Sugar Cane Spirit Research Articles

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 × 10(3) 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. Based on the fluorescence properties of the reaction product between cyanate and 2-aminobenzoic acid, a method for assaying cyanate was devised. This procedure applied to the sugarcane distillate showed for the first time a correlation between cyanate presence and ethyl carbamate (EC) formation in the different fractions of the product. Therefore, the proposed methodology can be used to predict in freshly distillate sugar cane spirits the potential total concentration of EC to be formed. Therefore, these data could be used to advise about the necessity of implementing a procedure to reduce spirit EC concentration before the product reaches the market.

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

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 cachaca, a Brazilian sugarcane spirit aged in oak barrels. Aged cachaca 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 cachaca and the identification of product maturity. Copyright © 2014 The Institute of Brewing & Distilling

Ocorrência de carbamato de etila em cachaças de alambique e em aguardentes industriais

Este trabalho teve como objetivo verificar a ocorrência de carbamato de etila, o grau alcoólico e a acidez volátil em cachaças e aguardentes de cana. As amostras foram obtidas de fabricantes de São Paulo, Minas Gerais, Rio de Janeiro, Espírito Santo e Ceará, de sistema de produção em destilador de cobre ou coluna de aço inoxidável, e de estabelecimentos registrados ou não. As análises de acidez volátil e de grau alcoólico foram realizadas conforme metodologia descrita pelo Ministério da Agricultura, Pecuária e Abastecimento. Os teores de carbamato de etila foram determinados pelo método de padronização externa, em sistema de cromatografia gasosa acoplada a espectrometria de massa (CG/EM), utilizando-se o modo MSI (Monitoramento Seletivo de Íons) para a quantificação. Os valores obtidos para o grau alcoólico variaram de 32,4 a 49,2 ºGL, sendo o teor médio de 40, 4 ºGL. Observou-se que 17 (22,7%) das bebidas apresentaram o grau alcoólico abaixo de 38 ºGL, que representa o valor mínimo imposto pela legislação vigente. Somente uma cachaça apresentou o grau alcoólico acima de 48 ºGL, limite máximo para esta bebida. Dentre as bebidas analisadas, 24 (32%) apresentaram acidez volátil acima do limite máximo. Os valores obtidos das 75 bebidas para o carbamato de etila variaram de 20 a 948 µg/L, apresentando um teor médio de 378, 25 µg/L. Somente 10 das 75 bebidas apresentaram teores de carbamato de etila abaixo de 150 µg/L, que é o limite máximo permitido pela Instrução Normativa nº 13 de 21 de junho de 2005.

Natural clay and commercial activated charcoal: Properties and application for the removal of copper from cachaça

The influence of contact time and the amount of adsorbent on the removal of copper from distilled cachaca was evaluated. The adsorption of copper was favored by a 1:50 ratio of mass of adsorbent (g) to volume of sugar cane spirits (mL). An equilibration time of 120 min for clay and 360 min for activated charcoal resulted in the removal of 68.7% and 98.3% of the copper, respectivamente. The isotherms were studied in the range of copper concentrations of 0 to 2000 mg L−1. The amount of copper adsorbed per unit weight of clay was 10.8 mg g−1, and for charcoal, it was 5.9 mg g−1. The isotherm results were tested in the Langmuir and Freundlich models and were found to adapt better to the Freundlich model. The removal of copper by clay and activated charcoal could be explained by a pseudo-second-order kinetic model. Given the organic and inorganic complexity of cachaca, the influence of this process on the flavor of the beverage was also evaluated. To this end, the analyses of aldehydes, higher alcohols, furfural, esters and volatile acidity were performed according to the methods established by the Ministry of Agriculture, Livestock and Supply. The results showed that the samples treated with clay adsorbed 3.6, 8.7, 9.4, 2.2 and 3.9% of the aldehydes, higher alcohols, furfural, esters, and volatile acidity, respectively. For the samples treated with activated charcoal, the results were 6.5, 15.3, 95.31, 2.0 and 34.0% for the aldehydes, higher alcohols, furfural, esters, and volatile acidity, respectively.

