Rapid differentiation of new apple cultivars by headspace solid-phase microextraction in combination with chemometrical data processing

The aim of this study was to test a combination of automated headspace solid phase-microextraction gas chromatography (GC) with chemometrical data treatment for the rapid differentiation of enzyme-inactivated homogenates of new apple cultivars. The four cultivars Pinova, Piflora, Renora and Florina are characterized by different volatile patterns. Differences in the contents of volatiles were especially found for butyl acetate, ethyl butanoate, 2-methyl butanol, ethyl acetate and 6-methyl-5-hepten-2-ol. The used sample preparation method for GC coupled with pattern recognition of chromatograms is a useful tool for rapid and reliable determination of large numbers of samples.     

Identification of volatile organic compounds extracted by headspace solid‐phase microextraction in specialty beers produced in Brazil

Beer is a very complex mixture, being an alcoholic beverage obtained by fermentation processes. The consumption and production of specialty beers in Brazil have increased in the past years; however, most Brazilian brewers still depend on imported commercial starter yeast strains and raw materials. Our data also indicate that volatile profile of Brazilian beers is more influenced by raw materials. The analysis of volatile compounds in beer is important for its quality control, and the presence of aromatic substances is related to the beverage acceptance and quality. In this study, headspace solid phase microextraction in combination with gas chromatography coupled to mass spectrometric detection was used for the identification of the volatile organic compounds in 30 samples of Brazilian Pilsen and ale beers. Ninety‐nine volatile compounds were identified and grouped into ketones, terpenes, esters, higher alcohols, aldehydes, fatty acids, hydrocarbon and other minority compounds. Analysis of the principal components showed that the majority of specialty beers have similar chemical characteristics, their volatile profile being characterized mainly by esters and higher alcohols. Additional studies are necessary to better characterize Brazilian specialty beers; however, our results open perspectives for future research of possible indicators and markers that may serve for the purposes of certification, as well as quality control of the beverage. Copyright © 2017 The Institute of Brewing & Distilling     

Rapid determination of ethyl carbamate in Chinese rice wine using headspace solid‐phase microextraction and gas chromatography–mass spectrometry

Ethyl carbamate (EC) is a naturally occurring toxic contaminant that may imply a risk to human health and is usually found in alcoholic beverages such as Chinese rice wine. An automated procedure for the rapid determination of EC in Chinese rice wine was developed by headspace solid‐phase microextraction (HS‐SPME) coupled to gas chromatography–mass spectrometry (GC‐MS). Using propyl carbamate as internal standard, the optimized HS‐SPME sampling with a polyacrylic fibre was 45 min at 70°C after applying 38.8% NaCl to saturate the sample. This method showed good linearity over a range of 25–600 µg L^?1 (R² = 0.997). The recovery, relative standard deviation and limit of detection were 90.21–97.35%, lower than 2.89% and 1.19 µg L^?1, respectively. Additionally, the ethanol concentration had no effect on the analysis of EC. The total analysis time of 57 min per sample in continuous determination was twice as fast as the widely used solid‐phase extraction–GC‐MS method. This solvent‐free HS‐SPME‐GC‐MS procedure is suitable for the rapid, automated, and therefore convenient, determination of EC in Chinese rice wine. Copyright © 2012 The Institute of Brewing & Distilling     

Chemical profiling of volatile compounds of various home‐made fruit spirits using headspace solid‐phase microextraction

Fruit spirits are typical alcoholic beverages in the Moravian region of the Czech Republic. The aim of this work was to find differences in chemical composition among volatile profiles of spirits produced from various kinds of fruits. Twenty‐four samples of seven kinds of fruit spirits (plum, apple, pear, cherry, mirabelle, apricot and raspberry spirits) were analysed for examination of their volatile profiles. The most abundant family of compounds was esters, particularly ethyl esters. Sesquiterpenes proved to be a significant group of volatile substances by observing the differences between pome and stone fruit spirits [by relative higher content of (E ,E )‐α‐farnesene and by presence of α‐zingiberene and (E )‐α‐bisabolene in volatile profiles of pome fruit spirits]. Only in stone fruit spirits were propyl decanoate and ethyl salicylate found. Some other compounds were observed as being characteristic for individual kinds of analysed fruit spirits, e.g. γ‐decalactone for apricot spirits, (E )‐β‐farnesene for apple spirits, (Z )‐9‐tetradecen‐1‐ol for mirabelle spirits or some apocarotenoids for raspberry spirits. This work could potentially be the basis for checking the fruit origin of these distillates, or a partial manual as to how to differentiate individual kinds of pome‐fruit spirits (pear and apple spirits) or stone‐fruit spirits (plum, mirabelle, apricot spirits). Copyright © 2017 The Institute of Brewing & Distilling     

