Dirk W Lachenmeier is Certified Food Chemist and Laboratory Head at the Chemical and Veterinary Investigation Laboratory (CVUA) of Karlsruhe. He holds a doctorate in Forensic Toxicology from the University of Bonn. His multi-facetted interdisciplinary research interests span from Food Science and Technology, Legal and Forensic Medicine and Toxicology to Biochemistry, Analytical Chemistry and Chemometrics. Dr. Lachenmeier authored more than 50 peer-reviewed publications.
Abstract: The aim of this work was to analyse the furan concentrations in coffee products targeted to adolescents and to estimate the health risk for those consumers by using the consumption data of the Dortmund Nutritional and Anthropometric Longitudinally Designed Study (DONALD). Three different kinds of coffee beverages were analysed: 'coffee ready to drink' (i.e. industrially manufactured and packaged products available in cans or plastic cups), 'coffee instant' (i.e. soluble coffee in powder form) and 'coffee from coffee chains' (i.e. freshly prepared coffee sampled on-site). Furan was analysed according to the US Food and Drug Administration (USFDA) method using headspace-GC-MS and quantification with standard addition. The lowest furan concentrations were found within the category 'coffee instant', with an average of 4.6 µg kg(-1), followed by the category 'coffee ready to drink', with an average of 41.3 µg kg(-1), while the products from the coffee chains showed the highest concentrations, on average 100.5 µg kg(-1). According to the obtained furan contents, it seems that the highest furan exposure for adolescents is generally given in the consumption of products within the category 'coffee from coffee chains', while the lowest is given in the category 'coffee instant'. Risk assessment based on the margin of exposure (MOE) approach showed that in different consumption scenarios except for consumers of instant coffee, the MOE lay below 10,000, a range that is judged to be of public health relevance. The lowest MOE was found for consumers in the age group 10-12 years (especially females) and for both sexes in the age group 16-18 years.
Abstract: Sage tea, the aqueous infusion of dried sage leaves (Salvia officinalis L.), is used as a form of food as well as a form of traditional herbal medicine. Several in vivo and in vitro studies point to sage polyphenols as active principles that may inhibit lipid peroxidation and improve antioxidant defences. This study describes an UHPLC methodology with MS/MS and UV detection, which allows the separation, identification and quantification of the major phenolic constituents in sage tea within 34 min, and was used to characterize 16 commercial brands of sage tea.The quantitatively dominating compounds were either rosmarinic acid (12.2–296 mg/l) or luteolin-7-o-glucuronide (37.9–166 mg/l) [corrected].In general, considerable differences in polyphenolic composition between the brands were detected, leading to the demand for quality standardization and control, especially if these sage teas are to be used for therapeutic purposes.
Abstract: The use of thujone, a monoterpene ketone often present in sage (Salvia officinalis L.) or wormwood (Artemisia absinthium L.), for the treatment of diabetes mellitus was recently suggested in a study published in this journal. Evidence was based on the findings obtained in a diabetic rat model. After oral treatment with thujone (5 mg/kg bodyweight (bw)/day for 28 days), the cholesterol and triglyceride levels were significantly adjusted to normal levels when compared to diabetic, untreated rats. While these results sound promising and worthy of further investigation, the well-defined profile of the adverse properties of thujone demands a cautious interpretation of these results. The therapeutic margin of thujone appears to be small, as a dose-related incidence of seizures was noted in 2-year National Toxicology Program studies in rats and mice. The dose level in the diabetic rat study is also considerably higher than a daily intake that is acceptable for humans (0.1 mg/kg bw/day).
Abstract: The 400 MHz (1)H NMR analysis of alcoholic beverages using standard pulse programs lacks the necessary sensitivity to detect minor constituents such as methanol, acetaldehyde or ethyl acetate. This study investigates the application of a shaped pulse sequence during the relaxation delay to suppress the eight (1)H NMR frequencies of water and ethanol (the OH singlet of both water and ethanol, as well as the CH(2) quartet and CH(3) triplet of ethanol). The sequence of reference measurement for frequency determination followed by the suppression experiment is controlled by a macro in the acquisition software so that a measurement under full automation is possible (12 min per sample total time). Additionally, sample preparation was optimized to avoid precipitation, which is facilitated by 1:1 dilution with ethanol and pH 7.4 buffer. Compared with the standard water presaturation pulse program, the eightfold suppression allowed a significantly higher setting of receiver gain without receiver overflow, which significantly increased the signal-to-noise ratio by an average factor of 10. The signal intensities increased by a factor of 20. The resulting limits of detection (below 1 g/hl of pure alcohol) now allow the control of legal requirements for minor compounds in alcoholic beverages.
Abstract: A strategy for analyzing formaldehyde in beer, wine, spirits, and unrecorded alcohol was developed, and 508 samples from worldwide origin were analyzed. In the first step, samples are qualitatively screened using a simple colorimetric test with the purpald reagent, which is extremely sensitive for formaldehyde (detection limit 0.1 mg/L). 210 samples (41%) gave a positive purpald reaction. In the second step, formaldehyde in positive samples is confirmed by quantitative spectrophotometry of the chromotropic acid-formaldehyde derivative combined with Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS). Calculation of UV-VIS and (13)C NMR spectra confirmed the monocationic dibenzoxanthylium structure as the product of the reaction and disproved the widely cited para,para-quinoidal structure. Method validation for the spectrophotometric procedure showed a detection limit of 0.09 mg/L and a precision of 4.2-8.2% CV. In total, 132 samples (26%) contained formaldehyde with an average of 0.27 mg/L (range 0-14.4 mg/L). The highest incidence occurred in tequila (83%), Asian spirits (59%), grape marc (54%), and brandy (50%). Our survey showed that only 9 samples (1.8%) had formaldehyde levels above the WHO IPCS tolerable concentration of 2.6 mg/L.
Abstract: A novel approach to derive a threshold dose with respect to alcohol-related harm, the benchmark dose (BMD) methodology, is introduced to provide a basis for evidence-based drinking guidelines. This study is the first to calculate a BMD for alcohol exposure using epidemiological cohort data. With this BMD we will be able to calculate the margin of exposure (MOE) for alcohol consumption, which can be used for comparative risk assessment and applied to setting public health policy.
Abstract: Sage (Salvia officinalis L.) is used as an herbal medicinal product, with the most typical form of application as infusion with boiling water (sage tea). The well-established traditional uses include symptomatic treatment of mild dyspeptic complaints, the treatment of inflammations in the mouth and the throat, and relief of excessive sweating and relief of minor skin inflammations. In this study, sage teas prepared from commercially available products were chemically analyzed for polyphenolic content using liquid chromatography, for antioxidant potential using the oxygen radical absorbance capacity method, and for the Folin-Ciocalteu (FC) index. The sage teas showed a high variation for all parameters studied (up to 20-fold differences for rosmarinic acid). Univariate and multivariate analyses showed that the antioxidant potential, which varied between 0.4 and 1.8 mmol trolox equivalents/100 mL, was highly dependent on rosmarinic acid and its derivatives. The FC index also showed a high correlation to these polyphenols, and could therefore be used as a screening parameter for sage tea quality. The considerable differences in polyphenolic composition and antioxidant capacity between the brands lead to a demand for quality standardization, especially if these sage teas are to be used for therapeutic purposes. Further research also appears to be necessary to characterize the dose-benefit relationship, as sage may also contain a constituent (thujone) with potentially adverse effects.