“Cachaças” (Sugarcane Spirit) Aged Quantitation of Phenolic Compounds, Antibacterial and Antioxidant Activity

The “cacha&ccedila” is currently one of the fastest growing agro-industrial industries in the country as the drink considered as a symbol of Brazilian nationality. This study aimed to quantify the phenolic compounds, evaluate the antioxidant and antibacterial activity of different samples of aged “cacha&ccedila”. The physic-chemical analysis was performed at the Brandy Quality Laboratory of the Federal University of Lavras, and the determination of phenolic compounds was performed by High Performance Liquid Chromatography (HPLC). The antimicrobial activity evaluation was held at the Food Mycology Laboratory through the cavity agar diffusion technique and by steam using the micro-organisms Escherichia coli, Staphylococcus aureus, Salmonella choleraesuis, Listeria monocytogenes and Pseudomonas aeruginosa. The antioxidant activity was evaluated using the DPPH radical sequestering method. The values obtained for the phenolic compounds ranged from 0.41 to 9.69 mg/L, observing the predominance of syringaldehyde, gallic acid and vanillic acid. The phenolic extracts showed a satisfactory antibacterial activity for both Gram-negative and Gram-positive but did not show inhibition against the bacteria Pseudomonas aeruginosa. The antioxidant activity was evidenced by the DPPH test for cacha&ccedilas tested and the “cacha&ccedila” aged in oak barrel showed the highest activity, followed by “cacha&ccedila” aged in jequitiba, amburana and balm barrels.

Evaluation of Glycerol Profiles in Sugarcane Spirits (Cachaças)

A new method for glycerol quantification in sugarcane spirits (cachacas) is proposed, based on sample derivatization using benzoyl chloride followed by solid-phase extraction and high performance liquid chromatography with diode array detection analysis. The limits of detection and quantification for glycerol analysis are 0.25 mg L−1 and 0.74 mg L−1, respectively. The accuracy is of 97.5%, the precision 93.5% and the linearity r2 = 0.998 in the range of 0.56 mg L−1 to 112.0 mg L−1 of glycerol. Experiments with forty eight samples of aged and non-aged cachacas and seven alcoholic extracts of wood showed that the aging process contributes to increase the glycerol concentration. The average concentration of glycerol in aged cachacas were about 10-fold higher than in non-aged cachacas.

Screening and determination of aliphatic organic acids in commercial Brazilian sugarcane spirits employing a new method involving capillary electrophoresis and a semi-permanent adsorbed polymer coating

A simple method for the screening and determination of short chain aliphatic carboxylic acids in Brazilian sugarcane spirits by indirect capillary zone electrophoresis was developed and validated according to Eurachem guidelines. The separations were performed in a coated capillary (Ltot 73cm×Ldet 64.5cm) with 2-hydroxy-propyltrimethyl-ammonium chloride chitosan. The background electrolyte was optimized using Peakmaster® software and was composed of 21mmolL−1 β-alanine and 10mmolL−1 3,5 dinitrobenzoic acid, at pH3.6, with an applied voltage of −30kV. The method was validated for formic, lactic and acetic acids. Linearity was demonstrated and significant matrix effects were not observed at between 2.8 and 144mgL−1. The recovery (means of 89.6–117.9%) was evaluated, and ANOVA was carried out to determine the RSD values for the repeatability (2.63–8.35%) and reproducibility (1.92–6.62%). The LOD and LOQ ranged from 0.69 to 2.70 and 2.76 to 8.11mgL−1, respectively. The concentrations detected in the samples were 0.19–106.43mg per 100g.

Sensory profile and acceptability of traditional and double-distilled cachaça aged in oak casks

Distillation is an important step to obtain a beverage of good quality, because it separates, selects and concentrates the components of the wine, as well as promoting some chemical reactions induced by the heat. Thus the volatile components of the wine can increase or decrease, or new components can even be produced. Recently, the technique of double distillation has been implemented to restructure the profile of organic compounds of sugar cane spirits produced in pot stills, with the aim of obtaining a sensorially differentiated product. In addition to the distillation, the ageing process is a key step in improving the quality of cachaça. This study aimed to describe the sensory profile of six samples of cachaça, with variations in the kind of distillation (traditional and double distillation) and ageing for 12 and 24 months in oak casks. The sensory profile was performed by descriptive analysis by a panel of nine trained assessors, using 18 terms to describe the similarities and differences between the samples. An acceptance test with 60 panellists, potential consumers of aged and non-aged cachaça, was also completed. The descriptors used revealed differences in the sensory profiles between the traditional and double-distilled samples, and that the double-distilled samples showed greater intensity of the attributes related to ageing in oak casks. Acceptance testing also showed a greater consumer preference for the double-distilled aged samples. Copyright © 2013 The Institute of Brewing & Distilling

