Single-laboratory validation of a GC/MS method for the determination of 27 polycyclic aromatic hydrocarbons (PAHs) in oils and fats.

A protocol for the measurement of 27 polycyclic aromatic hydrocarbons (PAHs) in vegetable oils by GC/MS has undergone single-laboratory validation. PAHs were measured in three oils (olive pomace, sunflower and coconut oil). Five samples of each oil (one unfortified, and four fortified at concentrations between 2 and 50 microg kg(-1)) were analysed in replicate (four times in separate runs). Two samples (one unfortified and one fortified at 2 microg kg(-1)) of five oils (virgin olive oil, grapeseed oil, toasted sesame oil, olive margarine and palm oil) were also analysed. The validation included an assessment of measurement bias from the results of 120 measurements of a certified reference material (coconut oil BCR CRM458 certified for six PAHs). The method is capable of reliably detecting 26 out of 27 PAHs, at concentration <2 microg kg(-1) which is the European Union maximum limit for benzo[a]pyrene, in vegetable oils, olive pomace oil, sunflower oil and coconut oil. Quantitative results were obtained that are fit for purpose for concentrations from <2 to 50 microg kg(-1) for 24 out of 27 PAHs in olive pomace oil, sunflower oil and coconut oil. The reliable detection of 2 microg kg(-1) of PAHs in five additional oils (virgin olive oil, grapeseed oil, toasted sesame oil, olive margarine and palm oil) has been demonstrated. The method failed to produce fit-for-purpose results for the measurement of dibenzo[a,h]pyrene, anthanthrene and cyclopenta[c,d]pyrene. The reason for the failure was the large variation in results. The likely cause was the lack of availability of (13)C isotope internal standards for these PAHs at the time of the study. The protocol has been shown to be fit-for-purpose and is suitable for formal validation by inter-laboratory collaborative study.     

Determination of mineral oil paraffins in foods by on-line HPLC–GC–FID: lowered detection limit; contamination of sunflower seeds and oils

A method is described to lower the detection limit for mineral oil saturated hydrocarbons (MOSH) in foods as compared to the on-line HPLC–LC–GC–FID method described previously: samples are preseparated (enriched) by conventional liquid chromatography on activated silica gel and activated aluminum oxide. The silica gel retains up to 1 g of fat or oil, the aluminum oxide up to 2 mg n-alkanes of at least 24 carbon atoms, i.e. plant paraffins which may severely hinder the analysis of the mineral paraffins. The efficacy of the method is shown for an apple and sunflower oil. Oils extracted from manually harvested seeds grown in fields or gardens contained between 0.14 and 0.77 mg/kg MOSH. In the oils from seeds sampled in an oil mill, this value was increased to 3.3–9.3 mg/kg, indicating a contamination during harvest, transport and/or storage. Concentrations in commercial refined sunflower oils ranged between 2.7 and 32 mg/kg, averaging 11.2 mg/kg. Since deodorization removes a substantial part of the MOSH, this suggests a further contamination in the oil mill. The contamination affected all samples at a similar level, indicating that it occurs systematically by the presently used technology.     

Saturated hydrocarbon content in olive fruits and crude olive pomace oils

Olive fruits contain an n-alkane series of saturated hydrocarbons mainly in the pulp. Lower amounts of a complex mixture of paraffins, unresolved by gas chromatography (UCM – unresolved complex mixture), have been found in cuticle, stone (woody shell and seed), olive leaves, and talc used as an aid to olive oil extraction. The amounts of both kinds of hydrocarbons are related to the olive cultivar and are transferred to oils in a proportion depending on the oil-obtaining process (centrifugation or solvent extraction). In olive oil obtained by centrifugation, only n-alkanes were detected. However, in olive oil extracted by second centrifugation, small amounts of UCM paraffins were detected together with the n-alkanes. Olive pomace oils showed a very variable content of both types of hydrocarbons according to the different obtaining process, such as double centrifugation, solvent extraction or centrifugation followed by solvent extraction. ‘White mineral oil’ used in oil extraction machinery is the source of the high concentrations of UCM paraffins found in some olive and olive pomace oils. In the case of second centrifugation olive oil, a maximum limit of 50 mg kg^?1 of UCM is suggested, whereas in the case of crude olive pomace oil, it amounts to 250 mg kg^?1 plus an additional minimum of 1.0 for the n-alkanes/UCM ratio.     

