Application of accelerating energies to the maceration of sherry vinegar with citrus fruits.

BACKGROUND: In the present work we propose the use of accelerating energies (microwaves and ultrasounds) to the maceration process of sherry vinegar with citrus fruit peels (orange and lemon). For the application of microwaves, an experimental design has been developed in order to optimize the maceration conditions. To evaluate the effect of these energies on the maceration, the volatile and polyphenolic content of the samples has been analyzed, as well as their sensory characteristics. RESULTS: Orange peel provided a higher number of volatile and polyphenolic compounds to the vinegar, while lemon's yielded a greater amount of some of them. The multivariate analysis showed that the samples macerated using microwaves were the most similar to the samples macerated in the traditional way. This aspect was corroborated by the sensory analysis, which was more noticeable when orange peel was used in the macerations. CONCLUSION: Therefore, it seems that the use of microwaves to accelerate maceration is a good alternative to the traditional method of making sherry vinegars macerated with citrus peel, since it cuts down the maceration time from 3 days to just a few minutes. © 2020 Society of Chemical Industry.

Effect of the type of wood used for ageing on the volatile composition of Pedro Ximénez sweet wine.

BACKGROUND: The present study investigated the volatile composition of a Pedro Ximénez sweet wine that had been aged in barrels made of different types of wood (Spanish oak, French oak, American oak and chestnut) and subjected to different degrees of toasting (medium toasting and intense toasting). The analyses were carried out using stir bar sorptive extraction gas chromatography-mass spectrometry after validation of the matrix in this case. RESULTS: Good values of linearity, precision, limits of detection and limits of quantification were obtained for the 36 compounds studied, six of which were identified for the first time in Pedro Ximénez (propyl acetate, cis-3-hexenyl acetate, benzyl acetate, guaiacol, trans-whiskeylactone and 4-ethylguaiacol). The volatile composition of the samples varied as the ageing process progressed, and higher volatile concentrations were obtained in samples aged in barrels that had been intensely toasted compared to in those with medium toasting. A multivariate statistical study allowed the samples to be correctly classified according to ageing time, wood toasting and the type of wood used for ageing. CONCLUSION: The organoleptic analysis performed on the Pedro Ximénez sweet wine samples resulted in differences between the wines aged in the different types of wood during the early weeks of ageing, and scarce differences towards the end of the study period. At the end of the process, all of the wines were better valued and wines aged in medium toasted barrels were the best rated by the panel of judges for all four woods under investigation. This fact could indicate the suitability of alternative woods for the ageing of Pedro Ximénez sweet wines. © 2020 Society of Chemical Industry.

Study of the Weathering Process of Gasoline by eNose.

In a fire investigation the rapid detection of the presence of ignitable liquids like gasoline is of great importance as it allows appropriate treatment of the remains, the identification of prevention methods and detects the possible presence of an arsonist. In some cases, analysts cannot access the fire scene in the first few hours due to the dangers involved in the situation and, as a consequence, phenomena such as weathering start. Ignitable liquid weathering is an evaporation process that results in an increase in the abundance of non-volatile compounds relative to volatile compounds, and this process changes the chemical composition. In the present work, the weathering of samples of gasoline at different times (from 0 h to a month) has been studied using an electronic nose (eNose). The influence of the volume used (40 µL and 80 µL) and the type of support (cork, wood, paper and cotton sheet) has been studied. Chemometric tools have been used with the aim of ascertaining the weathering time for which the developed method is capable of detecting the presence of gasoline. The eNose was able to discriminate samples of weathered gasoline. The support used for the samples did not seem to have an influence on the detection and the system.

An Electronic Nose Based Method for the Discrimination of Weathered Petroleum-Derived Products.

In recent years pollution due to hydrocarbon spills has increased markedly as a result of the numerous advances in technologies and industrial processes. Anthropogenic activities (accidental or illegal) are responsible for most of these incidents. In some cases, the spills are not detected at the moment they occur and the contaminants are subjected to different degradation phenomena that may change the chemical composition of the hydrocarbon over time. An incorrect or ineffective identification of the spill could lead to significant consequences, bearing in mind that most spills are hazardous to the environment. In the present work the capacity of the analytical technique based on the Electronic Nose (eNose) combined with chemometrics in the identification and discrimination of different weathered petroleum-derived products (PDPs) was studied. Different volumes (40 μL and 80 μL) of PDPs (gasoline, diesel, and paraffin) were poured onto different supports (wood, cork, paper, and cotton sheet) and subjected to a natural weathering process by evaporation for one month. The porosity of the support was also studied. The application of linear discriminant analysis allowed the full discrimination of the samples according to the presence/absence of PDP and a 97.7% of correct discrimination of the different PDPs regardless of the weathering time, support or volume used. The results show that the system is capable of detecting and discriminating the presence of petroleum-derived products in any of the situations studied.

