Aging marker profile in cachaça is influenced by toasted oak chips

Cachaça is the most important distilled spirit in Brazil and the fourth most consumed in the world. Aging is not mandatory for cachaça. When aging is carried out, casks generally do not undergo the final wood toasting. However the level of thermal degradation of wood influences the formation of new chemical compounds, which are released during the aging process and improve the quality of the spirit. The objective of this study was to verify the influence of origin of wood and toasting intensity of oak chips on the profile of aging markers in cachaça. Staves of oak wood from the forests of Allier, Vosges and Nièvre (France) were milled and screened at 9 mesh. The chips underwent light, medium and heavy toasting. The toasted chips were added to cachaça (1 g/L) and kept in a closed system at room temperature, without agitation, for 15 days. The aging congeners (gallic acid, 5‐hydroxymethylfurfural, furfural, vanillin, vanillic acid, syringaldehyde, sinapaldehyde, syringic acid and coniferaldehyde) were analysed using HPLC. The increase in toasting intensity enhanced the content of the aging markers in cachaça, especially syringic acid, vanillin, syringaldehyde, coniferaldehyde and sinapaldehyde. The generation of aging marker compounds was influenced only by the toasting intensity and not by the origin of the oak wood. Copyright © 2015 The Institute of Brewing & Distilling     

Fatty acid profile and glycerol concentration in cachaças aged in different wood barrels

The objective of this study was to evaluate the fatty acid profile and glycerol concentration in cachaças aged for 3 years in barrels made from different types of tropical woods and European oak. Glycerol gives body to spirits, whereas the fatty acid profile influences the spirit sensory characteristics. The concentration of these compounds in aged spirits depends on the wood composition. Tropical wood barrels made from amendoim (Pterogyne nitens Tul), araruva (Centrolobium tomentosum), cabreúva (Myrocarpus frondosus), cerejeira (Amburana cearensis), grápia (Apuleia leiocarpa), ipê roxo (Tabebuia heptaphylla), jequitibá (Cariniana estrellensis), jequitibá rosa (Cariniana legalis) and pereira (Platycyamus regnellii), as well as European oak (Quercus petraea), were used in this study. Glycerol concentrations in aged cachaças were measured using colorimetric methods, and fatty acid profiles were determined by GC‐MS analysis. The main fatty acids found were propanoic (C3:0), butanoic (C4:0), pentanoic (C5:0), octanoic (C8:0), decanoic (C10:0), dodecanoic (C12:0), hexadecanoic (C16:0), octadecanoic (C18:0) and octadecenoic (C18:1⁹) acids. Araruva barrels stood out as the major supplier of C4:0 and cabreúva barrels provided greater amounts of C18:0 to cachaça. Carvalho and araruva barrels conferred more complete fatty acid profiles and higher concentrations of glycerol. Copyright © 2016 The Institute of Brewing & Distilling     

Phenolic extracts of cachaça aged in different woods and quantifying antioxidant activity and antifungal properties

The antioxidant and antifungal activities of the phenolic compounds in different alcoholic extracts of aged cachaça were evaluated. The physico‐chemical analyses were performed in the Laboratório de Qualidade de Aguardente of the Universidade Federal de Lavras according to the methods of the Ministério Agricultura Pecuária e abastecimento. Total phenol content was determined by the Folin–Ciocalteu method, quantification of these compounds was performed by HPLC and antioxidant activities were determined by methods involving inhibition of the DPPH (1,1‐diphenyl‐2 picrylhydrazyl) radical, the β‐carotene/linoleic acid system, ABTS (2,2 azinobis‐[3‐ethyl‐6‐benzothiazolinesulfonic acid]) radical, reducing power and thiobarbituric acid. Determination of antifungal activity was accomplished through the technique of dissemination in discs using Aspergillus carbonarius, Aspergillus niger, Aspergillus flavus, Penicillium commune and Penicillium cladosporoides fungi at the Laboratório de Micologia de Alimentos. The values obtained for the phenolic compounds ranged from 0.41 to 9.69 mg L^?1; syringaldehyde, vanillic acid and gallic acid were predominant. A satisfactory antioxidant activity was observed in all of the tests with the alcoholic extracts. A moderate activity against P. commune and P. cladosporoides, but no inhibition of the growth of A. carbonarius, A. niger or A. flavus was observed. Copyright © 2016 The Institute of Brewing & Distilling     

