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     

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     

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     

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     

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     

Fast Sequential Determination of As and Sb, Bi and Pb by Continuous Flow Hydride Generation Atomic Absorption Spectrometry

In this study, two methods were developed for the sequential determination of As and Sb, Bi and Pb using fast sequential continuous flow hydride generation atomic absorption spectrometry. Limits of detection obtained for As and Sb were 0.15 and 0.16 μg?L^?1 and for Bi and Pb were 0.60 and 0.77 μg?L^?1, respectively. Arsenic, Sb, and Bi were free from the influence of possible interferents in the levels investigated, but Pb showed a significant analytical signal decrease when Co, Cu, Fe, Ni, and HNO₃ were presented in the solutions. The methods were applied to the analysis of water from the Tietê River (São Paulo State, Brazil), sea water from Praia Grande—Ubatuba (São Paulo State), chicken feed, trace elements in water (NIST 1643e), and trace metals in drinking water (HPS TMDW). The obtained recoveries varied from 88 (for As) to 116 % (for Bi).     

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     

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     

Electrospray Ionization Mass Spectrometry Characterization of Musts and Alembic Brazilian Cachaças Using Selected Yeast Strains

The choice of fermentation system during cachaça production can greatly influence the chemical composition of the beverage. In this work, Saccharomyces cerevisiae strains were selected based on fermentative properties and used as starters to produce alembic cachaça. In distillery scale production, the selected yeast strains exhibited greater adaptiblity to the fermentation environment and hence remained predominant throughout the process. Electrospray ionization mass spectrometry in the negative ion mode revealed that most of the compounds present in the must are different from those formed in the distillate for both cachaças obtained from spontaneous and selected strains. However, beverages produced using selected strains showed greater similarity in chemical profiles than those produced from spontaneous strain fermentation. Moreover, a smaller number of ions were detected in beverages produced by selected strain than from spontaneous strain fermentation. Our results indicate that the selected S. cerevisiae strains evaluated are able to produce cachaças less subject to variation in chemical composition. This could potentially improve brand consistency and thus commercial viability, particularly in the international market.     

Influence of the number of distillations on the composition of organic sugarcane spirit

Sugarcane spirit is the most consumed distilled beverage in Brazil. Currently the manufacturing industries are trying to widen their market and attract new consumers, and thus it has become necessary to elevate the product to national and international quality standards. This study's aim was to determine the influence of subsequent distillations on the composition of organic sugarcane spirit. From mono‐distilled organic sugarcane spirit, bi‐, tri‐, tetra‐ and penta‐distilled sugarcane spirits were obtained, and analysed for the following: relative density, alcoholic degree, volatile acidity, pH, copper, methanol, aldehydes, furfural, esters, ethyl carbamate and higher alcohols. The most relevant results were reductions of 69.57% volatile acidity, 98.4% copper, 40.9% methanol, 71.5% aldehydes, 100% esters, 100% ethyl carbamate and 32.2% higher alcohols in the penta‐distilled sugarcane spirit, as compared with the mono‐distilled. It was concluded that subsequent distillations would put sugarcane spirit in line with the international standards for distilled beverages. Copyright © 2013 The Institute of Brewing & Distilling     

The lack of reproducibility of different distillation techniques and its impact on pear spirit composition

We analysed the impact of operation variability on the composition of pear spirits obtained with a Charentais alembic and a packed distillation column. Lack of reproducibility significantly affected the spirits’ compositions, with batch distillation columns more difficult to operate reproducibly vs. traditional alembics. The composition of column distilled spirits differed more in esters, such as ethyl octanoate, ethyl decanoate and ethyl palmitate. In turn, alembic spirit compositions differed more in acetaldehyde and acetal. Moreover, column distilled spirits contained four times more esters, 20% more higher alcohols, 40% less acetaldehyde and 10% less methanol than alembic spirits. Spirits distilled with a rectification column were more concentrated in ethanol than alembic distilled spirits, although both distillation systems recovered the same amount of ethanol in the heart fraction.     

