Scotch Whisky is a complex mixture comprising thousands of chemical species at a diverse range of concentrations. The identities, origins, and significance of many of these compounds is largely unknown. Routine characterisation of Scotch Whisky mostly utilises techniques such as gas or liquid chromatography (GC, LC) coupled to a FID, UV, or low-resolution mass spectrometry (MS) detector. In this thesis, advanced spectroscopic and spectrometric techniques are investigated as potential complementary means to unravel the chemical complexity of Scotch Whisky. Chemometric methods are applied to decipher the significance or potential origin of many of these compounds. Being predominantly (ca. 99 %) protonated 'solvent' - ethanol and water - 1H and 13C Nuclear Magnetic Resonance (NMR) required solvent suppression to be implemented into the acquisition of high resolution spectra. A 1D NOESY-presaturation sequence was modified and implemented in automation for this purpose. Furthermore, this solvent suppression was coupled with several 1D and 2D homo- and heterocorrelated NMR experiments for the analysis of Scotch Whisky. With limited sample preparation - only addition of buffer - an approximate limit of detection of 50 μm was achieved. The developed NMR methodology was subsequently used for structural elucidation of dozens of compounds in Scotch Whisky. Quantification of these compounds was hindered by variable chemical shifts, signal overlap, and for some compounds the existence of equilibria of different forms. Quantification of ethanol concentrations in model solutions and genuine Scotch Whisky samples was successful. A large set of Scotch Whisky samples were analysed by the solvent suppressed 1D 1H NMR methodology and various statistical techniques including statistical total correlation spectroscopy (STOCSY), independent and principal component analysis (ICA, PCA), and orthogonal partial least squares discriminant analysis (OPLS-DA). Various parameters were modelled, and discrimination of 'malt' or 'blend' status was achieved, whilst maturation wood type discrimination was less successful. High resolution negative mode electrospray ionisation (ESI) Fourier transform ion cyclotron resonance (FTICR) MS was then used to examine a large set of Scotch Whisky samples. Thousands of unique molecular formulae were assigned within a 1 ppm threshold, representing an assignment rate of 72-88 % of the detected peaks in the spectra. Assignments were selectively confirmed by isotopic fine structure (IFS) analysis, and structural information obtained by both quadrupolar isolation and fragmentation, and in-cell isolation and fragmentation. Similar chemometric methods as applied to NMR data were used to model sample parameters, and identification of potential maturation wood marker compounds was achieved. Alternative ionisation sources - including atmospheric pressure chemical- and photo-ionisation (APCI, APPI), and laser desorption ionisation (LDI) - were compared for the analysis of Scotch Whisky by FTICR MS. The differing sources provide complementary compositional information on the sample set, with APCI and LDI being most different to ESI in terms of compounds ionised and spectral profiles. Positive mode ionisation was also successful, but molecular formula assignment was hindered by insufficient resolving power. Late experimentation pushed the achievable resolving power to 2.8 million at m/z 400, however the required approach is significantly more time consuming and prone to signal quality degradation. Formula assignment software, both commercial, open source, and in-house developed, were compared. The commercial and published open source software provided essentially identical results for Scotch Whisky, and whilst the in-house tools assigned fewer species (a subset of those assigned by the other tools), they did so with a smaller mean error of assignment. Various analysis and visualisation tools for MS data of complex mixtures were also developed.