Maturation related phenolic compounds in cachaça aged in new oak barrels

Aging cachaça in wooden barrels improves its chemical and sensory profile and adds quality. Maturation of distilled spirits is influenced by factors such as the species of wood to make the barrels, degree of internal toasting, number of uses of the barrel and aging time. The level of maturation of distillates can be determined based on the concentration of age marker phenolic compounds extracted from the lignin of the wooden barrel, as well as their relationships with each other. This study characterises the aging process of cachaça by analysing the mechanism of lignin degradation during maturation in new oak barrels for up to 60 months in order to establish the relationship between the age of the distillate and the content of phenolic compounds extracted from the wood. The evaluation was based on the analyses of liginin derived compounds using high‐performance liquid chromatography. The level of maturation of aged cachaça can be characterised by evaluating the low molecular weight lignin‐derived phenolic substances. The total amount of benzoic acids (vanillic and syringic acids) can be taken into consideration for predicting the level of maturation of distillates. Based on the composition of maturation related congeners, it is likely that for cachaça, each year of aging in new oak barrels corresponds to approximately five years of aging for spirits in general. © 2020 The Institute of Brewing & Distilling     

Chemical and microbiological quality of sugar cane juice influences the concentration of ethyl carbamate and volatile congeners in cachaça

The aim of this study was to assess the influence of heat treatment of sugar cane juice, supplementation with urea and double distillation on the concentration of volatile congeners (acetic aldehyde, ethyl acetate, n‐propyl, isobutyl and isoamyl alcohols and acetic acid) and contaminants (methanol, 1‐propyl and 2‐butyl alcohols, copper, and ethyl carbamate) in cachaça. Samples of fresh sugar cane juice, sugar cane juice submitted to heat treatment and contaminated sugar cane juice were supplemented (or not) with urea and fermented. The washes so obtained underwent single and double distillation. Supplementation with urea stimulated ethyl carbamate formation. The distilled products that originated from contaminated worts presented higher concentration of acetic acid and ethyl carbamate. Double distillation reduced the concentration of contaminants. The best quality pot still cachaça was obtained employing heat treatment of sugar cane juice, nonsupplementation with urea and double distillation. Copyright © 2015 The Institute of Brewing & Distilling     

GC‐MS analysis of ethyl carbamate in distilled sugar cane spirits from the northern and southern regions of Minas Gerais

Ethyl carbamate, also known as urethane, is the ethyl ester of carbamic acid. Animal studies with this compound have demonstrated its carcinogenic potential. In this study, gas chromatography coupled to mass spectrometry (GC‐MS) was applied for the determination of ethyl carbamate in sugar cane spirits in the northern and southern regions of the state of Minas Gerais in Brazil. The samples were collected from distillates from small‐ and medium‐scale stills. The concentrations determined for ethyl carbamate in the samples ranged from 23 to 980 µg L^?1. All of the samples analysed from the southern region of Minas Gerais had an ethyl carbamate content below the limit set by the Brazilian legislation for ethyl carbamate of 150 µg L^?1, while a number of samples from northern Minas Gerais exceeded this limit. No correlations were observed between the levels of ethyl carbamate and the alcohol content, acidity or copper concentrations in the samples. Copyright © 2014 The Institute of Brewing & Distilling     

Ethyl carbamate kinetics in double distillation of sugar cane spirit. Part 2: influence of type of pot still

This study aimed to assess the influence of the pot still configuration on the reduction of ethyl carbamate content in double‐distilled sugar cane spirit, as well as to describe the effects of double distillation on this reduction. Ethyl carbamate is a potentially carcinogenic compound that may be present in high concentrations in sugar cane spirit, and therefore could become a public health problem, as well as a factor hindering Brazilian exports of this beverage. In sugar cane spirit production in Brazil, neither pot still configuration nor distillate reflux and cooling/condensation systems are standardized. In this study, ethanol, copper and ethyl carbamate contents were assessed (GC‐MS) in sugar cane spirits that were double‐distilled in pot stills with different reflux and cooling systems. Double distillation removed 94–98.5% of ethyl carbamate from sugar cane spirit. Pot stills with high reflux rates (equipped with dephlegmator or rectifying system) were more effective in reducing the ethyl carbamate content in double‐distilled sugar cane spirit. Copyright © 2013 The Institute of Brewing & Distilling     