Levels of copper in Nile tilapia from Brazil

The purpose of this work was to determine the concentration of copper in samples of farmed Nile tilapia (Oreochromis niloticus L.) fillets purchased in the city of Botucatu (São Paulo, Brazil) and in fillet and liver samples of Tilapia fed diets supplemented with different concentrations of Cu from the Laboratory of Aquatic Organism Nutrition/FMVZ-UNESP (Botucatu, Brazil). The fillet samples were prepared by lyophilisation and cryogenic grinding into particles smaller than 60?µm, and copper was extracted ultrasonically using 0.10?mol?l^?1 HCl as extraction solution. Copper determination was performed by graphite furnace atomic absorption spectrometry (GFAAS) with optimised temperatures of drying, pyrolysis, atomisation and cleaning. Palladium nitrate was injected into the samples as a chemical modifier and tungsten as a permanent modifier. Copper concentrations of 0.70–1.60?mg?kg^?1 were found, which are in line with Brazilian regulations. The accuracy and precision of the copper concentrations determined in this study were evaluated using certified standard Lake Michigan fish tissue (NIST SRM 1947).     

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     

Streptomycin and dihydrostreptomycin residues in bovine milk from the Brazilian retail market

Pasteurised bovine milk from retail markets in the State of São Paulo, Brazil, was analysed for the presence of streptomycin (STP) and dihydrostreptomycin (DHSTP) residues. An ELISA kit was used for screening and a LC–APCI–MS/MS QToF method for confirmatory analysis. Both methods were intra-laboratory validated and found suitable for screening and confirmatory testing, respectively, for STP and DHSTP residues in pasteurised bovine milk at concentration levels below the maximum residue limit (MRL) established for these substances (200 µg kg^?1 expressed as the sum of the concentrations of STP and DHSTP). No residues of STP and DHSTP at detectable levels were found in the analysed samples (n = 299).     

Production of sensory compounds by means of the yeast Dekkera bruxellensis in different nitrogen sources with the prospect of producing cachaça

The distilled spirit made from sugar cane juice, also known as cachaça, is a traditional Brazilian beverage that in recent years has increased its market share among international distilled beverages. Several volatile compounds produced by yeast cells during the fermentation process are responsible for the unique taste and aroma of this drink. The yeast Dekkera bruxellensis has acquired increasing importance in the fermented beverage production, as the different metabolites produced by this yeast may be either beneficial or harmful to the end‐product. Since D. bruxellensis is often found in the fermentation processes carried out in ethanol fuel distillation in Brazil, we employed this yeast to analyse the physiological profile and production of aromatic compounds and to examine whether it is feasible to regard it as a cachaça‐producing microorganism. The assays were performed on a small scale and simulated the conditions for the production of handmade cachaça. The results showed that the presence of aromatic and branched‐chain amino acids in the medium has a strong influence on the metabolism and production of flavours by D. bruxellensis. The assimilation of these alternative nitrogen sources led to different fermentation yields and the production of flavouring compounds. The influence of the nitrogen source on the metabolism of fusel alcohols and esters in D. bruxellensis highlights the need for further studies of the nitrogen requirements to obtain the desired level of sensory compounds in the fermentation. Our results suggest that D. bruxellensis has the potential to play a role in the production of cachaça. Copyright © 2014 John Wiley & Sons, Ltd.     

Determination of ethyl carbamate in cachaça stored in newly made oak,amburana, jatobá, balsa and peroba vats and in glass containers

Ethyl carbamate was quantified in cachaça using high‐performance liquid chromatography with fluorescence detection during the production process and during storage in different types of wooden casks and glass containers, with and without the presence of light. According to the physicochemical analysis, the head and tail fractions are unacceptable for consumption. Ethyl carbamate was detected in sugarcane juice and during fermentation. During distillation, ethyl carbamate levels ranged from the limit of detection to 17.1 μg L⁻¹. Ethyl carbamate increased during storage in wooden casks. The presence (or absence) of light did not affect the formation of ethyl carbamate in cachaça stored in glass containers. Copyright © 2017 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     

Parboiled rice: A study about attitude,consumer liking and consumption in São Paulo,Brazil

The consumption of parboiled rice in Brazil is low when compared to milled rice, despite alleged nutritional, convenience and technological benefits. Data collected through a survey with 186 consumers in the city of São Paulo, Brazil, were analysed with the aim of gaining a better understanding of local consumer attitudes towards parboiled rice. Six attitudinal items were assessed as giving a score on a five‐point Likert scale. Cluster analysis was used to identify three segments of respondents with different attitudinal patterns. Subsequently, correspondence analysis revealed associations among clusters and educational level and liking/consumption data. Most consumers did not show an established opinion about the main characteristics of parboiled which indicates a weakness of the product promotion. A positive attitude, as demonstrated by a higher intake of parboiled rice, was a reflection of habit and liking, while a negative attitude seemed to be due to previous negative experience and misconceptions about the product. Copyright © 2007 Society of Chemical Industry