Geographical origin identification of propolis using GC–MS and electronic nose combined with principal component analysis

Dynamic headspace sampling (DHS) coupled with gas chromatography–mass spectrometry and olfactometry (GC–MS–O) analysis have been applied for the determination of the characteristic volatile profile of propolis with the aim to differentiate the propolis from different regions of China. Acids, esters, alcohols, terpenes, aromatics represented the most abundant compounds in propolis among the ninety-nine volatile components identified by comparing with mass spectra and retention indices (RI) or from literature. In addition, principal component analysis (PCA) based on the data of DHS–GC–MS and electronic nose was used to study and obtain the important volatile compounds contributed to the differentiation of the propolis samples from different regions. Furthermore, a total of 28 odor-active compounds were detected and characterized by the trained panel of judges in the sniffing port of GC–O by using detection frequency analysis (DFA). In conclusion, GC–MS analysis and electronic nose combining with PCA could successfully distinguish the twelve representative raw propolis samples from 4 different geographical regions of China. The samples have been assigned to four large groups in accordance with their vegetal sampling location and we also have observed the volatile compounds resulting in the odor differentiation.     

Classification of Pecorino cheeses using electronic nose combined with artificial neural network and comparison with GC–MS analysis of volatile compounds

An electronic nose based on an array of 6 metal oxide semiconductor sensors was used, jointly with artificial neural network (ANN) method, to classify Pecorino cheeses according to their ripening time and manufacturing techniques. For this purpose different pre-treatments of electronic nose signals have been tested. In particular, four different features extraction algorithms were compared with a principal component analysis (PCA) using to reduce the dimensionality of data set (data consisted of 900 data points per sensor). All the ANN models (with different pre-treatment data) have different capability to predict the Pecorino cheeses categories. In particular, PCA show better results (classification performance: 100%; RMSE: 0.024) in comparison with other pre-treatment systems.     

Volatile profiles of aromatic and non-aromatic rice cultivars using SPME/GC–MS

Rice (Oryza sativa L.) is enjoyed by many people as a staple food because of its flavour and texture. Some cultivars, like scented rice, are preferred over others due to their distinctive aroma and flavour. The volatile profile of rice has been explored by other investigators, some of whom have also determined a corresponding aroma using GC/olfactometry. However, little research has been done to determine if different aromatic rice cultivars produce different flavour volatiles that would make them more desirable than others when cooked. In this study, seven aromatic and two non-aromatic cultivars were examined for their volatile profiles both before and after storage using solid phase microextraction (SPME) fibres in conjunction with gas chromatography/mass spectrometer (GC–MS). Ninety-three volatile compounds were identified, 64 of which had not been previously reported in rice. Differences were found in the volatile compounds of aromatic and non-aromatic rice besides 2-acetyl-1-pyrroline (2-AP). Most of the volatile compounds were present in freshly harvested rice and rice following storage, with very few new compounds being identified only after storage. Dellrose, an aromatic cultivar, and Cocodrie, a non-aromatic cultivar, had the most complex volatile profiles (over 64 volatiles). Sixteen compounds were found only in the aromatic cultivars, and some volatiles were found to be unique to specific aromatic cultivars. However, no distinctive pattern was observed that would identify a cultivar as being derived from Basmati, Khao Dawk Mali 105 (i.e. jasmine), or other sources of aroma. This study showed that there is a great diversity of volatiles in both aromatic and non-aromatic rice cultivars and, with further research, this may lead to a better understanding of the combination of compounds that gives a cultivar a unique flavour.     

