxidative stability of the milk and changes in the protein composition of the milk fat globule membrane (MFGM) were examined. Results showed that high pressure and high temperature (72 degrees C and 22.5 MPa) resulted in less lipid oxidation, whereas low pressure and low temperature (50 degrees C and 5 MPa) resulted in faster lipid oxidation. Analysis of protein oxidation indicated that especially casein was prone to oxidation. The level of free thiol groups was increased by high temperature (72 degrees C) and with increasing pressure. Furthermore, SDS-PAGE and confocal laser scanning microscopy (CLSM) indicated that high temperature resulted in an increase in beta-lactoglobulin adsorbed at the oil-water interface. This was even more pronounced with higher pressure. Less casein seemed to be present at the oil-water interface with increasing pressure. Overall, the results indicated that a combination of more beta-lactoglobulin and less casein at the oil-water interface gave the most stable emulsions with respect to lipid oxidation.     

Protection against oxidation of fish-oil-enriched milk emulsions through addition of rapeseed oil or antioxidants

The ability of rapeseed oil and/or different antioxidants (alpha- and gamma-tocopherol mixture, ascorbyl palmitate, and EDTA) to protect fish-oil-enriched milk emulsions against oxidation was investigated. Tocopherol isomers in concentrations similar to those found in natural rapeseed oil were added to rapeseed oil stripped of natural tocopherols. The rapeseed oil with added tocopherols significantly inhibited oxidation in the fish-oil-enriched milk emulsions. In contrast, the emulsions with only fish oil and added alpha- and gamma-tocopherol were less stable than the emulsions with fish oil alone. When added individually, the gamma-tocopherol seemed to inhibit oxidation more efficiently than alpha-tocopherol. Ascorbyl palmitate (AP) almost completely retarded oxidation in the fish-oil-enriched milk emulsions, as determined by PV, volatile oxidation products, and sensory evaluation. AP also prevented the otherwise prooxidant effect of tocopherols added to fish oil before emulsification. No interactions between AP, tocopherols, and EDTA were observed, and EDTA added alone to fish oil did not show antioxidant properties in the milk emulsions. Overall, the results showed that addition of AP or rapeseed oil containing natural tocopherols to fish oil was equally efficient in inhibiting oxidation in the fish-oil-enriched milk emulsions.     

Antioxidant activity of oregano, parsley, and olive mill wastewaters in bulk oils and oil-in-water emulsions enriched in fish oil

The antioxidant activity of oregano, parsley, olive mill wastewaters (OMWW), Trolox, and ethylenediaminetetraacetic acid (EDTA) was evaluated in bulk oils and oil-in-water (o/w) emulsions enriched with 5% tuna oil by monitoring the formation of hydroperoxides, hexanal, and t-t-2,4-heptadienal in samples stored at 37 degrees C for 14 days. In bulk oil, the order of antioxidant activity was, in decreasing order (p < 0.05), OMWW > oregano > parsley > EDTA > Trolox. The antioxidant activity in o/w emulsion followed the same order except that EDTA was as efficient an antioxidant as OMWW. In addition, the total phenolic content, the radical scavenging properties, the reducing capacity, and the iron chelating activity of OMWW, parsley, and oregano extracts were determined by the Folin-Ciocalteau, oxygen radical absorbance capacity, ferric reducing antioxidant power, and iron(II) chelating activity assays, respectively. The antioxidant activity of OMWW, parsley, and oregano in food systems was related to their total phenolic content and radical scavenging capacity but not to their ability to chelate iron in vitro. OMWW was identified as a promising source of antioxidants to retard lipid oxidation in fish oil-enriched food products.     

Oxidation in fish oil enriched mayonnaise: ascorbic acid and low pH increase oxidative deterioration

The effect of ascorbic acid (0-4000 ppm) and pH (3.8-6.2) on oxidation and levels of iron and copper in various fractions of mayonnaise enriched with 16% fish oil was investigated. Ascorbic acid induced release of iron from the assumed oil-water interface into the aqueous phase at all pH levels, but this effect of ascorbic acid was strongest at low pH (pH 3.8-4.2). Ascorbic acid generally promoted formation of volatile oxidation compounds and reduced the peroxide value in mayonnaises. Peroxide values and total volatiles generally increased with decreasing pH values, suggesting that low pH promoted oxidation. It is proposed that iron bridges between the egg yolk proteins low-density lipoproteins, lipovitellin, and phosvitin at the oil-water interface are broken at low pH values, whereby iron ions become accessible as oxidation initiators. In the presence of ascorbic acid, oxidation is further enhanced due to the reduction of Fe(3+) to Fe(2+) that rapidly catalyzes lipid oxidation via lipid hydroperoxide decomposition at the oil-water interface in mayonnaise.     