Abstract: Acetaldehyde (ethanal) is a genotoxic carcinogen, which may occur naturally or as an added flavour in foods. We have developed an efficient method to analyze the compound in a wide variety of food matrices. The analysis is conducted using headspace (HS) gas chromatography (GC) with flame ionization detector. Using a robot autosampler, the samples are digested in full automation with simulated gastric fluid (1 h at 37°C) under shaking, which frees acetaldehyde loosely bound to matrix compounds. Afterwards, an aliquot of the HS is injected into the GC system. Standard addition was applied for quantification to compensate for matrix effects. The precision of the method was sufficient (<3% coefficient of variation). The limit of detection was 0.01 mg/L and the limit of quantification was 0.04 mg/L. 140 authentic samples were analyzed. The acetaldehyde content in apples was 0.97 ± 0.80 mg/kg, orange juice contained 3.86 ± 2.88 mg/kg. The highest concentration was determined in a yoghurt (17 mg/kg). A first-exposure estimation resulted in a daily acetaldehyde intake of less than 0.1 mg/kg bodyweight from food, which is considerably lower than the exposures from alcohol consumption or tobacco smoking.
Abstract: According to the World Health Organization, the public health impact of illicit alcohol and informally produced alcohol should be reduced. This paper summarizes and evaluates the evidence base about policy and intervention options regarding unrecorded alcohol consumption.
Abstract: An increasing body of evidence now implicates acetaldehyde as a major underlying factor for the carcinogenicity of alcoholic beverages and especially for oesophageal and oral cancer. Acetaldehyde associated with alcohol consumption is regarded as 'carcinogenic to humans' (IARC Group 1), with sufficient evidence available for the oesophagus, head and neck as sites of carcinogenicity. At present, research into the mechanistic aspects of acetaldehyde-related oral cancer has been focused on salivary acetaldehyde that is formed either from ethanol metabolism in the epithelia or from microbial oxidation of ethanol by the oral microflora. This study was conducted to evaluate the role of the acetaldehyde that is found as a component of alcoholic beverages as an additional factor in the aetiology of oral cancer.
Abstract: Analytical methods based on spectroscopic techniques were developed and validated for the determination of diethyl phthalate (DEP) and polyhexamethylene guanidine (PHMG), which may occur in unrecorded alcohol. Analysis for PHMG was based on UV-VIS spectrophotometry after derivatization with Eosin Y and (1)H NMR spectroscopy of the DMSO extract. Analysis of DEP was performed with direct UV-VIS and (1)H NMR methods. Multivariate curve resolution and spectra computation methods were used to confirm the presence of PHMG and DEP in the investigated beverages. Of 22 analysed alcohol samples, two contained DEP or PHMG. (1)H NMR analysis also revealed the presence of signals of hawthorn extract in three medicinal alcohols used as surrogate alcohol. The simple and cheap UV-VIS methods can be used for rapid screening of surrogate alcohol samples for impurities, while (1)H NMR is recommended for specific confirmatory analysis if required.
Abstract: 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.
Abstract: 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.
Abstract: Nontargeted 400 MHz (13)C and (1)H nuclear magnetic resonance (NMR) spectroscopy was used in the context of food surveillance to reveal Pinus species whose nuts cause taste disturbance following their consumption, the so-called pine nut syndrome (PNS). Using principal component analysis, three groups of pine nuts were distinguished. PNS-causing products were found in only one of the groups, which however also included some normal products. Sensory analysis was still required to confirm PNS, but NMR allowed the sorting of 53% of 57 samples, which belong to the two groups not containing PNS species. Furthermore, soft independent modeling of class analogy was able to classify the samples between the three groups. NMR spectroscopy was judged as suitable for the screening of pine nuts for PNS. This process may be advantageous as a means of importation control that will allow the identification of samples suitable for direct clearance and those that require further sensory analysis.
Abstract: 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.
Abstract: Thujone is a natural substance found in plants commonly used in foods and beverages, such as wormwood and sage, as well as in herbal medicines. The current limits for thujone in food products are based on short-term animal studies from the 1960s, which provided evidence for a threshold-based mechanism, yet only allowed for the derivation of preliminary values for acceptable daily intakes (ADI) based on the no-observed effect level (NOEL). While the 2008 European Union Regulation on flavourings deregulated the food use of thujone, the European Medicines Agency introduced limits for the substance in 2009. The present study re-evaluates the available evidence using the benchmark dose (BMD) approach instead of NOEL, and for the first time includes data from a long-term chronic toxicity study of the National Toxicology Program (NTP). The NTP data provide similar results to the previous short-term studies. Using dose-response modelling, a BMD lower confidence limit for a benchmark response of 10% (BMDL10) was calculated as being 11 mg/kg bw/day for clonic seizures in male rats. Based on this, we propose an ADI of 0.11 mg/kg bw/day, which would not be reachable even for consumers of high-levels of thujone-containing foods (including absinthe). While fewer data are available concerning thujone exposure from medicines, we estimate that between 2 and 20 cups of wormwood or sage tea would be required to reach this ADI, and view that the short-term medicinal use of these herbs can also be regarded as safe. In conclusion, the evidence does not point to any need for changes in regulations but confirms the current limits as sufficiently protective for consumers.
Abstract: Seeds of the opium poppy plant are legally sold and widely consumed as food. Due to contamination during harvesting, the seeds can contain morphine and other opiate alkaloids. The objective of this study is to review the toxicology of poppy seed foods regarding influence on opiate drug tests. Computer-assisted literature review resulted in 95 identified references. Normal poppy seed consumption is generally regarded as safe. During food processing, the morphine content is considerably reduced (up to 90%). The possibility of false-positive opiate drug tests after poppy food ingestion exists. There are no unambiguous markers available to differentiate poppy food ingestion from heroin or pharmaceutical morphine use. This is also a problem in heroin-assisted maintenance programs. A basic requirement in such substitution programs is the patients' abstinence from any other drugs, including additional illicit heroin. Also a lack of forensic ingestion trials was detected that consider all factors influencing the morphine content in biologic matrices after consumption. Most studies did not control for the losses during food processing, so that the initial morphine dosage was overestimated. The large reduction of the morphine content during past years raises questions about the validity of the "poppy seed defence." However, a threshold of food use that would not lead to positive drug tests with certainty is currently unavailable. Research is needed to prove if the morphine contents in today's foods still pose the possibility of influencing drug tests. Future trials should consider processing-related morphine losses.
Abstract: ABSTRACT: BACKGROUND: Ever since Gay-Lussac's time, the alcoholic strength by volume (% vol) has been determined by using densimetric measurements. The typical reference procedure involves distillation followed by pycnometry, which is comparably labour-intensive and therefore expensive. At present, infrared (IR) spectroscopy in combination with multivariate regression is widely applied as a screening procedure, which allows one to determine alcoholic strength in less than 2 min without any sample preparation. The disadvantage is the relatively large investment for Fourier transform (FT) IR or near-IR instruments, and the need for matrix-dependent calibration. In this study, we apply a much simpler device consisting of a patented multiple-beam infrared sensor in combination with a flow-through cell for automated alcohol analysis, which is available in a portable version that allows for on-site measurements. RESULTS: During method validation, the precision of the infrared sensor was found to be equal to or better than densimetric or FTIR methods. For example, the average repeatability, as determined in 6 different wine samples, was 0.05% vol and the relative standard deviation was below 0.2%. Accuracy was ensured by analyzing 260 different alcoholic beverages in comparison to densimetric or FTIR results. The correlation was linear over the entire range from alcohol-free beers up to high-proof spirits, and the results were in substantial agreement (R=0.99981, p<0.0001, RMSE=0.279% vol). The applicability of the device was further proven for the analysis of wines during fermentation, and for the determination of unrecorded alcohol (i.e. non-commercial or illicit products). CONCLUSIONS: The flow-through infrared device is much easier to handle than typical reference procedures, while time-consuming sample preparation steps such as distillation are not necessary. Therefore, the alcoholic strength can be economically and quickly controlled (requiring less than 60 s per sample). The device also gives the opportunity for mobile on-site control in the context of labelling control of wine, beer and spirits, the process monitoring of fermentations, or the evaluation of unrecorded alcohols.
Abstract: This contribution aims to examine systematically the evidence on the impact of the quality of unrecorded alcohol products on health consequences.
