Fatty acid esters of glycidol in refined fats and oils

Discrepancies in the analysis of 3‐chloropropane‐1,2‐diol (3‐MCPD) esters can be explained by the hypothesis that in some refined oils significant amounts of fatty acid esters of glycidol (glycidyl esters) are present in addition to 3‐MCPD esters. Glycidyl esters were separated from triacylglycerols by gel permeation chromatography (GPC) and detected by gas chromatography‐mass spectrometry (GC‐MS). Six samples of palm oil and palm oil‐based fats were analyzed by GPC and GC‐MS. In chromatograms of all samples, significant peaks, retention time and mass spectra in conformity with self‐synthesized glycidyl palmitate and glycidyl oleate were detectable. Quantification of individual glycidyl esters was not possible because of a lack of pure standards. Concentration of ester‐bound glycidol in different samples of fats and oils was estimated using an indirect difference method. Glycidyl esters could be detected only in refined, but not in crude or native, fats and oils. The highest concentrations were detected in palm oil and palm oil‐based fats. In a palm oil sample, glycidyl ester concentration varied according to different deodorization parameters, temperature, and time, while 3‐MCPD ester concentration was relatively constant, indicating that mitigation of glycidyl esters possibly may be achieved by optimizing refining parameters.     

Free and Esterified 4,4′-dimethylsterols in Hazelnut Oil and their Retention During Refining Processes

Free and esterified forms of sterols provide detailed information on the identity and the quality of vegetable oils. In this study, 4,4′-dimethylsterols in free and esterified forms were investigated in hazelnut and virgin olive oils. Moreover, a sample of solvent-extracted hazelnut oil was refined at the laboratory to monitor the effects of processing on the levels of 4,4′-dimethylsterols. Generally, the level of total 4,4′-dimethyslterols was higher in the esterified form (49–68%) compared with that in free form (32–51%) of these compounds in the hazelnut oil. In virgin olive oil samples, cycloartenol and 24-methylenecycloartanol were present in higher amounts in free forms (70–80%) than in esterified forms (20–30%). Among the refining processes, degumming, deodorization, neutralization and bleaching, only neutralization and bleaching considerably reduced 4,4′-dimethylsterols. In fully refined hazelnut oil, 18 and 37% of lupeol and an unknown compound X in the esterified form were lost, respectively. The loss of these two compounds in the free form was considerably higher, 26 and 72%, respectively. GC–MS analysis showed that adulteration of olive oil with a sample of fully refined hazelnut oil could be detected at a level as low as 2% by tracing lupeol in total or only in esterified forms of 4,4′-dimethylsterols. Further studies on the levels of free and esterified 4,4′-dimethylsterols and their retention during refining processes are anticipated in hazelnut cultivars from different origins.     

Identification of a TBHQ-Interfering Peak in Crude Canola Oil Using AOCS Official Method Ce 6-86 and its Chromatographic Resolution

AOCS Official Method Ce 6-86 “Antioxidants, Liquid Chromatographic Method” was originally developed to confirm the correct antioxidant was added at the specified concentration to refined oils. Today, this method is increasingly utilized to validate that antioxidants are absent from oil products. False positive results can have a significant impact on the ability to sell products in specific markets and can impart additional business expenditures for conclusive secondary analyses. In the current work, quantification of tert-butylhydroquinone (TBHQ) in crude canola/rapeseed oil using liquid chromatography (LC) with ultraviolet (UV) detection was compromised by an interfering peak. Analyses using liquid chromatography-mass spectrometry (GC–MS) and high-resolution accurate mass LC–MS identified the interferent as 2,6-dimethoxy-4-vinylphenol (canolol), an endogenous compound present in crude canola/rapeseed oil. Resolution of canolol and TBHQ using LC-UV can be achieved via minor modification of the chromatographic conditions.     