A cachaça é a segunda bebida alcoólica mais consumida no Brasil e vem ganhando espaço no mercado devido aos esforços do setor produtivo e também a ações governamentais. A produção de brasileira de cachaça é estimada em 1,7 bilhão de litros, sendo que cerca de 400 milhões são produzidas em alambiques. A cadeia produtiva não é tecnologicamente homogênea, havendo necessidade do desenvolvimento de tecnologias para aperfeiçoar e controlar a qualidade e a padronização da bebida. O objetivo do trabalho foi avaliar as curvas de volatilização dos principais compostos presentes em aguardente de cana, ao longo de um processo de dupla destilação, realizado em alambique simples, e quantificar a formação e recuperação de compostos voláteis típicos das frações cabeça, coração e cauda do destilado final, utilizando a metodologia da produção de whisky. Foram estudadas as curvas de volatilização dos componentes químicos do destilado ao longo da primeira e da segunda destilação, além da composição química das frações cabeça, coração (aguardente) e cauda produzidas durante o processo, seguindo as metodologias e critérios da legislação vigente no Brasil. Os resultados mostraram que a dupla destilação, baseada na metodologia utilizada para a produção de whisky, proporcionou a melhoria da qualidade química da aguardente de cana-de-açúcar, através da redução nos teores de cobre, acidez volátil, aldeídos e metanol, comparativamente à aguardente testemunha (monodestilada). As curvas de volatilização dos compostos químicos ao longo da destilação da aguardente duplamente destilada mostraram concentrações típicas dos componentes voláteis da fração cabeça (aldeídos, ésteres e metanol) e da fração cauda (acidez volátil e furfural). / The cachaça is the second most consumed beverage in Brazil and it has been gaining market share due to the efforts of the productive sector as well as governmental actions. The production of Brazilian cachaça is estimated at 1.7 billion liters, of which about 400 million are produced in stills. Production chain is not technologically homogeneous and there is need to develop technologies to improve and control the quality and standardization. The objective of this study was to evaluate the volatilization curves of the main compounds present in sugar cane spirits, during a process of double distillation carried out in pot still according the methodology for the production of whisky, and quantify the formation and recovery of volatile fractions of the typical \"head\", \"heart\" and \"tail\" of the final distillate. We studied the curves of volatilization of the chemical components of the distillate along the first and second distillation, and the chemical composition of fractions \"head\", \"heart\" (spirit) and \"tail\" produced during the process, following the methodologies and criteria of the current legislation in Brazil. The results showed that the double distillation, based on the methodology used for the production of whisky, enabled to improve the chemical quality of the sugar cane spirit by reducing the concentrations of copper, volatile acidity, aldehydes and methanol, when compared to the control spirit (single distilled). The volatilization curves of chemical compounds along the distillation of double distilled spirits showed concentrations typical of the volatile fraction of the \"head\" fraction (aldehydes, esters and methanol) and the \"tail\" fraction (volatile acid and furfural).

Thesis (doctoral)--Universität Münster, 2006. / Vita. Includes bibliographical references (p. 215-225).

Zweite Studienarbeit Hochschule für Angewandte Psychologie Zürich, 2005.

A cachaça é a segunda bebida alcoólica mais consumida no Brasil e vem ganhando espaço no mercado devido aos esforços do setor produtivo e também a ações governamentais. A produção de brasileira de cachaça é estimada em 1,7 bilhão de litros, sendo que cerca de 400 milhões são produzidas em alambiques. A cadeia produtiva não é tecnologicamente homogênea, havendo necessidade do desenvolvimento de tecnologias para aperfeiçoar e controlar a qualidade e a padronização da bebida. O objetivo do trabalho foi avaliar as curvas de volatilização dos principais compostos presentes em aguardente de cana, ao longo de um processo de dupla destilação, realizado em alambique simples, e quantificar a formação e recuperação de compostos voláteis típicos das frações cabeça, coração e cauda do destilado final, utilizando a metodologia da produção de whisky. Foram estudadas as curvas de volatilização dos componentes químicos do destilado ao longo da primeira e da segunda destilação, além da composição química das frações cabeça, coração (aguardente) e cauda produzidas durante o processo, seguindo as metodologias e critérios da legislação vigente no Brasil. Os resultados mostraram que a dupla destilação, baseada na metodologia utilizada para a produção de whisky, proporcionou a melhoria da qualidade química da aguardente de cana-de-açúcar, através da redução nos teores de cobre, acidez volátil, aldeídos e metanol, comparativamente à aguardente testemunha (monodestilada). As curvas de volatilização dos compostos químicos ao longo da destilação da aguardente duplamente destilada mostraram concentrações típicas dos componentes voláteis da fração cabeça (aldeídos, ésteres e metanol) e da fração cauda (acidez volátil e furfural). / The cachaça is the second most consumed beverage in Brazil and it has been gaining market share due to the efforts of the productive sector as well as governmental actions. The production of Brazilian cachaça is estimated at 1.7 billion liters, of which about 400 million are produced in stills. Production chain is not technologically homogeneous and there is need to develop technologies to improve and control the quality and standardization. The objective of this study was to evaluate the volatilization curves of the main compounds present in sugar cane spirits, during a process of double distillation carried out in pot still according the methodology for the production of whisky, and quantify the formation and recovery of volatile fractions of the typical \"head\", \"heart\" and \"tail\" of the final distillate. We studied the curves of volatilization of the chemical components of the distillate along the first and second distillation, and the chemical composition of fractions \"head\", \"heart\" (spirit) and \"tail\" produced during the process, following the methodologies and criteria of the current legislation in Brazil. The results showed that the double distillation, based on the methodology used for the production of whisky, enabled to improve the chemical quality of the sugar cane spirit by reducing the concentrations of copper, volatile acidity, aldehydes and methanol, when compared to the control spirit (single distilled). The volatilization curves of chemical compounds along the distillation of double distilled spirits showed concentrations typical of the volatile fraction of the \"head\" fraction (aldehydes, esters and methanol) and the \"tail\" fraction (volatile acid and furfural).

