Volatile aldehyde emissions from heated cooking oils

Low molecular weight aldehydes (LMWAs) formed during the heating of frying media (triglycerides) were adsorbed onto tenax and analyzed by GC‐MS after thermal desorption. Six alkanals (C₅ to C₁₀), seven 2‐alkenals (C₅ to C₁₁) and 3 alkadienals (C₇, C₉ and C₁₀) were found in the fumes of canola oil (control), extra virgin olive oil, and refined olive oil, heated at 180 and 240 °C. The emission rates of these aldehydes depended on the heating temperature. Frying in any type of olive oil, independently of its commercial category, will effectively decrease the emission of volatile aldehydes at temperatures below the smoking point. Thus, using the cheaper olive oil for deep‐frying purposes will not affect aldehyde emissions. This is important since olive oil is usually used for deep‐frying operations while extra virgin olive oil is used as salad dressing in Spain. The mixture of refined olive oil with some virgin olive oil is the most acceptable type of olive oil in non‐Mediterranean countries due to its milder flavor. However, if higher temperatures are needed the use of canola oil is more advisable due to its higher smoke point. Copyright © 2004 Society of Chemical Industry     

Volatile compounds from Chétoui olive oil and variations induced by growing area

Fruits from the same variety of Olea europaea L., grown under different environmental conditions in the north of Tunisia, were harvested at the same ripening degree and immediately processed. The volatile profile of virgin olive oils was established using solid phase, micro-extraction (SPME) and gas chromatography-mass spectrometry (GC-MS). Compounds belonging mainly to the following chemical classes characterised the volatile profiles: esters, aldehydes, ketons, aliphatic alcohols and hydrocarbons. Significant differences in the proportions of volatile constituents from oils of different geographical origins were detected and the major volatile in approximately 50% of the oil samples was the aldehyde (E)-2-hexenal. The results suggest that, beside the genetic factor, environmental conditions influence the volatile formation.     

Impact of olive oil phenolic concentration on human plasmatic phenolic metabolites

Three different functional phenol-enriched virgin olive oils (FVOO) were prepared with a phenolic content of 250 (L-FVOO), 500 (M-FVOO), and 750 mg (H-FVOO) total phenols/kg. In a randomised, cross-over study with 12 healthy volunteers, the pharmacokinetics of phenolic biological metabolites was assessed. An increasing linear trend was observed for hydroxytyrosol sulfate, the main phenolic metabolite quantified in plasma, with C_max values of 1.35, 3.32, and 4.09 μmol/l, and AUC mean values of 263.7, 581.4, and 724.4 μmol/min for L-FVOO, M-FVOO, and H-FVOO, respectively. From our data an acute intake of phenol-enriched olive oils promotes a dose-dependent response of phenol conjugate metabolites in human plasma. Also, we point out for the first time hydroxytyrosol acetate sulfate as a main biological metabolite of hydroxytyrosol from olive oil ingestion.     

Minor compounds in the phenolic fraction of virgin olive oils

The phenolic fraction of 34 virgin olive oils was analysed by gas chromatography–mass spectrometry (GC–MS) with the aim to identify new compounds at low level. Twenty-seven compounds previously described in olive oils were identified; several new minor compounds with phenolic structure were detected in the samples: amongst them, 4-hydroxyphenylacetaldehyde, trans-isoeugenol (trans-2-methoxy-4-(1-propenyl)-phenol), 1,4-dihydroxy-2,6-dimethoxybenzene, 3,4-dihydroxybenzyl alcohol and 3,4-dihydroxyphenylacetic acid were identified by their mass spectra and confirmed using standards. In 34 virgin olive oils (cv. Nocellara del Belice) the mean concentrations for these five substances were always below 0.2 mg kg⁻¹ and only in two samples the level of 3,4-dihydroxyphenylacetic acid reached 1.47 and 1.97 mg kg⁻¹, respectively. These compounds could be used to characterise olive oils; low concentrations of 3,4-dihydroxyphenylacetic acid may show the initial autoxidation processes of olive oils.     

Application of response surface methodology to optimise supercritical carbon dioxide extraction of essential oil from Cyperus rotundus Linn.