Selection and use of honey as an antioxidant in a French salad dressing system

Honeys from various floral sources were analyzed to select for utilization as a sweetener and potential source of antioxidants in the formulation of a salad dressing. On the basis of various indicators of potential antioxidant effectiveness, such as the ORAC (oxygen radical absorbance capacity) assay and identification of phenolic profile carried out by HPLC analysis, clover and blueberry honeys were selected. Dressings were stored under accelerated conditions (37 degrees C) for six weeks and at ambient (23 degrees C) and refrigeration (4 degrees C) temperatures for one year. Salad dressings incorporating honey provided protection against oxidation to a degree similar to that of EDTA, as determined by peroxide value and p-anisidine value. This demonstrates the potential for honey to be used as a substitute for EDTA and sweetener (such as HFCS) in commercial salad dressings.     

Dynamic headspace gas chromatography/mass spectrometry characterization of volatiles produced in fish oil enriched mayonnaise during storage

Protection against lipid oxidation and formation of unpleasant fishy and rancid off-flavors in oil-in-water food emulsions, such as fish oil enriched mayonnaise, is difficult to achieve. Volatile profiles from stored mayonnaises with different oil phase compositions were collected using a developed dynamic headspace sampling technique, in which interfering acetic acid was removed in situ with potassium hydroxide, and subsequently 148 volatiles were characterized and monitored by gas chromatography/mass spectrometry. Multivariate statistics showed correlation between the concentration of 62 volatiles and the fish oil and storage parameters, indicating the formation of lipid oxidation products, which impose fishy off-flavors. Further verification was obtained by gas chromatography/olfactometry, by which, among 78 odors, cis-4-heptenal and trans,cis-2,4-heptadienal were detected as distinct fishy notes. In total, 27 volatiles, including 1-penten-3-one, cis-2-penten-1-ol, cis-3-hexenal, cis-4-heptenal, 1-octen-3-one, 1,cis-5-octadien-3-one, 1-octen-3-ol, trans,cis-2, 4-heptadienal, and trans,cis-2,6-nonadienal, were suggested to contribute to the developed unpleasant fishy and rancid off-flavors.     

Determination of neutral lipid hydroperoxides by size exclusion HPLC with fluorometric detection. Application to fish oil enriched mayonnaises during storage

A fast (12 min) high-performance size exclusion chromatography (HPSEC) method for the separation of neutral lipid class hydroperoxides in the oil phases from fish oil enriched mayonnaises was developed. Detection and quantification were performed using the postcolumn fluorometric (FL) diphenyl-1-pyrenylphosphine oxidation principle. The reproducibilities judged by intra- and inter-assay variations were 0.64 and 7.2%, respectively. The HPSEC-FL method was applied to assess the effect of supplementations with emulsifier, gallic acid, and EDTA on the oxidative processes in the mayonnaises during storage. Substantial amounts of hydroperoxy triacylglycerols (TAGOOH) and cholesterol esters (CEOOH), together with traces of TAGOOH-dimers, were detected. All supplementations significantly decreased the levels of TAGOOH and to a lesser degree CEOOH. Supplementations with EDTA and gallic acid resulted in constant and slightly increasing levels of TAGOOH, respectively, thus affecting the oxidation mechanisms seen in reference mayonnaise. The emulsifier Panodan TR DATEM reduced the levels of TAGOOH as compared to the appropriate controls.     

Different tocopherols and the relationship between two methods for determination of primary oxidation products in fish oil

The effectiveness of 2.32 mmol/kg (approximately 1000 ppm) of alpha-, gamma-, or delta-tocopherol (TOH), as well as different levels of alpha TOH, on the formation of hydroperoxides in fish oil was studied by monitoring the peroxide value (POV) and the formation of conjugated dienes (CD) during storage at 30 degrees C. The same order of antioxidant activity was observed by both methods. Linear regression of POV on CD showed that these data were strongly correlated (r(2) > or = 0.98). The value of the slope of the regression lines, however, differed substantially and decreased with increasing hydrogen-donating ability of the different tocopherols and with increasing alpha TOH concentration. It is suggested that this is due, at least in part, to the contribution from hydroxy compounds to the CD measurements and a greater contribution from hydroperoxy epidioxides (two peroxide groups per conjugated diene unit) to the POV than to the CD value. The degrees of formation of both these groups of oxidation products are expected to be influenced by the rate of scavenging of lipid peroxyl and alkoxyl radicals by tocopherol (alpha TOH > gamma TOH > delta TOH).     