No description available.

De acordo com a legislação brasileira o uísque cortado é produzido com a mistura de, no mínimo, 30% de destilado alcoólico simples de malte envelhecido, com destilados alcoólicos simples de cereais envelhecidos ou não, e neste trabalho foi utilizada a quirera de arroz preto IAC-600 para produzir uísque, pois tem alto valor nutricional, propriedades antioxidantes e baixo custo. A quirera de arroz preto IAC-600 foi inicialmente hidrolisada em escala de bancada de 500mL seguindo o planejamento fatorial 23 completo, com seis experimentos no ponto central, analisando os parâmetros tempo, adição da enzima ProteMax N600® ou Maltezyn W® e a concentração das enzimas Brautec alfa TF® e Maltezyn W®. De acordo com a análise estatística, a melhor condição obtida na região estudada foi com a utilização de 1000mg de Brautec alfa TF®/kg de amido em base seca e 750mg de Maltezyn W®/kg de quirera de arroz preto IAC-600 em base seca a 95ºC por 30min, sendo adicionado posteriormente 500mg de Maltezyn W®/kg de quirera de arroz preto IAC-600 em base seca a 60ºC até a hidrólise do amido resultar em teste de iodo negativo, sendo esta condição utilizada em escala de bancada de 15L e em escala piloto de 125L. Em todas as fermentações com quirera de arroz preto IAC-600 adicionou-se 10g da enzima Panzyn GA®/hL de meio fermentativo, após a inoculação com a levedura. A levedura Saccharomyces cerevisiae, pré-tratada ou não a 40ºC/1h, foi utilizada na concentração de 0,4g peso seco/L de meio fermentativo. Em escala de bancada de 15 L os resultados de produtividade volumétrica em etanol, dos ensaios fermentativos com quirera de arroz preto IAC-600 e malte de cevada, com levedura pré-tratada ou não, não apresentaram diferença significativa. Portanto, nas fermentações das matérias-primas em escala piloto de 125L utilizou-se levedura sem pré-tratamento, e os fermentados obtidos foram destilados separadamente em alambique de 160L. O destilado alcoólico simples de malte de cevada que foi envelhecido aceleradamente por nove dias e o de quirera de arroz preto IAC-600 que não foi envelhecido foram misturados na proporção de 30% e 70%, e também 50% e 50%, respectivamente, resultando em dois uísques cortados a 40ºGL com o teor de polifenois de 141 e 229mg/L equivalente em ácido gálico, respectivamente. Estes dois uísques cortados foram analisados sensorialmente em relação a um uísque puro malte envelhecido 12 anos e um bourbon, encontrados no mercado mundial, por 125 provadores voluntários não treinados da EEL-USP. Considerando que o uísque cortado produzido com 50% de destilado alcoólico simples de malte de cevada envelhecido e 50% destilado alcoólico simples de quirera de arroz preto IAC-600 não envelhecido foi avaliado positivamente nos parâmetros cor e sabor quando comparado aos outros três uísques, e que não houve diferença significativa na aceitação global entre os quatro uísques avaliados, este uísque cortado possui potencial mercadológico como um produto novo, apresentando sabor diferenciado em relação aos dois uísques comerciais. Por outro lado, a análise descritiva quantitativa realizada por dez provadores treinados da Pernod Ricard, nos dois uísques produzidos neste trabalho, demonstrou que o processo de envelhecimento acelerado não forneceu os atributos aromáticos desejados, sendo necessário o aperfeiçoamento ou a substituição desta metodologia. / According to Brazilian law, the blended whisky is produced by mixing at least 30% of aged single malt distilled alcohol with aged or not single alcoholic distillates from cereal, and this study used broken IAC-600 black rice to produce whisky, due to its high nutritional value, antioxidant properties and low cost. The broken IAC-600 black rice was initially hydrolyzed at bench scale (500mL) following the 23 full factorial design with six assays at central point, analyzing the parameters time, addition of ProteMax N600® or Maltezyn W® enzymes and the concentration of the Brautec alfa TF® and Maltezyn W® enzymes. According to statistical analysis, the best condition obtained at the studied region was with1000mg Brautec alfa TF®/kg starch (dry basis) and 750mg Maltezyn W®/kg of broken IAC-600 black rice (dry basis) at 95°C for 30min. Subsequently, 500mg Maltezyn W®/kg