A Multi-Year Rancidity Analysis of 72 Marine and Microalgal Oil Omega-3 Supplements.

There exists significant heterogeneity in the 'freshness' of consumer marine- and plant-derived omega-3 (Ω3) supplements. Fears of rancidity, or the oxidation of consumer Ω3 supplements, has been debated in the literature with several prior authors reporting contradictory findings. We report the peroxide value (PV), para-anisidine value (p-AV) and total oxidation values (TOTOX) associated with 72 consumer Ω3 supplements sold in the United States sampled from 2014-2020. The effect of flavoring on the oxidation of the supplements was examined in an adjusted fixed effects model controlling for type of delivery system (enteric, liquid, animal- and vegetable-derived gelatin softgel, spray), source (algae, calamari, fish, krill, mussels), and certifications assigned by third-party organizations (e.g. USP). Overall, our results revealed that 68% (23/34) of flavored and 13% (5/38) unflavored consumer Ω3 supplements exceeded the TOTOX upper limit set by the Global Organization for EPA and DHA (GOED) voluntary monograph standard of ≤ 26, with 65% (22/34) flavored supplements and 32% (12/38) unflavored supplements failing the PV upper limit of ≤ 5 and 62% (21/34) flavored supplements exceeding the p-AV upper limit of ≤ 20. To our knowledge, no prior authors have modeled the impact of flavoring on oxidative status in 72 marine- and plant-derived Ω3 products sold in the U.S. We present our findings in this context and discuss the clinical implications related to the consumption of oxidized consumer fish oils and their effects on human health.

Novel Approaches for Elongation of Fish Oils into Very-Long-Chain Polyunsaturated Fatty Acids and Their Enzymatic Interesterification into Glycerolipids.

Elongation of the Very-Long-Chain Fatty Acids-4 (ELOVL4) enzyme that is expressed in neuronal tissues, sperm, and testes mediates biosynthesis of very-long-chain polyunsaturated fatty acids (VLC-PUFAs) from dietary long chain PUFAs (LC-PUFAs). The VLC-PUFAs are critical for neuronal and reproductive function. Therefore, mutations in ELOVL4 that affect VLC-PUFA biosynthesis contribute to retinal degenerative diseases including Autosomal Dominant Stargardt-like Macular Dystrophy (STGD3). Recent studies have also shown not only a depletion of retinal VLC-PUFAs with normal aging but also a more significant loss of VLC-PUFAs in donor eyes of patients with age-related macular degeneration (AMD). However, currently, there are no natural sources of VLC-PUFAs to be evaluated as dietary supplements for the attenuation of retinal degeneration in animal models of STGD3. Here, we report the development of a novel chemical approach for elongation of eicosapentaenoic (C20:5 n-3) and docosahexaenoic (C22:6 n-3) acids from fish oils by 6 carbon atoms to make a unique group of VLC-PUFAs, namely all-cis-hexacosa-11,14,17,20,23-pentaenoic acids (C26:5 n-3) and all-cis-octacosa-10,13,16,19,22,25-hexaenoic acids (C28:6 n-3). The three-step elongation approach that we report herein resulted in a good overall yield of up to 20.2%. This more sustainable approach also resulted in improved functional group compatibility and minimal impact on the geometrical integrity of the all-cis double bond system of the VLC-PUFAs. In addition, we also successfully used commercial deep-sea fish oil concentrate as an inexpensive material for the C6 elongation of fish oil LC-PUFAs into VLC-PUFAs, which resulted in the making of gram scales of VLC-PUFAs with an even higher isolation yield of 31.0%. The quality of fish oils and the content of oxidized lipids were key since both strongly affected the activity of the PEPPSI-IPr catalyst and ultimately the yield of coupling reactions. Downstream enzymatic interesterification was used for the first time to prepare structured glycerolipids enriched with VLC-PUFAs that could be evaluated in vivo to determine absorption and transport to target tissues relative to those of the free fatty acid forms. It turned out that in the synthesis of structured triacylglycerols and glycerophospholipids with VLC-PUFAs, the polarity of the immobilized lipase carrier and its humidity were essential.

POPs and PAHs in fish oil-based food supplements at the Czech market.