Characterization of aroma-active volatiles in three Chinese bayberry (Myrica rubra) cultivars using GC–MS–olfactometry and an electronic nose combined with principal component analysis

Chinese bayberry (Myrica rubra Sieb. et Zucc.) is one of the most popular and valuable fruits in China because of its unique and exquisite flavor. In this study, headspace solid-phase micro-extraction (HS-SPME) coupled with gas chromatography–mass spectrometry and olfactometry (GC–MS–O) analyses were used to characterize the aroma-active profiles of the fruits from three different bayberry cultivars. The aim was to differentiate the bayberry cultivars by their aroma. Fifty-five volatile components, composed of aldehydes (10), alcohols (9), esters (8), terpenes (17), and others (11), were identified by optimized HS-SPME/GC–MS. Meanwhile, 36 aroma-active compounds were detected by olfactometry using detection frequency analysis (DFA). Hexanal (grass-like), (E)-2-hexenal (green), nonanal (fruit, flower), 1-hexanol (flower), and isocaryophillene (wood) were identified in all three cultivars. Further principal component analysis (PCA) of the active aromas revealed their contributions to the odor differences among the bayberry cultivar groups. The BQ bayberry was characterized by having a stronger “herb” odor, which is mainly caused by benzoic acid and methyl ester. DK bayberry had a stronger “grass” odor, which is mainly caused by 2,6-dimethyl-2,4,6-octatriene, while FHZ bayberry had a stronger “pine” odor, which is caused mainly by α-pinene. The GC–MS–O and electronic nose techniques, when combined with PCA, could be used to successfully distinguish between different bayberry cultivars.     

Use of electronic nose,validated by GC–MS,to establish the optimum off-vine dehydration time of wine grapes

Pedro Ximénez grapes were sun dried for 0, 2, 4, 6 and 9 days and the resulting must was analysed by gas chromatography and by an electronic nose. In the last stages of the process compounds related with ripe fruity and toasty aromas decreased whereas the concentration of sugars increases slightly, which suggests that the optimum dehydration time is reached before the ninth day. A discriminant analysis of data by the electronic nose allows for the differentiation of the must from dried grapes. Multiple regression analysis was made with the aim of relating the aroma that best described the must from dried grapes with the data reported by the electronic nose, obtaining a correlation above 99%. Therefore, according to the obtained results the electronic nose can be used as a tool for quick analysis that can help winemakers to decide the optimum drying time, taking into account the concentration of volatile compounds.     

Volatile characteristics of 50 peaches and nectarines evaluated by HP–SPME with GC–MS

Using HS–SPME–GC–MS, characteristics of the volatiles of 50 peaches and nectarines representing different germplasm origins were investigated. Ten of these peaches and nectarines were studied in two successive years. Eighty-four compounds were identified. Volatile composition was relatively consistent, but the amount of total volatiles and certain individual compounds varied between years. Moreover, the composition of volatiles and their contents depended on genotypic background and germplasm origin. Total volatiles in wild peaches and a Chinese local cultivar ‘Wutao’ were much higher than in the other groups. All the peaches and nectarines could be classified into four groups by principal component analysis of the volatiles (excluding C₆ compounds): ‘Ruipan 14’ and ‘Babygold 7’ with high contents of lactones, Chinese wild peaches and ‘Wutao’ with high contents of terpenoids and esters, seven cultivars with American or European origins with high content of linalool, and others without characteristic composition of volatiles.     

Aroma characterisation of Pu-erh tea using headspace-solid phase microextraction combined with GC/MS and GC–olfactometry

Volatile compounds from Pu-erh tea were extracted using a headspace-solid phase microextraction (HS-SPME), and analysed with a gas chromatography–mass spectrometry (GC–MS) and a gas chromatography olfactometry (GC–O). Results showed that a total of 66 major volatile compounds were identified by GC–MS analysis; among them, methoxy-phenolic compounds (33.58%), alcohols (23.01%) and hydrocarbons (11.62%) were the major chemical classes. It was found that 1,2,3-trimethoxybenzene (17.16%) was the most abundant aroma components, followed by α-terpineol (5.68%), 1,2-dimethoxybenzene (4.64%) and linalool oxide II (4.29%) in order. Twenty-nine odour active compounds were perceived by GC–O analysis. Further investigation showed that 1,2-dimethoxybenzene, 1,2,3-trimethoxybenzene, 1,2,3-trimethoxy-5-methylbenzene, 4-ethyl-1,2-dimethoxy-benzene, β-ionone, β-linalool, linalool oxides, decanal, etc. were responsible for the special flavour in Pu-erh tea. It seems that the methoxy-phenolic compounds and alcohols play a vital role in the special flavour of Pu-erh tea.     