Effects of lactoferrin, phytic acid, and EDTA on oxidation in two food emulsions enriched with long-chain polyunsaturated fatty acids

The influence of the addition of metal chelators on oxidative stability was studied in a milk drink and in a mayonnaise system containing highly polyunsaturated lipids. Milk drinks containing 5% (w/w) of specific structured lipid were supplemented with lactoferrin (6-24 muM) and stored at 2 degrees C for up to 9 weeks. Mayonnaise samples with 16% fish oil and 64% rapeseed oil (w/w) were supplemented with either lactoferrin (8-32 muM), phytic acid (16-124 muM), or EDTA (16-64 muM) and were stored at 20 degrees C for up to 4 weeks. The effect of the metal chelators was evaluated by determination of peroxide values, secondary volatile oxidation products, and sensory analysis. Lactoferrin reduced the oxidation when added in concentrations of 12 muM in the milk drink and 8 muM in the mayonnaise, whereas it was a prooxidant at higher concentrations in both systems. In mayonnaise, EDTA was an effective metal chelator even at 16 muM, whereas phytic acid did not exert a distinct protective effect against oxidation. The differences in the equimolar effects of the metal chelators are proposed to be due to differences in their binding constants to iron and their different stabilities toward heat and low pH.     

Effect of ascorbic acid on iron release from the emulsifier interface and on the oxidative flavor deterioration in fish oil enriched mayonnaise

This research examines the effect of ascorbic acid (0-800 ppm) on the sensory perception of mayonnaises containing 16% fish oil and on the levels of iron and copper in the aqueous phase. Ascorbic acid increased the formation of fishy off-flavors in fresh mayonnaise. Simultaneously, the iron concentration increased from below the detection limit (1.8 microM) to 34 microM in the aqueous phase of mayonnaises. Model mayonnaises with various concentrations of egg yolk (1-7% w/w) and ascorbic acid (0-8000 ppm) were prepared. Iron concentrations in the aqueous phase increased with increasing ascorbic acid levels, whereas iron concentrations in the assumed interfacial layer decreased. It is proposed that ascorbic acid is able to complex and reduce Fe(3+) to Fe(2+) from phosvitin in the egg yolk, whereby iron is released from the interface. The ascorbic acid-iron complex subsequently reacts with lipid hydroperoxides, resulting in increased lipid oxidation and in the immediate formation of rancid and fishy off-flavors.     

Stearidonic acid soybean oil enriched with palmitic acid at the sn-2 position by enzymatic interesterification for use as human milk fat analogues

Stearidonic acid (SDA, C18:4n-3) enriched soybean oil may be added to the diet to increase intake of omega-3 fatty acids (FAs). Human milk fat has ≥60% of palmitic acid (PA), by weight, esterified at the sn-2 position to improve absorption of fat and calcium in infants. Enzymatic interesterification of SDA soybean oil and tripalmitin produced structured lipids (SLs) enriched with PA at the sn-2 position of the triacylglycerol. Reactions were catalyzed by Novozym 435 or Lipozyme TL IM under various conditions of time, temperature, and substrate mole ratio. Response surface methodology was used to design the experiments. Model optimization conditions were predicted to be 1:2 substrate mole ratio at 50 °C for 18 h with 10% (by weight) Lipozyme TL IM resulting in 6.82 ± 1.87% total SDA and 67.19 ± 9.59% PA at sn-2; 1:2 substrate mole ratio at 50 °C for 15.6 h resulting in 8.01 ± 2.41% total SDA and 64.43 ± 13.69% PA at sn-2 with 10% (by weight) Novozym 435 as the biocatalyst. The SLs may be useful as human milk fat analogues for infant formula formulation with health benefits of the omega-3 FAs.     

Temperature effect on lactose crystallization, maillard reactions, and lipid oxidation in whole milk powder

Whole milk powder with an initial water content of 4.4% (w/w) and a water activity of 0.23 stored in hermetically sealed vials for up to 147 days below (37 and 45 degrees C) and above (55 degrees C) the glass transition temperature (T(g) determined to have the value 48 degrees C) showed a strong temperature dependence for quality deterioration corresponding to energies of activation close to 200 kJ/mol for most deteriorative processes. The glass transition was found not to cause any deviation from Arrhenius temperature dependence. Lactose crystallization, which occurred as a gradual process as monitored by isothermal calorimetry, is concluded to liberate bound water (a(w) increase to 0.46) with a modest time delay (approximately 2 days at 55 degrees C) and with concomitant surface browning as evidenced by an increasing Hunter b-value. Browning and formation of bound hydroxymethyl-furfural determined by HPLC seem to be coupled, while formation of another Maillard reaction product, furosine, occurred gradually and was initiated prior to crystallization. Initiation of lipid oxidation, as detected by lipid-derived radicals (high g-value ESR spectra), and progression of lipid oxidation, as detected by headspace GC, seem not to be affected by lactose crystallization and browning, and no indication of browning products acting as antioxidants could be determined.     