Abstract: Benzene was previously detected as a heat-induced contaminant in infant carrot juices. This study shows that carrot juice contains substances such as beta-carotene, phenylalanine or terpenes that may act as precursors for benzene formation during food processing. As benzene exposure has been associated with childhood leukaemia and other cancers, this study aimed to provide a quantitative risk assessment. To accomplish this, we used measured food consumption data from the Dortmund Nutritional and Anthropometric Longitudinally Designed (DONALD) study, along with survey data on benzene in different juice categories. The calculated exposures for infants between 3 and 12 months were low, with averages between 1 and 10 ng/kg bw/day, resulting in a margin of exposure above 100,000. The exposures were judged as unlikely to pose a health risk for infants. Nevertheless, carcinogenic contaminants should be reduced to levels as low as reasonably achievable. The focus should be set on improving the sterilization conditions.
Abstract: BACKGROUND: Ethyl carbamate (EC) is a multi-site carcinogen in experimental animals and probably carcinogenic to humans (IARC group 2A). Traces of EC below health-relevant ranges naturally occur in several fermented foods and beverages, while higher concentrations above 1 mg/l are regularly detected in only certain spirits derived from cyanogenic plants. In Brazil this concerns the sugarcane spirit cachaça and the manioc (cassava) spirit tiquira, which both regularly exceed the national EC limit of 0.15 mg/l. This study aims to estimate human exposure in Brazil and provide a quantitative risk assessment. METHODS: The human dietary intake of EC via alcoholic beverages was estimated based on WHO alcohol consumption data in combination with own surveys and literature data. This data comprises the EC contents of the different beverage groups cachaça, tiquira, other spirits, beer, wine, and unrecorded alcohol (as defined by the WHO; including alcohol which is not captured in routine government statistics nor taxed). The risk assessment was conducted using the margin of exposure (MOE) approach with benchmark doses obtained from dose-response modelling of animal experiments. Lifetime cancer risk was calculated using the T25 dose descriptor. RESULTS: Considering differences between pot-still and column-still cachaça, its average EC content would be 0.38 mg/l. Tiquira contained a considerably higher average EC content of 2.34 mg/l. The whole population exposure from all alcoholic beverages was calculated to be around 100 to 200 ng/kg bw/day, with cachaça and unrecorded alcohol as the major contributing factors. The MOE was calculated to range between 400 and 2,466, with the lifetime cancer risk at approximately 3 cases in 10,000. An even higher risk may exist for binge-drinkers of cachaça and tiquira with MOEs of up to 80 and 15, respectively. CONCLUSIONS: According to our risk assessment, EC poses a significant cancer risk for the alcohol-drinking population in Brazil, in addition to that of alcohol alone. Model calculations show that the implementation of the 0.15 mg/l limit for cachaça would be beneficial, including an increase of the MOE by a factor between 3 to 6. The implementation of policy measures for tiquira and unrecorded alcohol also appears to be advisable.
Abstract: The medical use of the wormwood plant Artemisia absinthium L. dates back to at least Roman times, while during the last century this tradition was seemingly on the decline due to fears of absinthism, a syndrome allegedly caused by the wormwood-flavoured spirit absinthe and more specifically as a result of thujone, a monoterpene ketone often present in the essential oil of wormwood. If threshold concentrations are exceeded, thujone does in fact exhibit neurotoxic properties leading to dose-dependent tonic-clonic seizures in animals, likely caused by GABA type A receptor modulation. Research has shown that the concentrations of thujone present in absinthe were not sufficient to exceed these thresholds, and the marketing of wormwood-flavoured alcoholic beverages has ultimately been reinstated. The declining fears of absinthism may have led to a revival of the medical uses of wormwood, evidenced by several experimental reports, e.g. on the treatment of Crohn's disease. Most recently in this journal, neuroprotective properties of wormwood were detected in rats, and the plant was suggested to be possibly beneficial in the treatment of strokes. While these results sound promising and worthwhile for further investigation, the well-defined profile of adverse properties of wormwood demands a more cautious interpretation of these results. It remained unclear in the studies, for example, if the threshold dose for thujone (e.g. as set by the European Medicines Agency) would be exceeded during therapeutic usage. Due to the colourful history of wormwood, its application in humans should be preceded by a thorough and careful risk-benefit analysis.
Abstract: Furan is a possible human carcinogen regularly occurring in commercially jarred complementary foods. This paper will provide a detailed exposure assessment for babies consuming these foods considering different intake scenarios. The occurrence data on furan in complementary foods were based on our own headspace-gas chromatography/mass spectrometry (HS-GC/MS) analytical results (n = 286). The average furan content in meals and menus was between 20 and 30 µg kg(-1) , which is in excellent agreement with results from other European countries. Using measured food consumption data from the Dortmund Nutritional and Anthropometric Longitudinally Designed (DONALD) study, the average exposures for consumers of commercially jarred foods ranged between 182 and 688 ng kg(-1) bw day(-1) , with a worst case scenario for P95 consumers ranging between 351 and 1066 ng kg(-1) bw day(-1) . The exposure data were then used to characterize risk using the margin of exposure method based on a benchmark dose lower confidence limit for a 10% response (BMDL10) of 1.28 mg kg(-1) bw day(-1) for hepatocellular tumours in rats. The margin of exposures (MOEs) were below the threshold of 10 000, which is often used to define public health risks, in all scenarios, ranging between 7022 and 1861 for average consumers and between 3642 and 1200 for the P95 consumers. Mitigative measures to avoid furan in complementary foods should be of high priority for risk management.
Abstract: BACKGROUND: Phthalates are synthetic compounds with a widespread field of applications. For example, they are used as plasticizers in PVC plastics and food packaging, or are added to personal care products. Diethyl phthalate (DEP) may be used to denature alcohol, e.g., for cosmetic purposes. Public health concerns of phthalates include carcinogenic, teratogenic, hepatotoxic and endocrine effects. The aim of this study was to develop and validate a method for determining phthalates in alcohol samples and to provide a risk assessment for consumers of such products. METHODOLOGY/PRINCIPAL FINDINGS: A liquid-liquid extraction procedure was optimized by varying the following parameters: type of extraction solvent (cyclohexane, n-hexane, 1,1,2-trichlorotrifluoroethane), the ratio extraction solvent/sample volume (1 ratio 1 to 50 ratio 1) and the number of extraction repetitions (1-10). The best extraction yield (99.9%) was achieved with the solvent 1,1,2-trichlorotrifluoroethane, an extraction solvent volume/sample volume ratio of 10 ratio 1 and a double extraction. For quantification, gas chromatography/mass spectrometry with deuterated internal standards was used. The investigated samples were alcoholic beverages and unrecorded alcohol products from different countries (n = 257). Two unrecorded alcohol samples from Lithuania contained diethyl phthalate in concentrations of 608 mg/L and 210 mg/L. CONCLUSIONS/SIGNIFICANCE: The consumption of the phthalate-positive unrecorded alcohols would exceed tolerable daily intakes as derived from animal experiments. Both positive samples were labelled as cosmetic alcohol, but had clearly been offered for human consumption. DEP seems to be unsuitable as a denaturing agent as it has no effect on the organoleptic properties of ethanol. In light of our results that DEP might be consumed by humans in unrecorded alcohols, the prohibition of its use as a denaturing agent should be considered.