Supercritical fluid extraction with carbon dioxide (SC-CO₂ extraction) was performed to isolate essential oils from the rhizomes of Cyperus rotundus Linn. Effects of temperature, pressure, extraction time, and CO₂ flow rate on the yield of essential oils were investigated by response surface methodology (RSM). The oil yield was represented by a second-order polynomial model using central composite rotatable design (CCRD). The oil yield increased significantly with pressure (p < 0.0001) and CO₂ flow rate (p < 0.01). The maximum oil yield from the response surface equation was predicted to be 1.82% using an extraction temperature of 37.6 °C, pressure of 294.4 bar, extraction time of 119.8 min, and CO₂ flow rate of 20.9 L/h.     

Chemical changes in extra virgin olive oils from Slovenian Istra after thermal treatment

Changes in the physico-chemical parameters of extra virgin olive oils after heating for 142 h at 100 °C with an air flow 10 L/h were investigated. The experimental study was carried out on the two predominant olive cultivars in Slovenian Istra – cv. Istrska belica and cv. Leccino. The data obtained showed that oils from Istrska belica were more stable than those from Leccino. Peroxide values and spectrophotometric data showed higher amounts of oxidation products in oils from Leccino than in those from Istrska belica. After thermal treatment fatty acid composition was changed more in Leccino oils; particularly the amounts of polyunsaturated fatty acids dropped significantly, while α-tocopherol was completely depleted in all samples. The content of total biophenols decreased from 598 mg/kg to 241 mg/kg in Istrska belica oils and from 391 mg/kg to 176 mg/kg in Leccino oils. HPLC data showed that transformation of secoiridoid biophenols to the simple biophenols, tyrosol and hydroxytyrosol took place.     

Changes during storage of quality parameters and in vitro antioxidant activity of extra virgin monovarietal oils obtained with two extraction technologies

Extraction technology has a great effect on quality of olive oils. This paper studied 18 months of storage of two Sardinian extra virgin monovarietal oils obtained with a traditional and with a low oxidative stress technology. Oil samples were subjected to the following chemical analyses: acidity, peroxide value, ultraviolet light absorption K₂₃₂ and K₂₇₀, carotenoids, chlorophylls, tocopherols and total polyphenols. The antioxidant capacity of oils, polyphenol extract and oil extract (remaining after polyphenol extraction) was also determined as radical scavenging activity. The results show that both extraction technologies resulted in minor changes in legal and quality indices during storage, due surely to the high quality of the oils as well as to the very good storage conditions used. Oils obtained with the low oxidative stress technology showed lower peroxide value and acidity and resulted in up to 103% higher total polyphenol content as well as increased radical-scavenging activity, with respect to oils obtained with the traditional technology.     

Solid-phase extraction and gas chromatographic analysis of phenolic compounds in virgin olive oil

A careful investigation on the potential application of solid phase extraction (SPE)-gas chromatography procedure in the analysis of phenol compounds in virgin olive oils was carried out. In doped refined olive oil samples a comparison between liquid/liquid and SPE extraction evidenced higher recovery when the C₁₈ sorbent phase was employed whereas, in the case of total suppression of residual sylanolic group (C_{18 EC}), only contradictory data was obtained. The same procedures were carried out on 10 genuine samples of virgin olive oil. As observed with the standards, C₁₈ sorbent phase gave higher values compared to C_{18 EC} and the liquid/liquid extraction procedures. Satisfactory results were obtained in the detection of ligstroside aglycon but for the oleuropein aglycon the quantitative is not completely reliable for the overlap of some unknown no-phenol compounds.     

The effect of citric acid on the phenolic contents of olive oil

Response surface methodology was used to optimise the combined effects of malaxation time (t) and aqueous citric acid solution (C_A) added at the beginning of the malaxation step on total polyphenols (TP) and o-diphenols (OD) content and the antiradical power (ARP) of the olive oil extracted from the Italian olive fruits of Coratina cultivar. Different tests were performed according to a 3² full factorial design, varying t from 30 to 90 min and the C_A from 5 to 15 ml/kg_paste. Overall optimal conditions identified by a numerical optimisation for the three responses were found to be at t = 30 min and C_A = 13.79 ml/kg_paste under which the model predicted TP = 604.52 μgCAE/g_oil, OD = 80.44 μgCAE/g_oil and ARP = 28.73 μgDPPH/μlextract. There were also linear correlations between TP (R² = 0.8176) and OD (R² = 0.8633) values of olive oil and waste water. The results of this study demonstrate that considerably short malaxation time and relatively small amounts of citric acid were required to enhance the quality of olive oil. The outcome of our study will therefore be of great value for the commercial production of olive oil with high level of polyphenols and o-diphenols.     