Finding of pesticides in fashionable fruit juices by LC–MS/MS and GC–MS/MS

Products labelled as containing extracts from two mushrooms (cordyceps plus reishi) and the juices from açaí, goji, mangosteen, noni, pomegranate, and sea buckthorn have been analysed for 174 different pesticides, using the validated QuEChERS method for sample preparation and electrospray LC–MS/MS in the positive ion mode for analysis. Pesticides were found in 10 of the 21 samples analysed. Most pesticides found were below the tolerance levels (1–6 μg/g, depending on the pesticide), but some were not. This included boscalid, dimethomorph, iprovalicarb, pyridaben, pyrimethanil, and imazalil, for which there is no tolerance reported or zero tolerance in any fruit. However, genuine açaí that was harvested in the state of Pará and lyophilised in Rio de Janeiro had no detectable pesticides, when analysed by both LC–MS/MS and GC–MS/MS, which can detect 213 more pesticides and industrial chemicals. Likewise no pesticides were found in one sample each of cordyceps plus reishi, sea buckthorn and noni.     

Electronic nose and GC–MS analysis of volatile compounds in Tuber magnatum Pico: Evaluation of different storage conditions

The characteristic aromatic composition of white truffles (Tuber magnatum Pico) determines its culinary and commercial value. However modifications of truffle organoleptic proprieties occur during preservation. A study of headspace of white truffles by using Electronic nose (E-nose), gas chromatography–mass spectrometry (GC–MS) and sensory analyses was performed. Truffles were stored at different conditions for 7 days: +4 and +8 °C wrapped in blotting paper or covered by rice or none of the above. Headspace E-nose measurements and sensory analyses were performed each day. Statistical multivariate analysis of the data showed the capability of E-nose to predict sensorial analysis scores and to monitor aroma profile changes during storage. Truffle’s volatile molecules were also extracted by headspace solid phase microextraction technique and separated and identified by GC–MS. Partial Components Analysis of data was performed. E-nose and GC–MS results were in agreement and showed that truffle storage in paper at +8 °C seemed to be the best storage condition.     

Comparison of volatiles in raw and boiled potatoes using a mild extraction technique combined with GC odour profiling and GC–MS

Aromas of raw and boiled potatoes were compared using a mild extraction technique, ensuring preservation of the very labile composition of potato aroma during analysis. The extracts were evaluated by GC–MS and GC-sniffing using a panel of four judges. A total of 29 compounds were identified by GC–MS in raw potatoes and 25 in boiled. Twenty compounds were found in both raw and boiled potatoes, but most often in very different concentrations. During GC-sniffing, 33 odours were detected in boiled, and 27 in raw potatoes. Eight odours corresponded to compounds identified by GC–MS. Another four odours could be tentatively identified. It is concluded that the change in aroma during boiling of potatoes depends on compounds from lipid oxidation as well as compounds from other types of reactions, for instance the Strecker-degradation.     

Quantification of folpet and phthalimide in tea and herbal infusions by LC– high-resolution MS and GC–MS/MS

Two methods based on a modified QuEChERS sample preparation and either LC coupled to atmospheric pressure ionisation and high-resolution MS or GC coupled to electron ionisation and tripled quadrupole MS have been assessed for the quantification of folpet and phthalimide in tea and other dry herbal infusions. Both methods have been fully validated in green tea and further checked in black tea, verbena and rooibos, and they performed according to the SANTE/11813/2017 criteria at the target LOQ concentration level (50 µg/kg). These methods allow the accurate quantification of folpet in the selected matrices according to the new EU residue definition, which includes phthalimide. Phthalimide is the main metabolite and degradation product of folpet, although according to recent studies, it could be generated from different sources than folpet breakdown, such as food processing or analysis by GC.     

