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The use of ion chromatography to detect adulteration of vodka and rum
Abstract
The use of ion chromatography to determine anions (chloride, nitrate, and sulphate) for the characterisation of colourless spirits, such as vodka or white rum, is presented. After evaporation to remove the volatiles, the sample was injected directly into the ion chromatograph. The assay showed good precision, never exceeding 1.6% RSD. The analytical results of 51 samples under study reveal that, in particular, the adulteration of brand spirits can be proven by the method described.
... Этим жидкостнохроматографическим методом контролируется в первую очередь качество воды, входящей в состав дистиллятов, сортировок и водок. Ионный состав ликёроводочной продукции жёстко привязан к конкретному производству и может служить маркером при её идентификации [33,34,60]. Для определения содержания катионов и анионов в водке и ликёроводочной продукции применяют ИХ с кондуктометрическим детектированием (ИХ-КМД) и химическим подавлением фоновой электропроводности. ...
... Данный метод позволяет детектировать ионы лития, натрия, аммония, калия, кальция, магния, стронция, бария, фторидов, хлоридов, нитритов, фосфатов, сульфатов и др. Так, в работе [60] показано, что контролируя состав анионов (Cl -, NO 3 -SO 4 -2 ) методом ИХ-КМД в бесцветных спиртных напитках, таких как водка или белый ром, после выпаривания летучих веществ можно установить, фальсифицирована или нет марка напитка. Был исследован 51 образец водок и ромов, установлено, что сумма солей колеблется в образцах от 0,3 до 150 мг/л (погрешность определений не превышала 1.6 %), показано, что в качественных легально произведённых образцах солей мало, в низкокачественных на три порядка выше. ...
... Вне рамок рассмотрения обзора остались электрохимические методы, которые самостоятельно применяются в контроле ионогенных микропримесей в водно-спиртовых системах. Эти методы реализуются в различных электрохимических детектирующих устройствах в ионной хроматографии и ВЭЖХ [8,55,60], в МСС, основанных на электрохимических сенсорах [8,64]. Не затронуты и ряд других инструментальных методов анализа, использованных в исследованиях винных напитков, приведенных, например, в [8], ввиду малой вероятности перспектив их широкого применения для анализа пищевого спирта. ...
19 апреля 2017 г., после доработки ‒ 07 сентября 2017 г. Дан краткий анализ нормативных документов, патентов, оригинальных статей, обзоров и мо-нографий, посвященных проблемам контроля качества и безопасности ректификованного этано-ла и дистиллятов. Выделено два принципиально различных тренда в развитии методов аналитиче-ского контроля примесей в этаноле. Это совершенствование покомпонентного контроля примесей с применением различных гибридных методов, поиск и определение компонентов-маркеров каче-ственной и фальсифицированной продукции. Другой тренд ‒ определение интегральных показате-лей с применением оптических, спектральных или сенсорных методов. Обсуждены традиционные методы и современные разработки в качественном и количественном анализе примесей в питье-вом этаноле с применением хроматографических, оптических, спектральных и сенсорных методов химического анализа. Отмечено, что наиболее широкое применение при идентификации образцов этанола по составу и содержанию микропримесей получил метод капиллярной газожидкостной хро-матографии с пламенно-ионизационным детектированием. Эффективным методом идентификации, перспективным для внедрения в аналитическую практику контроля качества и безопасности пище-вого этанола признана капиллярная газожидкостная хроматография с тандемным масс-спектроме-трическим детектированием. Хроматографические методы позволили надежно охарактеризовать основные микропримеси этанола различного генезиса. При мониторинге технологии брагоректи-фикации, розлива и хранения, при распознавании контрафакта, бракованных партий и фальсифи-кации могут успешно применяться также газовая хроматография в сочетании с ольфактометрией, парофазный анализ, пиролитическая хроматография, высокоэффективная жидкостная хромато-графия, ионная хроматография и капиллярный электрофорез. Отмечена высокая эффективность в идентификации спирта различного происхождения в водках методом спектрально-люминесцент-ного анализа. Показана перспективность применения в контроле спиртового производства элек-тронных мультисенсорных систем, позволяющих оценивать тип и интенсивность запаха и вкуса с помощью наборов химических сенсоров. Ключевые слова: этиловый спирт из пищевого сырья, идентификация микропримесей, ор-ганолептический анализ, хроматография, оптические и спектральные методы, химическая сенсо-рика, интегральные показатели качества For citation: Analitika i kontrol'
... Traditional raw materials for vodka production were cereals, especially maize and wheat (Lachenmeier et al. 2008;Art Maski Company 2010). Currently, other raw materials can be also found on the bottle labels: potatoes, molasses or sugar beet (Ng et al. 1996;Lachenmeier et al. 2003;Art Maski Company 2010). ...
... In addition to the source of sugar, water is another very important raw material which has to have low hardness and, prior to use, typically undergoes several purification steps (e.g. sand filtration, deep filtration or various membrane filtrations etc.) (Blecha 2008;Lachenmeier et al. 2003Lachenmeier et al. , 2008. However, the appropriate parameters cannot be achieved by boiling or distilling, since water would then acquire the so-called distillation off-flavour (Art Maski Company 2010). ...
... Contemporary production technologies achieve a high degree of alcohol purification resulting in only trace amounts of volatile substances. Since GC-FID does not enable to do an analysis of trace components and has a limited identification capability, analytical approaches with a higher potential for characterisation of alcoholic beverages are applied, such as isotope analysis (NMR or mass spectrometry based) or ion chromatography (Lachenmeier et al. 2003(Lachenmeier et al. , 2008. Quality vodka should contain a minimal amount of any organoleptic compounds, including volatiles. ...
Siříšťová L., Přinosilová Š., Riddellová K., Hajšlová J., Melzoch K. (2012): Changes in quality parameters of vodka filtered through activated charcoal. Czech J. Food Sci., 30: 474–482. The production technology of high-quality vodka used in Russia involves filtration through activated charcoal. To approach the quality of renowned Russian vodka, one prominent Czech spirit-producing company installed on its production premises a filtration device including a charcoal column, and launched test runs during which different filtration conditions were tested. Samples collected during the test runs were analysed by GC-FID and GC-MS with the aim to compare their composition; sensory analysis was an integral part of the evaluation. The results documented a positive effect of charcoal filtration on the quality of produced vodka, which was not reduced when higher flow rates were applied.
... Vodka is a "tasteless" and colorless spirit drink produced by fermentation and distillation of grain, potatoes, sugar beets, grapes, or cassava (1,2). Vodka is defined in the United States by the Code of Federal Regulations title 27, volume 1, to be: "neutral spirits so distilled, or so treated after distillation with charcoal or other materials, as to be without distinctive character, aroma, taste, or color". ...
... Gas chromatography is generally used to determine the impurity concentrations in vodka (2,18). Ion chromatography to detect anions in vodka was also reported by Lachenmeier et al. (1). However, the amount of useful information obtained from chromatography is limited by the design of columns and the setting of injection and chromatographic conditions (18). 1 H NMR has been used extensively to investigate the hydrogen bonding in distilled spirits and alcohol systems (19)(20)(21)(22)(23)(24). ...
... However, the amount of useful information obtained from chromatography is limited by the design of columns and the setting of injection and chromatographic conditions (18). 1 H NMR has been used extensively to investigate the hydrogen bonding in distilled spirits and alcohol systems (19)(20)(21)(22)(23)(24). According to Nose et al. (21,22) impurities such as salts, acids, and phenols strengthen hydrogen bonding in E-W solutions and Japanese sake. ...
... The charcoal adsorbs impurities that cannot be removed by distillation alone. The vodka is now reduced to its bottling strength by adding further demineralised water [19]. After a final filtration and bottling, the vodka will remain stable for many years if very well demineralised water is used. ...
... Savchuk et al. concluded that vodka is characterised by the ionic composition of the water used in its production [2]. In our previous study, we likewise found no significant differences in anion concentration between samples of the same brand but with different dates of bottling [19]. It is concluded that the relatively stable conductivity of each specific vodka allows an allocation or a differentiation of vodka brands. ...
... We previously determined that Russian vodkas had a significantly lower total anion concentration (mean 3.8 mg L À1 ) than the ones bottled in Germany (mean 78.4 mg L À1 ). Particularly low anion concentrations were determined in premium products, which are manufactured using ion exchange or reverse osmosis for deionisation [19]. In contrast, manufacturers of discount brands tend to bottle their vodkas with standard tap water without any further water treatment; therefore, those brands have higher ionic contents and conductivities. ...
Conductivity measurement is introduced as a rapid, simple and cheap way to identify counterfeit vodka. It was found that the
conductivity of vodka derives exclusively from its content of inorganic anions which were previously suggested as markers
for vodka authenticity using ion chromatographic determination. The conductivity of vodka is very stable between different
batches of bottle filling of the same brand, but there are large differences between different brands. Especially discount
brands have significantly higher conductivities than premium products. The applicability of conductivity measurement was demonstrated
in authentic forensic cases of brand fraud. A large advantage above other methods of authentication is the possibility to
conduct conductivity measurements with mobile meters directly in gastronomy.
... Vodka is a "tasteless" and colorless spirit drink produced by fermentation and distillation of grain, potatoes, sugar beets, grapes, or cassava (1,2). Vodka is defined in the United States by the Code of Federal Regulations title 27, volume 1, to be: "neutral spirits so distilled, or so treated after distillation with charcoal or other materials, as to be without distinctive character, aroma, taste, or color". ...