Ethyl carbamate kinetics in double distillation of sugar cane spirit

The aim of this study was to verify the effect of a double distillation on the reduction of the ethyl carbamate content in sugar cane spirit. Ethyl carbamate is a potentially carcinogenic compound normally present at critical levels in sugar cane spirit, constituting a public health problem and therefore hindering the export of this beverage. The ethanol, copper and ethyl carbamate contents were evaluated, using gas chromatography/mass spectroscopy, during a double distillation of the fermented sugar cane juice. The distillate fraction from the first distillation accumulated 30% of the ethyl carbamate formed. In the second distillation, the ethyl carbamate and the copper content increased during the process as the alcohol content decreased, and only 3% of the ethyl carbamate formed was collected in the spirit. Double distillation decreased the ethyl carbamate content in the sugar cane spirit by 97%. Copyright © 2012 The Institute of Brewing & Distilling     

A Fluorescence‐Based Method for Cyanate Analysis in Ethanol/Water Media: Correlation between Cyanate Presence and Ethyl Carbamate Formation in Sugar Cane Spirit

Based on the fluorescence properties of 2,4‐(1H,3H)‐quinazolinedione, a product of the reaction between cyanate and 2‐aminobenzoic acid, a simple, sensitive, selective, and reproducible method for the cyanate analysis in aqueous ethanolic media is proposed. In this method, λ_exc and λ_em are 310 and 410 nm, respectively, and the limits of detection and quantification are 2.2 × 10^?7 and 6.7 × 10^?7 mol/L, respectively. Under optimal conditions (pH = 4.5, 40% ethanol), a concentration of 5.0 × 10^?6 mol/L cyanate can be determined in a single measurement, at a 95% level of confidence, with an uncertainty of ± 0.13 × 10^?6 mol/L. Cyanide, thiocyanate, chloride, nitrate, and sulfate ions, as well as urea and urethane in concentrations 1 × 10³ higher than that of cyanate do not interfere with the measurement. The methodology was applied to cyanate analyses in the different fractions of the sugarcane distillate and the data strongly suggest a correlation between the presence of urea in wine, and the cyanate and ethyl carbamate concentrations in the spirit.     

Formation of volatile and maturation‐related congeners during the aging of sugarcane spirit in oak barrels

The aging process of distilled spirits is a complex system based on the extraction of molecules from the wood and interactions with the liquid, the phenomenon of migration of wood constituents, as well as the formation and degradation of several compounds. Volatile and maturation‐related congeners were evaluated during the aging process of cachaça, a Brazilian sugarcane spirit aged in oak barrels. Aged cachaça presented alterations in the levels of ethanol, higher alcohols, acetaldehyde, volatile acidity, ethyl acetate, total volatile congeners, isoamyl alcohol, ethyl carbamate and copper. The aging markers (gallic acid, furfural, 5‐hydroxymethylfurfural, vanillic acid, syringic acid, vanillin, syringaldehyde, sinapaldehyde and coniferaldehyde) were compared with the compounds found in whisky, cognac, armagnac, bourbon and brandy. Monitoring the generation and evolution of congeners during the aging process allowed the characterization of cachaça and the identification of product maturity. Copyright © 2014 The Institute of Brewing & Distilling     

Determination of ethyl carbamate in cachaças produced by selected yeast and spontaneous fermentation

Cachaça is a beverage produced by the distillation of fermented must from sugarcane. During the manufacturing steps, producers commonly use naturally occurring yeasts in the preparation of the fermentation broth, resulting in spontaneous fermentation. The composition of the resulting beverages can vary greatly, especially if various species and strains of yeast are present. The beverages produced with selected yeast strains are an alternative, leading to the production of more standardized beverages. Ethyl carbamate, which is highly toxic and has carcinogenic potential, is among the possible contaminants. The objectives of this study were to determine the levels of ethyl carbamate in cachaça produced by different types of fermentation and follow its formation during the production stages. The cachaças that contained rice bran as a nutrient during the fermentation stage contained the highest levels of ethyl carbamate throughout the production process and storage. Copyright © 2016 The Institute of Brewing & Distilling     

Physicochemical profile and determination of volatile compounds in cachaça stored in new oak (Quercus sp.), amburana (Amburana cearensis), jatoba (Hymenaeae carbouril), balsam (Myroxylon peruiferum) and peroba (Paratecoma peroba) casks by SPME‐GC–MS