气相色谱-质谱与嗅觉测量法联用分析橙油中致香物质

采用气相色谱-质谱与嗅觉测量法(gas chromatography-mass spectrometry/olfactometry,GC-MS/O)联用的分析方法,对橙油的致香物质进行了分析与鉴别。GC-MS检测到35种挥发性物质,其中相对质量分数较高的化合物为柠檬烯(80.79%)、芳樟醇(3.85%)、癸醛(2.90%)、β-月桂烯(1.94%)、α-蒎烯(0.82%)、辛醛(0.71%)等。而GC-O分析到的具有香气的化合物为α-蒎烯、辛醛、柠檬烯、芳樟醇、α-松油醇、癸醛、肉豆蔻醛、(E,E)-2,4-癸二烯醛及一种具有花香、甜橘香的未知物质。采用强度法与稀释法相结合鉴别了橙油中的关键致香物质,结果表明,α-松油醇和未知物质具有最大的香气强度和稀释因子(FD因子),即二者对橙油整体香气贡献最大。采用GC-MS/O联用技术可以有效筛选出精油中的香味活性物质,而强度法与稀释法结合又可快速、准确、全面地分析样品中关键致香物质。     

Production of surface-active sophorolipid biosurfactant and crude oil degradability by novel Rhodotorula mucilaginosa strain SKF2

Biosurfactants are produced by important types of microorganisms such as bacteria, yeast, and filamentous fungi and have been used in a variety of industries. Among the 15 crude oil-degrading fungi, the two molds and one yeast were identified by 18S rDNA sequences as Mucor circinelloides strain SKMC, Fusarium fujikuroi strain DB2, and Rhodotorula mucilaginosa strain SKF2. These strains were isolated from crude oil–contaminated soil, diesel oil–contaminated soil, and activated sludge in the Oil Refinery Plant in Isfahan, Iran, respectively. The yeast strain was identified as a novel crude oil–degrading and biosurfactant-producing fungi in the presence of (1% v/v) Iranian light crude oil in the minimal salt medium (MSM). The highest amount of the dry weight of produced biosurfactant was measured at 6.2 g L⁻¹. Chemical nature of produced biosurfactant was determined as a surface-active sophorolipid biosurfactant compound by thin-layer chromatography, Fourier transform infra-red spectroscopy, and gas chromatography–mass spectrometry (GC–MS) analysis. The residual hydrocarbons in the MSM were analyzed by GC–MS, and it was shown that octadecane and docosane were eliminated by this novel strain completely.     

Effect of the full refining process on rice bran oil composition and its heat stability

The effects of the chemical refining process on the minor compounds of rice bran oil and its heat stability were investigated. After 8 h of heating, about 50% and 30% of total tocopherols remained in crude and refined rice bran oil, respectively. The individual tocopherols were differently affected by the refining process. The order of heat stability of tocopherols and tocotrienols in crude oil was found to be different from that in fully refined oil. A similar tendency was observed for sterols. After 8 h of heating, 65% and 72% of total sterols, and 14% and 46% of sterol esters, of crude or fully refined rice bran oil, respectively, disappeared. The heating process led to a 4% and 10.3% increase in polymer contents in crude and refined rice bran oil, respectively. Although refined rice bran oil showed good heat stability, when compared to crude oil its heat stability was decreased to some extent.     

Polyphenols of Pistachio (Pistacia vera L.) Oil Samples and Geographical Differentiation by Principal Component Analysis

The phenolic compounds of Italian and Turkish pistachio oil samples were investigated by gas chromatography–mass spectrometry (GC–MS) with the aim of identifying substances also present in very low concentration; 21 compounds were identified by means of the mass spectra of the trimethylsilyl (TMS) derivatives. Benzoic acid derivatives (protocatechuic acid, gallic acid, 4‐hydroxybenzoic acid) were the main components; 14 polyphenols were detected in pistachios for the first time. The concentrations of the compounds found were in the range 0.02–5.64 μg/g of fresh pistachio. No appreciable qualitative differences were found between samples of different origin; a multivariate approach was successfully tried to differentiate the samples according to their geographical origin, using Principal Component Analysis (PCA). Finally, Canonical Discriminant Analysis (CDA) was further conducted to classify different pistachio samples.     

