Polycyclic aromatic hydrocarbon profile analysis of high-protein foods, oils, and fats by gas chromatography.

A method is described for the determination of polycyclic aromatic hydrocarbons (PAHs) with 3-7 rings in (I) meat, poultry, fish, and yeast; and (II) oils and fats. The extraction of PAHs from group I is incomplete, and, therefore, group I samples must be dissolved homogeneously by saponification in 2N methanolic potassium hydroxide. The PAHs are concentrated by liquid-liquid extraction (methanol-water-cyclohexane, N,N - dimethylformamide - water-cyclohexane) and by column chromatography on Sephadex LH 20. The PAHs are separated by high-performance gas-liquid chromatography (GLC) with columns containing 5% OV-101 on Gas-Chrom Q and estimated by integration of the flame ionization detector signals in relation to an internal standard (3,6-dimethylphenanthrene and/or benzo(b)chrysene). The sensitivity is significantly higher than that obtained with ultraviolet spectroscopic methods. The reproducibility and margin of error were tested with meat samples fortified with 11 PAHs and with samples of sunflower oil. The method was further applied to meat, smoked fish, yeast, and unrefined sunflower oil. All samples investigated contained more than 100 PAHs (characterized by mass spectrometry) of which only the main components were determined: phenanthrene, anthracene, fluorene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene + benzo (j)fluoranthene + benzo(k) fluoranthene, benzo(e)pyrene, benzo(a)pyrene, perylene, dibenz(a,j)anthracene, dibenz(a,h)anthracene + indeno(1,2,3,-cd)pyrene, benzo(ghi)perylene, anthanthrene, and coronene. In contrast to other methods, the GLC profile analysis allows the recording of known and unknown PAH peaks simultaneously and also allows a compilation of all PAHs.     

Differential characteristics of fatty acids in cheese from milk of various animal species by capillary gas chromatography

The kind of milk used in the manufacture of cheese has been identified by analysis of the fatty acids. The milk fat is extracted from the cheese and saponified. The methyl esters of the fatty acids are prepared and determined by capillary column gas chromatography. Seven major fatty acids are separated and quantitated, namely, C8:0, C10:0, C12:0, C14:0, C16:0, C18:0, and C18:1. Many of the 21 simple ratios that can be formed from these 7 quantities are characteristic of the type of milk from which the fatty acids were obtained. The method allows the identification of cheese prepared with the milk of cows, buffalo, sheep, or goats. Substitution or adulteration of milk can also be detected.     

Determination of phytosterols in butter samples by using capillary column gas chromatography

A positive bias in the gas chromatographic (GC) analysis of butter for beta-sitosterol was discovered when attempting to confirm values by gas chromatography/mass spectrometry (GC/MS). The source of the problem was traced to an interfering material that was not effectively separated by packed column GC. Because capillary columns are known to provide superior separation, they were substituted for packed columns in the assay, and instrument parameters were modified accordingly. A compound with a similar retention time, identified by GC/MS as lanosterol, was separated from beta-sitosterol by the capillary column. The capillary column technique was applied to over 300 butter samples. The results indicate that the method can accurately quantitate beta-sitosterol in butter with no known interferences. The limit of detection for this method is 1 mg/100 g. Recoveries at a level of 3 mg/100 g averaged 98% with a coefficient of variation of 3.45%.     

Oxidative stability of fish and algae oils containing long-chain polyunsaturated fatty acids in bulk and in oil-in-water emulsions

The oxidative stability of long-chain polyunsaturated fatty acid (PUFA) and docosahexaenoic acid (DHA)-containing fish and algae oils varies widely according to their fatty acid composition, the physical and colloidal states of the lipids, the contents of tocopherols and other antioxidants, and the presence and activity of transition metals. Fish and algal oils were initially much more stable to oxidation in bulk systems than in the corresponding oil-in-water emulsions. The oxidative stability of emulsions cannot, therefore, be predicted on the basis of stability data obtained with bulk long-chain PUFA-containing fish oils and DHA-containing algal oils. The relatively high oxidative stability of an algal oil containing 42% DHA was completely lost after chromatographic purification to remove tocopherols and other antioxidants. Therefore, this evidence does not support the claim that DHA-rich oils from algae are unusually stable to oxidation. Addition of ethylenediaminetetraacetic acid (EDTA) prevented oxidation of both fish and algal oil emulsions without added iron and at low iron:EDTA molar concentrations. EDTA, however, promoted the oxidation of the corresponding emulsions that contained high iron:EDTA ratios. Therefore, to be effective as a metal chelator, EDTA must be added at molar concentrations higher than that of iron to inhibit oxidation of foods containing long-chain PUFA from either fish or algae and fortified with iron.     