Abstract: AIMS: In addition to being produced in ethanol metabolism, acetaldehyde occurs naturally in alcoholic beverages. Limited epidemiological evidence points to acetaldehyde as an independent risk factor for cancer during alcohol consumption, in addition to the effects of ethanol. This study aims to estimate human exposure to acetaldehyde from alcoholic beverages and provide a quantitative risk assessment. METHODS: The human dietary intake of acetaldehyde via alcoholic beverages was estimated based on World Health Organization (WHO) consumption data and literature on the acetaldehyde contents of different beverage groups (beer, wine, spirits and unrecorded alcohol). The risk assessment was conducted using the European Food Safety Authority's margin of exposure (MOE) approach with benchmark doses obtained from dose-response modelling of animal experiments. Life-time cancer risk was calculated using the T25 dose descriptor. RESULTS: The average exposure to acetaldehyde from alcoholic beverages was estimated at 0.112 mg/kg body weight/day. The MOE was calculated to be 498, and the life-time cancer risk at 7.6 in 10,000. Higher risk may exist for people exposed to high acetaldehyde contaminations, as we have found in certain unrecorded alcohol beverages in Guatemala and Russia, for which we have demonstrated possible exposure scenarios, with risks in the range of 1 in 1000. CONCLUSIONS: The life-time cancer risks for acetaldehyde from alcoholic beverages greatly exceed the usual limits for cancer risks from the environment set between 1 : 10,000 and 1 : 1,000,000. Alcohol consumption has thus been identified as a direct source of acetaldehyde exposure, which in conjunction with other sources (food flavourings, tobacco) results in a magnitude of risk requiring intervention. An initial public health measure could be to reduce the acetaldehyde content in alcoholic beverages as low as technologically possible, and to restrict its use as a food flavour additive.
Abstract: AIMS: 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. METHODS: 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. RESULTS: 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. CONCLUSIONS: Measures should be taken to reduce the harm associated with alcohol in this community, including efforts to reduce acetaldehyde levels in cuxa.
Abstract: AIMS: 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. METHODS: 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. RESULTS: 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. CONCLUSIONS: 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.
Abstract: Mercury is an environmental contaminant that appears in different chemical forms. Organic forms of mercury, such as methylmercury, can occur in marine organisms like fish and shellfish and are far more toxic than the inorganic form. It is therefore vital to have refined analytical methods for the different mercuric species in order to evaluate the potential risk for seafood consumers. The aim of our investigations was to develop a simple, robust and valid method for differentiation of the mercury species in marine organisms. Different alkaline and acidic digestion procedures were evaluated. The best performing methodology consisted of digestion of 0.5 g sample in methanolic potassium hydroxide solution. After derivatization with sodium tetraethylborate and extraction of the ethylated mercury species using n-hexane, a quantitative determination of the extract using gas chromatography, combined with atomic emission detection, was possible. The procedure was shown to be selective and sensitive with a limit of detection of 6.1 mu g/kg for methylmercury. The average recovery for the full procedure was 91 +/- 19%. A preliminary survey of sea-foods confirmed the previous observation that the proportion of methylmercury in the total mercury can vary widely, up to a complete occurrence as methylmercury.
Abstract: Research was conducted to ascertain whether analyses of vintage absinthe samples represent their original composition in the early 1900s. Absinthe stored in traditional green glass bottles and irradiated with ultraviolet light for up to 200 h exhibited unchanged composition. Samples stored in clear glass exhibited an 18% reduction in beta-thujone content and a concurrent decoloration. These experiments indicate the stability of thujone in vintage absinthes, as these were stored in green glass bottles. The preserved color of the preban absinthes subjected to analysis indicates that no significant light exposure occurred throughout the duration of storage, and therefore provides indirect proof that no loss of terpenes occurred. The stability of absinthe was further demonstrated through the reanalysis of samples from 2001-2005, which exhibited no changes in thujone content as of 2008. A previous evaluation of preban absinthe was therefore valid and not confounded by significant thujone deterioration over time.
Abstract: The recent melamine crisis in China has pointed out a serious deficiency in current food control systems, namely, they specifically focus on selected known compounds. This targeted approach allowed the presence of melamine in milk products to be overlooked for a considerable time. To avoid such crises in the future, we propose that nontargeted screening methods need to be developed and applied. To this end, NMR has an extraordinary potential that just started to be recognized and exploited. Our research shows that, from the very same set of spectra, (1)H NMR at 400 MHz can distinguish between melamine-contaminated and melamine-free infant formulas and can provide quantitative information by integration of individual lines after identification. For contaminated Chinese infant formulas or candy, identical results were obtained when comparing NMR with SPE-LC/MS/MS. NMR was found to be suitable for routine nontargeted and targeted analyses of foods, and its use will significantly increase food safety.
Abstract: Increasing evidence suggests that acetaldehyde, the first and genotoxic metabolite of ethanol, mediates the carcinogenicity of alcoholic beverages. Ethanol is also contained in a number of ready-to-use mouthwashes typically between 5 and 27% vol. An increased risk of oral cancer has been discussed for users of such mouthwashes; however, epidemiological evidence had remained inconclusive. This study is the first to investigate acetaldehyde levels in saliva after use of alcohol-containing mouthwashes. Ready-to-use mouthwashes and mouthrinses (n = 13) were rinsed in the mouth by healthy, nonsmoking volunteers (n = 4) as intended by the manufacturers (20 ml for 30 sec). Saliva was collected at 0.5, 2, 5 and 10 min after mouthwash use and analyzed using headspace gas chromatography. The acetaldehyde content in the saliva was 41 +/- 15 microM, range 9-85 microM (0.5 min), 52 +/- 14 microM, range 11-105 microM (2 min), 32 +/- 7 microM, range 9-67 microM (5 min) and 15 +/- 7 microM, range 0-37 microM (10 min). The contents were significantly above endogenous levels and corresponding to concentrations normally found after alcoholic beverage consumption. A twice-daily use of alcohol-containing mouthwashes leads to a systemic acetaldehyde exposure of 0.26 microg/kg bodyweight/day on average, which corresponds to a lifetime cancer risk of 3E-6. The margin of exposure was calculated to be 217,604, which would be seen as a low public health concern. However, the local acetaldehyde contents in the saliva are reaching concentrations associated with DNA adduct formation and sister chromatid exchange in vitro, so that concerns for local carcinogenic effects in the oral cavity remain.
Abstract: Ethyl carbamate (EC) is a recognized genotoxic carcinogen, with widespread occurrence in fermented foods and beverages. No data on its occurrence in alcoholic beverages from Mexico or Central America is available. Samples of agave spirits including tequila, mezcal, bacanora and sotol (n=110), and of the sugarcane spirit cuxa (n=16) were purchased in Mexico and Guatemala, respectively, and analyzed for EC. The incidence of EC contamination was higher in Mexico than in Guatemala, however, concentrations were below international guideline levels (<0.15 mg/L). Risk assessment found the Margin of Exposure (MOE) in line with that of European spirits. It is therefore unlikely that EC plays a role in high rates of liver cirrhosis reported in Mexico.
Abstract: A rapid HS-SPME-GC-MS (headspace solid-phase microextraction-gas chromatography-mass spectrometry) method has been developed for determination of menthone, isomenthone, neomenthol and menthol in serum samples with and without enzymatic cleavage. These flavour compounds are characteristic markers for consumption of peppermint liqueurs as well as certain digestif bitters, herbal and bitter liqueurs. This method enabled the detection of the four compounds with a limit of detection (LOD) of 2.1 ng mL(-1) (menthone and isomenthone), 2.8 ng mL(-1) (neomenthol) and 4.6 ng mL(-1) (menthol), and a limit of quantification (LOQ) of 3.1 ng mL(-1) (menthone and isomenthone), 4.2 ng mL(-1) (neomenthol) and 6.8 ng mL(-1) (menthol) in serum samples. The method shows good precision intraday (3.2-3.8%) and interday (5.8-6.9%) and a calibration curve determination coefficient (R(2)) of 0.990-0.996. Experiments were conducted with a volunteer, who consumed peppermint liqueur on three different days under controlled conditions. At defined intervals, blood samples were taken, and the concentration-time profiles for serum menthone, isomenthone, neomenthol and menthol, as free substances as well as glucuronides, were determined. Both menthol and neomenthol underwent a rapid phase II metabolism, but minor amounts of free substances were also detected. Menthone and isomenthone were rapidly metabolised and were found in lower concentrations and over a shorter time span than the other analytes. In blood samples taken from 100 drivers who claimed to have consumed peppermint liqueur prior to the blood sampling, menthone, isomenthone, neomenthol and menthol were detected in the serum as free substances in concentrations between 3.1 and 7.0 ng mL(-1) in eight cases (menthone), 3.1 and 11.3 ng mL(-1) in eight cases (isomenthone), 5.3 and 57.8 ng mL(-1) in nine cases (neomenthol) and 8.0 and 92.1 ng mL(-1) in nine cases (menthol). The sum values of free and conjugated substances ranged between 4.2 and 127.8 ng mL(-1) in 35 cases for neomenthol and 11.0 and 638.2 ng mL(-1) in 59 cases for menthol. Menthone and isomenthone were not conjugated. These test results confirmed that the analysis of characteristic beverage aroma compounds, such as menthone, isomenthone, neomenthol and menthol, can be used for specific verification of post-offence alcohol consumption claims.