Aging has become common practice among producers seeking to increase the value of their products. The objective of this work was to conduct periodic monitoring by solid‐phase microextraction–gas chromatography–mass spectrometry of the physical and chemical quality of aging cachaça in terms of the alcohol content, volatile acidity, esters, aldehydes, higher alcohols, furfural, methanol, dry extract, copper and volatile compounds in the production process (distilled fractions) and during storage in casks newly made from oak (Quercus sp.), amburana (Amburana cearensis), jatoba (Hymenaeae carbouril), balsam (Myroxylon peruiferum) and peroba (Paratecoma peroba). The barrels were made in a specialized cooperage, and cachaça was obtained from a production unit in the southern region of Minas Gerais. Distinct physicochemical values were obtained for the distilled fractions; head and tail fractions had inappropriate concentrations of alcohol, aldehydes and butan‐1‐ol. Values within the limits established by law were obtained for the heart fraction, both in the distillation process and during aging, and it is, therefore, suitable for consumption. Several important compounds responsible for the aroma and flavour of the cachaças were observed, and alcohols, acids, esters and sesquiterpenes were found to compose the main groups. Through variance and main component analysis, important chemical changes were observed in the beverages. Copyright © 2016 The Institute of Brewing & Distilling     

Multivariate analysis for the characterization of physico‐chemical profiles of cachaça produced in copper stills over a period of six years in Minas Gerais state

Cachaça, a traditional, popular Brazilian alcoholic drink, is increasingly appreciated in many countries. In Brazil, it is the most extensively consumed alcoholic beverage and it has great relevance for agribusiness in the country, especially for the state of Minas Gerais, which is the main centre for the production of alambic cachaça. Thus, attempts to standardize techniques in the production chain of the beverage have been made to maintain the quality required by law. The physico‐chemical profile of cachaça produced in copper stills in different cities of Minas Gerais, Brazil over the years 2006–2011 was determined by applying principal component analysis (PCA). According to the physico‐chemical data, 61.5–77.9% of the samples were within the boundaries of standards identity and quality established by Brazilian legislation. According to the PCA, the composition of the cachaça produced in Minas Gerais between the years 2006 and 2011 was homogeneous. Copyright © 2015 The Institute of Brewing & Distilling     

Comprehensive two-dimensional gas chromatography–mass spectrometry analysis and comparison of volatile organic compounds in Brazilian cachaça and selected spirits

This paper presents the application of comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry (GC×GC/TOFMS) using the longitudinal modulated cryogenic system (LMCS) device, to the aroma analysis of spirit samples. The volatile organic compounds present in samples of a Brazilian cane sugar spirit were collected by using a solid-phase microextraction (SPME) method. Other samples studied included gin, vodka, whiskey, tequila and flavoured liqueurs. In this study GC×GC/TOFMS with a bi-dimensional non-polar – polar phase column set comprising of a first dimension BPX5 primary column and a second dimension BP20 second column enabled the tentative identification of 95 compounds in cachaça. In excess of 200 compounds were found amongst group of samples that were analysed. The results, presented as peak apex plots, showed that groups of compounds were present in well-defined regions of the 2D separation space in each beverage, making it possible to recognise the differences and similarities among the spirit samples.     

Sensory properties of some synthetic high‐intensity sweeteners in water solutions

BACKGROUND: When sucrose is eliminated from products to meet consumers' demand for calorie‐free products and substitutes are used, sweetness becomes an important characteristic. The objective of this study was to compare sensory properties of four sucrose substitutes: aspartame, acesulfame K, sodium saccharin and sodium cyclamate in water solutions. RESULTS: The lowest concentrations of sweeteners such as 0.35 g kg^?1 for aspartame and acesulfame K showed an equi‐sweet level relative to approx. 55 g kg^?1 aqueous sucrose solution, whereas 2.3 g kg^?1 sodium cyclamate and 0.4 g kg^?1 sodium saccharin relative to approx. 65 g kg^?1. Aspartame had almost the same sweetness potency as acesulfame K, whereas the remaining sweeteners differed completely. The four sweeteners showed their specific sensory profiles. Besides the characteristics of sweetness and bitterness, metallic and astringent attributes plus warming and cooling effects were found. CONCLUSIONS: Of the four sweeteners, aspartame and sodium cyclamate can be considered as the best sucrose substitutes due to their similar sensory profiles to the sucrose. The data showing the interdependence between sweetness intensity of the sweeteners and sucrose are useful as a quick and easy indicator of the sweetener amount having equi‐sweet levels relative to sucrose. Copyright © 2009 Society of Chemical Industry