Load of polycyclic aromatic hydrocarbons in edible vegetable oils: importance of alkylated derivatives

The presence of polycyclic aromatic hydrocarbons (PAHs) has been studied in different samples of olive oil, extra virgin olive oil, and refined seed oils. A high number of PAHs have been found, with a wide range of molecular weights and in concentrations that are high or even very high compared with the data obtained by other authors, especially in the seed oils. Among the PAHs identified, more than half are alkylated compounds, which account for the major part of the total PAH concentration in some of the samples. The total PAH concentrations in olive oils and extra virgin olive oils are similar, but the former present a higher proportion of heavy PAHs than the latter. The seed oils, in general, have much higher concentrations than the different types of olive oil and their PAH profiles are different. One of the olive oil samples exhibited a PAH distribution similar to that observed in olive pomace oil, suggesting possible adulteration. These data reveal that, in some cases, PAH profile provides useful information in relation to the possible origin of the contamination. We also observed large differences in PAH distribution between oils with the same label but from different batches. PAHs with varying degrees of carcinogenicity have been identified in all the samples, including benzo[a]pyrene, although this PAH was identified neither in the extra virgin olive oils nor in two of the seed oil samples.     

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.     

28份国产特级初榨橄榄油中多酚含量及其变化规律北大核心CSCD

为了对我国油橄榄产业提供基础数据支持,采用国际油橄榄理事会推荐的HPLC法检测特级初榨橄榄油中的多酚含量,分析了我国不同产地的28份市售食用特级初榨橄榄油样品的多酚含量,并对不同生产年度和不同产地单果级特级初榨橄榄油中多酚含量变化规律进行了分析。结果表明:市售国产特级初榨橄榄油中均含有较为丰富的多酚类化合物,多酚含量范围为(63.885±2.345)mg/kg~(307.325±6.865)mg/kg;特级初榨橄榄油中多酚含量受贮存时间的影响较大,同时不同产地中适合生产高多酚含量特级初榨橄榄油的品种具有差异。不同特级初榨橄榄油样品之间多酚含量波动较大,需要通过多种方法来防止油脂中多酚类化合物的降解,以保证油品的质量,并因地制宜对油橄榄品种进行优化筛选。     

Determination of benzo(a)pyrene by GC/MS/MS in retail olive oil samples available in Qatar.

A survey was carried out for the presence of benzo(a)pyrene (B(a)P) in olive oils following reports that some batches of Spanish olive-pomace oil and its products contained high levels of B(a)P. Three types of olive oils (1) virgin olive oil, (2) refined olive oil and (3) olive-pomace oil, originating from France, Greece, Italy, the Lebanon, Spain, Tunisia and Turkey, and available on Qatar market, were analysed for B(a)P. Determination was carried out by extraction from a cyclohexane solution with N,N-dimethylformamide: water (9:1), back extraction with cyclohexane, followed by clean-up on a silica gel column and quantification by GC/MS/MS. The recovery and limit of quantitation of B(a)P in olive oils by this method were estimated as 88% and 0.5 microg kg(-1), respectively. B(a)P was detected in amounts below the permitted level of 2 microg kg(-1) in all 31 virgin olive oil samples and in 13 refined olive oil samples. However, all seven samples of Spanish olive-pomace oil produced and packed in Spain and three samples of olive-pomace oil produced in Spain, but packed in Saudi Arabia, were found to be contaminated with B(a)P, the level ranging from 3.1 to 70.8 microg kg(-1). In two samples of olive-pomace oil originating from Greece, B(a)P was not detected.     

Possibility of improving the quality characteristics of olive‐pomace oil and enhancing its differentiation from refined olive‐pomace oil

An investigation was carried out to evaluate the oxidative and hydrolytic degradation of 37 olive‐pomace oils marketed in southern Italy and to compare the results with those obtained from 10 deodorised olive‐pomace oils representative of large stocks of oil obtained after the final step of refining. One aim of the research was to ascertain the quality characteristics of commercial olive‐pomace oils; another was to verify whether the legally prescribed addition of virgin olive oil to refined pomace oil, so that the final product may be classified commercially as olive‐pomace oil, was actually sufficient to justify upgrading. The analytical methods used were silica gel column chromatography and high‐performance size exclusion chromatography. The data obtained showed that the final retail olive‐pomace oils had a lower degree of oxidative degradation than the refined oils, as indicated by the lower values obtained when summing the proportions of triglyceride oligopolymers and oxidised triglycerides. Conversely, hydrolytic degradation, which was evaluated by determining diglycerides, proved to be the same in the two categories of oil. The proportions of virgin olive oil added are small, as indicated by the statistically indistinguishable values of triglyceride oligopolymers and free fatty acids obtained. The possibility of setting a limit to the amount of triglyceride oligopolymers present in the commercial category of olive‐pomace oil has been considered. This limit would ensure standardisation of the level of oxidation and, consequently, of the quality of marketed oils and would enhance differentiation between olive‐pomace oil and refined olive‐pomace oil. © 2000 Society of Chemical Industry     