Abstract: 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.
Abstract: BACKGROUND: 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. METHODS: 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. RESULTS: 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. CONCLUSIONS: 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.
Abstract: 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.
Abstract: Furan is a possible human carcinogen (IARC group 2B) with widespread occurrence in many types of foods. In this study, a survey of furan contamination in 230 commercially jarred ready-to-eat infant food products was conducted using headspace sampling in combination with gas chromatography and mass spectrometry (HS-GC/MS) with a detection limit of 0.2 microg kg(-1). The incidence of furan contamination in jarred infant beverages, cereals and fruits was relatively low, with average concentrations below 10 microg kg(-1). Significantly higher concentrations were found in pasta (34.8 +/- 14.5 microg kg(-1)), meals containing meat (28.2 +/- 15.0 microg kg(-1)), and meals containing vegetables (31.2 +/- 17.3 microg kg(-1)). The average exposure of 6-month-old infants to furan was estimated to be 0.2 microg per kg bodyweight per day. The margin of exposure calculated using the T25 dose descriptor would be 2692, which points to a possible public health risk. In contrast to commercially jarred food products, none of 20 freshly home-prepared baby foods contained furan above the limit of detection. Only after re-heating in closed vessels was furan found to have formed. Furan was especially prevalent in reheated foods containing potatoes, with values ranging between 2.3 and 29.2 microg kg(-1). The formation of furan in potato-containing baby foods was increased by addition of ascorbic acid, by longer heating times above 1 h and by temperatures above 50 degrees C. Research regarding reduction of furan in commercial baby foods should be conducted, with a priority aimed at reducing this heat-induced contaminant without concomitantly increasing the microbiological risk.
Abstract: ABSTRACT: Ethanol is widely used in all kinds of products with direct exposure to the human skin (e.g. medicinal products like hand disinfectants in occupational settings, cosmetics like hairsprays or mouthwashes, pharmaceutical preparations, and many household products). Contradictory evidence about the safety of such topical applications of the alcohol can be found in the scientific literature, yet an up-to-date risk assessment of ethanol application on the skin and inside the oral cavity is currently lacking. The first and foremost concerns of topical ethanol applications for public health are its carcinogenic effects, as there is unambiguous evidence for the carcinogenicity of ethanol orally consumed in the form of alcoholic beverages. So far there is a lack of evidence to associate topical ethanol use with an increased risk of skin cancer. Limited and conflicting epidemiological evidence is available on the link between the use of ethanol in the oral cavity in the form of mouthwashes or mouthrinses and oral cancer. Some studies pointed to an increased risk of oral cancer due to locally produced acetaldehyde, operating via a similar mechanism to that found after alcoholic beverage ingestion. In addition, topically applied ethanol acts as a skin penetration enhancer and may facilitate the transdermal absorption of xenobiotics (e.g. carcinogenic contaminants in cosmetic formulations). Ethanol use is associated with skin irritation or contact dermatitis, especially in humans with an aldehyde dehydrogenase (ALDH) deficiency. After regular application of ethanol on the skin (e.g. in the form of hand disinfectants) relatively low but measurable blood concentrations of ethanol and its metabolite acetaldehyde may occur, which are, however, below acute toxic levels. Only in children, especially through lacerated skin, can percutaneous toxicity occur. As there might be industry bias in many studies about the safety of topical ethanol applications, as well as a general lack of scientific research on the long-term effects, there is a requirement for independent studies on this topic. The research focus should be set on the chronic toxic effects of ethanol and acetaldehyde at the point of impact, with special regard to children and individuals with genetic deficiencies in ethanol metabolism.
Abstract: A rapid headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) method has been developed for the determination of eugenol in serum samples after enzymatic cleavage. Eugenol is a characteristic marker for the consumption of certain alcoholic beverages including some digestif bitters and herbal liqueurs as well as wood-cask-aged spirits. This method enables the detection of eugenol with a limit of detection (LOD) of 3.2ng/ml and a limit of quantification (LOQ) of 4.8ng/ml in serum samples with excellent precision (5.3% intraday, 6.9% interday) and linearity (correlation coefficient R(2)=0.992). Our findings confirm that eugenol undergoes a rapid phase II metabolism as it occurs completely conjugated as eugenol glucuronide in serum. Free eugenol was not detectable in any of our samples, which necessitated enzymatic cleavage with beta-glucuronidase prior to HS-SPME sampling. In vivo experiments were conducted with a volunteer, who consumed a digestif bitter beverage on three different days under controlled conditions. At defined intervals, blood samples were taken from the subject. Using these blood samples, concentration/time profiles for serum eugenol glucuronide were determined. A rapid resorption leads to a peak eugenol glucuronide concentration directly after drinking (up to 1742ng/ml if 78mg of eugenol are ingested) followed by a decrease during the next 3h. Blood samples were also taken from 20 drivers claiming to have consumed drinks containing eugenol. In five of the samples, eugenol glucuronide was detected at serum concentrations ranging from 12.1 to 172.3ng/ml. These test results, in particular, confirm that the analysis of volatile compounds can be useful in forensic toxicology for the verification of post-offence alcohol consumption claims.
Abstract: A novel method using fluorescence-marked gene probes is introduced into beer analysis in the context of official food control. Two commercial test kits for the detection of Lactobacilli/Pediococci and Megasphaera/Pectinatus beer spoilage bacteria were used and compared to classical plating techniques. The new method was found to be very sensitive and convenient for the identification and assessment of hygienic risks in beer samples from all stages of production. Besides that, Fourier transform infrared spectroscopy (FTIR) in combination with multivariate data analysis was evaluated to detect beer spoilage directly from the sample without prior inoculation. However, the correlations of the FTIR calibrations showed only low sensitivity so that this approach is not yet usable in food control.
Abstract: Coumarin is a component of natural flavourings including cassia, which is widely used in foods and pastries. The toxicity of coumarin has raised some concerns and food safety authorities have set a maximum limit of 2 mg/kg for foods and beverages in general, and a maximum level of 10 mg/l for alcoholic beverages. An efficient method for routine analysis of coumarin is liquid chromatography with diode array detection. The optimal sample preparation for foods containing cinnamon was investigated and found to be cold extraction of 15 g sample with 50 mL of methanol (80%, v/v) for 30 min using magnetic stirring. In the foods under investigation, appreciable amounts of coumarin were found in bakery products and breakfast cereals (mean 9 mg/kg) with the highest concentrations up to 88 mg/kg in certain cookies flavoured with cinnamon. Other foods such as liqueurs, vodka, mulled wine, and milk products did not have coumarin concentrations above the maximum level. The safety assessment of coumarin containing foods, in the context of governmental food controls, is complicated as a toxicological basis for the maximum limits appears to be missing. The limits were derived at a time when a genotoxic mechanism was assumed. However, this has since been disproven in more recent studies. Our exposure data on coumarin in bakery products show that there is still a need for a continued regulation of coumarin in foods. A toxicological re-evaluation of coumarin with the aim to derive scientifically founded maximum limits should be conducted with priority. (C) 2008 Elsevier Ltd. All rights reserved.