Direct determination of phenolic compounds and phospholipids in virgin olive oil by micellar liquid chromatography

A simple HPLC method is reported for fast separation and determination of phenolic compounds (tyrosol, caffeic acid, p-coumaric acid and oleuropeina) and phospholipids (phosphatidylethanolamine and phosphatidylcholine) in virgin olive oil samples. The samples were diluted with 2-propanol and injected into the column directly without previous extraction. Samples with an olive oil content of up to 65% were injected without any problems. The analytes were separated on a C-18 column by a micellar mobile phase containing 0.07 M SDS and 2.5% 2-propanol at pH 3, and were detected at 210 nm. Linear calibration curves [r² > 0.997] were obtained with detection limits ranging from 0.052 to 0.16 μg/g and 1 to 8.6% repeatability for the phenolic compounds. Several virgin olive oil samples were analysed and the recovery values were around 110%.     

Aldehydes contained in edible oils of a very different nature after prolonged heating at frying temperature: Presence of toxic oxygenated α,β unsaturated aldehydes

The evolution of the abundance of the different types of aldehydes, including those that are genotoxic and cytotoxic, oxygenated α,β unsaturated, in the headspace of extra virgin olive, sunflower and virgin linseed oils, submitted to frying temperature for prolonged periods of time, in a discontinuous industrial fryer, was analysed. Very close relationships were found between the abundance of the aldehydes in the three oils at a certain heating time and the original oil composition in the main components. The equations that related these parameters, which can be used for predictive purposes, show not only which acyl group each aldehyde comes from, but also its quantitative influence. This is the first time that the presence of 4-oxo-(E)-2-decenal, and 4-oxo-(E)-2-undecenal have been detected, not only in frying oils, but also in foods. Furthermore, the concentration of aldehydes such as 4-hydroxy-(E)-2-nonenal, (E)-4,5-epoxy-(E)-2-decenal, 4-hydroxy-(E)-2-hexenal, and 4-oxo-(E)-2-nonenal have been determined simultaneously for the first time in these edible oils submitted to frying temperature. The fact that significant concentrations of these toxic compounds were found in some oils before the oil reached 25% of the polar compounds is a cause of concern for human health.     

High performance size-exclusion chromatography analysis of polar compounds applied to refined, mild deodorized, extra virgin olive oils and their blends: An approach to their differentiation

An investigation was carried out to evaluate the use of High Performance Size-Exclusion Chromatography (HPSEC) of polar compounds of refined, mild deodorized, extra virgin olive oils as well as of their blends, in attempting to reveal significant differences in the amounts of the substance classes constituting polar compounds among these oils. Two sets of blends were prepared by mixing an extra virgin olive oil with both refined and mild deodorized olive oils in increasing amounts. The obtained data highlighted that the triacylglycerol oligopolymers were absent or present in traces in the extra virgin olive oil, while their mean amount was equal to 0.04 g/100 g and 0.72 g/100 g in mild deodorized and refined olive oils, respectively. Oxidized triacylglycerols and diacylglycerols were more abundant in mild deodorized oil and refined oil than in extra virgin olive oil. The Factorial Discriminant Analysis of the data showed that the HPSEC analysis could reveal the presence of refined/mild deodorized oils in extra virgin olive oils. In particular, the classification functions obtained allowed designation of mixtures containing at least 30 g/100 g of mild deodorized oil and all those containing refined olive oil as deodorized oil, therefore as oils subjected to at least a mild refining treatment.     

Gas chromatography screening of bioactive phytosterols from mono-cultivar olive oils

Phytosterols (PS) from nine samples of olive oil from Olea europaea L., the Carolea, Cassanese and Coratina mono-cultivars, have been analyzed by gas chromatography. Coratina virgin olive oil (VOO) from the month of November showed highest contents of β-sitosterol (5491 mg kg⁻¹) and Δ⁵ avenasterol (1767 mg kg⁻¹). Olive pomace oil had the lowest total content of all PS, when compared to VOO. These results suggests that, PS can be an important regulatory factor for the functional quality of olive oil along the agro-industry chain from the orchard to nutraceutical.     