The objectives of this study were to assess concentrations of three groups of persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) in 44 fish oil-based food supplements, to estimate their daily intake by consumers and, to evaluate the compliance of the oil samples with the oil origin declarations (cod liver oil or fish oil). The concentrations of ∑PCBs (7 congeners), OCPs (19 compounds, represented mainly by ∑DDTs), ∑PBDEs (10 congeners), and ∑PAHs (16 compounds) found in samples ranged between 0.15-55.7 µg kg-1, 0.93-72.8 µg kg-1, 0.28-27.5 µg kg-1, and 0.32-51.9 µg kg-1, respectively. Besides, the authenticity of the oils was assessed based on the fingerprints obtained by DART-HRMS, an ambient mass spectrometry technique. Four samples declared as fish oil were probably prepared from cod liver oil, which is much cheaper. Furthermore, these samples contained elevated concentrations of halogenated POPs when compared to supplements produced from fish oil.

Mercury Exposure from the Consumption of Dietary Supplements Containing Vegetable, Cod Liver, and Shark Liver Oils.

Vegetable and fish oils constitute a significant part of all dietary supplements. Due to increasing environmental pollution, the raw materials used for their production may be contaminated with toxic substances, including metals. The aim of the present study was to determine the mercury (Hg) content in vegetable oils, shark liver oils, and cod liver oils. The tests conducted were to help determine the level of mercury contamination of the tested preparations and the related potential threat to human health. The amount of Hg in the tested dietary supplements was compared, and the amount of the metal consumed at various times of use was determined. A total of 36 preparations of dietary supplements available on the Polish market were used for the study. The method of atomic absorption spectrometry using the amalgamation technique was used for the determinations (AMA 254, Altec, Czech Republic). Among the sample of all of the tested preparations, the Hg concentration ranged from 0.023 to 0.427 µg/kg, with an average of 0.165 µg/kg. Differences in Hg content in the various tested preparations (shark liver oil, cod liver oil, and vegetable oils) were statistically significant. The average concentration of Hg in the vegetable oils (0.218 µg/kg) was more than twice that of the cod liver oils (0.106 µg/kg) and shark liver oils (0.065 µg/kg). In none of the tested preparations did the amount of Hg exceed the acceptable standard for dietary supplements (0.10 mg/kg). The analysis showed that the Hg content in vegetable oils, shark liver oils, and fish oils from the Polish market is at a low level, guaranteeing the safety of their use, and as such, they do not pose a threat to health.

Feed as a source of dioxins and PCBs.

Dioxins (PCDD/PCDF) and polychlorinated biphenyls (PCBs) are a group of undesirable chemicals classified as persistent organic pollutants (POPs). The main route of human exposure to these compounds is through the diet (about 80%), with food of animal origin being the predominant source. For this reason, animal feed can contribute significantly to the presence of these compounds in food. The aim of this study was to present the concentrations of dioxins and PCBs as well as congener profiles in feed exceeding the acceptable limits (277/2012/EU). In addition, an attempt was made to identify the source of contamination for the different types of contaminated feedstuffs. Among a total of 743 samples of feed materials from the Polish market tested between 2013 and 2021, exceedances of the maximum levels of dioxins and PCBs were found in 21 samples (2.8%). The largest group among the non-compliant feed samples were feed materials of plant origin (43%) followed in decreasing order by vegetable oils and fats of animal origin (24%), materials of mineral origin (9%), and fish oils and meals (5%). The exceedances of the dioxin limits in the category feed materials of plant origin were only caused by dried materials (pulp, dried alfalfa, dried apple). Furthermore, for 8 (1%) samples, the concentrations of test substances exceeding the Action Levels (AL) were recorded.

Quality of Fish-Oil-Based Dietary Supplements Available on the Italian Market: A Preliminary Study.