... Gas chromatography is generally used to determine the impurity concentrations in vodka (2,18). Ion chromatography to detect anions in vodka was also reported by Lachenmeier et al. (1). However, the amount of useful information obtained from chromatography is limited by the design of columns and the setting of injection and chromatographic conditions (18). 1 H NMR has been used extensively to investigate the hydrogen bonding in distilled spirits and alcohol systems (19)(20)(21)(22)(23)(24). ...
... However, the amount of useful information obtained from chromatography is limited by the design of columns and the setting of injection and chromatographic conditions (18). 1 H NMR has been used extensively to investigate the hydrogen bonding in distilled spirits and alcohol systems (19)(20)(21)(22)(23)(24). According to Nose et al. (21,22) impurities such as salts, acids, and phenols strengthen hydrogen bonding in E-W solutions and Japanese sake. ...
Although vodka is a reasonably pure mixture of alcohol and water, beverage drinks typically show differences in appeal among brands. The question immediately arises as to the molecular basis, if any, of vodka taste perception. This study shows that commercial vodkas differ measurably from ethanol-water solutions. Specifically, differences in hydrogen-bonding strength among vodkas are observed by (1)H NMR, FT-IR, and Raman spectroscopy. Component analysis of the FT-IR and Raman data reveals a water-rich hydrate of composition E x (5.3 +/- 0.1)H(2)O prevalent in both vodka and water-ethanol solutions. This composition is close to that of a clathrate-hydrate observed at low temperature, implying a cage-like morphology. A structurability parameter (SP) is defined by the concentration of the E x (5.3 +/- 0.1)H(2)O hydrate compared to pure ethanol-water at the same alcohol content. SP thus measures the deviation of vodka from "clean" ethanol-water solutions. SP quantifies the effect of a variety of trace compounds present in vodka. It is argued that the hydrate structure E x (5.3 +/- 0.1)H(2)O and its content are related to the perception of vodka.
... They indicated that the conductivity of vodka could be affected by additives that were used for water treatment and adjustment of alkalinity. Also, Lachenmeier et al. (34) found that there were no significant differences in anion concentrations between the same samples, which were bottled at different dates . Balcerzak and Kapica (29) analyzed formate by using the IC system. ...
... However, among the analyzed brands, some of the anion content was relatively bigger than the other anions, these amounts are not out of the limit values set by the authorities based on average consumption habits (7,11,14,18,20,22). Ionic composition of the water allows the differentiation of spirits, which are obtained from different manufacturers (34). If excellently demineralized soft water is used, the stability and sensory properties of drink will be improved. ...
A novel ion chromatography with suppressed conductivity detection method was developed for simultaneous determination of fluoride, acetate, formate, chloride, nitrate, and sulphate in distilled alcoholic beverages. In this study, bromide was used as an internal standard. The separation of the anions was accomplished by utilising an anion exchange column with gradient eluent program. The chromatographic conditions were as follows: the suppressor current was 31 mA; the flow rate of the mobile phase was 0.25 mL min-1; the column and detector compartment temperature were 35 °C and 40 °C, respectively; sample loop volume was 10 μL. All the calibration curves showed good linearity (r2 ≥ 0.999). The limits of detection (LOD) values were between 0.56 and 13.2 μg L-1 while the limits of quantification (LOQ) values were between 1.80 and 43.9 μg L-1. To evaluate the accuracy, a raki sample was spiked with standard solutions at three different concentration levels and the average recoveries were found in the range of 94.90% - 101.71%. Intra-day and inter-day precision studies were also investigated and the relative standard deviations (RSDs %) were less than 5.99%. The validated method was applied to the three kinds of commercial samples: Turkish raki, vodka, and gin.
... relabelling of cheap alcoholic beverages, sometimes including surrogate alcohols not originally intended for human consumption (Lachenmeier, Rehm, & Gmel, 2007)), but brand fraud has also been observed on a smaller scale in drinking venues such as bars and restaurants but especially in establishments that cheaply sell alcohol such as discotheques with flat-rate drinking offerings (Lachenmeier, 2016). In such cases often reported in Germany, the bar operator may refill the bottles of brand spirits with cheaper brands of the same type of spirit obtained from discount stores (Lachenmeier et al., 2003). Additionally, dilution of the brand spirits or cheaper spirits with water may occur. ...
... Several methods have been suggested for detection of adulterated spirits such as conductivity (Lachenmeier, Schmidt, & Bretschneider, 2008), ion chromatography (Lachenmeier, Attig, Frank, & Athanasakis, 2003), stable isotope ratio mass spectrometry (IRMS) (Kelly, 2003), portable alcohol IR sensors for rapid estimation of alcohol content (Lachenmeier et al., 2010), Fourier transform infrared (FT-IR) spectroscopy (Lachenmeier, Richling, López, Frank, & Schreier, 2005), gas chromatography (GC) and gas chromatographymass spectrometry (GC-MS) (De León-Rodríguez et al., 2008;MacKenzie & Aylott, 2004), ultra violet/visible (UV/Vis) spectroscopy (MacKenzie & Aylott, 2004), verification of tax stamps and electronic traceability systems (Lachenmeier, Taylor, & Rehm, 2011), and most recently nuclear magnetic resonance (NMR) spectroscopy (Monakhova et al., 2012;Neufeld et al., 2016;Hausler et al., 2016). ...
Beverage fraud involving counterfeiting of brand spirits is an increasing problem not only due to deception of the consumer but also because it poses health risks e.g. from possible methanol admixture. Suspicious spirit samples from Russia and Kenya were analysed using 1H nuclear magnetic resonance (NMR) spectroscopy in comparison to authentic products. Using linear regression analysis of spectral integral values, 4 counterfeited samples from Russia and 2 from Kenya were easily identifiable with R2 < 0.7. Sensory analysis using triangle test methodology confirmed significant taste differences between counterfeited and authentic samples but the assessors were unable to correctly identify the counterfeited product in the majority of cases. An important conclusion is that consumers cannot assumed to be self-responsible when consuming counterfeit alcohol because there is no general ability to organoleptically detect counterfeit alcohol.
... Small amounts of methanol can occur in commercial alcoholic drinks as a by-product of fermentation and distillation steps (5.2-85.6 mg/L in vodkas (Arbuzov and Savchuk 2002) and 3.1-4.6 mg/100 mL ethanol in rums (Lachenmeier et al. 2003)). Wide consumption of alcoholic beverages can make a source of formic acid for humans (Kapur et al. 2007). ...
... Such compounds can be consumed by microorganisms stimulating their regrowth. Simultaneous inorganic (cations and anions) multicomponent analytical results can make the basis of the differentiation in the originality of alcoholic products (Arbuzov and Savchuk 2002;Lachenmeier et al. 2003). Reliable determination of formates and acetates in the presence of inorganic anions requires careful optimization of the IC analytical procedure for effective baseline separation of formate, acetate, and fluoride signals exhibiting close retention times (Kontozova-Deutsch et al. 2008;Kontozova-Deutsch et al. 2011;Janiszewska and Balcerzak 2013). ...
Monitoring of human exposure to formic acid is important due to its high biological activity. Elevated amounts of formic acid in the human body can cause serious damage to optical nerve, respiratory failure, renal failure, deep metabolic acidosis, coma, and eventual death from cardiovascular arrest. Such symptoms are characteristic for methanol poisoning owing to rapid enzymatic conversion of methanol into formic acid of substantially higher than methanol alone toxicity. Early diagnosis of methanol consumed and formic acid produced is essential for successful medical treatment. Small amounts of methanol can be introduced into the human body with alcoholic drinks (methanol can be a by-product of distillation and fermentation processes). A fast method for the determination of formates in commercial alcoholic drinks by the use of suppressed ion chromatography (IC) with conductometric detection has been developed. The applicability of two anion-exchange columns, Metrohm Metrosep A Supp 7 and Dionex IonPac AS9-HC, for selective detection of formates in mixtures with acetates and common inorganic ions occurring in such kind of samples was examined. Quantitative isolation of formates from the matrix can be reached in less than 10 min using 3.6 mmol/L Na2CO3 as an eluent. Preliminary minimizing of alcoholic matrix by the evaporation (under IR source) allows to improve the quality of chromatographic results. The evaluated amounts of formates in two different Polish commercial products, “Absolwent vodka” and “Golden Rum,” tested in the work were in the range of 0.2–3.1 mg/L. The 96–107% recoveries of the formates from the examined samples were found out.
... This may be the case in large-scale counterfeiting (eg, relabeling of cheap alcohol types, sometimes including unrecorded alcohol types), but brand fraud has also been observed in gastronomy (especially in establishments that very cheaply sell alcohol such as discotheques with flat-rate drinking). In such cases, the bar operator may refill the bottles of brand spirits with cheaper brands of the same type of spirit (in Germany often from so-called discount stores) (Lachenmeier et al., 2003). Additionally, dilution of the brand spirits or cheaper spirits with some quantities of water may occur. ...
... In the case of vodka it was shown that the brand products had significantly lower conductivity than the discount products ( Fig. 21.5) (Lachenmeier et al., 2007b). The conductivity analyses can be confirmed in the laboratory using ion chromatography, as has been shown for brand confirmation in vodka and rum (Lachenmeier et al., 2003) or brandy (Lachenmeier and Attig, 2005). Figure 21.5 Brand authentication of vodka using portable conductivity measurement. ...