Effects, quenching mechanisms, and kinetics of water soluble compounds in riboflavin photosensitized oxidation of milk

To protect the nutrient and flavor stability of milk under light, the effects of 0, 0.01, 0.03, and 0.05 M 1,4-diazabicyclo[2,2,2]octane (DABCO) and 2,5-dimethylfuran (DMF) on the riboflavin photosensitized oxidation of milk were studied. The oxidation of milk was studied by measuring the headspace oxygen in sample bottles after 3 h of light exposure at 3000 lux. As the concentration of DABCO and DMF, which are water soluble compounds, increased in the sample from 0, 0.01, and 0.03 to 0.05 M, the depleted headspace oxygen content significantly decreased (P < 0.05). Steady state kinetic studies of singlet oxygen oxidation showed that the antioxidant activity of DABCO and DMF was due to singlet oxygen quenching. The reaction rate constant of singlet oxygen with milk fat was 8.1 x 10(5) M(-1) s(-1). Total singlet oxygen quenching rates of DABCO and DMF were 1.5 x 10(7) and 2.6 x 10(7) M(-1) s(-1), respectively. DABCO and DMF could be used to slow the reaction between singlet oxygen and milk components to protect nutrients, especially riboflavin, and to improve the oxidative stability of milk fat during storage or processing under light.     

Alpha-tocopherol oxidation in fish muscle during chilling and frozen storage

The oxidation of alpha-tocopherol (TH) in chilled and frozen fish muscle was determined using high-performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry. TH oxidation byproducts were identified as alpha-tocopherolquinone (TQ), 5,6-epoxy-alpha-tocopherolquinone (TQE1), and 2-3-epoxy-alpha-tocopherolquinone (TQE2). The concentration of TH decreased significantly during storage while those of TQ, TQE1, and TQE2 increased noteworthy. The relative amounts of TH and its oxidized products were significantly related with the extent of oxidation produced in postmortem fish, and the ratio TQ/TH is suggested as an index of oxidative stress in fish muscle. The effect of phenolic antioxidants supplementation on retarding TH oxidation was also studied. Data suggested that the addition of 100 ppm of caffeic acid, hydroxytyrosol, and propyl gallate could regenerate endogenous TH from its oxidized forms resulting in an antioxidant synergy consistent with the reduction of lipid oxidation observed in fish muscle supplemented with phenolic compounds.     

Pesticide residues in milk and fish samples collected from upper Egypt

In Egypt, buffalo milk is much preferred by consumers over cow's milk, while small catfish and bolti fish are common in the diet of farmers. Samples of buffalo milk, catfish, and bolti fish collected from Beni-Suef Governorate (Upper Egypt) were analyzed for organochlorines and polychlorinated biphenyls. The results obtained by gas chromatography and confirmed by thin-layer chromatographic techniques revealed high amounts of organochlorines in milk; residues were lower but occurred more frequently in fish samples. Pesticide contaminants found most often were HCH isomers including lindane, DDT complex, aldrin and dieldrin, heptachlor and heptachlor epoxide, hexachlorobenzene, and oxychlordane. Polychlorinated biphenyls were not detected in any of the analyzed samples.     

trans-C18:1 isomers in cheeses enriched in unsaturated fatty acids and manufactured with different milk fat globule sizes

Increasing the knowledge on dietary fat composition, mainly the minor components, will improve the nutritional value of foods and their labeling. In this study, we examined the trans-octadecenoic acid (C18:1) composition of Emmental cheeses enriched in unsaturated fatty acids (FA) and manufactured with milks produced by cows selected to produce small and large fat globules. The FA composition of the milks was not significantly ( P > 0.05) different from the FA composition of the corresponding Emmental cheeses. Increasing the unsaturated FA content of the cheeses using dietary manipulations lead to an increase in the trans-C18:1 and changed their isomeric profiles. In milk fat produced with the linseed-enriched diet, the trans-10 C18:1 concentration was greater than trans-11 C18:1 (vaccenic acid), which is classically the major trans-C18:1 in milk fat. The content in trans-C18:1 and more particularly in trans-10 C18:1 was negatively correlated with the size of fat globules ( r (2) = 0. 82 and 0.87, respectively) and related to milk fat depression. The trans-C18:1 content was negatively correlated with the saturated FA (slope = -0.35; r (2) = 0.81) and positively correlated with the unsaturated (slope = 0.29; r (2) = 0.85) and monounsaturated (slope = 0.32; r (2) = 0.81) FA. Focusing on the health-related considerations of fat in food products, further nutritional studies are needed to elucidate the role of trans-C18:1 isomers.