The global market of food supplements is growing rapidly with a large turnover. Fish oil supplements represent a significant part of this turnover as they are believed to have important health benefits. Conversely, there are few papers in the literature about the quality control of fish oil capsules. As prior studies illustrate, a perfect agreement with the label is rarely found, and in some isolated cases, large amounts of soybean oil are also detected, indicating a true adulteration rather than a non-compliance with the label. None of the available studies refer to the Italian market, which ranks first in Europe in the consumption of food supplements. In this present communication, a quality control of fish-oil-based supplements from the Italian market was carried out for the first time. With minor deviations, all results showed substantial agreement with the label. However, the most important conclusion from this research is that compliance with the label is not enough to judge a product of good quality. The analysis of the overall fatty acid composition showed that some supplements have a high level of saturated fatty acids, and therefore they did not undergo a proper purification process. This may represent a safety issue since the purification process also allows the removal of toxic contaminants.

Long-chain monounsaturated fatty acids improve endothelial function with altering microbial flora.

Fish oil-derived long-chain monounsaturated fatty acids (LCMUFAs) with a carbon chain length longer than 18 units ameliorate cardiovascular risk in mice. In this study, we investigated whether LCMUFAs could improve endothelial functions in mice and humans. In a double-blind, randomized, placebo-controlled, parallel-group, multi-center study, healthy subjects were randomly assigned to either an LCMUFA oil (saury oil) or a control oil (olive and tuna oils) group. Sixty subjects were enrolled and administrated each oil for 4 weeks. For the animal study, ApoE-/- mice were fed a Western diet supplemented with 3% of either gadoleic acid (C20:1) or cetoleic acid (C22:1) for 12 weeks. Participants from the LCMUFA group showed improvements in endothelial function and a lower trimethylamine-N-oxide level, which is a predictor of coronary artery disease. C20:1 and C22:1 oils significantly improved atherosclerotic lesions and plasma levels of several inflammatory cytokines, including IL-6 and TNF-α. These beneficial effects were consistent with an improvement in the gut microbiota environment, as evident from the decreased ratio of Firmicutes and/ or Bacteroidetes, increase in the abundance of Akkermansia, and upregulation of short-chain fatty acid (SCFA)-induced glucagon-like peptide-1 (GLP-1) expression and serum GLP-1 level. These data suggest that LCMUFAs alter the microbiota environment that stimulate the production of SCFAs, resulting in the induction of GLP-1 secretion. Fish oil-derived long-chain monounsaturated fatty acids might thus help to protect against cardiovascular disease.

Fish oil supplements, oxidative status, and compliance behaviour: Regulatory challenges and opportunities.

BACKGROUND: Fish oil supplements that are rich in omega-3 long-chain polyunsaturated fatty acids (n-3 PUFAs). PUFAs are among the most widely-used dietary supplements globally, and millions of people consume them regularly. There have always been public concerns that these products should be guaranteed to be safe and of good quality, especially as these types of fish oil supplements are extremely susceptible to oxidative degradation. OBJECTIVES: The aim of the current study is to investigate and examine the oxidation status of dietary supplements containing fish oils and to identify important factors related to the oxidation status of such supplements available in the United Arab Emirates (UAE). METHODS: A total of 44 fish oil supplements were analysed in this study. For each product, the oxidative parameters peroxide value (PV), anisidine value (AV), and total oxidation (TOTOX) were calculated, and comparisons were made with the guidelines supplied by the Global Organization for EPA and DHA Omega-3s (GOED). Median values for each of the above oxidative parameters were tested using the Kruskal-Wallis and Mann-Whitney U tests. P values < 0.05 were chosen as the statistically significant boundary. RESULTS: The estimate for the average PV value was 6.4 with a 95% confidence interval (CI) [4.2-8.7] compared to the maximum allowable limit of 5 meq/kg. The estimate for the average P-AV was 11 with a 95% CI [7.8-14.2] compared to the maximum allowable limit of 20. The estimate for the average TOTOX value was 23.8 meq/kg with a 95% CI [17.4-30.3] compared to the maximum allowable limit of 26 according to the GOED standards. CONCLUSION: This research shows that most, although not all, of the fish oil supplements tested are compliant with the GOED oxidative quality standards. Nevertheless, it is clear that there should be a high level of inspection and control regarding authenticity, purity, quality, and safety in the processes of production and supply of dietary supplements containing fish oils.

Are over-the-counter fish oil supplements safe, effective and accurate with labelling? Analysis of 10 New Zealand fish oil supplements.