Characterization and Differentiation of Petroleum-Derived Products by E-Nose Fingerprints.

Characterization of petroleum-derived products is an area of continuing importance in environmental science, mainly related to fuel spills. In this study, a non-separative analytical method based on E-Nose (Electronic Nose) is presented as a rapid alternative for the characterization of several different petroleum-derived products including gasoline, diesel, aromatic solvents, and ethanol samples, which were poured onto different surfaces (wood, cork, and cotton). The working conditions about the headspace generation were 145 °C and 10 min. Mass spectroscopic data (45-200 m/z) combined with chemometric tools such as hierarchical cluster analysis (HCA), later principal component analysis (PCA), and finally linear discriminant analysis (LDA) allowed for a full discrimination of the samples. A characteristic fingerprint for each product can be used for discrimination or identification. The E-Nose can be considered as a green technique, and it is rapid and easy to use in routine analysis, thus providing a good alternative to currently used methods.

Tryptophan Levels during Grape Ripening: Effects of Cultural Practices.

Some cultural practices that are carried out during the grape ripening period are associated with vine stress, including leaf removal, grape bunch removal, and vegetable cover crops. Additionally, several nitrogen and sulfur supplements have also been used directly on leaves during the last stage of the ripening period. In the work described here, five different cultural practices and the reference were applied in three replicates in the same vineyard. The evolution of tryptophan levels was evaluated from just after grape veraison until the harvest date. In some cases, certain specific treatments were also evaluated after the regular harvest date. The cultural techniques that involved the application of nitrogen led to higher levels of tryptophan at the harvest day when compared to other cultural techniques. It was also found that the application of nitrogen without sulfur had a faster effect on the level of tryptophan. It was established that a period of around 20 days is needed for the grapes to show clear differences in tryptophan levels after the application of nitrogen.

Ontogenetic Variation of Individual and Total Capsaicinoids in Malagueta Peppers (Capsicum frutescens) during Fruit Maturation.

The ontogenetic variation of total and individual capsaicinoids (nordihydrocapsaicin (n-DHC), capsaicin (C), dihydrocapsaicin (DHC), homocapsaicin (h-C) and homodihydrocapsaicin (h-DHC)) present in Malagueta pepper (Capsicum frutescens) during fruit ripening has been studied. Malagueta peppers were grown in a greenhouse under controlled temperature and humidity conditions. Capsaicinoids were extracted using ultrasound-assisted extraction (UAE) and the extracts were analyzed by ultra-performance liquid chromatography (UHPLC) with fluorescence detection. A significant increase in the total content of capsaicinoids was observed in the early days (between 12 and 33). Between day 33 and 40 there was a slight reduction in the total capsaicinoid content (3.3% decrease). C was the major capsaicinoid, followed by DHC, n-DHC, h-C and h-DHC. By considering the evolution of standardized values of the capsaicinoids it was verified that n-DHC, DHC and h-DHC (dihydrocapsaicin-like capsaicinoids) present a similar behavior pattern, while h-C and C (capsaicin-like capsaicinoids) show different evolution patterns.

Application of a stir bar sorptive extraction method for the determination of volatile compounds in different grape varieties.

BACKGROUND: Stir bar sorptive extraction (SBSE) has been employed for the analysis of aroma compounds directly from Spanish and Italian grape extracts. The extraction conditions have been optimized using a statistical approach, obtaining results that improve the current state of the art. RESULTS: The proposed analytical conditions were: sample volume 40 mL, extraction time 80 min, 25% (w/v) NaCl and stirring speed 750 rpm using 20 mm × 0.5 mm stir bars. Performance characteristics of the SBSE procedure were further studied and showed correlation coefficients, detection and quantification limits, linear ranges, recoveries and precision values adequate for analysing these compounds in grapes. Twenty-four grape varieties (aromatic and non-aromatic) were analysed. Statistically significant differences (P < 0.05) according to geographical origin were found, being derived mainly from the terpenoid content. By principal component analysis it was possible to note that the terpenoids were more effective in the separation of the non-aromatic samples, showing negative and positive scores for Italian and Spanish grapes, respectively. CONCLUSION: For non-aromatic grape varieties, the factor 'geographic location' was the most significant, thus corroborating the high influence of this parameter on the volatile composition of grapes and therefore on the genuineness of wines. © 2016 Society of Chemical Industry.

