Sugarcane spirits and cachaca are distilled beverages derived from the fermentation of sugarcane juice. The production of these spirits has significant influence on the economy of several regions in Brazil, being the third most consumed distilled beverage in the world. To ensure the safety for human consumption and also to add value to these products, it is imperative to apply quality control techniques. The complexity of food matrices along with the fact that the currently used instrumental techniques have several disadvantages, such as being expensive, laborious and time-consuming, have turned research attention to multivariate analysis techniques. In consequence, chemometric techniques have been applied in laboratories around the world aiming at data reduction, pattern recognition, cluster analysis, classification and quantification of data. This article provides an overview of the application of analytical techniques with nonsupervised and supervised pattern recognition methods for the analysis of sugarcane spirits samples. Assessments discussed include promising results for the discrimination among samples, verification of adulteration, tendencies in sensorial characteristics as well as relationships between chemical information and the geographical origins.

Overview of Analytical Techniques Associated with Pattern Recognition Methods in Sugarcane Spirits Samples

Among the family of sugarcane spirits, those made from juice are diverse and often produced in a traditional way. They must be distinguished from other sugarcane spirits, which are more widely produced and made from other sugarcane derivatives, such as molasses. These alcoholic beverages contribute significantly to the socio-economic development of many countries. However, despite ancestral know-how, there is a lack of contemporary data required to characterize some sugarcane juice spirits (SCJSs) and to overcome the current and future threats that producers will have to face. While preserving their authenticity and specificity, SCJS producers expect to improve and ensure sufficient yield and a superior quality product. Even if the scientific knowledge on these spirits is not comparable, the available data could help identify the critical points to be improved in the making process. This review aims to present the main SCJSs encountered worldwide, defining their specific features through some important aspects with, notably, references to the complex notion of terroir. To continue, we discuss the main steps of the SCJS process from harvesting to aging. Finally, we expose an inventory of SCJS’s chemical compositions and of their sensory description that define the specific organoleptic properties of these spirits.

An Overview of Spirits Made from Sugarcane Juice

A cachaca e a bebida mais consumida no Brasil, com uma producao anual de 1,3 bilhao de litros. Uma boa cachaca, alem de atender as exigencias legais com relacao a sua composicao, deve tambem apresentar qualidade sensorial capaz de satisfazer ou mesmo ultrapassar as expectativas de seus consumidores. Os compostos volateis como alcoois superiores, esteres, acidos carboxilicos e compostos carbonilicos sao importantes para o sabor caracteristico das bebidas alcoolicas. A revisao da literatura mostrou que, ate o presente momento, nao existe um estudo sobre a composicao de volateis de cachaca, abrangendo todas as classes quimicas presentes na bebida, assim como nao se conhece os compostos volateis odoriferos importantes para a sua qualidade sensorial. Para isso, um metodo foi desenvolvido em extracao em fase solida para a analise dos compostos volateis da cachaca por cromatografia gasosa. Os compostos volateis foram extraidos de uma solucao de cachaca/agua (1:1) em um cartucho contendo 200 mg de resina Licrolut EN da Merck e a eluicao feita com 1,5 mL de diclorometano/dimetil eter (9:1 v/v). O extrato obtido foi representativo da amostra original de cachaca. O metodo mostrou-se simples, rapido e com recuperacao dos compostos volateis acima de 93%. Os compostos volateis de 13 amostras comerciais de cachaca foram determinados por dois metodos, sendo os compostos majoritarios por CG-DIC e os minoritarios por CGEM, atraves do monitoramento de ions selecionados, para maior sensibilidade e empregando-se o metodo desenvolvido. Os compostos volateis foram identificados por indice de retencao, espectrometria de massas e padroes puros. Foram identificados 65 compostos volateis nas 13 amostras analisadas, dos quais 48 foram relatados pela primeira vez em cachaca. Os compostos identificados compreenderam 21 esteres, 10 acidos, 9 alcoois, 9 fenois, 6 terpenos, 4 aldeidos, 4 cetonas e 2 lactonas. Nao houve diferenca qualitativa entre os compostos volateis detectados nas cachacas, mas houve uma grande variacao na quantidade encontrada de cada composto nas diferentes amostras. A classe dos alcoois foi a mais abundante na maioria das cachacas comerciais, sendo que o alcool isoamilico foi o composto majoritario presente na maioria das amostras, excetuando-se o etanol. Foi realizada analise de aceitacao das 13 cachacas comerciais por trinta consumidores, familiarizados com a bebida. As amostras nao diferiram significativamente (p£0,05) entre si em relacao ao aroma. Entretanto, em relacao ao sabor, as cachacas 2, 4, 6, 7, 8 e 13 foram as de maior aceitacao e diferiram significativamente (p£0,05) da cachaca 9, de menor aceitacao, sendo que as demais amostras nao diferiram significativamente (p£0,05) das amostras mais e menos aceitas. Na avaliacao da impressao global, as cachacas 2 (mais aceita) e 9 (menos aceita) diferiram significativamente (p£0,05) entre si e as demais amostras obtiveram aceitacao intermediaria, nao diferindo significativamente (p£0,05) destas duas amostras. A Analise Descritiva Quantitativa de quatro cachacas, selecionadas de acordo com o teste de aceitacao, foi realizado por nove provadores selecionados e treinados. O perfil sensorial mostrou que a cachaca de maior aceitacao (amostra 2) foi a que apresentou maior intensidade dos atributos aroma adocicado, ardencia inicial, sabor encorpado e gosto adocicado, enquanto uma cachaca de aceitacao intermediaria (amostra 6) apresentou maior intensidade dos atributos corpo, aroma alcoolico e sabor alcoolico. As cachacas de menor aceitacao (amostra 9) e outra tambem de aceitacao intermediaria (amostra 3) apresentaram maiores intensidades dos atributos ardencia final, aroma irritante e gosto amargo, sendo que a amostra 9 apresentou os maiores valores desses atributos. A amostra 2, selecionada devido a intensidade e qualidade do sabor, foi escolhida para o estudo de CG-olfatometria (AEDA). Foram detectados 59 compostos odoriferos nesta amostra comercial, dos quais 45 foram identificados. O alcool isoamilico foi o odorante mais relevante, sendo detectado em todas as diluicoes pelos quatro provadores treinados, seguido da vanilina, que foi detectada por tres provadores no extrato mais diluido. Para uma melhor visualizacao dos compostos volateis que poderiam estar associados a aceitacao das 13 cachacas comerciais, fez-se a correlacao entre as medias de aroma, sabor e impressao global de cada amostra e suas respectivas coordenadas nos eixos I e II associadas as ACP, geradas utilizando-se a concentracao dos compostos volateis, agrupados em classes quimicas. Estes dados permitiram sugerir que a aceitacao das cachacas em relacao ao aroma parece estar relacionada principalmente a presenca de lactonas e alguns terpenos, enquanto a baixa aceitacao em relacao ao sabor, a presenca de fenois, principalmente 4-vinil fenol e 4-vinil guaiacol. Estes dados revelam que as amostras de cachaca apresentaram perfis sensoriais e de volateis distintos, evidenciando a falta de um padrao de qualidade. 
Abstract

