Effect of light on the concentration of ethyl carbamate in cachaça stored in glass bottles

This study sought to evaluate the influence of natural light on the concentration of ethyl carbamate (EC) in cachaças aged in wooden barrels and stored in glass bottles for a period of 6 months. The quantification of EC was achieved by HPLC using a fluorescence detector after previous derivation of the samples and standards with 9‐xanthydrol. All of the samples presented an EC concentration below the limit established by Brazilian legislation. The highest concentration found was 79.70 µg L^?1. As for the influence of light and storage period, 70% of the samples exhibited an influence of these parameters. Copyright © 2015 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     

Cachaça stored in casks newly constructed of oak (Quercus sp.), amburana (Amburana cearensis), jatoba (Hymenaeae carbouril), balsam (Myroxylon peruiferum) and peroba (Paratecoma peroba): alcohol content,phenol composition,colour intensity and dry extract

Aging is the last stage of the cachaça production process. The containers used for aging are wooden barrels and casks, which act as a semi‐permeable membrane, allowing the passage of alcohol and water vapours. This passage is a function of the relative humidity and the temperature of the storage location. The wood traditionally used in Brazil is oak. However, various native woods of Brazilian origin have been used in the manufacture of barrels. The principal compounds extracted from wood by the distillates are volatile compounds, phenolic compounds, tannic substances, sugars, glycerol and non‐volatile organic acids. The objectives of this study were to evaluate and compare the phenolic substances found in cachaça stored in recently constructed oak, amburana, Jatoba, balsam and peroba casks. We evaluated some physicochemical parameters that changed during the storage process. After 12 months of storage, we observed a decrease in alcohol content and an increase in dry extract. An increase in total phenolic compounds and colour intensity was observed, and there was a strong linear correlation between total phenolic compounds, solids and colour intensity. According to the results for the phenols analysed by HPLC, a progressive increase in all the compounds and a heterogeneity in all woods used for the storage of beverages were observed. Copyright © 2017 The Institute of Brewing & Distilling     

Ethyl carbamate in the production and aging of cachaça in oak (Quercus sp.) and amburana (Amburana cearensis) barrels

There are residual organic and inorganic contaminants in the cachaça production chain. Among the organic contaminants, ethyl carbamate has been widely studied. It is formed naturally during the fermentation processes and can be found in many foods and beverages such as bread, yoghurt, wine, beer and especially in fermented–distilled beverages such as whiskey, rum, vodka, grappa, cachaça and tiquira. The objective of this study was to identify and quantify ethyl carbamate during the steps of the production process and aging of cachaça in oak (Quercus sp) and amburana (Amburana cearensis) barrels. The cane used for cachaça production, as well as the process for obtaining the fermentation broth, did not affect the formation of ethyl carbamate, as it was not detected. Carbamate was detected in low concentrations, but was not quantified, in the fermentation, distillation and aging steps. Copyright © 2014 The Institute of Brewing & Distilling     

Quantification of ethyl carbamate in cachaça produced in different agro‐industrial production systems

Popularly known by various names such as caninha, dangerous, drips, damned and many other denominations, cachaça is the genuine Brazilian drink, produced by the fermentation of sugarcane juice by yeast, followed by distillation in alambics. Considering that cachaça is the most widely consumed distilled beverage from Brazil, the knowledge of the chemical composition and the presence of potentially toxic compounds such as ethyl carbamate, considered a human carcinogen, is important. The aim of this study was to evaluate the influence of different conditions of the agro‐industrial cachaça production systems, including the variety of sugarcane, on the quantification of ethyl carbamate through the chromatographic. Thirteen unaged beverage samples, produced from different varieties of sugarcane, were analysed. Using analysis of variance and comparison of average concentrations of ethyl carbamate (Scott–Knott, α = 5%), all of the samples were found to contain contaminant levels below the ceiling established by the legislation, which is 210 µg L^?1. Copyright © 2016 The Institute of Brewing & Distilling     

Influence of fast and slow distillation on ethyl carbamate content and on coefficient of non‐alcohol components in Brazilian sugarcane spirits

Ethyl carbamate is an impurity present in distilled beverages. Given the risk of it being a carcinogenic substance, Brazilian legislation has determined that its presence in distilled beverages, such as ‘aguardente’ and ‘cachaça’ (two types of sugarcane spirits), should be limited to a maximum of 150 µg/L. Ordinary spirits usually contain variable amounts of ethyl carbamate, although in lower concentrations than the maximum determined by law. The finding that commercial spirits had a much lower concentration of this impurity (around 50 µg/L) led the authors to research the reasons for the differences, and these are explored in this paper, with a focus on the speed of the distillation process and its influence on the spirit's composition. The team conducted research in a sugarcane distillery producing ‘aguardente’ using a simple pot still and measured the influence of fast and slow distillation on the presence of ethyl carbamate and non‐alcohol components in the process. The results demonstrated that the speed of distillation was proportionally related to the concentration of ethyl carbamate and secondary components in the beverage's composition. Copyright © 2012 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     

ETHYL CARBAMATE FORMATION IN GRAIN BASED SPIRITS: PART I: POST-DISTILLATION ETHYL CARBAMATE FORMATION IN MATURING GRAIN WHISKY

Distilled spirits are subject to post-distillation ethyl carbamate formation in the presence of appropriate precursors. Freshly distilled grain whisky, produced by the continuous distillation Coffey still process, normally contains ethyl carbamate concentrations not exceeding 20 ppb (normalized to 43% v/v alcoholic strength). Further ethyl carbamate formation, dependent upon the presence of trace anionic precursors such as cyanate, cyanide, and copper cyanide complexes, may take place during normal maturation in oak casks. Related but different mechanisms may induce ethyl carbamate formation under normal daylight and artificial light in the laboratory. Ethyl carbamate precursors convert into ethyl carbamate during the initial three months of maturation and are not detectable in the final bottled product. Thus the final ethyl carbamate concentration in spirit is dependent upon the initial ethyl carbamate level measured after distillation plus ethyl carbamate formed from precursors. It is important during process control to monitor not only the ethyl carbamate level in freshly distilled spirit but also the spirit's potential to form ethyl carbamate from precursors with the objective of minimizing these components in the freshly distilled and maturing spirit. A scheme for predicting final ethyl carbamate concentrations from precursor concentrations in freshly distilled spirit is presented.     