Influence of the different oils used in dough formulation on the lipid fraction of taralli

Abstract: An experimental investigation was carried out to evaluate the quality of taralli as a function of the type of oil used in their dough formulation. To this end, 4 types of oil (extra virgin olive oil, olive oil, olive‐pomace oil, and refined palm oil) were utilized to prepare taralli to investigate on the lipid fraction degradation and evaluate the taralli acceptability by consumers. The data obtained pointed out that taralli manufactured with extra virgin olive oil were significantly more appreciated than those made with refined oils due to their visual appearance and odor. Moreover, with respect to the other kinds of oil, the use of extra virgin olive oil led to significantly lower values (P < 0.05) of specific absorption at 232 and 270 nm (K₂₃₂ and K₂₇₀, respectively) and of triacylglycerol oligopolymers. It also proved to present a much lower content in oxidized triacylglycerols and diacylglycerols than olive‐pomace oil and refined palm oil, respectively. Furthermore, trans fatty acid isomers were absent in taralli made with extra virgin olive oil but were constantly present in those produced with refined oils.     

Phenolic content of commercial olive oils

The phenolic composition of commercial virgin olive oils (Picual, Hojiblanca, Arbequina and Cornicabra varieties) was studied by high performance liquid chromatography, sampling oils over 1 year. Oils sold in March displayed the lowest polyphenol concentration, particularly in secoiridoid aglycons. In contrast, lignans and tocopherols concentrations were not affected by sampling date. Among varieties, Picual and Cornicabra oils had slightly higher concentrations of polyphenols than Hojiblanca and Arbequina. Overall, the concentration of polyphenols in commercial Spanish virgin olive oils ranged from 330 to 500 mg/kg oil, which is higher than data reported previously. In contrast, "olive oil" and "pomace-olive oil" (mixtures of refined and virgin olive oils) had much lower concentrations in polyphenols than virgin olive oil, although higher than other edible vegetable oils. Thus, olive oil can be considered a good source of natural antioxidants. Moreover, the polyphenol and tocopherol contents of virgin olive oils were also found useful for the classification of the different commercial monovarietal oils when analysing the data by chemometric methods.     

Effect of cultivar and ripening on minor components in Spanish olive fruits and their corresponding virgin olive oils

Phenolics and volatiles are the compounds mainly responsible for the desirable flavour of extra virgin olive oils and therefore to a large extent determine the degree of consumer preference for this highly regarded product. The effect of both (i) the nature of the cultivar and (ii) the degree of ripening of the olive fruit on the biophenolic and volatile profiles of six different Spanish varieties (Arbequina, Cornicabra, Morisca, Picolimón, Picudo and Picual) and their corresponding virgin olive oils was determined in this study. A clear and statistically significant difference was observed for the oleuropein content, the main phenolic component found in the olive varieties studied. Demethyloleuropein was only found in the Arbequina variety and its content doubled during the ripening process. Verbascoside steadily increased throughout fruit maturation and cyanidin 3-O-rutinoside was the most abundant anthocyanin in all the varieties studied. Within the same cultivar a relationship between the oleosides content in the fruit and the presence of secoiridoids in the virgin olive oils was observed; however, the ratio between biophenols content in the olive fruit and in the virgin olive oil varied significantly for each of the cultivars studied (ranging from 2.3 for Picudo and 28 for Picolimon). The major volatile component was the C6 aldehyde fraction whose content varied greatly between the different varieties studied: E-2-hexenal content ranged from 20.5 mg of internal standard (4-methyl-2-pentanol) per kg of oil in the Arbequina variety to 3.1 mg/kg for Cornicabra; the amount of hexanal ranged from 1.75 mg/kg in Morisca to 0.70 mg/kg for Picual samples.     

Application of partial least square regression to differential scanning calorimetry data for fatty acid quantitation in olive oil

A chemometric approach based on partial least (PLS) square methodology was applied to unfolded differential scanning calorimetry data obtained by 63 samples of different vegetable oils (58 extra virgin olive oils, one olive and one pomace olive oil, three seed oils) to evaluate fatty acid composition (palmitic, stearic, oleic and linoleic acids, saturated (SFA), mono (MUFA) and polysaturated (PUFA) percentages, oleic/linoleic and unsaturated/saturated ratios).     