Analysis of brandy aroma by solid‐phase microextraction and liquid–liquid extraction

Headspace solid‐phase microextraction (SPME) and continuous liquid–liquid extraction (LLX) with Freon were used to extract and analyse aroma volatiles in brandy. In general, SPME using a non‐polar polydimethylsiloxane coating was more selective for esters and acids than was LLX. LLX using Freon 11 extracted the higher alcohols more efficiently than SPME. Relative differences in volatiles between brandies made from Vitis vinifera L cv Colombard and Vitis vinifera L cv Ugni blanc were observed, particularly for hexanol, 3‐methylbutylacetate, 3‐methylbutanol and 3‐methylbutyloctanoate. In addition, a combination of SPME with GC–olfactometry was used to provide more detailed information on sensory characteristics of varietal brandies. © 2000 Society of Chemical Industry     

Optimization of solid‐phase microextraction methods for GC‐MS determination of terpenes in wine

Solid‐phase microextraction using a 100 µm poly(dimethylsiloxane) fiber, followed by gas chromatography–mass spectrometry determination, has been optimized for the analysis of some terpenes in wine samples. The best results were obtained by direct immersion of the fiber using a sampling period of 15 min with constant magnetic stirring (1100 rpm) and an extraction temperature of 20 °C. The sample volume was 7 ml with 25% NaCl, in a 15 ml capped vial. Desorption was performed directly in the gas chromatograph injector port over 5 min at 250 °C using the splitless mode. The method is sensitive, with detection limits between 11 and 25 µg l^?1, precise, with variation coefficients in the range 1.28–3.71%, and linear over more than one order of magnitude. The related conditions were used for wine sample analyses with recoveries between 71.8 and 90.9%. Solid‐phase microextraction remains an attractive alternative technique due to its rapidity and because it is a solvent‐free extraction. Copyright © 2005 Society of Chemical Industry     

Estimation of the main dill seeds odorant carvone by solid‐phase microextraction and gas chromatography

Solid‐phase microextraction (SPME) was examined for its suitability for isolation of volatiles from seeds of dill in comparison with the traditional steam distillation procedure. Two main dill seeds volatiles, carvone and limonene, were taken into consideration. Two Supelco SPME fibers were used for the extraction: polyacrylic (PAc) and polydimethylsiloxane (PDMS). The time required to saturate the fibers was 3 min, while distillation took 3 h. Gas chromatography (GC) separation was reduced to 5 min by use of microcapillary column HP‐5 cross‐linked 5% Ph Me Siloxane. The standards of limonene and carvone were used to prepare calibration curves. PAc fiber responses were described by quadratic curves while PDMS responded linearly. Six varieties of dill were examined by distillation and SPME with both fibers. The good results were achived for carvone by SPME‐PDMS with significant regression between distillation and SPME. This compound can be measured in dill seeds samples within 10 min. The SPME‐PDMS were also tested for its application to chiral resolution of carvone and limonene enantiomers in dill seeds oil. The enantiomeric separation was done with two chiral columns. The enantiomeric ratios measured by SPME were just the same as with distillation.     

Analysis of odour‐active compounds of black mangrove (Avicennia germinans L.) honey by solid‐phase microextraction combined with gas chromatography–mass spectrometry and gas chromatography–olfactometry

The volatile compounds of Cuban black mangrove (Avicennia germinans L.) honey were analysed by solid‐phase microextraction (SPME) followed by gas chromatography–mass spectrometry and gas chromatography–olfactometry. A total of 66 compounds were positively identified in this product for the first time. Application of the aroma extract dilution analysis in a novel approach, which consisted of carrying out successively dilutions of the honey sample with a synthetic honey before the SPME, revealed 17 odour‐active areas in the flavour dilution factor range of 32–1024. On the basis of the quantitative data and odour thresholds, odour activity values (OAV; ratio of concentration to odour threshold) were calculated. Sixteen compounds showed OAVs >1, among which dimethyl sulphide, 3‐methyl butanal, 2‐methylbutanal, heptanal, octanal, phenylacetaldehyde, (Z)‐linalool oxide, (E)‐linalool oxide, nonanal, hotrienol, isophorone, lilac aldehyde A, 1‐nonanol, decanal, 4‐vinyl‐2‐methoxyphenol and (E)‐β‐damascenone showed the highest values and should be considered as the most odour‐active compounds, particularly (E)‐β‐damascenone, nonanal and decanal.     