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     

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     

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     

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     

Effect of co-inoculation of Saccharomyces cerevisiae and Lactobacillus fermentum on the quality of the distilled sugar cane beverage cachaça

Abstract: The effect of Lactobacillus fermentum in co‐inoculation with Saccharomyces cerevisiae UFLA CA11 on the quality of cachaça (sugar cane spirit) was evaluated. The co‐inoculation was first evaluated in flask fermentation, and subsequently, yeast and bacteria were co‐cultured at approximately 10⁵ CFU/mL and 10⁸ CFU/mL, respectively, in 4 consecutive batches. L. fermentum did not affect the growth or activity (sugar consumption and fermentation rate) of S. cerevisiae UFLA CA11 during fermentation. The physicochemical analysis revealed a higher concentration (Tukey test) of aldehydes (22.07 mg/100 mL anhydrous alcohol) in cachaça produced by co‐inoculation. Analysis of volatile compounds using GC‐FID demonstrated that cachaça produced by co‐inoculation had higher concentrations of acetaldehyde (25.15 mg/L), ethyl acetate (30.17 mg/L), and 2,3‐butanedione (170.39 μ/L), while cachaça produced by UFLA CA11 contained higher concentrations of ethyl lactate (1205.98 μ/L), propionic acid (127.97 μ/L), butyric acid (2335.57 μ/L), and 1‐pentanol (469.23 μ/L). The lowest concentration of acetic acid measured by HPLC was found in cachaça obtained with UFLA CA11. The sensory analysis, performed using the Mann–Whitney test, revealed that cachaça produced by co‐inoculation differed from that produced by UFLA CA11 in taste and aroma. Practical Application: This study reports on the use of a mixed culture of Saccharomyces cerevisae and Lactobacillus fermentum to produce cachaça and shows the influence of co‐inoculation of yeast and bacteria on the quality of this beverage.     

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     

Temperature and Light Effects on Ethyl Carbamate Formation in Wine During Storage

The formation and/or increase of ethyl carbamate during storage of wine was monitored at 43°C, 32°C and 22°C in the dark, at 22°C under fluorescent light and in a greenhouse with naturally fluctuating temperature and light conditions simulating commercial display of wines. The ethyl carbamate concentration of fifteen selected red and white table and dessert wines was determined initially, and after 3, 6, and 12 months storage. In most wines ethyl carbamate increased as a function of time and temperature. After 12 months in the dark at 43°C, the ethyl carbamate in two red wines increased 20 to 30 times. It increased three to nine-fold in nine of the wines, but remained unchanged in four. Light did not significantly influence ethyl carbamate formation, whether in clear or green bottles.     

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     

黄酒中氨基甲酸乙酯的研究进展

氨基甲酸乙酯（EC）是发酵食品和酒精饮品在发酵或贮存过程中产生的对人类健康存在潜在危害的一种物质。近年来,随着黄酒产业的兴起,在有关黄酒中氨基甲酸乙酯的控制的食品质量安全问题也越来越受到人们的关注。该文在检索近年来氨基甲酸乙酯相关文献和标准的基础上,对发酵产品中氨基甲酸乙酯的形成机理,以及黄酒食品安全性评价、氨基甲酸乙酯检测方法及其含量控制等方面的国内外研究现状进行综述,旨在为黄酒生产中降低氨基甲酸乙酯的含量、提升黄酒品质提供借鉴和参考。     

Exposure assessment and risk characterisation of ethyl carbamate from Korean traditional fermented rice wine,Takju and Yakju

Ethyl carbamate is one of the most hazardous chemicals naturally occurring in food, and is present in alcoholic beverages. Korean traditional rice wine, Takju and Yakju, is frequently consumed in Korea, but there have been no studies characterising the risks of ethyl carbamate in these products. In order to assess and characterise the exposure risk of ethyl carbamate in Korean traditional rice wines, ethyl carbamate was investigated by means of GC-MS. The analytical methods were optimised and validated through determining linearity, detection limit, quantification limit, recovery and precision. A total of 283 traditional Korean rice wines, including 175 Takju and 108 Yakju samples, were analysed. Exposure assessment was performed by factoring in ethyl carbamate content, daily consumption and body weight. Daily exposures of ethyl carbamate were estimated for adults in four age groups, and risks of ethyl carbamate were characterised by the margin of exposure, which is more than 10 000. Based on this study, the risks of ethyl carbamate in Korean traditional rice wine were shown to be of low concern.     

黄酒中氨基甲酸乙酯形成、控制及检测方法的研究进展

氨基甲酸乙酯(EC)是一种存在于黄酒中的基因致癌物。本文就EC的形成途径及致癌机理方面进行了概述,重点阐述了黄酒酿造生产中EC的控制措施,并就常用的检测方法进行了比较分析,同时对未来研究方向做了展望,旨在为我国的黄酒生产技术提供理论参考。