Characterization of aroma-impact compounds in yerba mate (Ilex paraguariensis) using GC–olfactometry and GC–MS

The volatile compounds of 18 yerba mate (YM) commercial brands from Argentina, Brazil, P.araguay and Uruguay were extracted using a Likens–Nickerson simultaneous distillation–extraction (SDE) apparatus, and analyzed by gas chromatography–mass spectrometry (GC–MS). Results showed that a total of 35 major volatile compounds were identified by GC–MS; among them, norisoprenoid compounds. A principal component analysis (PCA) was carried out in order to ascertain the degree of differentiation between samples and which compounds were involved. The results showed three main groups of YM corresponding to the places where they are commercialized. The first group (samples from Paraguay and Argentina) correlated positively with 6-methyl-5-hepten-2-one, octanal and 1-octanol. The second group (YM marketed in Uruguay but produced in Brazil) correlated positively with α- and β-ionone, linalool, nerol, α-terpineol, (Z)-linalool oxide and the aliphatic hydrocarbons undecane, dodecane and heptadecane. The third group (YM produced and marketed in Brazil) correlated positively with 2,4-heptadienal isomers, (E)-linalool oxide and β-cyclocitral. Through a preference test, one commercial brand was selected to be analyzed by gas chromatography–olfactometry (GC–O). Sixteen odor active compounds were perceived by GC–O analysis. It seems that the norisoprenoid compounds and components produced by fatty acid degradation play a vital role in the special aroma of yerba mate.     

Determination of 66 pesticide residues in livestock products using QuEChERS and GC–MS/MS

Food Science and Biotechnology - Determinations of 66 pesticide residues in different matrices including beef, pork, chicken, eggs, and milk were conducted using GC–MS/MS combined with the...     

Volatiles of plums evaluated by HS-SPME with GC–MS at the germplasm level

The volatiles of 75 plums belonging to five species and one interspecific hybrid were investigated by headspace-SPME–GC–MS; 88 volatiles were identified. Prunus salicina and its hybrids had much more compounds and higher contents of volatiles than Prunusdomestica and other three Chinese wild species. Aldehydes were the dominant volatiles in P.domestica and Prunus spinosa while esters were the major volatiles in P. salicina, P. salicina hybrids and Prunus ussuriensis fruits. Regarding terpenoids and alcohols, they were relatively high in several P. salicina cultivars, P. salicina hybrids and P. spinosa, and in Prunus cerasifera, respectively. All the plum germplasms could be divided into three groups via principal component analysis: (1) nine cultivars of P. salicina with high ester content, (2) nine Chinese cultivars and one P. salicina hybrid with ester content and two terpenoids, and (3) the rest of the cultivars and three Chinese wild species without characteristic volatiles.     

Characterization and differentiation of high quality vinegars by stir bar sorptive extraction coupled to gas chromatography-mass spectrometry (SBSE–GC–MS)

A stir bar sorptive extraction gas chromatography–mass spectrometry (SBSE–GC–MS) method has been used for the characterization of the volatile composition of 26 high quality vinegars of three different protected geographical indications (traditional balsamic vinegar of Modena, balsamic vinegar of Modena, and Sherry vinegar). SBSE technique provided the identification of 113 volatile compounds, which belong to different chemical families (short-chain esters, acids, acetates and alcohols, phenols, lactones and benzenic and furanic compounds). 39 volatile compounds were never previously reported in wine vinegars. This characterization contributed to the differentiation of the 100% of the studied samples on the basis of raw material (two different types of wine, and cooked must), aging type (static and dynamic) and aging time (<5 years, between 5 and 25 years, and >25 years). Furanes and terpenes together with acids and alkanes were the most discriminant variables for raw material and aging time, respectively, whereas for aging type, these ones were acetates and esters.     