This chapter discusses methods for the detection and confirmation of the adulteration of alcoholic beverages, including wine, beer, spirits, and unrecorded alcohol. Unrecorded alcohol comprises illicitly produced alcohol and so-called surrogate alcohol not initially intended for human consumption (eg, industrial, cosmetic, or medicinal alcohol). Focus is set on the applicability of rapid-screening methodologies such as infrared or nuclear magnetic resonance spectroscopy, in complement to reference methodologies such as gas or liquid chromatography. Case studies regarding falsification of brand spirits, authentication of vintage wines and spirits, and methanol poisoning outbreaks are presented. The chapter concludes with remarks on future trends, such as the need for establishment of open-source databases with food authenticity data.
... A particular advantage of ion chromatography over traditional techniques is the capability for simultaneous determination of several species [17]. Ion chromatography has been shown to be a simple, fast method of proving identity or brand of many types of spirits on the basis of anion composition [18]. This will enable the testing of suspicions that arise during food control [18]. ...
... Ion chromatography has been shown to be a simple, fast method of proving identity or brand of many types of spirits on the basis of anion composition [18]. This will enable the testing of suspicions that arise during food control [18]. Ion chromatography is shown to be a simple, rapid and accurate method for the quantitative determination of fluoride, chloride, nitrate, phosphate and sulphate ions in green, black and white tea infusions [19]. ...
... Dazu wurde eine ionenchromatographische Methode entwickelt, die einfach, schnell und kostengünstig ist. Produkte unterschiedlicher Herkunft -z.B. russische und in Deutschland hergestellte Wodkas -konnten damit eindeutig identifiziert werden [1] ...
... Die von den Lebensmittelüberwachungsbehörden an-das CVUAKarisruhe übergebenen Weinbrandproben wurden mittels Ionenchromatographie nach ISO 10304-2 auf die Anionen Chlorid, Nitrat und Sulfat untersucht (Dionex DX-IOO System, Säule: IonPac AS4A, 4x250 mm) [1]. Daneben wurde eine organoleptische Untersuchung und eine chemische Analyse durchgeführt. ...
Bei Gaststättenkontrollen, die routinemäßig oder im Falle von Anzeigen gegen Gastwirte durchgeführt werden, stellt sich der Lebensmittelüberwachung die Aufgabe, neben einer sensorischen Prüfung auch chemisch-analytische Nachweise dafür zu liefern, daß dem Gast statt einer auf der Speisekarte aufgeführten teuren Markenspirituose (z.B. Smirnoff Wodka, Bacardi Rum, Asbach Uralt Weinbrand) ein billiges und u. U. minderwertigeres Produkt ausgeschenkt wird. Mit Hilfe der üblichen Me-thodik zur Unterscheidung von Spirituosen anhand der Zusammensetzung der leicht-flüchtigen Inhaltsstoffe (GC, GC-MS) kann vor allem bei Spirituosen mit niedrigen Gehalten an Gärungsalkoholen wie z.B. Wodka keine eindeutige Markenzuordnung getroffen werden. Aber auch bei extrakthaltigen Produkten wie Weinbrand ist die Unterscheidung anhand der Gärungsbegleitstoffe oft nur eingeschränkt möglich, besonders wenn Mischungen der Markenspirituose mit dem minderwertigen Produkt vorliegen. Für extraktfreie Spirituosen wie Wodka und weißer Rum konnte bereits gezeigt werden, daß ein eindeutiger Identitätsnachweis bzw. eine Markenzuordnung anhand der Anionenzusammensetzung möglich ist. Dazu wurde eine ionenchromatographische Methode entwickelt, die einfach, schnell und kostengünstig ist. Produkte unterschied-licher Herkunft -z.B. russische und in Deutschland hergestellte Wodkas -konnten damit eindeutig identifiziert werden [1]. Die Unterscheidungsmöglichkeit beruht darauf, daß Spirituosen aus hochprozentigen Destillaten hergestellt und mit Wasser auf Trinkstärke verdünnt werden. Je nach Anionengehalt des verwendeten Wassers und markenspezifischen Zusätzen zur Allcalitätseinstellung des Wassers sind charakteris-tische Unterschiede in der Anionenzusammensetzung festzustellen. In dieser Arbeit wurde die für extraktfreie Spirituosen entwickelte Methode auf extrakthaltige Spirituosen übertragen. Dazu wurde die Probenvorbereitung um einen Schritt ergänzt, bei dem störende Substanzen entfernt werden. Die Anwendbarkeit der Methode wird anhand der Markenzuordnung von Weinbrand demonstriert.
... Vodka is a tasteless and colorless alcoholic beverage fermented and distilled from grains, potatoes, beets, grapes or cassava [52]. In vodka production, the alcohol obtained from the fermentation and distillation processes undergoes further processing, such as charcoal or carbon filters. ...
Baijiu is a unique and traditional distilled liquor in China. Flavor plays a crucial rule in baijiu. Up to now, the research on the flavor of baijiu has progressed from the identification of volatile compounds to the research on key aroma compounds, but the release mechanism of these characteristic compounds is still unclear. Meanwhile, volatile compounds account for only a tiny fraction, whereas ethanol and water account for more than 98% of the content in baijiu. By summarizing the ethanol–water hydrogen bond structure in different alcoholic beverages, it was found that flavor compounds can affect the association strength of the ethanol–water hydrogen bond, and ethanol–water can also affect the interface distribution of flavor compounds. Therefore, the research on ethanol–water microstructure in baijiu is helpful to realize the simple visualization of adulteration detection, aging determination and flavor release mechanism analysis of baijiu, and further uncover the mystery of baijiu.
... It has unique characteristics compared to other whiskeys, and are dry and spicy (Lahne 2010). The raw spirit produced from the grains such as rye and wheat have been used for the manufacturing of the Vodka after rectification of the spirit (Lachenmeier et al. 2003). Benzoxazinoids is introduced in the barley-fermented beer by the addition of rye or wheat malt. ...
Gluten intolerance is one of the significant symptoms associated with different health disorders, which has become an increasing concern worldwide. A gluten-free diet is considered a curative product for the problem, which has been steadily increasing in the market. Gluten plays a key role in developing gluten-containing products with desired attributes. Elimination of gluten in staple food is not an easy task and it is difficult to provide the gluten-free product with similar characteristics as gluten-based products. Gluten-free products are produced from gluten-free cereals with different kinds of additives that modify the product according to the desired properties. Gluten-free cereals such as rice, sorghum, maize, and corn are some of the raw materials that are the major replacement cereals for producing gluten-free products. Fermentation is also an avital step in the preparation of the gluten-based product for attaining optimum texture and sensory properties. Sourdough fermentation is an important process employed in the fermentation of gluten-free products for creating resemblance with the gluten-based product. Lactic acid bacteria species have been mostly used in the fermentation process to produce gluten-free products of equivalent quality. Enzymes are also utilized in the production of non-gluten products such as gluten-free beer. The major drawbacks of gluten-free products include the cost of production, nutritional deficiency, and lack of simpler methods to produce the final products. Lack of nutrients in gluten-free products is due to the replacement of raw materials that can be recovered by the incorporation of nutrients from different sources such as vegetables and grains containing vitamins, minerals, and high-level dietary fiber. The modification of physical, chemical, and aromatic properties by the incorporation of additives also influences the final product quality. The future market scenario mainly depends on the adaptation of new lifestyle diets by the respective consumers for the respective abnormality and disease.
... The ionic composition is mainly represented by cations of sodium, potassium, calcium and magnesium and anions of chlorides, nitrates, phosphates and sulfates. Table 4 presents the ranges of mass concentrations of cations and anions of the studied samples and, for comparison, shows the ranges of the anionic composition of foreign vodkas (France, Germany, Italy) [5]. In the alcohol quality control system along with physicochemical methods of analysis, one of the leading positions is organoleptic analysis (OA), which includes determining the appearance (transparency, presence of foreign matter), color, smell, aroma (bouquet) and taste through the human senses. ...
The analysis of the regulatory documentation in the Russian industry of ethanol and vodka, overview of the main methods of finished products quality control are presented in this article. The generalized research data of vodka from different manufacturers are presented; the ranges of volatile components mass concentrations, the ionic composition of vodka and special vodka are given.
... Однако техническая сложность такого сочетания приводит к высокой стоимости приборов. Так, примерная стоимость прибора ВЭЖХ-МС/МС составляет около25 млн руб., а типовые жидкостные хроматографы в 2-3 раза более дорогие, чем газовые. Метод ВЭЖХ с УФД или СФД пригоден для контроля примесей с ароматическим кольцом (бензиловый спирт, 2-фенилэтанол, бензальдегид, бензойная кислота, фталаты, фураны, фурфурол) и широко применяется в химическом контроле слабоалкогольных напитков и вина, а также в оценке качества исходного сырья (сусла, бражки) [1, 2], для этого обычно применяют обращенно-фазовый вариант ВЭЖХ с водно-ацетонитрильными (метанольными, буферными) элюентами. ...
... Jamaican "heavy rums" typically made by batch distillation) [8]. The resulting distillate is diluted with pure demineralized water to obtain an alcohol percentage of around 35-40%, which is then aged in oak barrels previously used for whiskey or brandy production [9,10]. The aging step gives rum its characteristic flavor as a large number of new compounds emerge. ...