Determination of flavour compounds in beer using stir‐bar sorptive extraction and solid‐phase microextraction

The analysis of volatile compounds in beer is important for quality control in the brewing industry. In this study, stir‐bar sorptive extraction (SBSE) and solid‐phase microextraction (SPME), two solvent‐less enrichment techniques, were applied in combination with gas chromatography flame ionization detection (GC/FID) for the determination of four flavour compounds (isoamyl acetate, ethyl hexanoate, benzaldehyde, myrcene) in beer. Limits of detection, linearity and repeatability of both methods were determined using standard ethanol solutions, while accuracy was determined by conducting recovery tests on commercial beer samples. Both methods were characterized by high linearity (r > 0.996) and repeatability (RSD = 1.76–10.66%). When both methods were compared, higher recoveries were obtained by SBSE, with limits of detection 1.8–2.8 times lower compared with SPME. In the analysis of commercial beer samples using both methods, SBSE analysis resulted in higher recoveries, therefore demonstrating promise for the analysis of beer volatiles. Copyright © 2015 The Institute of Brewing & Distilling     

Determination of volatile compounds to characterize fish spoilage using headspace/mass spectrometry and solid‐phase microextraction/gas chromatography/mass spectrometry

Changes in volatile compounds were monitored in whiting (Merlangius merlangus), cod (Gadus morhua) and mackerel (Scomber scombrus) and related to spoilage. Data are presented from headspace/mass spectrometric (HS/MS) analysis and solid‐phase microextraction/gas chromatographic/mass spectrometric (SPME/GC/MS) analysis at two time points (day 0 and day 10) during storage at 4 °C. HS/MS revealed 24 ions that could be used as markers of spoilage. SPME/GC/MS identified 86 compounds, 20 of which could perhaps be used to characterize freshness: principally alcohols, ketones, aldehydes and C₂–C₁₁ esters. Compounds common to the three species studied appear to be generated by microbial degradation. Copyright © 2005 Society of Chemical Industry     

顶空-固相微萃取与气质联用法分析草菇中的香味成分

本文以享有“中国蘑菇”之称的草菇为原料，采用碳分子筛-聚二甲基硅氧烷（CAR／PDMS）涂层的固相微萃取头分别萃取新鲜草菇和干草菇蒸馏后的挥发性成分，并通过气质联用仪分析鉴定了其主要的香味成分。结果表明，固相微萃取有效地吸附了草菇中的挥发性成分，经NIST质谱数据库和文献对照，分别从干草菇和新鲜草菇中检测出48和29种成分，其中八碳化合物是最要的风味主体。     

Comparison of aromatic and phenolic compounds in cherry wines with different cherry cultivars by HS‐SPME‐GC‐MS and HPLC

To compare the influence of cultivars on the production of aroma compounds and polyphenols, eight cherry varieties (six sweet and two sour) were fermented into cherry wines, and their compositions were analysed. Results showed that by headspace solid microextraction coupled to gas chromatography–mass spectrometry (HS‐SPME‐GC‐MS), a total of twenty‐first aromatic compounds, mostly consisting of esters, acids, terpenoids and C₁₃‐norisoprenoids, were identified, and eleven polyphenols including five anthocyanins and six phenolic acids were quantified using HPLC. May Duck and Early Richmond wines contained significantly higher levels of phenolic acids (>42 mg L^?1) that were associated with high contents of chlorogenic and neochlorogenic acids and also relatively high amounts of octanoic acid and β‐damascenone (odour activity values ≥1000). Hongdeng, Zhifuhong and Bing wines were characterised by higher concentrations of anthocyanins (>41 mg L^?1) and also relatively higher levels of isopentyl acetate. Lapins and Governer Wcod wines were distinguished by lower concentrations of polyphenols and relatively higher contents of ethyl 3‐methylbutanoate.     

Headspace solid‐phase microextraction analysis of volatile compounds from spice essential oils in dry flavourings

The composition of volatile compounds in nine spices was analysed by means of headspace solid‐phase microextraction (HS‐SPME) from dry flavourings of the spice essential oils, to devise an effective method to determine the content of the essential oils. The HS‐SPME was combined with GC‐MS and GC‐FID for identification and quantification of the volatile compounds. The optimisation of the extraction conditions was carried out by response surface methodology. The evaluation of the analytical parameters indicated that the method had a high precision (coefficient of variations lower than 3%), it was linear (response factors were smaller than 5%) and recoveries were higher than 89%. In the ruggedness test, sample quantity and pre‐extraction time were the factors that stood out as the causing of the greater effects on the analytical results.     