Preparation of interesterified plastic fats from fats and oils free of trans fatty acid

Interesterified plastic fats were produced with trans-free substrates of fully hydrogenated soybean oil, extra virgin olive oil, and palm stearin in a weight ratio of 10:20:70, 10:40:50, and 10:50:40, respectively, by lipase catalysis. The major fatty acids of the products were palmitic (32.2-47.4%), stearic (12.0-12.4%), and oleic acid (33.6-49.5%). After storage at 5 degrees C (refrigerator temperature) or 24 degrees C (room temperature) for 16 h, the physical properties were evaluated for solid fat content, texture, melting, and crystallization behavior, viscoelastic properties, crystal polymorphism, and crystal microstructure. The interesterified fats contained desirable crystal polymorphs (beta' form) as determined by X-ray diffraction spectroscopy. They exhibited a wide plastic range of solid fat content of 52-58% at 10 degrees C and 15% at 40 degrees C. The physical properties were influenced by the ratio of palm stearin and olive oil. Harder and more brittle texture, crystallization and melting at higher temperature, higher solid fat contents, and more elastic (G') or viscous (G') characteristics were observed in the produced fats containing a higher content of palm stearin and lower content of olive oil. The produced fats stored at 5 degrees C consisted mostly of beta' form crystal together with a small content of beta form, while those at 24 degrees C had only beta' form. The produced fat with a higher amount of palm stearin appeared to have more beta' form crystal and small size crystal clusters. Thus, the physical properties of the produced plastic fats may be desirable for use in a bakery product.     

Amino acid analysis by capillary gas chromatography

Two developments have enabled major advancements in the use of capillary gas chromatography (GC), the result being its much more widespread use in investigations on a broad range of chemical and biological problems. The 2 technological developments were the introduction of fused silica capillary columns and the development of immobilized stationary phases for capillary GC columns. Because fused silica columns with immobilized stationary phases of varying polarities are offered by numerous vendors of chromatographic equipment, they have become widely used for many analytical tasks. We conducted a study to compare the effectiveness of commercially available fused silica capillary columns with the classical ion-exchange method in the separation and quantitation of amino acids. We selected the N-trifluoroacetyl (TFA) n-butyl and the N-heptafluorobutyryl (HFB) isobutyl ester derivatives for this study because of the extensive research and application of these derivatives during the past 20 years. The amino acid content of hydrolysates of 5 materials was measured: ribonuclease, beta-lactoglobulin, lysozyme, soybean meal, and a commercial poultry feed. Single 6N HCl hydrolysates of each material were prepared to minimize sample preparation differences, and 3 independent analyses of each hydrolysate were made by each of 3 techniques: the N-TFA n-butyl and N-HFB isobutyl ester methods using capillary gas chromatography and the ion-exchange chromatographic method using a Beckman 121 M amino acid analyzer. Our results clearly demonstrate that capillary GC analysis of amino acids using fused silica bonded-phase columns provides data with good precision and in general excellent agreement with ion-exchange analyses.     

超声提取-毛细管气相色谱法分析植物细胞膜脂脂肪酸成分与含量研究

建立了超声提取-毛细管气相色谱法分析植物细胞膜脂脂肪酸组成与含量的快速检测方法,以用于植物生理抗逆性研究。采用氯仿-甲醇-水体系超声提取植物总类脂,改变KOH浓度为0.05～0.075mol/L,利用叶绿素的皂化反应产物溶于水的性质除去色素干扰,膜脂经氢氧化钾-三氟化硼法甲酯化后上机分析。采用100∶1分流比进样,220～240℃程序升温操作,BPX70毛细管柱分离,FID检测。主要脂肪酸在12min内出峰,分离度>2,利用线性程序升温等当碳长度(ECLT)值结合标准品对照的方法对脂肪酸组分包括存在双键异位的不饱和脂肪酸进行定性。面积归一法或标准系数法定量,在31.25～5000ng的实验浓度范围内线性良好。实测了经乙烯利和多效唑处理后狗牙根叶片膜脂脂肪酸中10种脂肪酸组成与含量。该方法准确、简便、实用,可应用于植物叶片膜脂脂肪酸分析。     