Sulfur specificity in the bench‐scale biological desulfurization of crude oil by Rhodococcus IGTS8

Biological removal of organic sulfur from petroleum feedstocks may offer an attractive alternative to conventional thermochemical treatment due to the mild operating conditions and greater reaction specificity afforded by the nature of biocatalysis. Previous investigations have either reported the desulfurization of model sulfur compounds in organic solvents or gross desulfurization of crude oil without data on which sulfur species were being removed. This study reports initial sulfur speciation data for thiophenic sulfur compounds present in crude oil which may be used as a guide both as to which species are treated by the biocatalyst investigated as well as to where biocatalyst development is needed to improve the extent of biological desulfurization when applied to whole crudes. Biodesulfurization of two different crude oils in the 22–31 ° API specific gravity range with total sulfur contents between 1 and 2% is demonstrated in 1‐dm³ batch stirred reactors using wild type Rhodococcus sp IGTS8. While analysis of the crudes before and after biodesulfurization did not reveal a decrease in total sulfur, GC–MS did reveal significant (43–99%) desulfurization of dibenzothiophenes (DBT) and substituted DBTs. Fractionation of the whole crude, followed by analysis using gas chromatography–sulfur chemiluminescence detection (GC–SCD) of the aromatic fraction of the Van Texas crude oil, demonstrated a reduction of sulfur in this fraction from 3.8% to 3.2%. This research indicates that IGTS8 may be capable of biodesulfurization of refined products such as gasoline and diesel whose predominant sulfur species are dibenzothiophenes. Further biocatalyst development would be needed for effective treatment of the spectrum of sulfur‐bearing compounds present in whole crudes.     

自制吸附萃取搅拌棒结合气相色谱嗅觉计（GC/O）、气质联用仪（GC/MS）分析肉味香精呈香组分

采用自制吸附萃取搅拌棒对肉味香精呈香组分进行提取,利用热脱附仪进样,结合气相色谱嗅觉计联用（GC/O）、气质联用（GC/MS）双重定性方式,令组分富集率更高,检测结果更加真实、客观地反映出香精的香气组成。为高级香精的调配及仿香工作提供有力依据。实验仪器采用在色谱柱出口安装＂石英三通＂进行1∶1分流,样品被同时引入质谱和嗅觉计,避免了单一定性方法存在的不足。其中,两种方法共同检出的物质31种,仅GC/O检出的物质24种,仅GC/MS检出的物质26种。     

超临界CO2萃取橙花精油及GC/MS分析

用超临界CO2萃取技术结合分子蒸馏纯化制取橙花精油。通过正交实验确定了超临界CO2萃取最佳工艺条件,即萃取时间240min,萃取温度40℃、萃取压力20MPa、萃取流速20L.h-1。用气相色谱/质谱(GC/MS)联用仪对橙花精油成分进行了分析,共检测出54种化合物。用超临界CO2萃取结合分子蒸馏制取橙花精油的方法具有工艺操作温度低、基本上不破坏热敏性物质、精油香气更接近天然、无溶剂残留等优点。     

Up to 21 Different Sulfur-Heterocyclic Fatty Acids in Rapeseed and Mustard Oil

Three sulfur-heterocyclic fatty acids (SHFA) had been tentatively identified in rapeseed oil in the late 1980s. In this study we aimed to enrich and verify the presence of potential SHFA in one sample of native rapeseed oil, refined rapeseed oil and mustard seed oil. Fifty-gram samples of the three oils were individually saponified and converted into methyl esters. The resulting samples were hydrogenated and subjected three times to urea complexation. The resulting extracts of native rapeseed oil and mustard oil contained 21 different SHFA with 18, 20, 22 or 24 carbons. The refined rapeseed oil contained only nine C₁₈-SHFA. Structure investigation of the SHFA was performed by gas chromatography with mass spectrometry (GC/MS) using methyl esters and also 3-pyridylcarbinol esters. A direct screening of non-enriched samples by GC/MS in the selected ion monitoring mode and by GC with flame photometric detector (sulfur-selective) verified that the SHFA were native compounds of the oils and no artefacts of the sample preparation. Similar abundances of the four isomer groups of SHFA with monoenoic fatty acids of the same carbon number in these and five further rapeseed and mustard samples indicated that these could be the precursors of the SHFA.     