In this study, targeted and untargeted analyses based on headspace solid phase microextraction coupled to gas chromatography-mass spectrometry (HS-SPME-GC-MS) method were developed for classifying 33 different commercial rums. Targeted analysis showed correlation of ethyl acetate and ethyl esters of carboxylic acids with aging when rums of the same brand were studied, but presented certain limitations when the comparison was carried out between different brands. To overcome these limitations, untargeted strategies based on unsupervised treatments, such as hierarchical cluster analysis (HCA) and principal component analysis (PCA), as well as supervised methods, such as linear discriminant analysis (LDA) were applied. HCA allowed distinguishing main groups (with and without additives), while the PCA method indicated 40 ions corresponding to 13 discriminant compounds as relevant chemical descriptors for the correct rum classification (PCA variance of 88%). The compounds were confirmed based on the combination of retention indexes and low and high-resolution mass spectrometry (HRMS). Using the obtained results, LDA was carried out for the analytical discrimination of the remaining rums based on manufacturing country, raw material type, distillation method, wood barrel type and aging period and 94%, 91%, 92%, 95% and 94% of rums, respectively, were correctly classified. The proposed methodology has led to a robust analytical strategy for the classification of rums as a function of different parameters depending on the rum production process.
... Several studies have reported suitable methods for detecting adulteration of various food products, including analytical protein methods such as electrophoresis, immuno chemistry, and chromatography methods (EGITO et al., 2006;LACHENMEIER et al., 2003). According to SENTANDREU & SENTANDREU (2014), such methods have limitations regarding reproducibility and specificity and may generate ambiguous results. ...
The aim of the present study was to assess the efficacy ofmultiplex PCR in detecting the adulterationof commercially available ground beefvia addition and/orsubstitution ofground buffalo meat. Experimentally adulterated ground beefsamples were prepared in triplicate, and dilutions of DNA from Bos taurus and Bubalusbubalis were prepared to determine the detection limit of the method. Concurrently, 91 ground meatsamples sold as “ground beef” were collected from differentstores in northern Brazil andanalyzed bymultiplex PCR. Buffalo DNA was detected in 17.5% of the collected ground meat samples.Our results showed that multiplex PCR is an efficient method for detectingthe incorporation of groundbuffalo meatatpercentages ranging from 10 to 100% and the incorporation of beef at percentages ranging from0.1 to 100% intoground meat samples.
... Otros autores que han trabajado en bebidas destiladas son Lachenmeier y colaboradores, quienes han probado la detección de vodkas adulterados a partir de mediciones de conductividad [15], en tequilas y su control de calidad [16], la adulteración en vodka y rones [17], [18]. Estos trabajos representan un indicio fundamentado de que la investigación presentada en el artículo tiene realmente un futuro de aplicabilidad en la industria del ron en Cuba. ...
Several instrumental analytical techniques that are employed in food analysis produce a large amountof data. The employment of the multivariate analysis allows extracting the most important informationfrom these data efficiently. Supervised classification is primarily used to build classification rules fora number of known subgroups. New samples are then assigned to the most likely subgroup based onthese rules. The present work had as objective the application of two techniques of supervisedclassification, modeling independent class analysis (SIMCA) and partial least square discriminantanalysis (PLS-DA) to data of gas chromatography and acidity for 52 samples of aged Cuban rum, toachieve the dark aged rum classification among several aged rum analyzed in the Reference center ofdrinks and alcohols (CERALBE) of the Instituto Cubano de Investigaciones de los Derivados de laCaña de Azúcar (ICIDCA). The software UNSCRAMBLER v. 8.0 (CAMO ÅS, N-7401) was used. Themore important result obtained is that 100% of the samples of aged dark rum was very well classifiedby the SIMCA and by PLS-DA. The advantages and disadvantages of both methods are analyzed aswell as the future use of these models in the industry.
... Ion chromatography was also employed to detect falsified rum and vodka based on the analysis of chloride, nitrate and sulphate ions, and the sum of anions. This allowed for discriminating between Russian and German vodkas (Lachenmeier et al. 2003). Near infrared (NIR) spectroscopy was used for distinguishing the vodkas made in Fig. 2 Comparison of the principles of natural and artificial sense of taste Russia from those produced in other countries. ...
Vodka is the most popular alcoholic beverage in Poland, Russia and other Eastern European countries, made from ethyl alcohol of agricultural origin that has been produced via fermentation of potatoes, grains or other agricultural products. Despite distillation and multiple filtering, it is not possible to produce 100 % ethanol. The solution with a minimum ethanol content of 96 %, which is used to produce vodkas, also contains trace amounts of other compounds such as, esters, aldehydes, higher alcohols, methanol, acetates, acetic acid and fusel oil. Regarding that fact, it is very important to carry on research on the analysis of the composition and verifying the authenticity of the produced vodkas. This paper summarizes the studies of vodka composition and verifying the authenticity and detection of falsified products. It also includes the methods for analysing vodkas, such as: using gas, ion and liquid chromatography coupled with different types of detectors, electronic nose, electronic tongue, conductivity measurements, isotope analysis, atomic absorption spectroscopy, near infrared spectroscopy, spectrofluorometry and mass spectrometry. In some cases, the use of chemometric methods and preparation techniques were also described.
... Many studies classified and verified the adulteration of alcoholic beverages (Da Costa et al., 2004;Lachenmeier et al., 2003;Pontes et al., 2006;Sarvarova et al., 2011;Savchuk et al., 2001;Savchuk et al., 2007). The most evaluated compounds present in spirit drinks and other alcoholic beverages are phenolic and volatile compounds (Castro et al., 2008;Duran Guerrero et al., 2011;Korhonova et al., 2007;Madrera et al., 2005;Mangas et al., 1996;Schwarz et al., 2011;Versini et al., 2009). ...
Due to their high alcohol content, distilled spirits are not susceptible to microbial contamination. Because moulds were found in samples of vodka and spirit drinks, the present study was conducted to identify the sources of microbial contamination during the manufacturing process.
Total bacterial count (TBC), total yeast and mould count (TYMC) and total coliform count (TCC) were determined in water and from different processing area surfaces, TBC and TYMC in the air of processing areas and TYMC in distilled spirits samples. The source of microbial contamination of distilled spirits was microaeroflora from processing areas.
... With heightened international biosecurity and biodefence investment (Madden & Wheelis, 2003), it is expected that the intensive development of new technologies will provide new, more effective, quicker and less labour intensive methods both for validating the origin and tracing the movements of plant consignments and also for detecting and identifying pests. Innovations in labelling, e.g. using radio frequency identifi cation microchips, and analysis, using chemical and biochemical profi ling, will provide greater assurance in certifying the area of origin of plants and detecting fraudulent mixing or substitution (Lachenmeier et al., 2003). Visual inspection is increasingly likely to be complemented by alternative techniques. ...
International actions to combat the threat posed by invasive alien species (IAS) to crops and biodiversity have intensifi ed in recent years. The formulation of 15 guiding principles on IAS by the Convention on Biological Diversity (CBD) stimulated the International Plant Protection Convention (IPPC) to review its role in protecting biodiversity. IPPC standards now demonstrate clearly that the risks posed by any organism that is directly or indirectly injurious to cultivated or uncultivated plants can be assessed and managed under the IPPC. Since the IPPC, unlike the CBD, constitutes an international legal instrument recognised by the World Trade Organization, greater protection from the introduction of IAS is now available. However, phytosanitary measures can only be enacted if they can be justifi ed by risk analysis and we outline some novel strategies to improve the assessment and management of the risks posed by IAS, highlighting some of the key challenges which remain.
... Ethyl carbamate was determined using GC with tandem mass spectrometry (GC-MS/MS) (Lachenmeier et al., 2005). Anionic composition was analyzed using ion chromatography (Lachenmeier et al., 2003). Conductivity was measured using the procedure in Lachenmeier et al. (2007b). ...
The quality of home brewed beverages (e.g., ogogoro) in Nigeria has been a source of concern for some time. However, the composition of these beverages remains largely unknown. In this pilot study samples of surrogate alcohol from the southeastern parts of Nigeria were analyzed for alcohol concentration, composition of volatile and non-volatile components and water quality. The results showed that the samples contained concentrations of alcohol that were in agreement with those previously reported for ogogoro. However, the concentrations of other components (e.g., methanol, lead) were well below those associated with acute toxic effects. One sample contained an unknown additive and was being sold as an ‘antimalarial’. The implications of these findings are discussed.
... 12,13 Ethyl carbamate (urethane) was determined using GC with tandem mass spectrometry (GC-MS/MS). 14 Anionic composition 13,15 and conductivity 14,16 were measured. All samples were screened for unknown substances (including flavour compounds) using gas chromatography with mass spectrometry (GC-MS), 17 the GC/MS assay also included phthalates. ...
In the WHO region Europe, the average unrecorded adult per capita alcohol consumption was 2.67 L pure ethanol in 2005, which is 22% of the total consumption of 12.20 L. Despite concerns about potential health harms from the chemical composition of unrecorded alcohol, there are surprisingly few data on the problem in the European Region. This study reports the results from the Alcohol Measures for Public Health Research Alliance (AMPHORA) project, which assessed the quality of unrecorded alcohol in a Europe-wide study.
Samples of unrecorded alcohol were collected in 16 European countries and chemically analyzed for potentially health-relevant parameters. Thresholds for parameters were defined based on potential health hazards of daily drinking.
The average alcoholic strength of unrecorded wine products was 14.9% vol, and 47.8% vol in unrecorded spirits. One half of the samples (n=57) showed acceptable alcohol quality. The other half (n=58) showed one or several deficits with the most prevalent problem being ethyl carbamate contamination (n=29). Other problems included copper (n=20), manganese (n=16) and acetaldehyde (n=12). All other parameters (including methanol, higher alcohols, phthalates) were only seldom problematic (limit exceedance in less than 10 samples). The price of unrecorded alcohol was approximately 45% of the price of recorded alcohol.