液液萃取-气相色谱法测定发酵液中的有机酸与乙醇

嗜热菌降解纤维素是第二代燃料乙醇发展的重要方向。测定发酵液中乙醇和有机酸组成的变化,对发酵过程控制具有重要意义。该文以正丙醇为内标,建立了发酵液中乙醇、乙酸、丙酸和丁酸的气相色谱检测方法。该方法为:发酵液调节pH值、与内标混合、添加氯化钠至饱和、乙酸乙酯萃取,有机相进气相色谱检测。该方法下几种化合物的检出限范围为10~45 mg/L,低、中和高3个水平的加标回收率范围为80.65%~107.94%,相对标准偏差范围为1.71%~4.98%,该方法能用于纤维素菌群降解体系有机酸与乙醇的检测。该文还测算了20℃时乙醇、正丙醇、乙酸、丙酸和丁酸在乙酸乙酯和饱和氯化钠溶液中的分配系数,其值分别为0.28、1.64、1.37、2.51和3.29。该检测方法还可以推广应用于其他水相体系中有机酸和乙醇的检测,如废水厌氧消化液中挥发性脂肪酸的检测以及发酵醪中乙醇的检测。     

Determination of ethalfluralin in canola seed, meal, and refined oil by capillary gas chromatography with mass selective detection

Ethalfluralin is a herbicide that is effective for weed control on a wide variety of crops, including canola. A method is described for the determination of ethalfluralin residues in canola seed, meal, and refined oil. Residues are extracted from canola sample matrixes with acetonitrile. An aliquot of the extract is diluted with water and purified by C(18) solid-phase extraction prior to analysis by capillary gas chromatography with mass selective detection. For all three sample matrixes, the method has a validated limit of quantitation of 0.02 microg/g and a limit of detection of 0.006 microg/g. Recoveries averaged 96 +/- 7% for canola seed, 87 +/- 6% for canola meal, and 89 +/- 5% for refined oil. In a magnitude-of-residue study, canola seed from field plots that had been treated with ethalfluralin at one to three times the maximum label rate for weed control were found to contain no detectable residue of the herbicide.     

Determination of the enantiomeric composition of gamma-lactones in edible oils by on-line coupled high performance liquid chromatography and gas chromatography

A new method is proposed for the determination of the enantiomeric composition of gamma-lactones in different vegetable edible oils (i. e., olive oil, almond oil, hazelnut oil, peanut oil, and walnut oil), and its potential for authenticity control is underlined for a limited number of samples. The method is based on the direct injection (i.e., without requiring a sample pretreatment step) in on-line coupled reversed phase liquid chromatography to gas chromatography (RPLC-GC) using a chiral stationary phase in the GC-step. Different experimental values for both speed of sample introduction into GC and volume of the transferred fraction are considered to improve the recoveries obtained. Relative standard deviations lower than 10% and detection limits ranging from 0.06 to 0.22 mg/L were achieved for the investigated gamma-lactones.     

Determination of neutral sugars in soil by capillary gas chromatography after derivatization to aldononitrile acetates

We have quantified ribose, rhamnose, arabinose, xylose, fucose, mannose, glucose, and galactose in soil by gas chromatography (GC) simultaneously after converting to aldononitrile acetate derivatives. A recommended single-hydrolytic step by 4 M trifluoroacetic acid (TFA) at 105 °C for 4 h was more effective for releasing soil neutral sugars from non-cellulosic carbohydrates and better suited to our purification procedure compared with the sulphuric acid hydrolysis. Linearity of the GC detection for each neutral sugar was in the range of 10-640 μg ml⁻¹ and the recovery of neutral sugars from the spiked soil samples ranged from 76% to 109.7%. The coefficients of variation of the neutral sugars in four soils were lower than 2.0% for the instrument and 4.6-7.6% for the whole determination procedures. Compared with the trimethylsilyl (TMS) derivatization, the recovery of our newly modified method was more satisfactory and the reproducibility of ribose was improved significantly. Moreover, the aldononitrile acetate derivative was more stable than TMS derivative. Therefore, it is a promising approach suitable for a routine use in the quantitative analysis of soil neutral sugars, since it is fast, sensitive, and reproducible.     