Emissions of volatile aldehydes from heated cooking oils

Emissions of volatile organic compounds, including aldehydes, formed during heating of cooking oils: coconut, safflower, canola, and extra virgin olive oils were studied at different temperatures: 180, 210, 240, and 240 °C after 6 h. Fumes were collected in Tedlar^® bags and later analysed by GC–MS. The emissions of volatiles were constant with time and increased with the oil temperature. When the temperature of the oil was above its smoke point, the emission of volatiles drastically increased, implying that oils with low smoke point, such as coconut, are not useful for deep-frying operations. Canola was the oil generating the lowest amount of potentially toxic volatile chemicals. Acrolein formation was found even at low temperatures, indicating that home cooking has to be considered as an indoor pollution problem.     

Pigments composition in monovarietal virgin olive oils from various sicilian olive varieties

This paper presents the first investigation of the chlorophyll and carotenoid pigments composition in sicilian monovarietal virgin olive oils from the three (Cerasuola, Nocellara, Biancolilla) main olive varieties cultivated in Sicily (Italy). In all, 19 compounds were identified and quantified in 24 olive oil samples. The application of reversed-phase liquid chromatography with photodiode array detection using a C-30 column in the simultaneous qualitative–quantitative analysis of virgin olive oils pigments, has been shown. The qualitative pigment pattern was similar among the varieties investigated, whereas quantitative differences were found among the different cultivars, which can all be considered as having an high pigment content. Pheophytin a, was the major component (19.36–25.04 ppm), followed by β-carotene (8.06–16.27 ppm). Pheophytin a′ (2.92–4.17 ppm), lutein (2.28–4.49 ppm) and neoxanthin (1.54–2.11 ppm) were also well represented. The presence of carotenoid esters was also detected. The neoxanthin and β-carotene contents were higher compared to reports present in the literature for other olive oil varieties. This may be due to genetic factors and/or geographical differences. The ratio between the two isochromic pigment fractions, namely the chlorophyll and the carotenoid fractions, was around one in all varieties, showing that they were in balance. The lutein/β-carotene ratio was less than one in all cases. These parameters, along with other analytical parameters, could be used as indicators of typicality in olive oils. The presence of a specific pigment profile in olive oils could in fact be used to guarantee the genuineness of the product, since the quality control of food requires a precise knowledge of the pigments composition of the original products.     

Determination of acrylamide in potato chips by a reversed-phase LC–MS method based on a stable isotope dilution assay

Potato-based products represent an important part of the daily intake of food-derived acrylamide, mainly on adolescent population from western countries. A reversed-phase liquid chromatography-mass spectrometry based on a stable isotope dilution assay was used for acrylamide analysis. Aqueous sample extraction, cleaning with Carrez solution and solid phase extraction with methanol was applied. The ratio potato/NaCl solution is critical during extraction where the optimum ratio is 0.125 g/ml NaCl 2 M solution. The use of virgin olive oil, as retaining matrix, during methanol desiccation was critical to achieve high recoveries. The method performance was validated for limit of detection (23.2 μg/kg) and quantitation (91.8 μg/kg), linearity (r > 0.999, 25–1000 μg/kg), recovery (98.8%). The method was applied on commercial potato chips; the intra-day repeatability was set at 3.9% and values were corrected with a labeled internal standard (¹³C₃-acrylamide). No significant differences on the acrylamide content were observed between industrial-scale and local-scale processed potato chips.     