The major problem regarding unrecorded alcohol appears to be ethanol itself, as it is often higher in strength and its lower price may further contribute to higher drinking amounts. Compared to the health effects of ethanol, the contamination problems detected may be of minor importance as exposure will only in worst-case scenarios reach tolerable daily intakes of these substances.
... Ethyl carbamate (urethane) is determined using GC with tandem mass spectrometry (GC-MS/MS) [40]. Anionic composition is analysed using ion chromatography [41]. Inorganic elements are analysed using semi-quantitative inductively coupled plasma mass spectrometry (ICP-MS) after evaporation of the sample and reconstitution in ultrapure water. ...
Some European countries with high levels of unrecorded alcohol consumption have anomalously high rates of death attributable to liver cirrhosis. Hepatotoxic compounds in illegally produced spirits may be partly responsible. Based on a review of the evidence on the chemical composition and potential harm from unrecorded alcohol, the Alcohol Measures for Public Health Research Alliance (AMPHORA) project's methodology for identifying, analysing and toxicologically evaluating such alcohols is provided.
A computer-assisted literature review concentrated on unrecorded alcohol. Additionally, we refer to our work in the capacity of governmental alcohol control authority and a number of pilot studies.
The risk-oriented identification of substances resulted in the following compounds probably posing a public health risk in unrecorded alcohol: ethanol, methanol, acetaldehyde, higher alcohols, heavy metals, ethyl carbamate, biologically active flavourings (e.g. coumarin) and diethyl phthalate. Suggestions on a sampling strategy for identifying unrecorded alcohol that may be most prone to contamination include using probable distribution points such as local farmers and flea markets for selling surrogate alcohol (including denatured alcohol) to focusing on lower socio-economic status or alcohol-dependent individuals, and selecting home-produced fruit spirits prone to ethyl carbamate contamination.
Standardized guidelines for the chemical and toxicological evaluation of unrecorded alcohol that will be used in a European-wide sampling and are applicable globally are provided. These toxicological guidelines may also be used by alcohol control laboratories for recorded alcohol products, and form a scientific foundation for establishing legislative limits.
... Ethyl carbamate (urethane) was determined using GC with tandem mass spectrometry (GC-MS/MS) (Lachenmeier et al., 2005a). Additionally, anionic composition (Lachenmeier et al., 2003) and conductivity (Lachenmeier et al., 2008a) were measured (mainly to characterize quality of the dilution water). Furthermore, all samples were screened for unknown substances using gas chromatography with mass spectrometry (GC-MS) (Ejim et al., 2007), the GC/MS assay also included diethyl phthalate (Leitz et al., 2009). ...
In 2005, approximately half of all alcohol consumption in Ukraine was unrecorded. This paper investigates the chemical composition of unrecorded and low-cost alcohol, including a toxicological evaluation. A sample of alcohol products (n=78) from both recorded and unrecorded sources was obtained mainly from eastern Ukraine, and chemically analyzed. Analysis entailed alcoholic strength, levels of volatile compounds (methanol, acetaldehyde, higher alcohols), ethyl carbamate, anions, and inorganic elements. The majority of unrecorded alcohol was homemade samohon with alcoholic strength averaging close to 40% vol. A limited number of samples, advertised for medicinal purposes, were identified with high alcoholic strengths (above 60% vol.). Single samples showed contamination with acetaldehyde and ethyl carbamate above the levels of toxicological concern. Metal contamination was frequent, with copper levels above 2mg/l in 33 samples, and zinc above 5mg/l in 10 samples. Overall, however, the composition of unrecorded samples did not raise major public health concerns other those for ethanol. The priority of alcohol policy in Ukraine should be the general reduction of alcohol consumption with a specific focus on that from small-scale home production. Further research is needed on potential mitigative measures and the origin of the metal contamination in particular alcoholic beverages.
... Ethyl carbamate (urethane) was determined using GC with tandem mass spectrometry (GC-MS/MS) [32]. Anionic composition was analyzed using ion chromatography [33]. Conductivity was measured using the procedure outlined in Lachenmeier et al. [34] . ...
Four homemade (artisanally manufactured and unrecorded) and seven commercial (industrially manufactured and taxed) alcohol products from Vietnam were collected and chemically analyzed for toxicologically relevant substances. The majority of both types had alcohol contents between 30 and 40% vol. Two homemade samples contained significantly higher concentrations of 45 and 50% vol. In one of these homemade samples the labeled alcoholic strength was exceeded by nearly 20% vol. All other analyzed constituents of the samples (e.g., methanol, acetaldehyde, higher alcohols, esters, metals, anions) were found in concentrations that did not pose a threat to public health. A peculiarity was a homemade sample of alcohol with pickled snakes and scorpions that contained 77% vol of alcohol, allegedly used as traditional Chinese medicine. Based on this small sample, there is insufficient evidence to conclude that alcohol quality, beyond the effects of ethanol, has an influence on health in Vietnam. However, future research with larger samples is needed.
... A screening for toxic metals was conducted using semi-quantitative inductively coupled plasma mass spectrometry (ICP-MS) after evaporation of the sample and re-constitution in ultrapure water (limit of detection 0.001 mg/l). Anionic composition was analyzed using ion chromatography (Lachenmeier et al., 2003). Conductivity was measured using the procedure outlined in Lachenmeier et al. (2008a). ...
There is a lack of knowledge regarding the composition, production, distribution, and consumption of artisanal alcohol, particularly in the developing world. In Nahualá, an indigenous Mayan municipality located in highland Guatemala, heavy alcohol consumption appears to have had a significant negative impact on health, a major role in cases of violence and domestic abuse, and a link to street habitation. Cuxa, an artisanally, as well as commercially produced sugarcane alcohol, is widely consumed by heavy drinkers in this community. Cuxa samples from all distribution points in the community were obtained and chemically analyzed for health-relevant constituents and contaminants including methanol, acetaldehyde, higher alcohols, and metals. From those, only acetaldehyde was confirmed to be present in unusually high levels (up to 126 g/hl of pure alcohol), particularly in samples that were produced clandestinely. Acetaldehyde has been evaluated as "possibly carcinogenic" and has also been identified as having significant human exposure in a recent risk assessment. This study explores the reasons for the elevated levels of acetaldehyde, through both sampling and analyses of raw and intermediary products of cuxa production, as well as interviews from producers of the clandestine alcohol. For further insight, we experimentally produced this alcohol in our laboratory, based on the directions provided by the producers, as well as materials from the town itself. Based on these data, the origin of the acetaldehyde contamination appears to be due to chemical changes induced during processing, with the major causative factors consisting of poor hygiene, aerobic working conditions, and inadequate yeast strains, compounded by flawed distillation methodology that neglects separation of the first fractions of the distillate. These results indicate a preventable public health concern for consumers, which can be overcome through education about good manufacturing practices, as well as financial incentives to separate the acetaldehyde-rich fractions during distillation.
... Ethyl carbamate (urethane) was determined using GC with tandem mass spectrometry (GC-MS ⁄ MS) (Lachenmeier et al., 2005a). Anionic composition was analyzed using ion chromatography (Lachenmeier et al., 2003). Inorganic elements were analyzed using semiquantitative inductively coupled plasma mass spectrometry (ICP-MS) after evaporation of the sample and reconstitution in ultrapure water. ...
The research aimed to study the quality of cheap alcohol products in Poland. These included unrecorded alcohols (i.e., home-produced or illegally imported), estimated to constitute more than 25% of total consumption and fruit wines.
A sample of alcohol products (n = 52) was collected from local markets and chemical analyses were conducted. The parameters studied were alcoholic strength, volatiles (methanol, acetaldehyde, and higher alcohols), ethyl carbamate, inorganic elements, and food additives including preservatives, colors, and sweeteners. The compositions of the beverages were then toxicologically evaluated using international standards.
With the exception of 1 fortified wine, the unrecorded alcohols were home-produced fruit-derived spirits (moonshine) and spirits imported from other countries. We did not detect any nonbeverage surrogate alcohol. The unrecorded spirits contained, on average, 45% vol of alcohol. However, some products with considerably higher alcoholic strengths were found (up to 85% vol) with no labeling of the content on the bottles. These products may cause more pronounced detrimental health effects (e.g., liver cirrhosis, injuries, some forms of malignant neoplasms, alcohol use disorders, and cardiovascular disease) than will commercial beverages, especially as the consumer may be unaware of the alcohol content consumed. Fruit wines containing between 9.5 and 12.2% vol alcohol showed problems in terms of their additive content and their labeling (e.g., sulfites, sorbic acid, saccharin, and artificial colors) and should be subjected to stricter control. Regarding the other components investigated, the suspected human carcinogens, acetaldehyde and ethyl carbamate, were found at levels relevant to public health concerns. While acetaldehyde is a typical constituent of fermented beverages, ethyl carbamate was found only in home-produced unrecorded alcohols derived from stone fruits with levels significantly above international guidelines.
The contamination of unrecorded alcohols with ethyl carbamate should be analyzed in a larger sample that also should include legal alcoholic beverages. Furthermore, the impacts of unrecorded alcohol on the health of people with lower socioeconomic status should be studied in detail. Overall, given the extent of the alcohol-attributable disease burden in Poland, the highest priority should be given to the problem of ethanol and its very high content in unrecorded alcohol products.
... Additional details on the GC-FID procedure are published elsewhere [16]. Anionic composition was analysed using ion chromatography [17]. ...
To describe the consumption, distribution, production and chemical composition of alcohol, including cuxa (pronounced 'coo sha'), in Nahualá, a highland Mayan municipality in Guatemala. Cuxa is a sugarcane-derived spirit, in part produced clandestinely, that has been distributed in the community for several decades.
