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.     

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.     

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.     

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.     

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...     

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.     

Application of GC–MSD and LC–MS/MS for the determination of priority pesticides in baby foods in Serbian market

Babies and small children are especially sensitive population to the exposure to environmental contaminants. Their small mass and developing systems, including brain development may show adverse health effects from even low levels of contamination on a chronic or single dose case. In this paper one extraction method and two chromatographic techniques for the determination of pesticide residues in baby food were evaluated. A liquid chromatography–tandem mass spectrometry technique combined with electrospray ionization (ESI), (LC–MS/MS) and gas chromatography–mass spectrometry detection (GC–MSD) technique were applied in the detection of 50 pesticides in baby food. So-called QuEChERS (quick, easy, cheap, effective, rugged and safe) method was used as a sample preparation procedure. The recoveries were investigated at three levels (5, 10 and 50 μg/kg) and the results obtained showed compliance with the contemporary EU requirements with a few exceptions. LOQs for most of the tested pesticides were below the EU MRLs (10 μg/kg), except deltamethrin, cypermethrin, fenvalerate, phosalone and beta-cyfluthrin (LOQs were 10 μg/kg). Both techniques were applied in the analysis of 50 samples of baby food manufactured in Serbia.     

HS-SPME/GC–MS and chemometrics for the classification of Balsamic Vinegars of Modena of different maturation and ageing

Head space solid-phase microextraction (HS-SPME) coupled with GC–MS analysis has been applied for the determination of the characteristic volatile profile of Balsamic Vinegar of Modena (BVM) with the aim to distinguish the less matured products (matured in wooden barrels for at least 60 days) from the aged ones (aged in wooden barrels for at least 3 years). Coupling the HS-SPME/GC–MS analysis data with multivariate statistical techniques, such as Principal Components Analysis (PCA) and Classification Trees (CT), it has been possible to classify BVMs on the basis of different maturation and ageing. A matured BVM presents an aromatic profile characterised by high contents of 3-methyl-1-butanol, 4-ethyl-phenol, and 3-methyl-1-butanol acetate, while an aged BVM is characterised by a prevalence of ethyl acetate, ethyl acetoacetate, furans, 2,3-butanediol and 2,3-butanediol acetate. This work represents a first attempt to classify Balsamic Vinegars of Modena on the basis of their maturation and ageing.     

Evaluation of the volatile profile of 33 Pyrus ussuriensis cultivars by HS-SPME with GC–MS

Evaluation of the volatile compounds in fruit provides useful information for plant breeding for improved fruit aroma. In this study, headspace solid-phase microextraction (HS-SPME) combined with gas chromatography–mass spectrometry (GC–MS) was used to assess the volatile profile of 33 cultivars of the Chinese pear Pyrus ussuriensis. In all, 108 volatile compounds were identified and there were significant differences in the composition and concentration of volatiles among cultivars. On the basis of principal components analysis (PCA), the cultivars could be divided into four groups: Group 1 contained Reli, Jinxiang, Hongbalixiang, Baibalixiang and Fuwuxiang, cultivars with a high concentration of esters and a low concentration of hydrocarbons. Group 2 contained Qiuxiang, Fuanjianba, Longxiang, Guanhongxiao, Shanli24 and Wuxiangli, cultivars with high concentrations of hydrocarbons and low concentrations of esters. Group 3 contained Shatangli and Manyuanxiang, cultivars with high concentrations of aldehydes. Group 4 contained the other 25 cultivars.     

Identification of buckwheat (Fagopyrum esculentum Moench) aroma compounds with GC–MS

Buckwheat has a strong characteristic aroma, but its phytochemical background has not yet been fully elucidated. The aims of this study were identification and quantification of individual compounds responsible for the buckwheat aroma. Volatiles from a freshly ground buckwheat flour were extracted by different methods: direct extraction with petroleum ether, pentane or methanol, distillation with Clevenger apparatus and a headspace solid-phase microextraction method. The extracts were analysed by GC–MS with electron ionisation. Compounds were identified by MS and by comparison of retention times with reference compounds. Direct extraction with methanol and distillation proved to be very efficient. In these extracts twenty-five and thirty-five compounds were identified, respectively. The first extract contained more hydrophilic compounds and the latter more volatile compounds. Most of the compounds were quantified and their odour activity value (OAV) calculated. Only two compounds (salicylaldehyde and phenylacetaldehyde) were found in both extracts. The compounds with the highest contribution to the buckwheat aroma were: 2,5-dimethyl-4-hydroxy-3(2H)-furanone, (E,E)-2,4-decadienal, phenylacetaldehyde, 2-methoxy-4-vinylphenol, (E)-2-nonenal, decanal, hexanal and salicylaldehyde (2-hydroxybenzaldehyde).     