Authentication of Olive Oil Adulterated with Vegetable Oils Using Fourier Transform Infrared Spectroscopy

Determination of the authenticity of extra virgin olive oils has become more important in recent years following some infamous adulteration and contamination scandals. The study focused on application of Fourier transform infrared spectroscopy to identify the adulteration of olive oils. Single-bounce attenuated total reflectance measurements were made on pure olive oil and olive oil samples adulterated with varying concentrations of sunflower oil (20-100 mL vegetable oil/L of olive oil). Discriminant analysis using 12 principal components was able to classify the samples as pure and adulterated olive oils based on their spectra. A partial least squares model was developed and used to verify the concentrations of the adulterant. Furthermore, the discriminant analysis method was used to classify olive oil samples as distinct from other vegetable oils based on their infrared spectra.     

Effect of phospholipids on extraction of hydrophilic phenols from virgin olive oils

Three methods, most frequently used in hydrophilic phenols extraction from virgin olive oils (liquid–liquid, solid-phase with C18 and solid phase with diol-bound sorbents), were applied on virgin olive oils enriched with 2.0–10.0 mg/kg of phospholipids (granular de-oiled soy lecithin). Phospholipids addition significantly decreased the total phenols concentration determined colorimetrically. Liquid–liquid extraction showed the best repeatability and recovery, and the lowest decrease of total phenols extracted in the presence of phospholipids. Extraction rate declined with the increase of phospholipids concentration, but showed a kind of saturation behaviour. Addition of phospholipids (5 g/kg) to various commercial extra virgin olive oils resulted in a different degree of total phenols decrease (from 1% to 45%), probably because of different affinity of phospholipids toward different classes of phenolic compounds. During prolonged contact time between phenols and phospholipids (60-days storage), oxidation monitored by K270 and a decrease of total phenols concentration proceeded more rapidly in the presence of phospholipids.     

Extra‐virgin and refined olive oils decrease plasma triglyceride,moderately affect lipoprotein oxidation susceptibility and increase bone density in growing pigs

The objective of this study was to determine the health benefits of extra‐virgin and refined olive oils, which are high in mono‐unsaturated fatty acids (MUFAs) and polyphenolic compounds using the pig as a model. Thirty‐two cross‐bred pigs were individually penned, allocated to one of four dietary treatments and fed ad libitum for 28 days. Two of the experimental diets consisted of a basal diet containing 12% tallow and either 7% sunflower oil (TSO) or 7% extra‐virgin olive oil (TEVO) on a w/w basis. The remaining diets contained 19% extra‐virgin olive oil (EVO) or 19% of refined olive oil (RO). On days 7, 14 and 28 fasted and 3‐h post‐prandial blood samples were taken. Body composition was measured at the beginning and end of the study using dual energy X‐ray absorptiometry. Daily gain, feed intake and lean and fat deposition were not significantly different between the treatments. However, the daily increase in bone mineral density was higher in pigs fed diets containing olive oil (1.23 vs 2.54, 6.28, 5.20 mg cm^?2 per day for TSO, TEVO, EVO and RO, respectively, P = 0.050). Both fasting and non‐fasting plasma triglycerides were lower (P = 0.003) in pigs fed MUFA‐rich diets, while the cholesterol profile was not significantly different between the treatments. The results from in vitro copper‐induced lipid peroxidation, expressed in terms of conjugated dienes, showed that low density lipoprotein (LDL) particles in postprandial serum from pigs fed olive oil were moderately more resistant to oxidative modification. In conclusion, these data demonstrate that both extra‐virgin and refined olive oils attenuate postprandial hypertriglyceridaemia, moderately affect oxidation susceptibility and increase bone mineral density in growing pigs. Copyright © 2006 Society of Chemical Industry     

Identification of 3-MCPD esters to verify the adulteration of extra virgin olive oil

ABSTRACT

The adulteration of olive oil is an important issue around the world. This paper reports an indirect method by which to identify 3-monochloropropane-1,2-diol (3-MCPD) esters in olive oils. Following sample preparation, the samples were spiked with 1,2-bis-palmitoyl-3-chloropropanediol standard for analysis using gas chromatograph-tandem mass spectrometry. The total recovery ranged from 102.8% to 105.5%, the coefficient of variation ranged from 1.1% to 10.1%, and the limit of quantification was 0.125 mg/kg. The content of 3-MCPD esters in samples of refined olive oil (0.97–20.53 mg/kg) exceeded those of extra virgin olive oil (non-detected to 0.24 mg/kg). These results indicate that the oil refining process increased the content of 3-MCPD esters, which means that they could be used as a target compound for the differentiation of extra virgin olive oil from refined olive oil in order to prevent adulteration.     