Key informant interviews with alcohol distributors and consumers, cuxa producers and health professionals, as well as analyses of questionnaires from a sample of 47 spouses who came to the local health centre for problems related to their husband's drinking. Sampling and chemical analysis of cuxa from 12 of 13 identified sales points in the head-town of Nahualá and its nearby settlements (10 km radius). Fieldwork was conducted between November 2007 and March 2008.
Alcohol consumption was found to be integrated culturally in this community. The overall drinking culture was marked by irregular heavy drinking occasions, especially around market days, with substantial inebriation and health problems, especially among street inhabiting drinkers. Cuxa contributed to these problems, and cuxa drinking was socially stigmatized. Cuxa was produced both clandestinely and industrially, and sold legally by taverns and illegally by clandestine distributors. The alcoholic strength of the samples was typically between 17 and 19% vol.; clandestinely produced cuxa samples showed acetaldehyde contamination.
Measures should be taken to reduce the harm associated with alcohol in this community, including efforts to reduce acetaldehyde levels in cuxa.
... Ethyl carbamate (urethane) was determined using GC with tandem mass spectrometry (GC-MS/MS) (Lachenmeier et al., 2005a). Anionic composition was analysed using ion chromatography (Lachenmeier et al., 2003). Conductivity was measured using the procedure outlined inLachenmeier et al. (2008a). ...
The rates of alcohol-attributable mortality in Lithuania and Hungary have been shown to be higher than those in most other European countries. Quality of alcohol products is investigated as a possible explanation.
In a descriptive pilot study, a convenience sample of alcohol products was collected from local city markets in both countries (Lithuania n = 10, Hungary n = 15) and chemical analyses, including some that have not been done in prior studies, were conducted. The parameters studied were alcoholic strength, volatiles (methanol, acetaldehyde, higher alcohols), ethyl carbamate, anions (including nitrate) and inorganic elements (including lead). Additionally, a multi-target screening analysis for toxicologically relevant substances was conducted.
The majority of samples (64%) had an alcohol content between 35% vol. and 40% vol., being in accordance with the typical strength of legal spirits in Europe. Three samples containing significantly higher concentrations of alcohol above 60% vol. were found to be unrecorded alcohol products, defined as any alcohol that is outside of legal and taxed production. Screening analysis showed that those samples contained various flavourings, including the hepatotoxic substance coumarin, at concentrations above the legal limit for foods. All other substance classes under study were found to be at levels of no toxicological concern.
Although some problems with the quality of the alcohol samples were found, there is insufficient evidence from this pilot study to conclude that alcohol quality has an influence on health as reflected in alcohol-attributable mortality rates. Given the extent of alcohol-attributable disease burden in central and eastern European countries, future research should focus on collection of large, representative samples, particularly of unrecorded sources, which was the most problematic product group in our study.
The market value of distilled beverage relies on its quality with a major contribution of distinctive and fascinating aromas. The aroma of distilled beverage is built on the basis of chemical components and can be modified through a series of physical and chemical processes such as aging. Revealing the hidden knowledge behind the evolution of numerous chemical components during these physicochemical processes in distilled beverages is not only significant but also challenging due to its complex system. In this review, the trends in the changes of associated aroma compounds over aging are proposed on the basis of understanding the relationship between chemical components and aroma profiles of numerous typical distilled beverages. The different aging systems, both classical platforms from Eastern countries (pottery jars) to Western countries (wood barrels), and modern platforms such as artificial aging technologies are outlined and compared with their respective applications. Optimizing aging processes is a challenging but imperative step, which warrants further fundamental knowledge from targeting aging-related molecules to the exploration of multitude physicochemical reaction mechanisms that occur during this process, such as the formation of potent odorant compounds in specific containers and environments, as well as mass transfer processes between solid and liquid interfaces. Understanding these maturation mechanisms of distilled beverages expressed by chemosensory signature holds promise for major improvements in future aging technologies that can efficiently yield stable and high-quality products.
An artificial neural network was used to build models caple of predicting and quantifying vodka adulteration with methanol and/or tap water. A voltammetric electronic tongue based on gold and copper microelectrodes was used, and 310 analyses were performed. Vodkas were adulterated with tap water (5 to 50% (v/v)), methanol (1 to 13% (v/v)), and with a fixed addition of 5% methanol and tap water varying from 5 to 50% (v/v). The classification model showed 99.5% precision, and it correctly predicted the type of adulterant in all samples. Regarding the regression model, the root mean squared error was 3.464% and 0.535% for the water and methanol addition, respectively, and the prediction of the adulterant content presented an R2 0.9511 for methanol and 0.9831 for water adulteration.
Wine and other alcoholic beverages are susceptible to fraud and adulteration due to their complex nature, high values, and extensive global supply chains. Fraud can take place at several points in the production process as well as throughout the supply chain. In addition to wine, other alcoholic beverages that are susceptible to fraud include vodka, rum, and whiskey. There are several methods of fraud that are commonly committed with alcoholic beverages, including dilution with water, addition of ingredients, and mislabeling. For example, diethylene glycol has been illegally added to wine to improve sweetness, but this compound is harmful to consumers’ health. There are multiple methods available for the detection of fraud in alcoholic beverages, including stable isotope analysis, chromatography, and nuclear magnetic resonance. This chapter provides an overview of fraud associated with wine and other alcoholic beverages, including case studies, detection methods, and future trends.
This chapter describes the ion chromatography theory and applications in detail. At present, there are three main separation methods in ion chromatography, including Ion chromatography (IC), Ion exclusion chromatography (IEC), and Ion pair chromatography (IPC). The stationary phases used in ion chromatography are also known as ion exchangers. The stationary-phase type in the analytical column and the detection method constitute the first two most important aspects affecting the separation quality. Eluents are the third factor. Bromate determinations with ion chromatography can be divided into three method groups: direct, indirect, and hyphenated methods. IC-ICP-MS and IC-MS constitute the final group of the bromate determination methods, that is, hyphenated techniques. Such systems provide very good detectability, precision, and limits of quantifications. Ion chromatography can be used to determine: trace amounts of anions and cations in high-purity water; inorganic anions in mineral acids; anions and cations in mineral water and sea water.
quantify methanol, a spurious adulterant in alcoholic beverages, attenuated total reflectance (ATR) technique is used. Synthetic samples (100) are prepared for developing a suitable calibration model. Spectra are recorded for all samples in wavelength region 4000-600 cm(-1) using Bio-Rad 175 C FTS spectrophotometer in ATR mode. Calibration equation is obtained using partial least squares (PLS) method. Correlation coefficient and root mean square error values for methanol are R-cal(2): 0.9860, R-val(2): 0.9839 and RMSEC: 0.0470, RMSEV: 0.0505. Spectral measurement is done for 10 samples and their methanol concentration (0.5-2.5%) is predicted using the developed calibration model. The reliability and repeatability of spectroscopic technique may be appreciated by the agreement between ATR predicted results to those of actual values.
Spirit drinks are food products and represent a major outlet for the agricultural industry all over the world. This outlet is largely the result of the flavour quality and reputation these products have acquired on the world market over hundreds of years; various national and international legal decrees, standards, and specifications lay down rules on the definition, description, and presentation of the different categories of spirit drinks [1-4] which can be separated in two main categories, distilled spirits and liqueurs. Distilled spirits have alcoholic strengths between 30 and 50% v/v and are produced by distillation from fermented agricultural products containing carbohydrates; their flavour is not only characterised by aroma compounds originating from the raw material and the alcoholic fermentation, but also from distillation, storage, and ageing. Liqueurs are spirits with a minimum ethanol content of 15% v/v and a sugar content of 100 g L-1; they are produced by flavouring ethanol of agricultural origin, distillates of agricultural origin, or one or more spirit drinks with natural plant materials such as herbs, fruits, fruit juice, cream, chocolate, steam-distilled essential oils, distilled spirit drinks, or natural or artificial flavouring extracts.
Steigende Anforderungen an lebensmittelanalytische Laboratorien erfordern eine immer rationellere Arbeitsweise. Vor allem bei Probenvorbereitung und Datenauswertung gibt es Potenziale, Arbeitsschritte zu automatisieren. Zuverlässige Screeningmethoden helfen, den Probendurchsatz zu steigern.
An automatic flow-batch analyzer is proposed for detection of adulteration in distilled spirits (whiskey, brandy, cachaça, rum and vodka) using UV-Vis spectrophotometry. The analyzer was employed to dilute the non-adulterated samples and to simulate adulteration with addition of 5 and 10% (v/v) of water, ethanol or methanol. SIMCA (soft independent modelling of class analogies) classification models were built using spectra of non-adulterated and adulterated samples in the region of 235-355 nm. By applying the SIMCA models to a test set, all adulterated and non-adulterated samples were correctly discriminated at a confidence level of 95% with an analytical throughput larger than 120 samples per hour.
The authenticity of some mixed drinks like vodka or rum was correlated to the conductivity of the dilution water. Authentic drinks demonstrated low conductivity suggesting the use of treated water whereas fraud drinks were mixed with regular tap water. The objective of the present study was to test if this criterion is valid for distilled anis or in other words, ouzo. Several Greek distilled anis samples, mostly ouzo samples, were tested for different parameters including conductivity, pH, and percentage of different alcohol constituents. Since ouzo in Greece is commonly produced by small enterprises, no correlation between conductivity and the size of the producer was possible. Neither it was possible to correlate the price or high consumption with conductivity and thus, prior water treatment. Alcohol quality in terms of undesirable constituents -- such as methanol - content was good and comparable among samples. In ouzo, water is related to the producer quality goal for the final product and thus, it is treated and used accordingly.