Composition of goat's milk fat triglycerides analysed by silver ion adsorption-TLC and GC–MS

The triglyceride (TG) composition of goat's milk fat (from the milk of five herds collected monthly, from November to May) was studied using AgNO₃-TLC and GC–MS. Two of the four fractions obtained by TLC contained trisaturated TGs (SSS) and represented 55% of the total TGs; they were separated by the chain length of short-chain fatty acid (FA). The TGs of the remaining fractions were identified as mono- (SSM) and polyunsaturated, representing 29 and 16% of the total TGs, respectively. The distribution of two SSS fractions by carbon number (CN) was unimodal, with maxima at CN40 and CN36 respectively. The proportions of SSM and polyunsaturated TG were high between CN38–CN44 and CN46–CN54, respectively (mean values, 35 and 52%). One hundred and twenty-four peaks (some containing more that one molecular species of TGs) were detected in the chromatogram of total fat; the sum of the 30 peaks representing >1 mol% was 70% of the total TGs. One hundred and thirty-seven molecular species were identified in the total goat's milk fat: 50% SSS, 30% SSM and 20% polyunsaturated. The most important in quantitative terms were medium-chain TGs containing C8, C10 or C12, and C18 : 1 as unsaturated FA.     

Determination of phthalate esters in non-alcoholic beverages by GC–MS and optimization of the extraction conditions

A quantificational method for 7 phthalate esters in non-alcoholic beverages was developed. Dimethyl phthalate, di-ethyl phthalate, di-propyl phthalate (DPP), di-butyl phthalate (DBP), benzyl butyl phthalate, di-(2-ethylhexyl) phthalate (DEHP), and di-octyl phthalate (DOP) were extracted from non-alcoholic beverages with the optimized solid-phase extraction method, and quantification was achieved by gas chromatography–mass spectrometry with isotope internal standard of d₄-di-(2-ethylhexyl) phthalate (DEHP-d₄). The inter-day method repeatability (RSD) was 8–13 %, whereas the intra-day method repeatability (RSD) was 9–15 %. The mean spiking recoveries were 84–105 %. A wide variety of phthalate concentrations was observed in 48 non-alcoholic beverages. DEHP was the most abundant phthalate compound followed by DBP, DPP, and DOP. DEHP was found in sport drinks (0.015–0.098 mg L^?1), tea (0.016–0.123 mg L^?1), coffee (0.028–0.159 mg L^?1), and fruit juices (0.022–0.126 mg L^?1).     

Hydrolysis of β-lactoglobulin by trypsin under acidic pH and analysis of the hydrolysates with MALDI–TOF–MS/MS

Trypsin (EC 3.4.21.4) hydrolysis of food proteins are done at the optimum pH (7.8) and temperature (37 °C). Little information is available on the effect of sub-optimal conditions on hydrolysis. Bovine β-lactoglobulin (β-Lg) was hydrolysed by trypsin under acidic pH (pH 4–7) between 20 and 60 °C and the substrate concentration from 2.5% to 15% (w/v) and compared with hydrolysis at pH 7.8 and 37 °C. Aliquots were taken at different times (t = 0 up to 10 min). Samples were analysed using matrix-assisted laser desorption/ionisation time-of-flight tandem mass spectrometry (MALDI–TOF–MS/MS) with α-cyano-4-hydroxycinnamic acid (HCCA) and 2,5-dihydroxyacetophenone (DHAP) matrices. Hydrolysis patterns of β-Lg were generally similar at pH 7.8, 7, 6 and 5 while at pH 4 fewer peptides were detected except a unique fragment f(136–141). The different cleavage sites of β-Lg showed low resistance to trypsin at optimum conditions and pH 7 while being random and simultaneous. At lower pH, some cleavage sites showed increased resistance, while hydrolysis was relatively slow and ordered. Initial attack by trypsin occurred at Arg⁴⁰–Val⁴¹, Lys¹⁴¹–Ala¹⁴² and Arg¹⁴⁸–Leu¹⁴⁹ resistance was at Lys⁶⁰–Trp⁶¹, Arg¹²⁴–Thr¹²⁵ and Lys¹³⁵–Phe¹³⁶. Five domains were identified based on β-Lg resistance to trypsin in the order f(1–40) < f(41–75) < f(76–91) > f(92–138) > f(139–162). Results suggest that hydrolysis away from trypsin optimum offer better hydrolysis process control and different peptides. This strategy may be used to protect target bioactive or precursor peptides, or avoid the production of unwanted peptides.