Feasibility of different chemometric techniques to differentiate commercial Brazilian sugarcane spirits based on chemical markers

Chemometric techniques were used to assess the quality of 51 commercial Brazilian sugarcane spirits (cachaça) based on chemical markers. Benzo(a)pyrene, methanol, 2,3-methyl-1-butanol, acetaldehyde, isobutyl alcohol, n-propanol, density, alcoholic strength, and higher alcohols were quantified using chromatographic methods and results were subjected to Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA), and Linear Discriminant Analysis (LDA). No significant differences (p≥0.071) were observed in the chemical markers of Brazilian aged and non-aged cachaça samples. Besides non-significant (p=0.922), the content of benzo(a)pyrene in aged sugarcane spirits was 1.83 times higher than in non-aged ones. Differences in alcoholic strength (p=0.001) and n-propanol (p=0.015) were observed among cachaças produced by double distilling, alembic and in stainless steel columns. PCA was not suitable to separate the samples according to the provenance, aging and distilling process, while HCA was effective in separating alembic cachaças produced by from two distinct producing regions. LDA seemed to be very suitable to assess not only the provenance but also the distilling and aging processes that cachaça undergoes, yielding about 91% accuracy to discriminate non-aged from aged cachaça, 81.82% and 86.61% accuracy to discriminate samples from Minas Gerais and São Paulo, respectively.

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

ENVELHECIMENTO PRECOCE DE CACHAÇA COM IRRADIAÇÃO GAMA (Co60) ATRAVÉS DA EXTRAÇÃO DE COMPOSTOS DA UVA

The sugar cane spirit is a drink distilled and for this reason your bouquet and flavor need enhanced. Usually the sugar cane spirit goes through a process of maturation in wooden barrels. However it is possible to obtain similar results with the use of gamma radiation emitted by the radioisotope Co60. This research aimed to evaluate the effects of irradiation in the sugar cane spirit including the possibility of premature aging having as reference the color change through the extraction of existing compounds in the grape. Sugar cane spirit samples were prepared with grapes like Crimson in polypropylene bottles. The samples were irradiated at doses of 0 (control); 300Gy; 2kGy; 6kGy and then colorimetric analysis was performed in periods of 5; 10; 20 and 50 days after irradiation treatment. There was no statistically significant difference in measurements of L, a, b or the Chroma and Hue-Angle from 5; 10 and 20 days. In the 50 th day just to measure a significant difference in the dose of 300Gy which was higher than 2 and 6kGy and not different from control sample. Therefore this study showed that the irradiation at doses of 300Gy; 2kGy and 6kGy are not efficient for the purpose of extracting the compounds of the grape for a change in color that is the indicative of possible premature aging.

Physico-chemical and sensorial evaluation of sugarcane spirits produced using distillation residue

The objective of the present study was to analyze the use of vinasse from cachaca as an ingredient of the fermentation medium for the spirit production. The fermentations were conducted out in three successive batches using a Saccharomyces cerevisiae isolate. In the first batch, the sugarcane broth was only diluted with distilled water. In the second and third batches, the fermentations were carried out using the cane broth diluted with vinasse from the distillation of the sugarcane wines of the first and second batches, respectively at a concentration of 10% (v/v). The spirits were submitted to the physicochemical and sensorial analyses. The results showed that vinasse addition did not affect the fermentation, distillation and chemical-sensorial quality of the beverage. Therefore, the vinasse addition could be an alternative use for that residue.