Bei der Überprüfung der Authentizität alkoholischer Getränke im offenen Ausschank muss die auf der Flasche bzw. Speisekarte angegebene Marke bestätigt oder ausgeschlossen werden. Als einfaches und schnelles Screening-Verfahren kann dazu eine Leitfähigkeitsmessung durchgeführt werden. Diese führt zu signifikanten Ergebnissen, weil hochwertige Premiumprodukte durch umfangreiche Wasseraufbereitungsmaßnahmen eine deutlich geringere Leitfähigkeit aufweisen als häufig zur Verfälschung eingesetzte Discount-Produkte. Eine Absicherung des Befundes kann mittels ionenchromatographischer Bestimmung der Anionengehalte erfolgen.
While in Europe vodka is mainly derived from potatoes or cereals, a large proportion of Brazilian vodka is likely obtained from sugarcane, which contains ethyl carbamate (EC) precursors. EC, in addition to several other contaminants and congeners, were investigated in 32 samples of Brazilian vodka. All samples complied with the Brazilian regulations for congeners and contaminants, having EC content below 0.01 mg/L (detection limit). These results are probably related to the processing of vodka, in particular the use of extractive and rectifying stainless steel distillation columns, which allow the production of high strength spirits with low levels of congeners and contaminants.
The objective of this study was to determine the potential of using near infrared (NIR) transmission spectroscopy to build calibration models for the quantitative characterisation and qualitative discrimination of Russian and non-Russian (foreign) vodkas. The results of partial least squares models based on the NIR spectra of 109 vodka samples showed that the major constituent alcoholic strength [root mean square error of prediction (RMSEP) 0.25% vol] and the physical parameter relative density (RMSEP 0.0003) could be successfully determined quantitatively. The method failed, however, in quantifying certain minor components such as anions, cations and sugars. For qualitative discrimination, soft independent modelling of class analogy analysis (SIMCA) and linear discriminant analysis (LDA) were applied to the sample set containing both the Russian and the foreign vodkas. Despite the correct assignment of unknown test samples to the respective vodka species, both modelling approaches, however, did not prove reliable enough for unambiguous authentication purposes.
This work describes the preparation of aromatised liquors using deodorised and concentrated fruit distillates. The raw spirits were improved by making a partial deodorisation, using activated charcoal, followed by concentration, using a distiller. The liquors were prepared by a maceration process. The procedure is exemplified using fig distillates to prepare myrtle berry liquors. The acidity, copper, polyphenol and anthocyanin indexes and volatile and anthocyanin profiles were monitored in each preparation step. The concentration process increased the ethanol proof to 75% v/v and decreased the acidity and the copper content. The partial deodorisation decreased the levels of high molecular weight volatiles, while the content of lower molecular weight compounds that contribute to flavour was maintained. Delphinidin-3-O-glucoside, cyanidin-3-O-glucoside, petunidin-3-O-glucoside and malvidin-3-O-glucoside were the major anthocyanins.
The origin of the raw spirits influences the sensory quality of rectified spirits that are subsequently used for the production of vodka. The aim of this research was to evaluate the effectiveness of two methods based on the comparison of profiles of volatile compounds [solid phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) and gas chromatography with flame ionisation detection (GC-FID)] for the determination of origin of raw spirits obtained from rye, corn (maize) and potato.
Profiles obtained for the volatile compounds by using these methods were different and were influenced by the sample introduction method. The main groups of volatiles obtained using SPME-GC-MS method were fatty acid ethyl esters, while in the case of GC-FID fusel alcohols and ethyl acetate dominated. Data obtained from these methods were treated using principal component analysis and linear discriminant analysis to test the possibility of sample differentiation and classification. It was relatively easy to differentiate potato spirits from the remainder; however, it was not possible to fully distinguish the corn samples from rye samples. The classification ability of the SPME-GC-MS method was 95% but the prediction ability was 97.4%. For the GC-FID method the classification ability was 90.1%, whereas the prediction ability was 94.27%.
The methods presented can be used for reliable differentiation of potato spirits from corn and rye spirits. Copyright © 2012 Society of Chemical Industry.
Principal component analysis (PCA) was applied to the chromatographic and spectroscopic data of authentic Mexican tequilas (n = 14) and commercially available samples purchased in Mexico and Germany (n = 24). The scores scatter plot of the first two principal components (PC) of the anions chloride, nitrate, sulfate, acetate, and oxalate accounting for 78% of the variability allowed a classification between tequilas bottled in Mexico and overseas; however, no discrimination between tequila categories was possible. Mexican products had a significantly (p = 0.0014) lower inorganic anion concentration (range = 1.5-5.1 mg/L; mean = 2.5 mg/L) than the products bottled in the importing countries (range = 3.3-62.6 mg/L; mean = 26.3 mg/L). FTIR allowed a rapid screening of density and ethanol as well as the volatile compounds methanol, ethyl acetate, propanol-1, isobutanol, and 2-/3-methyl-1-butanol using partial least-squares regression (precisions = 5.3-29.3%). Using PCA of the volatile compounds, a differentiation between tequila derived from "100% agave" (Agave tequilana Weber var. azul, Agavaceae) and tequila produced with other fermentable sugars ("mixed"tequila) was possible. The first two PCs describe 89% of the total variability of the data. Methanol and isobutanol influenced the variability in PC1, which led to discrimination. The concentrations of methanol and isobutanol were significantly higher (methanol, p = 0.004; isobutanol, p = 0.005) in the 100% agave (methanol, 297.9 +/- 49.5; isobutanol, 251.3 +/- 34.9) than in the mixed tequilas (methanol, 197.8 +/- 118.5; isobutanol, 151.4 +/- 52.8).
A large collection (n = 95) of Mexican Agave spirits with protected appellations of origin (Tequila, Mezcal, Sotol, and Bacanora) was analyzed using ion and gas chromatography. Because of their production from oxalate-containing plant material, all Agave spirits contained significant concentrations of oxalate (0.1-9.7 mg/L). The two Tequila categories ("100% Agave" and "mixed") showed differences in the methanol, 2-/3-methyl-1-butanol, and 2-phenylethanol concentrations with lower concentrations in the mixed category. Mezcal showed no significant differences in any of the evaluated parameters that would allow a classification. Sotol showed higher nitrate concentrations and lower 2-/3-methyl-1-butanol concentrations. Bacanora was characterized by exceptionally high acetaldehyde concentrations and a relatively low ethyl lactate content. The methanol content was the most problematic compound regarding the Mexican standards: two Tequilas (4%), five Sotols (31%), and six Bacanoras (46%) had levels above the maximum methanol content of 300 g/hL of alcohol. In conclusion, the composition of Mexican Agave spirits was found to vary over a relatively large range.
Based on the UV-vis absorption spectra of commercially bottled tequilas, and with the aid of multivariate analysis, it is proved that different brands of white tequila can be identified from such spectra, and that 100% agave and mixed tequilas can be discriminated as well. Our study was done with 60 tequilas, 58 of them purchased at liquor stores in various Mexican cities, and two directly acquired from a distillery. All the tequilas were of the "white" type, that is, no aged spirits were considered. For the purposes of discrimination and quality control of tequilas, the spectroscopic method that we present here offers an attractive alternative to the traditional methods, like gas chromatography, which is expensive and time-consuming.
The use of gas chromatography (GC), gas chromatography–mass spectrometry (GC–MS), and UV–VIS spectrophotometry for identifying the falsification of strong alcoholic beverages (vodka, gin, cognac, and whiskey) was considered. In the GC analysis of ethyl alcohol and vodkas based on it, the test alcohol was assigned to synthetic alcohol or to biochemically produced alcohol using a set of typical impurities, markers of the alcohol nature, which present in the test alcohol in a certain ratio and can be determined by GC or GC–MS analysis. The multicomponent analysis of cognacs and related liquors can reveal the replacement of cognac spirit with alcohol produced from nongrape raw materials, to determine whether the cognac spirit was in contact with oak wood and how long was the duration of its aging, and to detect the falsification of the age by adding certain ingredients. The limitations of chromatographic and spectrometric analytical techniques in the identification of adulterated alcoholic beverages was demonstrated. The validation criteria for testing the identification of alcoholic beverage components by chromatographic techniques received special attention.
This review covers mainly publications that appeared in Analytical Abstracts (Royal Society of Chemistry) from January 1990 to February 2001. The number of publications on this topic continues to grow, and during the past three years (1998-2000) about 150 reviews and/or overviews have been published in the area of food. Numerous techniques and food matrices or chemical components are presented and discussed in these reviews. The present review is intentionally limited to eight techniques or classes of techniques and intends to be a "technique by technique" presentation of "what was used" or "what is used" to characterize food products and to detect their possible adulteration. The present review focuses on the following techniques: microscopic analysis; HPLC; GC, GC-(MS, FTIR); UV-visible spectrophotometry; AAS/AES, ICP-(AES, MS); IRMS, GC-IRMS, GC-C-IRMS; DSC; IR, mid-IR, and NMR (202 references). Emphasis is placed as much as possible on chemometrical treatment of analytical data, which are commonly used to achieve the final objective, either food characterization or adulteration detection. Finally, a brief description is given of the new generation of analytical systems that combine powerful analytical techniques and powerful computer software for a best extraction of the information from analytical data.