Optimization of extraction parameters for quantification of fermentation volatile by‐products in industrial ethanol with solid‐phase microextraction and gas chromatography

The rapid growth of the biofuels industry resulted in new research needs in chemical analysis. Methods for screening and quantification of impurities resulting from changes in feedstock, process and purification are needed. Direct sample injection methods are often not sensitive for lower concentrations. This research, developed an analytical method to simultaneously quantify fermentation volatile by‐products in industrial corn‐based ethanol. These include acetaldehyde, ethyl vinyl ether, 1,1‐diethoxyethane, isoamyl alcohol, isoamyl acetate, styrene, 2‐pentylfuran, ethyl hexanoate, ethyl octanoate, and ethyl decanoate. Headspace solid‐phase microextraction (SPME) coupled with gas chromatography–mass spectrometry (GC–MS) and GC‐FID were used. The effects of SPME coating, concentration, time, and salting out were tested. The optimized method used Carboxen/PDMS 85 µm coating with 10% (v/v) ethanol, 20 s headspace extraction, and no salt addition. The method had values of R² between 0.93 and >0.99 and relative standard deviations between 0.10 and 11.96%. The method detection limits were between 9.5 × 10^?4 to 9.7 × 10^?8 mol/L.This is one of the most comprehensive quantification methods for volatile impurities in raw ethanol to date. This new method was used to quantify 10 prevalent impurities in corn‐based industrial ethanol. Copyright © 2015 The Institute of Brewing & Distilling     

Analysis of flavour compounds in beer with extruded sorghum as an adjunct using headspace solid‐phase micro‐extraction and gas chromatography–mass spectrometry

Sorghum is a widely used adjunct that is used in the production of beer and increasingly affects beer flavour as the amount added increases. The aim of this work was to establish a simple, solvent‐free technique, without derivatization, to analyse flavours and typical volatile compounds present in extruded and unextruded sorghum beer, and to compare the flavour differences of the two types of beer. Headspace solid‐phase micro‐extraction gas chromatography–mass spectrometry was used to determine the flavours in the two beers and eight typical volatile compounds were quantified using GC. Forty‐five flavour compounds were identified and quantified in extruded white sorghum beer, while 31 flavour compounds were identified in unextruded white sorghum beer. Extruded or unextruded white sorghum can be used to produce ale beer, but the primary flavour content in the extruded white sorghum beer was higher than in the unextruded white sorghum beer. Copyright © 2016 The Institute of Brewing & Distilling     

顶空固相微萃取-气相色谱-质谱法分析脐橙中挥发性成分

目的 探究脐橙果皮和果肉中挥发性成分的种类、相对含量及其风味的差异。方法 将脐橙洗净后切分为果皮及果肉部分, 经粉碎后, 通过顶空固相微萃取(headspace solid phase microextraction, HS-SPME)技术分别富集果皮和果肉的挥发性成分, 再经气相色谱-质谱法(gas chromatography-mass spectrometry, GC-MS)分析其挥发性成分的种类及相对含量, 同时计算各物质的相对气味活度值(relative odor activity value, ROAV)。结果 脐橙中鉴定出烯烃类、醛类、醇类、酮类、酯类和酸类等挥发性成分共82种, 果皮中有59种, 果肉中有51种, 两者共有成分28种, 其中果皮特有挥发性成分31种, 果肉23种; 对果皮风味起关键作用和修饰作用的挥发性成分分别有20种和7种, 果肉分别有9种和7种。脐橙果皮和果肉中相对含量最高的成分均为D-柠檬烯, 分别达到43.97%和41.25%, 果皮次主要成分为芳樟醇, 含量为5.38%, 果肉次主要成分为巴伦烯亚橘烯, 含量为18.50%; 对果皮风味贡献最高的物质为芳樟醇, 主要提供麻香、青香和花香, 对果肉贡献最高的物质为β-紫罗酮, 主要提供花香; 此外果皮和果肉的木调香和清香差异不大, 但果皮的果香、花香、甜香和脂香更加丰富。结论 脐橙果皮和果肉中挥发性成分的种类和含量差异较大, 且造成其关键香气的物质有明显区别。