Phenolic and aroma compositions of pitomba fruit (Talisia esculenta Radlk.) assessed by LC–MS/MS and HS-SPME/GC–MS

Pitomba (Talisia esculenta Radlk.) is a Brazilian exotic fruit consumed specially in the Amazonian region. Because of its large consumption and also due to the lack of knowledge regarding its chemical composition, pitomba fruit was studied in relation to its phenolic and aroma constitution. Using liquid chromatography tandem mass spectrometry (LC–MS/MS), 13 phenolic compounds (catechins, flavonoids and organic acids) were tentatively identified by comparison with standards and by fragmentation patterns. A validated method was applied to quantify common phenolic compounds of the pitomba pulp, for which quinic acid was the main compound (507.8 ± 7.4 μg g^− 1 DWP). Gas chromatography mass spectrometry (GC–MS) was employed along with headspace solid-phase microextraction (HS-SPME) to assess the aroma composition of pitomba fruit. A total of 27 volatile organic compounds (VOCs) were tentatively identified for pitomba fruit, for which 2-phenethyl acetate (17.89%) and isopentyl acetate (13.43%) esters were the main VOCs, contributing to the characteristic aroma of pitomba. The antioxidant capacity of the extract of pitomba fruit was evaluated by ABTS, DPPH and ORAC assays. We observed that pitomba has a moderate antioxidant activity.     

GC–MS quantification and sensory thresholds of guaiacol in orange juice and its correlation with Alicyclobacillus spp.

Guaiacol is a profoundly negative taint/off-flavour produced by the increasingly common microbial contamination of fruit juices with Alicyclobacillus spp. The objectives of this study included: determining sensory thresholds for guaiacol in orange juice (OJ), developing an analytical method whose detection limits were equivalent to sensory thresholds and determining levels of Alicyclobacillus spp. that would produce detectable levels of guaiacol. A 12 member trained panel was used to establish guaiacol detection and recognition thresholds. Guaiacol ortho and retro nasal detection thresholds in OJ were 0.70 and 0.53 μg/l respectively. Odour recognition threshold was 2.0 μg/l. A SPME GC–MS Selected Ion Monitoring (SIM) procedure was optimised to achieve analytical detection limits of 0.5 μg/l. Optimum guaiacol detection limit was achieved using only responses from m/z 109 and 124. Ion ratios (m/z 109/124) and linear retention index value matching were used to confirm the identification of guaiacol. Quantification was achieved using peak areas from standard guaiacol additions in orange juice between 0.5 and 100 μg/l. Alicyclobacillus growth of 2.2 log CFU/ml in OJ produced just detectable levels (0.7 μg/l) of guaiacol.     

Volatiles of grape berries evaluated at the germplasm level by headspace-SPME with GC–MS

Volatile aroma compounds are one of the important characteristics determining fruit quality. Evaluation of volatiles at the germplasm level is useful for future breeding efforts, aimed at improvement of fruit quality, via effects on fruit aroma. The composition and concentration of volatiles in berries of forty-two grape cultivars belonging to seven genotypic groups were evaluated by headspace solid-phase microextraction with GC–MS. Sixty volatiles were detected, of which C₆ compounds were the dominant volatiles in V. amurensis grape, neutral cultivars V. vinifera grapes and hybrid grapes between V. vinifera with V. thunbergii or V. amurensis. Alcohols and carbonyls were relatively low in all Vitis germplasm studied. Terpenoids were abundant in V. vinifera with muscat aroma, while esters were dominant in V. labrusca and its hybrids with V. vinifera or V. amurensis. Via principal component analysis, all the grape germplasm studied could be divided into three groups: (1) V. labrusca and its hybrids with V. vinifera or V. amurensis, (2) V. vinifera with muscat aroma and (3) the others, including V. vinifera without muscat aroma plus V. amurensis, and hybrids between V. vinifera and V. thunbergii or V. amurensis. Seasonal quantitative variations of volatiles were observed, but the qualitative volatile composition of the cultivars was consistent.