The efficiency of the application of ion-chromatographic analysis in distillery production is evaluated. A method for determination of inorganic anions that makes it possible to reduce substantially the duration of analysis in comparison with other methods with good metrological characteristics is developed and tested.
The use of ion chromatography for analysis of Fe, Cd, Co, Mn, Cu, Ni, Pb, and Zn in vodka and liqueur products is demonstrated. A method is developed that involves steps of preconcentration, separation using a sulfo cation exchanger, and postcolumn reaction with spectrophotometic detection. The results of ion-chromatographic determination are in good agreement with the data of atomic-absorption analysis.
Bromate ion occurs during ozonation of bromide-containing waters. The current WHO guideline for bromate ion is 25 μg/L. Bromate analysis in drinking waters can be performed by various techniques. However, given the commonly low concentrations of bromate ion found in drinking waters, the classical methods do not fit for bromate analysis in most cases.A specific conductimetric method with anion suppression which enhances analyte detection by lowering the eluent conductivity is described in this paper for low bromate level analysis. Three eluents have been tested in order to have the best signal to noise ratio. Some other parameters likely to interfere in bromate ion detection (nitrate and sulfate in particular) are also investigated. Taking into account the results of three interlaboratory trials between six European laboratories, a 2 μg/L detection level for bromate can be established.
Gas chromatography and the determination of natural isotope ratios are powerful analytical methods which can be used to check
the authenticity of alcoholic beverages and to detect any adulteration. To check the origin and the authenticity of commercial
fruit spirits, whiskies, etc., 197 samples were analysed by gas chromatography, 2H-NMR and 13C isotope mass spectrometry. The discrimination between different varieties was demonstrated by bivariate and multivariate
discriminant analysis using different concentrations of volatile compounds such as methanol, butan-1-ol, 2- and 3-methyl-butanol,
benzaldehyde and hexanol as well as isotopic data like (D/H)I, (D/H)II and 13C/12C isotopomers of ethanol. The results show that by using multivariate discriminant analysis it is possible to distinguish
not only between different groups of spirits, e.g. those made of stone-fruit, malaceous fruit, grain and corn, but also between
individual varieties, such as cherry, plum, mirabelle and apple. If the detection of highly rectified ethyl alcohol of agricultural
origin and the identification of its raw materials are required, then natural isotope ratios are the only discriminant analytical
parameters available.
A reliable method for the characterisation of vodkas has been developed by application of solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GCMS). Sixty-four samples of commercial Canadian and American vodkas, and one sample each of Japanese and German vodkas, were investigated in this study. The procedure yielded reproducible chromatographic profiles. The detected components were ethyl esters of C8 to C18 fatty acids at μg litre−1 levels, various additives and contaminants. Distinctive profiles were observed for various brands. Markers for differentiating between Canadian and American vodkas were identified. The results of this study indicate that vodkas are differentiated by the combined effects of the original raw materials, any added substances, and differences in processing.
The aim was to achieve a simple method or methods by which different countries' and regions' brands of whisky, brandy and
rum could be identified on the basis of chemical composition, ultraviolet-visible (UV-vis) absorption, and/or pH. The analytical
results were processed statistically using principal components analysis. To determine whether the concentrations of chemical
components in a particular brand remain constant, samples of batches bottled over a period of 3–4 years and those bottled
within the same year were compared. In study 1 (14 whiskies, 7 rums and 9 brandies) the main distinguishing factors among
the three categories of beverages were the UV-vis absorbances at 220, 275, 360 and 440 nm, concentrations of four fermentation
alcohols and ethyl acetate, and pH. In study 2 (27 whiskies and 2 rums), brands could be identified on the basis of the concentrations
of five fermentation alcohols and ethyl acetate. Even though it was possible to distinguish brandy from whisky and rum without
quantitative component analysis, whisky and rum clusters could not be clearly separated from each other or by brand on the
basis of pH and absorbances at discrete wavelengths. UV spectra of whiskies, rums, and brandies were recorded and compared
statistically. Whisky brands could not be differentiated but it was possible to distinguish among brands of rum and brandy.
Vodka samples from various distilleries were analyzed by ion chromatography in combination with gas chromatography for the identification of alcoholic products. It was shown that vodkas of the same name manufactured at the same distillery exhibited relatively stable anion–cation compositions; therefore, the ionic composition of vodka can serve as an identification feature. The use of methanol, 2-propanol, and 1-propanol concentrations, which were determined by gas chromatography, as identification features of vodka enhances the probability of detecting adulterated alcoholic products.
A review of the applications of ion chromatography (IC) to the determination of inorganic ions in food is presented. The most promising sample preparation techniques, such as accelerated solvent extraction, supercritical fluid extraction, solid-phase extraction, UV photolysis, microwave-oven digestion and pyrohydrolysis are discussed. Among the various inorganic anions, nitrogen, sulphur and phosphorus species and halides are widely determined in foods and to a lesser extent only, cyanide, carbonate, arsenic and selenium species are considered. IC determination of inorganic cations deals with ammonium ion, alkali, alkaline-earth, heavy and transition metals particularly and only a small amount of literature is found on the other ones, like aluminium and plantinum. A particular advantage of IC over traditional techniques is the simultaneous determination of several species.
The time period covered for this review includes articles published from 1997 to 1999, with the addition of a few classic references. The purpose of the review is to include the most relevant works from each topic area of the determination of inorganic anions by ion chromatography, including new sample pretreatments, new separation methods, new detection systems and the latest applications in the field of environmental, water, foods, etc. samples. Experimental conditions such as stationary phase, eluent, detection mode, as well as matrix are summarized in a table.
Fatty acid ethyl esters are the main components of rum aroma and play an important sensorial impact in these distilled alcoholic beverages. Herein, a method for analysing these volatile compounds is described. It involves a separation and concentration step using headspace solid-phase microextraction and determination by capillary gas chromatography using flame ionisation detection. The influence of different parameters related to the isolation and concentration step, such as ethanol concentration, ionic strength, sample volume, time and temperature of extraction, was studied. The developed method enabled recoveries >91% for the analyzed compounds with limits of detection between 0.007 and 0.027 mg/l, all of them lower than the range of concentrations found in rum samples. The method was successfully applied to the analysis of fatty acid ethyl esters in different commercial white rums.
Qualitätssicherung, Organisation und Analysenmethoden
- W Frank
- Sa Savchuk
- Vn Vlasov
- Sa Appolonova
- Vn Arbuzov
- An Vedenin
- Ab Mezinov
- Grigor 'yan
- Br
Savchuk SA, Vlasov VN, Appolonova SA, Arbuzov VN,
Vedenin AN, Mezinov AB, Grigor'yan BR (2001) J Anal Chem
56:214–231
ISO 10304–2 Water quality—Determination of dissolved anions by liquid chromatography of ions—part 2: Determination of bromide, chloride, nitrate, nitrite, orthophosphate and sulphate in waste water 21
International Organisation for Standardisation (1995) ISO
10304–2 Water quality—Determination of dissolved anions
by liquid chromatography of ions—part 2: Determination of
bromide, chloride, nitrate, nitrite, orthophosphate and sulphate
in waste water
21. European Commission (2000) Off J Eur Comm L333:20–46
- Vn Arbuzov
- Sa Savchuk
Arbuzov VN, Savchuk SA (2002) J Anal Chem 57:428–433
- European Council
European Council (1989) Off J Eur Comm L160:1–17
- L-K Ng
- M Hupø
- J Harnois
- D Moccia
Ng L-K, HupØ M, Harnois J, Moccia D (1996) J Sci Food Agric
70:380–388
- On Obrezkov
- Va Tolkacheva
- Gi Zaikanova
- Va Yamnikov
- Ov Krokhin
- Oa Shpigun
Obrezkov ON, Tolkacheva VA, Zaikanova GI, Yamnikov VA,
Krokhin OV, Shpigun OA (1997) Ind Lab Diagn Mat 63:71–73
- Wa Simpkins
Simpkins WA (1985) J Sci Food Agric 36:367–376
- C Cordella
- I Moussa
- Ac Martel
- N Sbirrazzuoli
- L Lizzani-Cuvelier
Cordella C, Moussa I, Martel AC, Sbirrazzuoli N, Lizzani-
Cuvelier L (2002) J Agric Food Chem 50:1751–1764
Extraktfreie und extraktarme Spirituosen (ed) Spirituosen-Technologie. Behr's Verlag
- G Ströhmer
Ströhmer G (2002) Extraktfreie und extraktarme Spirituosen.
In: Kolb E (ed) Spirituosen-Technologie. Behr's Verlag,
Hamburg, Germany, pp 56–153
- On Obrezkov
- Va Tolkacheva
- Gi Zaikanova
- Va Yamnikov
- Ov Krokhin
- Sp Zhukov
- Oa Shpigun
Obrezkov ON, Tolkacheva VA, Zaikanova GI, Yamnikov VA,
Krokhin OV, Zhukov SP, Shpigun OA (2000) Ind Lab Diagn
Mat 66:18–21
- Pj Lehtonen
- La Keller
- Et Ali-Mattila
Lehtonen PJ, Keller LA, Ali-Mattila ET (1999) Z Lebensm
Unters Forsch A 208:413–417
- C Bauer-Christoph
- H Wachter
- Christoph N Roßmann
- A Adam
Bauer-Christoph C, Wachter H, Christoph N, Roßmann A,
Adam L (1997) Z Lebensm Unters Forsch A 204:445–452
- Pl Buldini
- S Cavalli
- A Trifiro
Buldini PL, Cavalli S, Trifiro A (1997) J Chromatogr A
789:529–548