Supercritical carbon dioxide fluid extraction of Hibiscus cannabinus L. seed oil: A potential solvent-free and high antioxidative edible oil

The supercritical fluid extraction (SFE) trends and antioxidant activities of Hibiscus cannabinus seed oils were studied. SFE results indicate that extraction pressure is the major factor determining the oil yield. In comparison, classic Soxhlet extraction (SOX/L) yielded higher oil content than SFE (P < 0.05). However, no significant differences in oil content were observed in SFE at 600 bars/80 °C, rapid Soxhlet extraction (SOX/S) and conventional ultra-sonic assisted solvent extraction (SONIC) (P > 0.05). Antioxidant activities of H. cannabinus seed oils were compared with 7 types of commercial edible oils. DPPH scavenging activity test indicated that H. cannabinus seed oil extracted by SFE at 200 bars/80 °C possessed the highest antiradical activity whereas beta-carotene bleaching (BCB) assay revealed that all H. cannabinus seed oils (except for SFE at 400 bars/80 °C and 600 bars/80 °C) exhibited higher antioxidant activity than all commercial edible oils (P < 0.05). Thus, SFE – H. cannabinus seed oil may serve as an excellent source of solvent-free edible oil with high antioxidant properties.     

Discrimination of olive oil adulterated with vegetable oils using dielectric spectroscopy

The study focused on application of dielectric spectroscopy to identify the adulteration of olive oil. The dielectric properties of binary mixture of oils were investigated in the frequency range of 101 Hz–1 MHz. A partial least squares (PLS) model was developed and used to verify the concentrations of the adulterant. Furthermore, the principal component analysis (PCA) was used to classify olive oil sample as distinct from other adulterants based on their dielectric spectra. The results showed that the dielectric spectra of binary mixture of olive oil spiked with other oils increased with increasing concentration of soy, corn, canola, sesame, and perilla oils from 0% to 100% (w/w) over the measured frequency range. PLS calibration model showed a good prediction capability for the concentrations of the adulterant. For olive oil adulterated with soy oil, the results showed that the RMS was 0.053, sd(RMS), 0.017 and Q² value was 0.967. PCA classification plots for all oil samples showed clear performance in the differentiation for the different concentrations of the adulterant. Each of the oil samples could be easily grouped in different clusters using dielectric spectra. From the results obtained in this research, dielectric spectroscopy could be used to discriminate the olive oil adulterated with the different types of the oils at levels of adulteration below 5%.     

Optimised off-line SPE–GC–FID method for the determination of mineral oil saturated hydrocarbons (MOSH) in vegetable oils

An optimised off-line SPE–GC–FID method based on the use of silver-silica gel was developed for the determination of mineral oil saturated hydrocarbons (MOSH) in vegetable oils, including olive pomace oil. The method is specific in not including the aromatic hydrocarbons. The performance of different silica gels (untreated, activated and treated with silver nitrate) was compared in terms of capacity to retain fat and retention of interfering olefins present in particularly large amounts in refined olive oils. A coefficient of variation of 9% was obtained performing six replicate analyses of an extra virgin olive oil fortified with an amount of MOSH near the estimated LOQ (15 mg/kg). Recoveries were close to 100%. The use of activated aluminium oxide as an additional tool to eliminate interference by endogenous long-chain n-alkanes, is discussed.     

Oviposition attractants for Plodia interpunctella (Hübner) (Lepidoptera: Pyralidae) in the volatiles of whole wheat flour

Plodia interpunctella is attracted to whole wheat flour. Volatiles obtained from whole wheat flour by Porapak Q trapping were assayed using pitfall olfactometers, and were attractive to mated females (active at 10⁻¹ gram/day equivalent, gde), but not to males or unmated females, suggesting that the volatiles are oviposition attractants for P. interpunctella. Silicon dioxide column chromatography of the crude volatiles revealed that the fraction recovered with 3% ether in pentane (3% EP) was active and contained at least 27 components, in which alkanals (C₆-C₁₀) and 2E-alkenals (C₇-C₁₁) were active as individual aldehydes or mixtures. Nonanal was most active (the lowest active limit, LAL: 10⁻² μg), followed by 2E-nonenal and 2E-decenal (1 μg each). The synthetic mixture of the 27 components identified from 3% EP was attractive at 1.59×10⁻⁴ μg, which was equal in activity to the crude volatiles at 10⁻¹ gde (LAL) for mated females. The ether fraction (E) showed no activity by itself but synergistically enhanced the activity of the 10% EP fraction (LAL: 10⁻⁴ μg). Alkanols (C₅-C₉), lactones and carboxylic acids (C₅-C₁₈) were identified from the E fraction, in which hexanol and hexanoic acid were the major components. Both hexanol and palmitic acid were synergistic in combination with the aldehyde mixture.