of broken IAC-600 black rice was added at 60°C until starch hydrolysis results in negative iodine test, and this condition was used at bench scale (15L) and at pilot scale (125L). In all the fermentations with broken IAC-600 black rice 10g Panzyn GA®/hL of fermentative medium was added after the inoculation with the yeast. The Saccharomyces cerevisiae yeast, pretreated or not at 40°C/1h, was used at 0.4g dry weight/L of fermentative medium. At bench scale (15L), the results of ethanol volumetric productivity in the fermentation assays with broken IAC-600 black rice and barley malt with yeast, pre-treated or not, showed no significant difference. Therefore, in the raw materials fermentations at pilot-scale (125L), the yeast without pretreatment was used, and the obtained washes were separately distilled into 160L still. The single alcoholic distillate of barley malt that was rapidly aged for nine days and the broken IAC-600 black rice that was not aged were mixed at ratios of 30% and 70% and also 50% and 50%, respectively, obtaining two blended whiskies at 40ºGL with 141 and 229mg/L polyphenol contents equivalent to gallic acid, respectively. These two blended whiskies were sensory analyzed in relation to a 12 year-old pure malt whisky and to a bourbon found in the world market, by 125 volunteers untrained tasters of EEL-USP. Considering that the blended whisky produced with 50% of aged single alcoholic distillate of barley malt and 50% of not aged single alcoholic distillate of broken IAC-600 black rice was positively evaluated in color and taste parameters when compared to the other three whiskies, and that there was no significant difference in acceptability among the four whiskies evaluated, this blended whisky has marketing potential as a new product, presenting distinctive taste compared to the two commercial whiskies. In the other hand, the quantitative descriptive analysis made by ten trained tasters of Pernod Ricard about the two whiskies produced in this work showed that the process of rapid aging did not provide the desired aromatic attributes, requiring the improvement or substitution of this methodology.

De acordo com a legislação brasileira o uísque cortado é produzido com a mistura de, no mínimo, 30% de destilado alcoólico simples de malte envelhecido, com destilados alcoólicos simples de cereais envelhecidos ou não, e neste trabalho foi utilizada a quirera de arroz preto IAC-600 para produzir uísque, pois tem alto valor nutricional, propriedades antioxidantes e baixo custo. A quirera de arroz preto IAC-600 foi inicialmente hidrolisada em escala de bancada de 500mL seguindo o planejamento fatorial 23 completo, com seis experimentos no ponto central, analisando os parâmetros tempo, adição da enzima ProteMax N600® ou Maltezyn W® e a concentração das enzimas Brautec alfa TF® e Maltezyn W®. De acordo com a análise estatística, a melhor condição obtida na região estudada foi com a utilização de 1000mg de Brautec alfa TF®/kg de amido em base seca e 750mg de Maltezyn W®/kg de quirera de arroz preto IAC-600 em base seca a 95ºC por 30min, sendo adicionado posteriormente 500mg de Maltezyn W®/kg de quirera de arroz preto IAC-600 em base seca a 60ºC até a hidrólise do amido resultar em teste de iodo negativo, sendo esta condição utilizada em escala de bancada de 15L e em escala piloto de 125L. Em todas as fermentações com quirera de arroz preto IAC-600 adicionou-se 10g da enzima Panzyn GA®/hL de meio fermentativo, após a inoculação com a levedura. A levedura Saccharomyces cerevisiae, pré-tratada ou não a 40ºC/1h, foi utilizada na concentração de 0,4g peso seco/L de meio fermentativo. Em escala de bancada de 15 L os resultados de produtividade volumétrica em etanol, dos ensaios fermentativos com quirera de arroz preto IAC-600 e malte de cevada, com levedura pré-tratada ou não, não apresentaram diferença significativa. Portanto, nas fermentações das matérias-primas em escala piloto de 125L utilizou-se levedura sem pré-tratamento, e os fermentados obtidos foram destilados separadamente em alambique de 160L. O destilado alcoólico simples de malte de cevada que foi envelhecido aceleradamente por nove dias e o de quirera de arroz preto IAC-600 que não foi envelhecido foram misturados na proporção de 30% e 