煤液化油中酚类化合物分布特征研究

采用气相色谱/质谱联用研究分析了胜利褐煤在0.1t/d直接液化连续实验装置上所得煤液化油中酚类化合物的分布特征.实验通过碱液洗涤法富集煤液化油中混合酚组分,并对该组分进行衍生化处理,以提高色谱柱对混合物的分离性能.以混合衍生物为主要分析对象,共定性出煤液化油中134种个体酚,分属于苯酚、茚满酚、萘满酚和萘酚等四种类型,且绝大多数酚类化合物都带有烷基侧链.苯酚类化合物数量最多,在混合酚组分中含量最大,其次为茚满酚和萘满酚.萘酚类化合物的数量最少,相对含量最小.     

Acephate,methamidophos and monocrotophos residues in a laboratory‐scale oil refining process

Acephate, methamidophos and monocrotophos are insecticides used in oil palm plantations for the control of bagworms and leaf‐eating caterpillars. The main purpose of this study was to determine whether the physical refining process at laboratory scale, which simulated the manufacturing process, could remove the residues of these three insecticides in crude palm oil, in the unlikely event that crude palm oil were contaminated with these organophosphorus insecticides. A series of crude palm oil samples spiked with low (0.1 µg/g) and high (1.0 µg/g) levels of these insecticides were subjected to a laboratory‐scale physical oil refining process. Oil samples drawn at various stages of the refining process, namely, degumming, bleaching and deodorization, were analyzed using an in‐house analytical method. The results obtained from these experiments suggest that the physical refining process is capable of effectively removing residual insecticides from crude palm oil. The final product of crude palm oil refining, the refined, bleached and deodorized palm oil, was found to have no detectable levels of acephate, methamidophos and monocrotophos.     

超临界CO_2萃取橙花精油及GC/MS分析

用超临界CO2萃取技术结合分子蒸馏纯化制取橙花精油。通过正交实验确定了超临界CO2萃取最佳工艺条件,即萃取时间240min,萃取温度40℃、萃取压力20MPa、萃取流速20L.h-1。用气相色谱/质谱（GC/MS）联用仪对橙花精油成分进行了分析,共检测出54种化合物。用超临界CO2萃取结合分子蒸馏制取橙花精油的方法具有工艺操作温度低、基本上不破坏热敏性物质、精油香气更接近天然、无溶剂残留等优点。     

新疆黑山煤液化重质油340-360℃馏分离及分析

用气相色谱/质谱联用仪(GUMS)分析馏程为340-360℃的新疆黑山煤液化重质油,检测出的主要成分为稠环芳烃及其衍生物,此外还有正构烷烃和少量含氧化合物.在超声辅助条件下,对液化重质油进行甲醇萃取,所得第一次甲醇萃取物用硅胶柱层析法分离.各洗脱馏分用GC/MS分析,其可测成分与直接检测相比更丰富,表明合适的预分离对提...     