Compostos de volateis e qualidade de sabor da cachaça.

The objective of this study was to ferment sugarcane juice using two types of yeast and evaluate the quality of the distillate after beverage filtration in a column filled with ground charcoal derived from cane bagasse. The experimental design was randomized block (split plots, 2 x 2) with three replicates. The primary treatment involved two types of yeast: CA-11 and baker’s yeast. Secondary treatment involved filtration or not of the beverage in the charcoal column. The following procedures were adopted: percolation of all samples to a single column and passage of the distillate from each repetition (blocks) using three similar columns. Selected yeast had similar cachaca production as compared to the baker’s yeast. However, higher acidity occurred in the distillate using the selected yeast, which contributed to the increased transfer of copper to the beverage. In the charcoal filtration that used one column per block, the copper was removed from the beverage, and the acidity was decreased, whereas the alcohol content, fixed acidity, pH, and turbidity of the cachaca did not change.

	Key words: Spirits, yeast strains, fermentation, distillation, filtration columns.

Post-treatment of cachaca (Brazilian sugarcane spirit) with charcoal made from cane bagasse

In our study, rapid methods were developed for the quantitative determination of cations (sodium, potassium, ammonium, calcium, magnesium) and anions (chlorides, nitrites, nitrates, phosphates, sulfates) using ion chromatography with conductometric detection; phenolic and furan compounds (gallic acid, ellagic acid, vanillin, syringaldehyde, vanillic acid, syringic acid, furfural, 5-HMF, coniferyl aldehyde, sinapaldehyde) by high performance liquid chromatography with spectrophotometric detection; volatile organic impurities (acetaldehyde, ethyl acetate, acetal, methanol, 1-propanol, isobutanol, 2-methylbutanol, 3-methylbutanol) by gas chromatography with flame ionization detection. The developed methods will allow monitoring the technological process of rum production, studying the aging dynamics, and identifying counterfeit products.

An integrated approach to the rum identification

This work focuses on the development, validation, and use of analytical methods for the identification and quantitation of relevant constituents in sugar cane spirits from Brazil and Cape Verde. The compositions of both artisanal and industrial products were investigated. Repeatability, recovery, linearity of analytical curves, limits of detection, and limits of quantitation were parameters considered for methods validation. Gas chromatography was used for the analyses of acetaldehyde, ethyl acetate, and alcohols. Anions were analyzed by ion chromatography, while metal ions were analyzed by inductively coupled plasma optical emission spectrometry. Good precision and accuracy were achieved, and the concentrations of some constituents were found to be higher than that allowed by law, namely: acetaldehyde, in five samples from Cape Verde and in three samples from Brazil; n-butyl alcohol, in two samples from Cape Verde and in three samples from Brazil; higher alcohols, in three samples from Cape Verde and in two samples from Brazil. On the other hand, mean concentrations of acetaldehyde and higher alcohols were in accordance with legal requirements. Further discussion is presented regarding differences observed between the compositions of the samples studied.

Comparative study of chemical constituents in sugar cane spirits from Brazil and Cape Verde

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Comparative study of chemical constituents in sugar cane spirits from Brazil and Cape Verde