A comparison between olive oil and extra-virgin olive oil used as covering liquids in canned dried tomatoes: hydrolytic and oxidative degradation during storage

The hydrolytic and oxidative degradation of olive oil and extra‐virgin olive oil, used as covering liquids in canned dried tomatoes, was studied during storage by means of conventional (acidity, peroxide value, p‐anisidine value) and non conventional (polar compounds) analyses. The effects of the addition of spices were also considered. The hydrolysis and oxidation of olive oil increased faster and was higher than that of extra‐virgin olive oil in terms of absolute values but some other indices, such as percentage of oligopolymers and percentage of oxidized triglycerides, increased faster in extra‐virgin olive oil than in olive oil. The antioxidant effect given by a higher concentration of polyphenols in the extra‐virgin olive oil was shown by a reduced amount of secondary oxidation. However, olive oil and extra‐virgin olive oils showed similar behaviour in terms of peroxide formation.     

特级初榨橄榄油基本质量指标及要求

目的 介绍2022年5月1日起实施的GB/T 23347—2021《橄榄油、油橄榄果渣油》,对当前市售进口特级初榨橄榄油质量情况进行评估。方法 采购20种市售标称意大利、希腊、西班牙等国进口的特级初榨橄榄油,检验酸价、过氧化值、消光系数变异值、水分及挥发物和不溶性杂质5个基础项目,对所得数据进行分析。通过与国际橄榄理事会标准的对比,讨论限量及测定方法等方面的细微差异,并说明这些项目对于橄榄油质量评估的现实意义。结果 所测样品的酸价、过氧化值、不溶性杂质3个项目均符合我国标准对该产品等级的限量要求。对比GB/T 23347—2021和国际橄榄理事会贸易标准,发现对于优质初榨橄榄油的酸价限量,国内标准比国外标准更为严格,橄榄油进口贸易需要注意这一差异。结论 2021年新颁布的GB/T23347—2021在质量要求上有所提高,消费者购买橄榄油时应优先选择“特级初榨橄榄油”。橄榄油质量初步评估需要加快时间和减少成本,检验以上5个项目为最低要求。     

Pigment profile and colour of monovarietal virgin olive oils from Arbequina cultivar obtained during two consecutive crop seasons

Monovarietal virgin olive oils are labelled with the olive varieties giving them their distinctive character. There are numerous studies focussed on the characterisation and quantification of the minor fractions of virgin olive oils that have generated databases on varietal olive oils. However, few studies have focussed on the components of the pigment fraction of virgin olive oils. The aim of this work was to quantify the components of the chlorophyll and carotenoid fractions of the monovarietal virgin olive oils from the Arbequina cultivar, growing in the Spanish area of Catalonia, during two consecutive crop seasons. Additionally the pigment changes occurring during 24 months of oil storage were evaluated. The results of this study showed minor qualitative differences between monovarietal virgin olive oils from two consecutive seasons. The quantitative differences could be attributed to the harvest period in each season rather than to the year’s weather conditions. Storage of the monovarietal virgin olive oils probably caused an important loss of the chlorophyll fraction, mainly chlorophyll a, during the first 6 months of storage. On the other hand, the carotenoid fraction was very stable and the retention of provitamin A was close to 80%, even after 24 months of storage.     

Effects of stir-fry cooking with different edible oils on the phytochemical composition of broccoli

ABSTRACT:  Numerous epidemiological studies indicate that Brassica vegetables in general and broccoli in particular protect humans against cancer; they are rich sources of glucosinolates and posses a high content on flavonoids, vitamins, and mineral nutrients. The contents of total intact glucosinolates, total phenolics, vitamin C, and minerals (potassium, sodium, calcium, magnesium, iron, manganese, zinc, and copper) in the edible portions of freshly harvested broccoli (florets), which was subjected to stir-frying treatments, were evaluated. In the present work, the stir-fry cooking experiments were carried out using different edible oils from plant origin (refined olive oil, extra virgin olive oil, sunflower oil, peanut oil, soyabean oil, and safflower oil) known and used worldwide. Results showed that during stir-frying, phenolics and vitamin C were more affected than glucosinolates and minerals. Stir-fry cooking with extra virgin olive, soybean, peanut, or safflower oil did not reduce the total glucosinolate content of the cooked broccoli compared with that of the uncooked sample. The vitamin C content of broccoli stir-fried with extra virgin olive or sunflower oil was similar to that of the uncooked sample, but greater than those samples stir-fried with other oils.