Abstract: There is a large variety of food products intended for athletes and sportsmen on the market. These products are often advertised with claims such as enhancement of performance, ability for regeneration, or even with an influence on hormonal balance. In recent years, the number of such products marketed on the internet has been considerably increased. In this study, we have examined the marketing of 'sports food' offered on the internet with special focus on products that are advertised as hormone-modulating or pharmaceutically active. Of the 79 controlled products, 44 (56 %) contained herbal ingredients such as Lepidium meyenii, Avena sativa, Tribulus terrestris or Trigonella foenum-graecum. The advertised effects of these herbs are in most cases scientifically unproven. An additional 17 products (22 %) contained pharmaceutically active substances in an inadmissible manner, including dehydroepiandrosterone, its 7-keto derivative, and somatotropine as well as some traditional herbal medicines such as extracts of Serenoa repens or of Mucuna pruriens, which contains L-dopa. To protect athletes from health risks as well as from financial fraud, procedures should be developed to place a high priority on controlling the grey market for such products on the internet.
Abstract: Fourier transform infrared (FTIR) spectroscopy allows fast throughput screening of beverages (less than 2 min per sample). Using partial least squares (PLS) regression, it was demonstrated that relative density and alcohol content, which have previously been calibrated only for extract-free spirits, can also be determined in highly viscous liqueur samples. In addition, total dry extract (TDE) was successfully calibrated for the first time for both spirit and liqueur screening. An inter-laboratory validation showed that the standard errors of prediction, ranging between 0.0006 and 0.0078 (relative density), 0.23 and 0.74% vol (alcoholic strength), and 0.55 and 7.53 g/l (TDE), were satisfactory for use of the FTIR-PLS method in the context of screening analysis in official food control of alcoholic beverages.
Abstract: Borderline products, which are products that fall into categories between foods, cosmetics and pharmaceuticals, are found more and more in grey areas of the internet. Currently there are no adequate methods for efficient surveillance of internet marketing for these products by the governmental food control authorities. The aim of this study, which was initiated by the 'Ministerium fur Ernahrung und Landlichen Raum Baden-Wurttemberg' (Ministry of Nutrition and Rural Affairs of the German Federal State of Baden-Wurttemberg), was firstly, to gain insight into internet marketing of borderline products and secondly, to identify the areas of concern. For this purpose, we analyzed a range of anti-aging and weight-loss products offered on the internet. The research was based on information collected using typical search terms in search engines, internet auctions and online shops. During autumn 2007, we collected data during 300 working hours and entered them into a database for analysis. We found more than 200 anti-aging products. Approximately one-third of them were offered as dietary supplements and two-thirds as cosmetics. Nearly 40% of all the products found are not available through conventional retail trade. In the group of weight loss supplements we found 371 products, most of them declared to be dietary supplements (88%). Of the cosmetics in this group, only one-third have been evaluated as 'harmless', while doubts exist with the remainder regarding their safety, efficacy or pharmaceutical purpose. From those marketed as dietary supplements, only one-third were additionally classified as marketable food, while we found active pharmaceutical ingredients in one quarter of these products. The dietary supplements group commonly contained products featuring misleading claims, non-licensed additives and ingredients classified as 'novel food'. Trial purchases showed us that these questionable products are in fact available in Germany by mail order over the internet. Our research shows that internet marketing of borderline products may in fact be contrary to a number of European and national food laws, particularly with regard to misleading statements or illegal health claims. High priority should therefore be given to the development of concepts to ensure consumer protection in this area.
Abstract: Thirteen samples of authentic absinthe dating from the preban era (i.e., prior to 1915) were analyzed for parameters that were hypothesized as contributing to the toxicity of the spirit, including naturally occurring herbal essences (thujone, pinocamphone, fenchone), methanol, higher alcohols, copper, and antimony. The total thujone content of preban absinthe was found to range between 0.5 and 48.3 mg/L, with an average concentration of 25.4 +/- 20.3 mg/L and a median concentration of 33.3 mg/L. The authors conclude that the thujone concentration of preban absinthe was generally overestimated in the past. The analysis of postban (1915-1988) and modern commercial absinthes (2003-2006) showed that the encompassed thujone ranges of all absinthes are quite similar, disproving the supposition that a fundamental difference exists between preban and modern absinthes manufactured according to historical recipes. Analyses of pinocamphone, fenchone, base spirits, copper, and antimony were inconspicuous. All things considered, nothing besides ethanol was found in the absinthes that was able to explain the syndrome "absinthism".
Notes: Free fulltext available at: http://dx.doi.org/10.1021/jf703568f
Abstract: 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.
Abstract: Higher alcohols occur naturally in alcoholic beverages as by-products of alcoholic fermentation. Recently, concerns have been raised about the levels of higher alcohols in surrogate alcohol (i.e., illicit or home-produced alcoholic beverages) that might lead to an increased incidence of liver diseases in regions where there is a high consumption of such beverages. In contrast, higher alcohols are generally regarded as important flavour compounds, so that European legislation even demands minimum contents in certain spirits. In the current study we review the scientific literature on the toxicity of higher alcohols and estimate tolerable concentrations in alcoholic beverages. On the assumption that an adult consumes 4x25ml of a drink containing 40% vol alcohol, the maximum tolerable concentrations of 1-propanol, 1-butanol, 2-butanol, isobutanol, isoamyl alcohol and 1-hexanol in such a drink would range between 228 and 3325g/hl of pure alcohol. A reasonable preliminary guideline level would be 1000g/hl of pure alcohol for the sum of all higher alcohols. This level is higher than the concentrations usually found in both legal alcoholic beverages and surrogate alcohols, so that we conclude that scientific data are lacking so far to consider higher alcohols as a likely cause for the adverse effects of surrogate alcohol. The limitations of our study include the inadequate toxicological data base leading to uncertainties during the extrapolation of toxicological data between the different alcohols, as well as unknown interactions between the different higher alcohols and ethanol.
Abstract: In the discussion about thujone as possible toxic constituent of the wormwood-containing alcoholic beverage absinthe, the dose-response-relationship is frequently ignored. The effects of absinthe are very often attributed only to thujone, an association that is not scientifically proven. Especially the alleged psychotropic effects of thujone are scientifically unproven. However, the question about thujone effects in absinthe is irrelevant, because thujone is contained in both modern commercial absinthes and historic pre-ban products in such low amounts that a pharmacological effect can be excluded per se. The effects of the spirit that are summarized under the term absinthism observed in late 19th century's France, can be explained by chronic alcohol misuse and dependence alone according to today's standards of knowledge. Especially from the perspective of youth and public health protection, an ambiguous and biased reporting about absinthe should be avoided. For example, the alleged antagonistic effects of thujone on the action of ethanol might lead to a trivialization of alcohol-related harms. Scientifically unproven speculations about the influence of certain drinking rituals of absinthe on its toxicity must be rebutted. A return to more evidence and less conjecture in the reporting about absinthe would be desirable.
Abstract: A survey of benzene contamination of 451 beverage samples, using headspace sampling combined with gas chromatography and mass spectrometry (HS-GC/MS) with a quantification limit of 0.13 microg l(-1), was conducted. Artefactual benzene formation during headspace sampling was excluded by gentle heating at 50 degrees C only and adjustment of sample pH to 10. The incidence of benzene contamination in soft drinks, beverages for babies, alcopops and beer-mixed drinks was relatively low, with average concentrations below the EU drinking-water limit of 1 microg l(-1). Significantly higher concentrations were only found in carrot juice, with the highest levels in carrot juice specifically intended for infants. About 94% of 33 carrot juice for infants had detectable benzene levels, with an average concentration of 1.86 +/- 1.05 microg l(-1). Benzene contamination of beverages was significantly correlated to iron and copper concentrations, which act as catalyst in benzene formation. The formation of benzene in carrot juice was predominantly caused by a heat-induced mechanism, which explains the higher levels in infant carrot juices that are subject to higher heat-treatment to exclude microbiological contamination.