Evolution of Capsaicinoids in Peter Pepper (Capsicum annuum var. annuum) During Fruit Ripening.

The evolution of individual and total contents of capsaicinoids present in Peter peppers (Capsicum annuum var. annuum) at different ripening stages has been studied. Plants were grown in a glasshouse and the new peppers were marked in a temporal space of ten days. The extraction of capsaicinoids was performed by ultrasound-assisted extraction with MeOH. The capsaicinoids nordihydrocapsaicin (n-DHC), capsaicin, dihydrocapsaicin, homocapsaicin, and homodihydrocapsaicin were analyzed by ultraperformance liquid chromatography (UHPLC)-fluorescence and identified by UHPLC-Q-ToF-MS. The results indicate that the total capsaicinoids increase in a linear manner from the first point of harvest at ten days (0.283 mg/g FW) up to 90 days, at which point they reach a concentration of 1.301 mg/g FW. The evolution as a percentage of the individual capsaicinoids showed the initial predominance of capsaicin, dihydrocapsaicin, and n-DHC. Dihydrocapsaicin was the major capsaicinoid up to day 50 of maturation. After 50 days, capsaicin became the major capsaicinoid as the concentration of dihydrocapsaicin fell slightly. The time of harvest of Peter pepper based on the total capsaicinoids content should be performed as late as possible. In any case, harvesting should be performed before overripening of the fruit is observed.

Determination of Ignitable Liquids in Fire Debris: Direct Analysis by Electronic Nose.

Arsonists usually use an accelerant in order to start or accelerate a fire. The most widely used analytical method to determine the presence of such accelerants consists of a pre-concentration step of the ignitable liquid residues followed by chromatographic analysis. A rapid analytical method based on headspace-mass spectrometry electronic nose (E-Nose) has been developed for the analysis of Ignitable Liquid Residues (ILRs). The working conditions for the E-Nose analytical procedure were optimized by studying different fire debris samples. The optimized experimental variables were related to headspace generation, specifically, incubation temperature and incubation time. The optimal conditions were 115 °C and 10 min for these two parameters. Chemometric tools such as hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA) were applied to the MS data (45-200 m/z) to establish the most suitable spectroscopic signals for the discrimination of several ignitable liquids. The optimized method was applied to a set of fire debris samples. In order to simulate post-burn samples several ignitable liquids (gasoline, diesel, citronella, kerosene, paraffin) were used to ignite different substrates (wood, cotton, cork, paper and paperboard). A full discrimination was obtained on using discriminant analysis. This method reported here can be considered as a green technique for fire debris analyses.

Development of a new stir bar sorptive extraction method for the determination of medium-level volatile thiols in wine.

A fast, simple, and reliable analytical method for the determination of medium-level volatile thiols in wines is presented. Stir bar sorptive extraction using ethylene glycol-silicone coated stir bars has been used in combination with thermal desorption gas chromatography with mass spectrometry for the analysis of 4-mercapto-4-methylpentan-2-one, 2-furanmethanethiol, 3-mercaptohexyl acetate, and 3-mercaptohexanol in wine. Optimization of the extraction technique was performed using a two-level fractional factorial design. For the extraction step, the optimum conditions were: Ethylene glycol and silicone coated stir bars, pH at 3.5, sample volume of 25 mL, extraction time of 90 min, NaCl content 4.0 g, and stirring speed at 500 rpm. The optimized method achieved good linearity for all studied compounds (r(2) > 0.995) and it provided detection limits of 21.52, 0.36, 0.73, and 2.55 µg/L for 4-mercapto-4-methylpentan-2-one, 2-furanmethanethiol, 3-mercaptohexyl acetate, and 3-mercaptohexanol, respectively. It was repeatable, with precisions lower than 18% relative standard deviation for both intraday and interday repeatability. The developed procedure is suitable for the determination of these kinds of compounds when they are present at medium concentration levels. It was finally applied to real wine samples with negative aroma derived from the high concentration levels of these compounds.

Stability of anthocyanins from red grape skins under pressurized liquid extraction and ultrasound-assisted extraction conditions.