AIM: Fish oil supplements are regulated in New Zealand under the Dietary Supplement Regulations (Section 42, Food Act 1981) and therefore are not subject to the same level of scrutiny and regulations as medicines. We investigated accuracy of labelling, stated health benefits of fish oil supplements sold in New Zealand, and risks relating to possible mercury content. METHOD: The amounts of omega-3 fatty acids contained per capsule were determined by an independent laboratory using gas chromatography on 10 of the most popular over-the-counter fish oil supplements sold in New Zealand and were compared with amounts stated on product labels. Information on doses recommended to achieve a specific health benefit were taken from the 10 labels as well as the company websites. These recommended doses were compared with published recommended doses identified as being effective in those health areas stipulated on the labels, based on either systematic reviews, meta-analyses and/or consensus statements. Mercury was analysed by an independent laboratory using inductively coupled plasma mass spectrometry. RESULTS: The actual amounts of EPA and DHA per capsule in 90% of the over-the-counter fish oil supplements analysed were within 10% of the amount stated on the product labels. Only one product was greater than 10% below the stated dose on the label. All products suggested benefit across heart, brain and joint health and all but two products stated a range of capsules required to achieve that health benefit (eg, 2-6 capsules). Based on the maximum number of capsules recommended (which ranged from 3-6 capsules), only three products would likely confer the dose identified as optimal for achieving a health benefit across all three health areas. Only two products recommended doses that would likely confer a health benefit both at the minimum and maximum number of capsules. More products would likely benefit brain and heart health than joint health. Mercury was not detected in any sample. CONCLUSIONS: It is reassuring that the doses of 90% of the products were accurate and that mercury was not detected in any sample; however, less than a third of the supplements would likely confer all the health benefits stated, even at the highest recommended daily doses. This paper has highlighted the ongoing challenges associated with the regulation of "health claims" associated with dietary supplements in New Zealand. Indeed, the literature on health effects is contradictory at best. Clearer definitions of the types of health statements that can be made and the research necessary to support them requires regulatory clarification.

Monochloropropanediol esters and glycidyl esters in dietary supplements based on fish oils.

Dietary supplements based on fish oils might be contaminated with thermal processing contaminants, which are generated during the fish oil deodorisation. In the study, 30 samples of dietary supplements were analysed in terms of the occurrence of 3-monochloropropane-1,2-diol esters (3-MCPDE), 2-monochloropropane-1,3-diol esters (2-MCPDE) and glycidyl esters (GE). The results showed that the highest levels of 3-MCPDE (mean: 1461 µg kg-1) as well as 2-MCPDE (mean: 357 µg kg-1) were observed in the products containing shark liver oil. In the case of GE, they were mainly detected in the supplements including shark liver and cod liver oils. Although the results indicated that the consumption of the investigated supplements constituted no more than 1% of tolerable daily intake (TDI), the occurrence of MCPDE and GE in fish oil dietary supplements with a special attention to the origin of ester precursors should be thoroughly investigated in further studies.

Quantitation of Oxylipins in Fish and Algae Oil Supplements Using Optimized Hydrolysis Procedures and Ultra-High Performance Liquid Chromatography Coupled to Tandem Mass-Spectrometry.

Fish and algae oil supplements are enriched with eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), which are precursors to oxidized fatty acids, known as oxylipins. Here, we optimized a base hydrolysis method for measuring oxylipins in oil with ultrahigh-performance liquid chromatography coupled to tandem mass-spectrometry (UPLC-MS/MS) and quantified them in fish and algae oil supplements. Hydrolysis of 2 µL of oil with sodium carbonate resulted in greater oxylipin concentrations and minimal matrix effects, compared to higher oil volumes (10, 20, and 30 µL). Oxylipin yield was higher when oil was hydrolyzed in methanol containing 0.1% acetic acid and 0.1% butylated hydroxytoluene, compared to no methanol, and using sodium hydroxide versus sodium carbonate. Oxylipins extracted from 2 µL of oil using sodium hydroxide in solvent showed that EPA-derived oxylipins were most abundant in fish oil (84-87%), whereas DHA-oxylipins were abundant in algae oil (83%). This study shows that fish and algae oils are direct sources of EPA- and DHA-derived oxylipins.

Polycyclic aromatic hydrocarbons in edible oils and fatty foods: Occurrence, formation, analysis, change and control.