70%, e também 50% e 50%, respectivamente, resultando em dois uísques cortados a 40ºGL com o teor de polifenois de 141 e 229mg/L equivalente em ácido gálico, respectivamente. Estes dois uísques cortados foram analisados sensorialmente em relação a um uísque puro malte envelhecido 12 anos e um bourbon, encontrados no mercado mundial, por 125 provadores voluntários não treinados da EEL-USP. Considerando que o uísque cortado produzido com 50% de destilado alcoólico simples de malte de cevada envelhecido e 50% destilado alcoólico simples de quirera de arroz preto IAC-600 não envelhecido foi avaliado positivamente nos parâmetros cor e sabor quando comparado aos outros três uísques, e que não houve diferença significativa na aceitação global entre os quatro uísques avaliados, este uísque cortado possui potencial mercadológico como um produto novo, apresentando sabor diferenciado em relação aos dois uísques comerciais. Por outro lado, a análise descritiva quantitativa realizada por dez provadores treinados da Pernod Ricard, nos dois uísques produzidos neste trabalho, demonstrou que o processo de envelhecimento acelerado não forneceu os atributos aromáticos desejados, sendo necessário o aperfeiçoamento ou a substituição desta metodologia. / According to Brazilian law, the blended whisky is produced by mixing at least 30% of aged single malt distilled alcohol with aged or not single alcoholic distillates from cereal, and this study used broken IAC-600 black rice to produce whisky, due to its high nutritional value, antioxidant properties and low cost. The broken IAC-600 black rice was initially hydrolyzed at bench scale (500mL) following the 23 full factorial design with six assays at central point, analyzing the parameters time, addition of ProteMax N600® or Maltezyn W® enzymes and the concentration of the Brautec alfa TF® and Maltezyn W® enzymes. According to statistical analysis, the best condition obtained at the studied region was with1000mg Brautec alfa TF®/kg starch (dry basis) and 750mg Maltezyn W®/kg of broken IAC-600 black rice (dry basis) at 95°C for 30min. Subsequently, 500mg Maltezyn W®/kg of broken IAC-600 black rice was added at 60°C until starch hydrolysis results in negative iodine test, and this condition was used at bench scale (15L) and at pilot scale (125L). In all the fermentations with broken IAC-600 black rice 10g Panzyn GA®/hL of fermentative medium was added after the inoculation with the yeast. The Saccharomyces cerevisiae yeast, pretreated or not at 40°C/1h, was used at 0.4g dry weight/L of fermentative medium. At bench scale (15L), the results of ethanol volumetric productivity in the fermentation assays with broken IAC-600 black rice and barley malt with yeast, pre-treated or not, showed no significant difference. Therefore, in the raw materials fermentations at pilot-scale (125L), the yeast without pretreatment was used, and the obtained washes were separately distilled into 160L still. The single alcoholic distillate of barley malt that was rapidly aged for nine days and the broken IAC-600 black rice that was not aged were mixed at ratios of 30% and 70% and also 50% and 50%, respectively, obtaining two blended whiskies at 40ºGL with 141 and 229mg/L polyphenol contents equivalent to gallic acid, respectively. These two blended whiskies were sensory analyzed in relation to a 12 year-old pure malt whisky and to a bourbon found in the world market, by 125 volunteers untrained tasters of EEL-USP. Considering that the blended whisky produced with 50% of aged single alcoholic distillate of barley malt and 50% of not aged single alcoholic distillate of broken IAC-600 black rice was positively evaluated in color and taste parameters when compared to the other three whiskies, and that there was no significant difference in acceptability among the four whiskies evaluated, this blended whisky has marketing potential as a new product, presenting distinctive taste compared to the two commercial whiskies. In the other hand, the quantitative descriptive analysis made by ten trained tasters of Pernod Ricard about the two whiskies produced in this work showed that the process of rapid aging did not provide the desired aromatic attributes, requiring the improvement or substitution of this methodology.