Abstract: In the analysis of food additives, past emphasis was put on the development of chromatographic techniques to separate target components from a complex matrix. Especially in the case of artificial food colors, direct spectrophotometric measurement was seen to lack in specificity due to a high spectral overlap between different components. Multivariate curve resolution (MCR) may be used to overcome this limitation. MCR is able to (i) extract from a complex spectral feature the number of involved components, (ii) attribute the resulting spectra to chemical compounds, and (iii) quantify the individual spectral contributions with or without a priori knowledge. We have evaluated MCR for the routine analysis of yellow and blue food colors in absinthe spirits. Using calibration standards, we were able to show that MCR equally performs as compared to partial least-squares regression but with much improved chemical information contained in the predicted spectra. MCR was then applied to an authentic collective of different absinthes. As confirmed by reference analytics, the food colors were correctly assigned with a sensitivity of 0.93 and a specificity of 0.85. Besides the artificial colors, the algorithm detected a further component in some samples that could be assigned to natural coloring from chlorophyll.
Abstract: Acetaldehyde is a volatile compound naturally found in alcoholic beverages, and it is regarded as possibly being carcinogenic to humans (IARC Group 2B). Acetaldehyde formed during ethanol metabolism is generally considered as a source of carcinogenicity in alcoholic beverages. However, no systematic data is available about its occurrence in alcoholic beverages and the carcinogenic potential of human exposure to this directly ingested form of acetaldehyde outside ethanol metabolism. In this study, we have analysed and evaluated a large sample collective of different alcoholic beverages (n=1,555). Beer (9+/-7 mg/l, range 0-63 mg/l) had significantly lower acetaldehyde contents than wine (34+/-34 mg/l, range 0-211 mg/l), or spirits (66+/-101 mg/l, range 0-1,159 mg/l). The highest acetaldehyde concentrations were generally found in fortified wines (118+/-120 mg/l, range 12-800 mg/l). Assuming an equal distribution between the beverage and saliva, the residual acetaldehyde concentrations in the saliva after swallowing could be on average 195 microM for beer, 734 microM for wine, 1,387 microM for spirits, or 2,417 microM for fortified wine, which are above levels previously regarded as potentially carcinogenic. Further research is needed to confirm the carcinogenic potential of directly ingested acetaldehyde. Until then, some possible preliminary interventions include the reduction of acetaldehyde in the beverages by improvement in production technology or the use of acetaldehyde binding additives. A re-evaluation of the 'generally recognized as safe' status of acetaldehyde is also required, which does not appear to be in agreement with its toxicity and carcinogenicity.
Abstract: Due to major concerns about morphine present in poppy seed intended for use in food, the establishment of maximum limits is currently discussed and options to reduce its content are searched. With the aim to propose guidelines for consumers and bakeries about minimization of the morphine content in poppy seed, the kinetics of morphine degradation during grinding as well as the possibility to reduce the morphine content by washing steps are evaluated in this study. A significant reduction of morphine by grinding using standard poppy seed mills was ascertained. The degradation occurs directly at grinding and does not continue during subsequent storage. Washing the poppy seed with hot water (60 degrees C) is an effective way to reduce the morphine content by approx. 70%. The optimal treatment of poppy seed consists of washing, drying, and grinding. This process significantly reduces the morphine content and simultaneously improves the organoleptical quality of the product.
Abstract: A discrepancy in the magnitude of thujone concentrations in distilled pre-ban absinthe has existed until now. Concentrations of 260 mg L-1 were derived at by theoretical calculations. Tests of authentic pre-ban absinthes and studies concerning absinthes produced according to historic recipes found concentrations below 10 mg L-1. In this study, the behaviour of thujone during distillation was studied and a significant discrimination was determined (80% yield in water-cum-steam distillation). The thujone concentrations in distilled pre-ban absinthe were then calculated with regard to the composition of wormwood derived from a literature review. Due to the large deviations of oil content and thujone concentration of wormwood, a typical Absinthe Suisse de Pontarlier from Duplais' 1855 recipe might have contained between zero and a maximum of 76 mg L-1 of thujone, the average was calculated as 23 mg L-1 with a standard deviation of 21 mg L-1. It was proven that the previous calculations overestimated the thujone content of distilled absinthe and the discrepancy was resolved as our new calculations are in good accord with the experimental findings. (C) 2007 Society of Chemical Industry
Abstract: The media coverage about absinthe, a bitter spirit containing wormwood (Artemisia absinthum L.), continues to repeat unsubstantiated myths and legends and the public is systematically misinformed. Especially, the theory about a significant thujone content in absinthe must be put into perspective as there are a number of different wormwood chemotypes with a large variance in thujone content (0-70.6% in essential oil) from which a mean thujone content of about 20 mg/l in distilled absinthe with a large standard deviation of up to 20 mg/l may be calculated. However, a higher thujone amount of 260 mg/l derived from erroneous and out-ofdate calculations is generally presented as "historical content" in addition to reports about unsubstantiated psychoactive or aphrodisiac properties. Other studies used unauthentic recipes with unrealistically high amounts of wormwood that would produce undrinkable bitter products. In general, a previous overestimation of the thujone content of pre-ban absinthe was detected.
Abstract: Absinthe is a spirit drink that owes its bitter taste to substances found in the wormwood plant (Artemisia absinthium L.). The prohibition against absinthe has recently been annulled, giving rise to numerous inferior products that lack the organoleptic characteristics of wormwood. The monoterpene thujone, which occurs in the essential oil fraction of wormwood, has previously been used as a marker substance to confirm the authenticity of absinthe. However, thujone possesses adverse toxicological properties; thus modern procedures have been developed to remove this substance from absinthe. In addition, thujone-free wormwood is also available from certain cultivation areas. This study is the first to use sensory evaluation of wormwood taste, louche effect, and bitterness in order to classify absinthes. This study also introduces a simple, fast, and sensitive procedure using high-performance thin-layer chromatography (HPTLC) to assess the levels of absinthin, a characteristic bitter substance found in wormwood. Results of this study demonstrate a strong correlation between the concentration of wormwood and the organoleptically determined bitterness value (R = 0.75). (c) 2006 Elsevier Ltd. All rights reserved.
Abstract: Since 2005, the official food surveillance in Baden-Wurttemberg (Germany) has continously been analysing the contents of opiate alkaloids in poppy seeds and foods made thereof. Ready-made bodies, poppy seeds from bakeries, and poppy seeds dedicated directly to the consumer were investigated. In 2005 opiate contents especially morphine were high enough to cause adverse health effects in several cases, whereas average findings in 2006 were somewhat lower. 76% of the 110 samples exceeded the guidance value of 4 mg morphine/kg poppy seed proposed by the Federal Institute for Risk Assessment (BfR), but less than 30% showed a higher content than 20 mg/kg, a value estimated as tolerable by the BfR, if warning notices are given. All of the poppy ready-mixes fell below the guidance value of the BfR. Poppy seeds from bakeries averaged higher values than those for the consumers' sale. When the guidance value was derived, the well-known decomposition characteristics o the alkaloids during technological processes (like grinding, heating, etc.) were not taken into account. For this reason, poppy seeds with higher morphine contents for commercial further processing have not to be considered as crucial, as long as the producer of poppy foods is able to ensure the compliance of his product with the guidance value. In contrast, the situation concerning poppy seeds for the consumers' sale is not yet satisfactory, since 28% of the respective samples showed higher morphine contents than 20 mg/kg. Because recommendations for alkaloid reducing measurements often are not followed, these samples had to be judged as unsafe and therefore objectionable.