Numerous studies have demonstrated that dozens of polycyclic aromatic hydrocarbons (PAHs) are mutagenic, genotoxic and strongly carcinogenic. PAHs are found to be widely present in foods contaminated through multiple paths. Due to their lipophilic nature, these compounds easily accumulate in edible oils and fatty foods where they can range from no detection to over 2000µg/kg. Compared to precursor PAHs, researchers have seldom studied the presence of PAH derivatives, especially in food matrices. This chapter includes the physical and chemical characteristics of PAHs and their types, occurrence, sample pretreatment and instrumental determination methods, and their formation, change and control in edible oils and fatty foods. The occurrence and formation of PAH derivatives in foods are much less investigated compared to those of their precursor PAHs. Although the removal of matrix effects and accuracy remain difficult for current rapid determination methods, a prospective research direction of PAH analysis for large-scale screening is in demand. To date, physical absorption, chemical oxidation and biodegradation have been widely used in PAH removal techniques. Specific types of bacteria, fungi, and algae have also been used to degrade PAHs into harmless compounds. However, most of them can only degrade a range of LPAHs, such as naphthalene, anthracene and phenanthrene. Their ability to degrade HPAHs requires further study. Moreover, it is still a great challenge to maintain food nutrition and flavor during the PAH removal process using these methods.

Waste salt from the manufacturing process of mullet bottarga as source of oil with nutritional and nutraceutical properties.

BACKGROUND: The Sardinian food delicacy 'bottarga' is the final product of a number of treatments (salting and drying) on the ovaries of mullet (Mugil spp) and represents an important natural source of n-3 polyunsaturated fatty acids (n-3 PUFA) with nutraceutical properties. During the salting process of mullet roes to obtain bottarga, huge amounts of waste salt are generated, rich in residual ovary material. RESULTS: We evaluated the lipid composition (main lipid components and fatty acids) and bioactivity of oil obtained from the ovary material separated from waste salt (waste salt oil). Oil was obtained by supercritical fluid extraction with carbon dioxide (SFE-CO2 ), an environmentally friendly separation technique. The lipid composition of waste salt oil was determined by carbon-13 nuclear magnetic resonance (13 C-NMR) spectroscopy and reversed-phase high-performance liquid chromatography with diode array detector and an evaporative light scattering detector (HPLC-DAD/ELSD) chromatography. The oil was characterized by a relatively high level of n-3 PUFA (122 ± 7 g kg-1 of oil), and these beneficial health compounds were mainly present in the form of wax esters. Waste salt oil showed a marked cytotoxic effect [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay] in cancer B16F10 melanoma cells, with a slight cytotoxic effect in normal cells (3T3 fibroblasts). Waste salt and its derivatives (salt oil and residual material after oil extraction) were also tested for the attractant effect and acceptability to insects (Ceratitis capitata) to gain preliminary information about their potential application for animal supplementation. CONCLUSION: The results qualify waste salt as a potential resource for veterinary dietary supplements, nutraceuticals, and pharmaceutical applications. © 2020 Society of Chemical Industry.

Characteristic and shelf life of fish sausage: fortification with fish oil through emulsion and gelled emulsion incorporated with green tea extract.

BACKGROUND: Silver carp (Hypophthalmichthys moltrix) fish sausages incorporated with three forms of refined cod liver oil (as a source of polyunsaturated fatty acids: fish oil, oil-in-water emulsion (E), gelled oil-in-water emulsion (G)) and lyophilized aqueous extract of green tea (Camellia sinensis; 700 and 900 mg kg-1 ) were developed. The composition, technological properties (cooking loss, pH, texture, and color), sensory analysis, and microbial and oxidative stability of fish sausages during storage (4 °C) were evaluated. RESULTS: Lower value of cooking loss and thiobarbituric acid value were observed by addition of fish oil in emulsions forms. The incorporation of green tea showed no significant differences in preventing oxidation in related samples. Gelled-emulsified fish oil had better textural properties, including hardness and decreased springiness of the sausages. The G and E sausages showed higher values of lightness (L* ) than the control did. Emulsification had no significant effect on total viable count. Panelists could not distinguish between samples incorporated with fish oil whether in emulsified, gelled-emulsified, or control. Gelled-emulsified treatments were awarded higher scores by panelists for all of the sensory attributes (P < 0.05). Eicosapentaenoic acid and docosahexaenoic acid quantities significantly increased from control (0.48 mg g-1 and 0.46 mg g-1 sample respectively) to the enriched batches (>1.50 mg g-1 sample). The lowest ratio of ω6 to ω3 in batches was observed for gelled-emulsified samples. CONCLUSION: Overall, the addition of free fish oil affected the properties of the sausages. The gelled-emulsified treatment was a suitable fish oil delivery system in fish sausages, which maintained sensory properties during refrigerated storage.