Valuation draws heavily on the economic theory of demand. This tells us that users have preferences for water and are willing to pay different amounts for units of water put to different uses. Water should be allocated between these uses to the point that equalises the value of the last or 'marginal' unit. In other words, it is impossible to find a higher value for this marginal unit. Application of this principle of equi-marginal returns requires us to have some clarity about water values in competing uses. This is also important since water is rarely free to supply, and therefore suppliers need to charge a price that is in some sense equal to the supply cost and value to achieve full cost recovery. Even though inclusion of this economic rationale in the management of water resources has been a widely accepted principle, and is included in national and the EU policies, the actual practice does not fully reflect this endorsement. While many countries recognise the vital nature of water resources, few, if any, pursue a rigorous analysis of revealing the explicit value of water as a basis for determining whether water is actually being allocated to sectors in order to maximise its overall benefit to society. Aspiring to be the first Hydro Nation, maximising the social return from its water uses ought to be a policy objective in Scotland. This thesis constructs a portfolio of different water uses, estimating the approximate value for each and their current allocation in Scotland. This aims to stimulate an informed debate on actual allocation of water among different uses, relative values and trade-offs of these allocations in Scotland so that alternative allocation scenarios can also be discussed. I then focus on the valuation of water by manufacturing industries, the biggest consumptive use and a significant added value creator in Scotland. I investigate the factors that affect the valuation of water and the responsiveness to prices in manufacturing industries using a meta-analysis technique. These values are obviously not the same for each manufacturing sector due the nature of their use and value of their final output. Some sectors create premium value out of their use. The whisky industry stands out as a water-intensive and high value creating sector, as well as a vital contributor to the rural and overall Scottish economy. It is analysed here as the first case study using water footprint and marginal productivity analyses methods, both analyses highlighting the importance of quality and quantity of local water resources in Scotland and its value to the industry. The second case study is the livestock industry, which has been overlooked in the valuation of water use literature yet is significant for livelihoods in rural Scotland where reduced land capability limits agricultural production options. Following the portfolio of water uses, meta-analysis and case studies that analyse the current situation of value and allocation, I explore how the current situation can be improved through the application of tradability. Currently the main problem in Scotland is not the amount of water used or abstracted, but the pollution reaching water bodies as the result of run-off and leaching from agricultural fields. Therefore, the feasibility of trading water rights is more concerned with the permits to pollute rather than the rights to use. Using a linear optimisation I look into the potential of designing a payment for ecosystem services scheme based on tradability of water pollution in agricultural catchments that are affected by from diffuse pollution. The results indicate that trading schemes help reduce the cost of pollution to all users while creating additional income for farms. For constructing more precise pollution rights and robust schemes more research efforts are required.

This study investigates decision-making processes in respect to the maturation time and the marketed quantities of single malt whisky in a Swedish distillery start-up. At first, the literature regarding decision-making in both start-ups and larger organisations has been reviewed. It can be concluded that decision-making in start-ups, compared to their established counterparts, is more based on heuristics and continuously exposed to several biases. In the following, a general resource exploitation model is presented in the context of deterministic decision-making and adjusted towards whisky casks as deposits of nonrenewable resources. The consecutive case study is conducted in a Swedish distillery start-up. Findings indicate that the start-up is exposed to a high market dynamic and expert-knowledge is of high importance. In the start-up, these experts make decisions regarding the maturation times and the quantities of the marketed whisky. Nevertheless, the optimal exploitation model can be implemented into daily operations and delivers additional data for decisions. Planning can evolve from a mainly cost-based towards a profit-maximising perspective. However, the quality of the model results are expected to be limited, due to the deterministic nature of the model in a highly dynamic environment. This effect may be even amplified by input parameters, which cannot be precisely determined.Therefore, the industry knowledge of the decision-maker appears to be the most important factor for decision-making processes in this industry.