The stability of anthocyanins from grape skins after applying different extraction techniques has been determined. The following compounds, previously extracted from real samples, were assessed: delphinidin 3-glucoside, cyanidin 3-glucoside, petunidin 3-glucoside, peonidin 3-glucoside, malvidin 3-glucoside, peonidin 3-acetylglucoside, malvidin 3-acetylglucoside, malvidin 3-caffeoylglucoside, petunidin 3-p-coumaroylglucoside and malvidin 3-p-coumaroylglucoside (trans). The techniques used were ultrasound-assisted extraction and pressurized liquid extraction. In ultrasound-assisted extraction, temperatures up to 75 °C can be applied without degradation of the aforementioned compounds. In pressurized liquid extraction the anthocyanins were found to be stable up to 100 °C. The relative stabilities of both the glycosidic and acylated forms were evaluated. Acylated derivatives were more stable than non-acylated forms. The differences between the two groups of compounds became more marked on working at higher temperatures and on using extraction techniques with higher levels of oxygen in the extraction media.

A new solid phase extraction for the determination of anthocyanins in grapes.

A method for the concentration and cleaning of red grape extracts prior to the determination of anthocyanins by UPLC-DAD has been developed. This method is of special interest in the determination of phenolic maturity as it allows the analysis of the anthocyanins present in grapes. Several different SPE cartridges were assessed, including both C-18- and vinylbenzene-based cartridges. C-18-based cartridges presented a very low retention for the glucosylated anthocyanidins while vinylbenzene-based cartridges showed excellent retention for these compounds. The optimized method involves the initial conditioning of the cartridge using 10 mL of methanol and 10 mL of water, followed by loading of up to 100 mL of red grape extract. Ten mL of water was used in the washing step and anthocyanins were subsequently eluted using 1.5 mL of acidified methanol at pH 2. This method simplifies the determination of individual anthocyanins as, on the one hand, it cleans the sample of interference and, on the other hand, it increases the concentration to up to 25:1.5. The developed method has been validated with a range of different grapes and it has also been tested as a means of determining the different anthocyanins in grapes with different levels of maturity.

Influence of Temperature during Pre-Fermentative Maceration and Alcoholic Fermentation on the Phenolic Composition of 'Cabernet Sauvignon' Wines.

This study presents the effects of different working temperatures on the transfer of compounds during the pre-fermentative and fermentative stages of the wine making process with 'Cabernet Sauvignon' grapes. Two different procedures have been evaluated. Firstly, the pre-fermentative maceration of the crushed grapes at two different temperatures (20 °C and 10 °C). Then, the alcoholic fermentation under two different sets of conditions, the fermentation at a constant temperature of 20 °C and the fermentation under a positive temperature gradient from 10 to 20 °C. According to the experimental results, the phenolic contents (total phenolics, total anthocyanins, and total tannins) were mainly conditioned by the fermentation temperature, however the pre-fermentative conditions also affected the content levels of these compounds. Furthermore, the use of a fermentation temperature gradient improved the organoleptic characteristics of the wines. However, the color was not as stable as that of wines produced through fermentation at a higher constant temperature. Consequently, the implementation of a temperature gradient during the alcoholic fermentation process is recommended and a longer period at high temperature over the last phase of the process would be desirable to obtain aromatic wines with the desirable color stability.

Suitability of alternative wood types other than American oak wood for the ageing of Sherry vinegar.

The present study has consisted on the monitoring of Sherry vinegar during a whole year ageing in American oak, French oak, Spanish oak and chestnut barrels in order to determine the suitability of alternative wood types other than American oak for the ageing of this type of vinegar. Thirty-two volatile compounds were quantified, CIELab parameters were determined and sensory analyses were carried out during the whole process. The multivariate analysis of the data revealed that the samples that had been aged in Spanish oak barrels were getting more similar to those aged in French oak as the ageing process was progressing. Furthermore, the samples that had been aged in chestnut presented some volatile compounds significantly different from American oak. Finally, although French oak wood transferred the best organoleptic characteristics to Sherry vinegar, Spanish oak and chestnut seemed to be satisfactory alternatives for the ageing process.

Influence of Two Different Cryoextraction Procedures on the Quality of Wine Produced from Muscat Grapes.

Freezing grapes is a winemaking technique known as cryoextraction that intends to modify the composition of the final wines. The changes that take place in the frozen grapes facilitate the transfer of certain compounds from the grape skins into the musts because of the grape's unstructured tissues. For this study, the white grape variety Muscat of Alexandria was selected. Two different cryoextraction procedures have been analyzed as follows: (i) Ultrafast freezing, and (ii) liquid nitrogen freezing. The wines obtained using liquid nitrogen freezing exhibited higher levels of terpenoids, as well as higher levels of hydroxylic compounds and fatty acids than both the wines obtained through traditional methods and ultrafast freezing wines. In any case, both freezing techniques produced wines of a more intense aroma compared with those wines obtained by traditional methods. In fact, liquid nitrogen freezing produced the wines with the most intense aroma and were the best valued by the tasting panel.