Determination of Aroma Profiles of Olive Oils from Turkish Olive Cultivars

This study analyzed volatile aromatic compounds present in the oils of Turkish olive cultivars. The cultivars Gemlik, Ayval?k, Memecik, Domat, Uslu, Halhal?, Kilis ya?l?k, Nizip ya?l?k, Ha?ebi and Karamani were harvested from important Turkish olive‐growing locations, such as Bal?kesir, Bursa, Manisa, Ayd?n, Mu?la, ?zmir, Kilis, Mersin, Hatay and Gaziantep during the 2007–2008 and 2008–2009 growing seasons. Olive samples were collected in two harvest years, at almost the same maturity stage, and processed under the same conditions. Headspace solid‐phase microextraction (HS‐SPME) was used to analyze volatile aroma compounds in the olive oil samples. Forty‐seven compounds were characterized and quantified using gas chromatography‐mass spectrometry/flame ionization detector (GC–MS/FID). The most abundant identified compounds were trans‐2‐hexenal, hexanal and 3‐methyl‐1‐butanol. The trans‐2‐hexenal, hexanal and 3‐methyl‐1‐butanol contents of oil samples varied between 0.86–67.15, 3.93–61.82 and 0.48–84.74 %, respectively.     

Refining of Roundup Ready® soya bean oil: Effect on the fatty acid,phytosterol and tocopherol profiles

In this study, genetically modified (GM) soya bean seeds with the event known as Roundup Ready® were used for the production of soya bean oil and their fatty acid, phytosterol and tocopherol composition was characterised. Since these compounds can be partially lost during refining, this study also aimed at evaluating the compositional changes along the GM soya bean oil extraction and refining processes carried out industrially. During the refining process of crude soya bean oil, neutralisation was responsible for the major losses on phytosterols (15%). The greatest reduction of tocopherols was also caused by the neutralisation step (20%), while the deodorisation step caused minor losses (9%). Along the refining process, the decreases of total phytosterols and total tocopherols were 20 and 30%, respectively, which are lower than the losses reported in other studies, reflecting the industrial improvements in preserving beneficial health compounds in the refined oil. The results showed that the refined GM soya bean oil presented higher contents of phytosterols (313 mg/100 g) and tocopherols (931 mg/kg) comparing to other reports.     

Characterization of Aroma-Active Compounds in Iranian cv. Mari Olive Oil by Aroma Extract Dilution Analysis and GC–MS-Olfactometry

Aroma, aroma‐active compounds and fatty acid profiles of Iranian olive oil obtained from the cv. Mari were investigated for the first time in the current study. Aroma extracts were isolated from the oil by using a purge and trap extraction system and their compositions were analyzed by gas chromatography‐mass spectrometry‐olfactometry (GC–MS‐O). A total of 35 aroma compounds comprising alcohols, aldehydes, acids, esters, ketones, terpenes and volatile phenols were identified and quantified in the assayed samples. Aldehydes were present at the highest levels, followed by ketones and alcohols. (E)‐2‐Hexenal was quantitatively (1589 µg kg^?1) the main aroma compound in the analyzed oils, followed by hexanal and (E)‐2‐heptenal. The aroma‐active volatiles were elucidated in the aromatic extract by applying aroma extract dilution analysis (AEDA). The results of AEDA revealed 17 aroma‐active compounds. Under these condition it was possible to completely identify 16 of these compounds. Regarding to the flavor dilution (FD) factor, the most potent odorants with the highest FD factor were (E)‐2‐hexenal (512), followed by hexanal, 6‐methyl‐5‐hepten‐2‐one, (E)‐2‐decenal and one unknown compound (LRI = 1871). The fatty acid profile of the tested oils was composed of thirteen compounds. Oleic acid was the main fatty acid (76.01 %) followed by palmitic acid.     

Effects of cultivar and tempering procedures on crude soybean oil volatiles

The effects of soybean cultivar and tempering procedures on crude soybean oil volatiles were investigated by gas chromatography/mass spectrometry (GC/MS). Varietal differences in volatiles were not obvious. Trends in volatile contents due to tempering were noted primarily when comparing mean peak areas of these compounds in oils stored 16 days at 60°C. Differences in volatiles in response to tempering were not apparent in oils that had not been stored. Equilibration of beans with water resulted in oils with higher volatile contents than those from untempered beans. Steaming lowered volatiles from equilibrated values, and pressure steaming had an even more dramatic lowering effect.