Determination of methyl bromide in foods by headspace capillary gas chromatography with electron capture detection

Methyl bromide (MB, bromomethane) is determined in a variety of foods by headspace capillary gas chromatography with electron capture detection. The comminuted food sample as an aqueous sodium sulfate slurry is equilibrated with stirring for 1 h at room temperature before a 1 mL headspace aliquot is removed and injected using a modified on-column syringe needle. Methyl bromide is cryogenically focussed at -60 degrees C and then eluted by temperature programming. The procedure requires blending of soft samples, e.g. raisins, prunes, or oranges, and ultrasonic homogenization of hard samples, e.g. wheat, cocoa beans, corn, or nuts, with portions of water and ice so the final temperature of the food-water slurry is less than 1 degree C. A 20 g aliquot (4 g food) is then added to a cold headspace vial containing 4 g sodium sulfate. Losses of MB during a 3.5 min ultrasonic homogenization of wheat were 11% at 0.95 ppb and 4.4% at 4.8 ppb. For flour, cocoa, and finely divided spices, which do not require blending, 4 g is added to the cold headspace vial containing 16 mL cold water and 4 g sodium sulfate. Studies show that comminution of wheat or peanuts must be carried out to release MB trapped within the food so the headspace equilibrium can be attained in 1 h as well as to obtain homogeneous samples and representative sampling. No interferences were noted with the above foods or with many grain-based baking mixes analyzed.(ABSTRACT TRUNCATED AT 250 WORDS)     

Determination of esters of fatty acids with low molecular weight alcohols in olive oils

A simple and precise analytical method was developed for the simultaneous determination of squalene and methyl, ethyl, propyl, and butyl esters of fatty acids present in olive and olive pomace oils. A fraction containing squalene and fatty acid alkyl esters was isolated from the oil by solid phase extraction on silica gel cartridges and quantitatively analyzed by gas chromatography. A modification of the procedure allowed the isolation of squalene and esters separately. Repeatability and recovery of the method were good. The method was applied to extra and lampant virgin olive oil categories and also to oils obtained from olive pomace by second centrifugation and solvent extraction. Extra virgin olive oils contained low amounts of fatty acid methyl and ethyl esters, while oils obtained from altered olive or olive pomace showed high concentrations of fatty acid alkyl esters, mainly ethyl esters. Correlation between oil acidity and ethyl esters concentration was poor.     

Determination of linuron in potatoes using capillary column gas chromatography/mass spectrometry

A convenient method for the determination of the N-methyl,N-methoxy-phenylurea herbicide (linuron) in potatoes has been developed. The herbicide is extracted from potatoes using a slightly modified Luke multiresidue procedure. The extract is analyzed directly by gas chromatography with cold on-column injection, using an ion trap mass spectrometer in the chemical ionization mode as the detector. Quantitation is performed using p-bromonitrobenzene as the internal standard. The limit of detection is 0.1 ppm. Recoveries of linuron in potatoes averaged 112 +/- 6% at the 0.5 ppm level, and 110 +/- 2% at the 0.2 ppm level. No linuron residues were found in 25 potato samples that were analyzed by this method. Two other N-methyl,N-methoxy-phenylurea herbicides, metobromuron and chlorbromuron, are also sufficiently stable to be determined by this method, but the N,N-dialkyl-phenylurea herbicides neburon, diuron, and monuron are too thermally unstable and degrade in the gas chromatograph.     

Determination of ethylene dibromide in foods and grains by high resolution capillary gas chromatography with electron capture detection

Ethylene dibromide (EDB) levels in food samples were determined by gas chromatography with a high-resolution capillary column and electron capture detector. The capillary column used was 3 mm id X 25 m cross-linked 5% phenylmethyl silicone. Column temperature was set at 40 degrees C by a coolant containing carbon dioxide gas. Optimum temperatures of the injection port and detector were 200 and 350 degrees C, respectively. The detection limit was 0.5 ppb and linear from 1 to 20 pg on the dynamic range. EDB residues in food samples were extracted with n-hexane by steam distillation. A few impurity peaks appeared near EDB on the chromatogram; however, the EDB peak was resolved. Recoveries of EDB from wheat and brown rice ranged from 66.1 to 99.6%. EDB was detected in 3 samples of imported wheat at a range of 0.74-1.70 ppb, and was not detected at all in 37 samples. The EDB remaining in EDB-fortified cookies after baking was examined. The amounts of EDB were reduced to 30 to 50% of the original amounts by kneading the dough, and to below 1.5% by baking.     