Congeners in sugar cane spirits aged in casks of different woods

The profile of volatile compounds and aging markers in sugar cane spirits aged for 36months in casks made of 10 types of wood were studied. The ethanol content, volatile acidity, aldehydes, esters, higher alcohols, and methanol were determined. In addition, gallic, vanilic and syringic acids, siringaldehyde, coniferaldehyde, sinapaldehyde, vanillin, 5-hydroxymethylfurfural and furfural were identified and quantified. The profile of volatile compounds characterised aging in each type of wood. The beverage aged in oak cask achieved the highest contents of maturation-related congeners. The Brazilian woods, similar to oak, were jequitibá rosa and cerejeira, which presented the highest contents of some maturation-related compounds, such as vanillin, vanilic acid, syringaldehyde and sinapaldehyde. Although oak wood conferred more chemical complexity to the beverage, Brazilian woods, singly or complementarily, present potential for spirit characterisation and for improving the quality of sugar cane spirits.

Determination of Copper in Different Ethanolic Matrices Using a Chloropropyl Silica Gel Modified with a Nanostructured Cubic Octa(3‐aminopropyl)octasilsesquioxane

The chloropropyl silica gel was modified with octa(3‐aminopropyl)octasilsesquioxane and characterized by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), spectroscopies, and surface and area porosity. The specific sorption capacity of metallic ions (Cu2+ and Ni2+) increases in the following solvent order: water < ethanol 42% < ethanol < ketone. The high values of the constant (K) in the order of 103 L mol−1 suggested the high adsorbent capacity of the modified silica (SGAPC) for Cu2+ and Ni2+. SGAPC was applied to a separation column and shows recoveries of around 100% of copper in samples of sugar cane spirit, vodka, ginger brandy, and ethanol fuel.

Determination of Nickel in Alcoholic Beverages by FAAS after online Preconcentration using Mandarin Peel (Citrus reticulata) as Biosorbent

A solid phase extraction method was developed for the direct determination of nickel in alcoholic beverages. This method is based on the adsorption of nickel onto the peel of Citrus reticulata (mandarin orange). The solution pH, amount of adsorbent, sample and eluent flow rates, eluent concentration and matrix effects were investigated using multivariate optimization strategies. Desorption studies were carried out with 1 mol L-1 HCl. The optimum extraction conditions were obtained using a sample pH of 6.0, sample flow rate of 4.3 mL min-1, 50 mg of sorbent mass and 1.0 mol L-1 HCl at a flow rate of 2.0 mL min-1 used as eluent. The preconcentration factor, precision, limit of detection (LOD), limit of quantification (LOQ), consumption index and sample throughput were estimated as 12, 0.9% (30.0 µg L-1, n = 7), 3.1 µg L-1, 10.3 µg L-1, 0.85 mL and 15 samples per h, respectively. The method was applied to sugar cane spirit and whisky samples and the results for recovery tests were higher than 99%.

Correlation between Chemical Composition and Sensory Properties of Brazilian Sugarcane Spirits (Cachaças)

The correlation between the chemical composition and the sensory data for 28 cachaca samples was investigated using principal component analysis (PCA). A chemical model was then developed using linear discriminant analysis (LDA) to classify the distillate samples according to their sensory qualities. This model presented predictive abilities of calibration and validation of 87.4 and 100%, respectively, and was able to recognize correctly 7 out of 9 additional samples according to their sensory evaluations, showing itself as a potential alternative tool of recognizing cachaca sensory qualities.

Evaluation of Methods Used for the Analysis of Volatile Organic Compounds of Sugarcane (Cachaça) and Fruit Spirits

Sugarcane spirits are defined as beverages with an alcohol content ranging from 38 to 54 % v/v at 20 °C, obtained from the simple alcoholic distillation of sugarcane or fermented sugarcane must. Fruit spirits may be obtained directly from fruit or from fruit must that may or may not contain seeds by distillation, and present specific organo- leptic characteristics and an alcohol content of 36 to 54 % v/ v at 20 °C. The physicochemical and sensory qualities of these beverages are dependent on the nature and quality of the raw materials, fermentation, distillation and aging, and are organoleptically characterised by the presence of volatile organic compounds (VOC) (organic acids, aldehydes, esters, higher alcohols, terpenes, lactones and others). This paper presents studies performed to evaluate VOC in spirits. Among the volumetric and instrumental methods described to evaluate VOC in spirits, chromatographic methods are the most cited. Chromatographic techniques employed include high performance liquid chromatography, gas chromatogra- phy with flame ionisation detection, gas chromatography with mass spectrometric detection and two-dimensional gas chromatography with time-of-flight mass spectrometry.

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

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