Development of Head Space Sorptive Extraction Method for the Determination of Volatile Compounds in Beer and Comparison with Stir Bar Sorptive Extraction.

A headspace sorptive extraction method coupled with gas chromatography-mass spectrometry (HSSE-GC-MS) was developed for the determination of 37 volatile compounds in beer. After optimization of the extraction conditions, the best conditions for the analysis were stirring at 1000 rpm for 180 min, using an 8-mL sample with 25% NaCl. The analytical method provided excellent linearity values (R2 > 0.99) for the calibration of all the compounds studied, with the detection and quantification limits obtained being low enough for the determination of the compounds in the beers studied. When studying the repeatability of the method, it proved to be quite accurate, since RSD% values lower than 20% were obtained for all the compounds. On the other hand, the recovery study was successfully concluded, resulting in acceptable values for most of the compounds (80%-120%). The optimised method was successfully applied to real beer samples of different types (ale, lager, stout and wheat). Finally, an analytical comparison of the optimised HSSE method, with a previously developed and validated stir bar sorptive extraction (SBSE) method was performed, obtaining similar concentration values by both methods for most compounds.

Use of Sensory Analysis to Investigate the Influence of Climate Chambers and Other Process Variables in the Production of Sweet Wines.

In this study, a climate chamber, as an alternative method, has been used to dry raisins and the sensory profiles of the sweet sherry wines obtained have been evaluated. Other important factors, namely grape variety, vintage, vinification conditions, as well as the ageing method and its length of time, have also been considered. When heavy rainfall had been registered, the musts extracted from grapes dried under controlled conditions in a climate chamber showed a lower intensity of the musty off-odor compared to those elaborated with sun-dried grapes. The wine fermented at low temperature with Saccharomyces bayanus scored the highest in citric and floral notes, and this was preferred over all the other wines that were evaluated. The wines aged in oak barrels were preferred to both, wines aged in the presence of oak chips as well as those aged without any wood contact. The use of climate chambers to dry the grapes that are going to be used for the elaboration of sweet wines appears to be an advantageous alternative to the traditional method, since it allows a more precise control of the process and highly valued sweet wines from a sensory point of view are obtained thereby.

Use of ultrasound at a pilot scale to accelerate the ageing of sherry vinegar.

In the present work, the accelerated ageing process of sherry vinegar has been studied at pilot scale by means of the joint application of ultrasound, micro-oxygenation and wood chips (American oak, French oak and Spanish oak). The CIELab parameters have been studied as well as the polyphenolic and volatile content of the aged vinegar samples. Vinegars aged with American oak presented different chromatic characteristics to those aged with French and Spanish oak and a lower polyphenolic and volatile content than the latter ones. On the other hand, Spanish oak generated vinegars with a higher content of volatile compounds and an intermediate polyphenolic profile between those obtained using French and American oak. In addition, the use of ultrasound for a period between 4 and 21 days, generated vinegars with similar characteristics to others that were aged in the traditional way for between 2 and 6 months. It has been demonstrated that the use of ultrasound, combined with micro-oxygenation and chip addition, is a technique which can accelerate the ageing process of vinegars at a pilot scale, so it could be a viable alternative to obtain sherry vinegars aged in a shorter time.

Development and validation of UPLC for the determination of phenolic compounds and furanic derivatives in Brandy de Jerez.

Brandy and other aged distillates are a rich source of polyphenols. For brandies, contact with wood during ageing makes an important contribution to their polyphenols content. This paper describes the use of a previously devised ultra performance LC (UPLC) method to study the polyphenols content of Brandy de Jerez. UPLC is a new technique in LC offering several potential advantages, especially the reduction of time. Analyses of brandy performed by HPLC were repeated by UPLC. A special UPLC analytical column (Acquity UPLC BEH C18 column, 100 x 2.1 mm), with a particle size of 1.7 microm, forms part of this system. Using the UPLC system enabled the time needed for analysis to be reduced to one tenth of the time needed in the conventional HPLC system. In conclusion, the separation factor results of the UPLC were compared to those obtained using HPLC methods; this demonstrated that simple, high efficiency UPLC gradients are viable and advantageous substitutes for traditional analysis of polyphenols in brandy by HPLC. The method enabled 14 phenolic compounds to be identified and determined in 33 different commercial brandies, and this allowed them to be differentiated in function of quality.