Quantitative determination of short-chain free fatty acids in milk using solid-phase microextraction and gas chromatography

The objective was to establish a rapid, precise, and accurate methodology for the quantification of short-chain free fatty acids (FFA) (C(4)-C(12)) in milk by solid-phase microextraction and gas chromatography. Sampling conditions such as fiber type, pH, salt addition, temperature, volume, and time were investigated. FFA extraction consisted of placing 40 mL of milk containing 28% NaCl at pH 1.5 in a sealed vial and equilibrating for 30 min at 70 degrees C. A polyacrylate fiber was exposed to the sample headspace for 60 min and desorbed for 5 min into the gas chromatograph. Calibration curves for FFA followed linear relationships with highly significant (p < 0.001) correlation coefficients (R(2) = 0.99). Coefficients of variation of less than 7.7% for FFA concentrations indicated that the technique was reproducible. The limits of quantification for C(4)-C(10) were in the low parts per million level, which were below the concentration range found in fresh pasteurized milk (0.48-2.52 ppm) or rancid milk (4.73-32.31 ppm).     

Comparison and analysis of fatty acids, sterols, and tocopherols in eight vegetable oils

The similarities and differences of eight vegetable oils produced in China were investigated in terms of their fatty acid, sterol, and tocopherol compositions and subsequent data processing by hierarchical clustering analysis and principal component analysis. The lipid profiles, acquired by analytical techniques tailored to each lipid class, revealed great similarities among the fatty acid profiles of corn and sesame oil as well as few differences in their sterol profiles. It turns out that not only was there great similarity between the fatty acid profiles of corn oil and sesame oil but also there were not too many differences for the sterol profiles. Sunflower and tea-seed oil showed similar sterol compositions, while the tea-seed oil tocopherol was very similar to palm oil. The results demonstrated that the use of only one of these profiles was unreliable for indentifying oil origin and authenticity. In contrast, the use of the sterol or tocopherol profile together with the fatty acid profile more accurately discriminates these oils.     

Determination of polysorbates in foods by colorimetry with confirmation by infrared spectrophotometry, thin-layer chromatography, and gas chromatography

A method is presented for the detection of polysorbates (PSs) in 8 kinds of processed foods by colorimetric and thin-layer chromatographic (TLC) techniques. The PSs are extracted from processed foods with a mixture of methylene chloride and ethanol by using an Extrelut column. The extract is further purified by using a silica gel column. The PS extract is complexed with cobalt-thiocyanate (Cothiocyanate) reagent and is determined spectrophotometrically at 620 nm. The recoveries and coefficients of variation for 8 kinds of processed foods fortified with 0.1% PS 80 were 67.9-94.6% and 4.0-11.3%, respectively. The detection limit of TLC corresponded to 50 mg PS 80/kg. PS identity was confirmed by infrared spectrophotometry of PS extract, and gas chromatography of fatty acids and thin layer chromatography of POE-sorbitan residues after saponification.     

Determination of acidic herbicides and related compounds in water and soil by capillary gas chromatography using a nitrogen-phosphorus detector

Methods are described for the determination of acidic herbicides and related compounds in water and soil. Eight acidic herbicides and related compounds were extracted from water using either dichloromethane or an XAD-2 resin column. The acidic moieties were derivatized with 2-cyanoethyldimethyl(diethyl)aminosilane. The derivatized compounds were separated using capillary gas chromatography and quantitated using a nitrogen-phosphorus detector. Extraction from water using dichloromethane or an XAD-2 resin column resulted in recoveries greater than 90% at 0.1 ppb with an average coefficient of variation (CV) of 6%. In soils extracted with aqueous acetonitrile-acetic acid and partitioned into dichloromethane, recoveries at 500 ppb were greater than 75% with an average CV of 3.3%. The methods are rapid and there are few interferences.