Effect of aroeira (Schinus terebinthifolius Raddi) fruit against polyunsaturated fatty acids and cholesterol thermo-oxidation in model systems containing sardine oil (Sardinella brasiliensis).

This study evaluated the protective effect of ground aroeira (Schinus terebinthifolius Raddi) fruit addition against fatty acids and cholesterol oxidation in model systems containing sardine oil (Sardinella brasiliensis) during heating (150 and 180 °C). High temperatures reduced the amount of essential polyunsaturated fatty acids and caused the formation of oxidized products. Total cholesterol oxides content increased from 58.9 ± 0.26 to 577.5 ± 2.14 µg/g oil, after heating at 180 °C. However, aroeira significantly protected lipids from oxidation. Although the synthetic antioxidant applied as standard (butylated hydroxytoluene) showed greater results, it was used in the maximum concentration permitted by Brazilian legislation (0.01%), suggesting that aroeira fruit could be used as a natural antioxidant for the food industry. The protective effect of aroeira may be correlated to its antioxidant capacity and the presence of bioactive compounds which were identified by UHPLC-ESI-MS in the aroeira extract.

Serum nonesterified fatty acids have utility as dietary biomarkers of fat intake from fish, fish oil, and dairy in women.

Nutritional studies rely on various biological specimens for FA determination, yet it is unclear how levels of serum NEFAs correlate with other circulating lipid pools. Here, we used a high-throughput method (<4 min/sample) based on multisegment injection-nonaqueous capillary electrophoresis-mass spectrometry (MSI-NACE-MS) to investigate whether specific serum NEFAs have utility as biomarkers of dietary fat intake in women. We first identified circulating NEFAs correlated with long-term/habitual food intake among pregnant women with contrasting dietary patterns (n = 50). Acute changes in serum NEFA trajectories were also studied in nonpregnant women (n = 18) following high-dose (5 g/day) fish oil (FO) supplementation or isoenergetic sunflower oil placebo over 56 days. In the cross-sectional study, serum ω-3 FAs correlated with self-reported total ω-3 daily intake, notably EPA as its NEFA (r = 0.46; P = 0.001), whereas pentadecanoic acid was associated with full-fat dairy intake (r = 0.43; P = 0.002), outcomes consistent with results from total FA serum hydrolysates. In the intervention cohort, serum ω-3 NEFAs increased 2.5-fold from baseline within 28 days following FO supplementation, and this increase was most pronounced for EPA (P = 0.0004). Unlike for DHA, circulating EPA as its NEFA also strongly correlated to EPA concentrations measured from erythrocyte phospholipid hydrolysates (r = 0.66; P = 4.6 × 10-10) and was better suited to detect dietary nonadherence. We conclude that MSI-NACE-MS offers a rapid method to quantify serum NEFAs and objectively monitor dietary fat intake in women that is complementary to food-frequency questionnaires.

Phytosterolaemia associated with parenteral nutrition administration in adult patients.

Vegetable lipid emulsions (LE) contain non-declared phytosterols (PS). We aimed to determine PS content depending on the brand and LE batch, and in adult hospitalised patients treated with parenteral nutrition (PN), to establish the association between plasma and administered PS. Part I was the LE study: totals and fractions of PS in three to four non-consecutive batches from six LE were analysed. Part II was the patient study: patients with at least 7 previous days of PN with 0·8 g/kg per d of an olive/soyabean (O/S) LE were randomised (day 0) 1:1 to O/S or 100 % fish oil (FO) at a dose of 0·4 g/kg per d for 7 d (day 7). Plasma PS, its fractions, total cholesterol on days 0 and 7, their clearance and their association with PS administered by LE were studied. In part I, LE study: differences were found in the total PS, their fractions and cholesterol among different LE brands and batches. Exclusive soyabean LE had the highest content of PS (422·36 (sd 130·46) µg/ml). In part II, patient study: nineteen patients were included. In the O/S group, PS levels were maintained (1·11 (sd 6·98) µg/ml) from day 0 to 7, while in the FO group, significant decreases were seen in total PS (-6·21 (sd 4·73) µg/ml) and their fractions, except for campesterol and stigmasterol. Plasma PS on day 7 were significantly associated with PS administered (R2 0·443). PS content in different LE brands had great variability. PS administered during PN resulted in accumulation and could be prevented with the exclusive administration of FO LE.

First Use of Handheld Raman Spectroscopy to Analyze Omega-3 Fatty Acids in Intact Fish Oil Capsules.

Eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) are commercially important omega-3 fatty acids found in fish oils. Here we demonstrate that a handheld Raman spectrometer can be used to quantitate these compounds in intact fish oil capsules, avoiding oxidizing risk. Partial least squares regression models were prepared by relating Raman spectral variance to EPA and DHA concentrations determined using gas chromatography-mass spectrometry (GC-MS) analysis of fatty acid methyl esters in 15 commercial samples containing 145-473 mg g-1 EPA and 101-260 mg·g-1 DHA. Handheld Fourier transform (FT)-Raman models had root mean square errors of cross-validation of 38 mg g-1, 24 mg g-1, and 32 mg·g-1 for EPA, DHA, and EPA+DHA, respectively. Models generated from a benchtop FT-Raman spectrometer had corresponding errors of 32 mg·g-1, 22 mg·g-1, and 26 mg·g-1. By comparison, average standard deviations from triplicate GC-MS analyses were 11 mg·g-1 for EPA and 9 mg·g-1 for DHA.

Microwave-Assisted, Base-Catalyzed Synthesis of Fatty Acid Methyl Esters from Seeds and Fish Oil Supplements.

Growing health awareness has resulted in the increased use of dietary supplements derived from plants and marine sources, leaving consumers unsure of their best options. There were three objectives of the present study. The first was to design and evaluate an efficient derivatization procedure. The second was to perform a comparative analysis of liquid oils and their corresponding capsules of hemp, chia, and flax seeds. The final objective was to determine the fatty acid (FA) composition of six fish oil products and compare it to the one provided on the label. For the FA profiling, we implemented two efficient, one-step, sustainable methods with high percentage recovery for the synthesis of FA methyl esters (FAME), which use base catalysis and microwave-assisted heating. Our results found no difference in nutritional value between liquid oils and capsules of the seed supplements, with flaxseed and chia offering a higher, beneficial n-3:n-6 ratio compared to hemp oil. Four of the fish oils analyzed contained significantly less eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) than their reported label, and the other two not only agreed with the manufacturers' declaration but were able to fulfill the daily adequate intake (AI) with fewer capsules.

Oxidomics on the omega-3 volatile degradation pattern to determine differences between vegetable and marine oils.

In this work, oxidation assessment of vegetable and marine oils was performed based on their quantitative volatile profile and data analysis by 3-way partial least square chemometrics. Classification models were obtained using broad-spectrum isotopically labelled standards on the analysis of 25 volatile compounds from omega-3 fatty acid (FA) degradation by headspace solid phase microextraction gas chromatography time-of-flight mass spectrometry. Our oxidomic approach was performed on edible oils that differed in their origin (marine or vegetable) and in their omega-3 FA profile. In order to achieve a 3D matrix, every oil was oxidized at 6 different time-points. The obtained models classified edible oils according to their volatile degradation pattern. Oxidation of eicosapentaenoic/docosahexaenoic FA was mainly related to 2-propenal, butanal and 2-ethylfuran while α-linolenic acid oxidation was linked to 1-hydroxy-2-butanone and 5-ethyl-2(5H)-furanone. The present research provides valuable information on the degradation differences of omega-3 oils and proposes specific oxidation markers that could be used to ensure their quality assurance and avoid intentional adulterations.