Abstract: In February 2007, the International Agency for Research on Cancer (IARC) has reassessed the carcinogenicity of alcoholic beverages within its monographs programme. Ethanol in alcoholic beverages was classified as "carcinogenic to humans" (Group 1). Many studies have consistently shown that regular alcohol consumption is causally related with an increased risk for cancer of the oral cavity, pharynx, larynx, oesophagus, liver, female breast and colorectum. In contrast to the previous evaluation of alcohol drinking in 1988, the IARC working group found evidence that ethanol and not other constituents or contaminants cause the carcinogenicity. In general, the risk for cancer increases with the amount of alcohol intake, e.g. the daily consumption of around 50 g of alcohol increases the risk of cancer of the oral cavity three-fold, compared to the risk of nondrinkers. An association with different types of alcoholic beverages (beer, wine, or spirits) was not observed. A separate evaluation was made for ethyl carbamate (urethane), a frequent contaminant of fermented foods and beverages. Ethyl carbamate was upgraded into Group 2A ("probably carcinogenic to humans"). The IARC evaluations emphasize the importance and necessity of avoiding and of controling further carcinogenic contaminants in alcoholic beverages (besides ethyl carbamate, e.g. nitrosamines, mycotoxins, lead, cadmium, arsenic), as there exists the possibility of synergistic effects on carcinogenicity between ethanol and other contaminants. In consideration of the IARC evaluation of alcohol as carcinogenic, the EU Health Claims Regulation is appreciated for its prohibiton of nutrition or health claims in the labelling of alcoholic beverages. Furthermore, the proposals for warning labels on alcoholic beverages similar to those on tobacco products are discussed.
Abstract: The use of headspace adsorbent traps in combination with gas chromatography was evaluated for the determination of volatile constituents (i.e. higher alcohols and other congeners of alcoholic fermentation) in spirits. The headspace trap technology comprises an enhanced static headspace system that allows enrichment and focusing of analytes on adsorbent traps prior to gas chromatographic separation. Extraction yields 35-55 times higher than those seen with static headspace sampling were achieved. An excellent agreement of analysis results in comparison to the European reference procedure was found (R>0.98, p<0.0001). The fully automated headspace trap procedure requires only minimal sample preparation and is easy to apply.
Abstract: Heat-induced food contaminants have attracted attention of both the scientific community and the public in recent years. The presence of substances considered possibly or probably carcinogenic to humans has triggered an extensive debate on the healthiness of even staple foods. In that respect, acrylamide, furan and chloropropanols are the main substances of concern. Their widespread occurrence in processed food, which concomitantly causes considerable exposure to humans, led either to the setting of maximum limits (for some chloropropanols) or at least the initiation of monitoring programmes in order to put risk assessment on a solid data basis. Acrylamide, furan and chloropropanols are small molecules with physicochemical properties that make their analysis challenging. Their amount in food ranges typically from below the limit of detection to hundreds of micrograms per kilo or even milligrams per kilo. However, a number of recently published scientific reports deal with the analysis of these substances in different kinds of food. The aim of this publication is to give an overview of analytical approaches for the determination of acrylamide, furan and chloropropanols in foodstuffs.
Abstract: BACKGROUND: Consumption of surrogate alcohols (i.e., nonbeverage alcohols and illegally produced alcohols) was shown to impact on different causes of death, not only poisoning or liver disease, and appears to be a major public health problem in Russia and elsewhere. METHODS: A computer-assisted literature review on chemical composition and health consequences of "surrogate alcohol" was conducted and more than 70 references were identified. A wider definition of the term "surrogate alcohol" was derived, including both nonbeverage alcohols and illegally produced alcohols that contain nonbeverage alcohols. RESULTS: Surrogate alcohol may contain substances that cause severe health consequences including death. Known toxic constituents include lead, which may lead to chronic toxicity, and methanol, which leads to acute poisoning. On the other hand, the role of higher alcohols (e.g., propanol, isobutanol, and isoamyl alcohol) in the etiology of surrogate-associated diseases is currently unclear. Whether other constituents of surrogates have contributed to the high all-cause mortality over and above the effect of ethanol in recent studies also remains unclear. CONCLUSIONS: Given the high public health importance associated with the consumption of surrogate alcohols, further knowledge on its chemical composition is required as well as research on its links to various disease endpoints should be undertaken with priority. Some interventions to reduce the harm resulting from surrogate alcohol could be undertaken already at this point. For example, the use of methanol or methanol-containing wood alcohol should be abolished in denatured alcohol. Other possible surrogates (e.g., automobile products) should be treated with bittering agents to avoid consumption.
Abstract: The etiopathology of absinthe dependence was previously attributed to the effects of the wormwood constituent thujone. Current research proves otherwise. Foremost, it must be considered that the wormwood plant shows a very large variance in quantity of thujone (0 - 70 % in essential oil) dependent on chemo type and cultivation area. Thus, absinthe does not contain thujone in general. Experimental production of absinthes and analyses of vintage absinthes (1900 - 1930) consistently showed that they contained only relatively low concentrations of thujone below today's maximum limits. Scientific literature contains no proof that historic absinthes may have contained thujone in concentrations able to produce toxic effects. The current state of research considers absinthism to be a type of alcoholism with thujone playing none or only a secondary role.
Abstract: Fourier Transform Infrared (FTIR) spectroscopy in combination with multivariate data analysis is introduced for the quality control and authenticity assessment of spirit drinks and beer in official food control. The spectra were measured using a FTIR interferometer, which is purpose-built for the analysis of alcoholic beverages and includes an injection unit for liquids with automatic thermostating of the sample. Only 2 min are required for FTIR measurement. For spirit drinks, no sample preparation is required at all. Carbon dioxide containing samples, such as beer were prepared by degassing. Using the partial least squares (PLS) method, FTIR spectra were correlated with results from reference methods. During validation with an independent set of samples, strong correlation with the reference values and great accuracy were demonstrated for the spirit parameters density, ethanol, methanol, ethyl acetate, propanol-1, isobutanol and 2-/3-methyl-l-butanol (R-2 = 0.90-0.98), as well as for the beer parameters ethanol, density, original gravity and lactic acid (R-2 = 0.97-0.98). Further beer parameters like pH, bitterness unit, and EBC colour (R-2 = 0.63-0.75) showed lower correlation and accuracy, but can be determined semi-quantitatively in the context of a screening analysis. In addition, principal component analysis (PCA) was applied to the analysis results. A differentiation of deteriorated fruit spirits distilled from microbiologically spoiled mashes was possible. The results obtained suggest that FTIR is a useful tool in the quality control of alcoholic beverages, since quantitative determination of essential compounds as well as chemometric classification are simultaneously possible. Through use of FTIR screening, the majority of all samples were classified as being in conformance with legal and quality requirements. Only conspicuous analysis results (approx. 12% of all samples), which exceeded the predefined limits, must be confirmed by complex and labour-intensive reference analyses. In comparison to conventional methods, FTIR spectroscopy is faster and only requires a simple sample preparation. (c) 2006 Elsevier Ltd. All rights reserved.
Abstract: Fermented fruit and beverages frequently contain ethyl carbamate (EC), a potentially carcinogenic compound that can be formed by the reaction of urea with ethanol. Both are produced by the yeast Saccharomyces cerevisiae with ethanol as the major end product of hexose fermentation and urea as a by-product in arginine catabolism. In spirit production, EC can also be derived from cyanide introduced by stone fruit. To determine the relative contribution of yeast metabolism to EC production, we genetically engineered a diploid laboratory strain to reduce the arginase activity, thus blocking the pathway to urea production. For this purpose, strains with either a heterozygous CAR1/car1 deletion or a homozygous defect (car1/car1) were constructed. These strains were compared to the parental wild type and to an industrial yeast strain in cherry mash fermentations and spirit production. The strain with the homozygous car1 deletion showed a significant reduction of EC in the final spirits in comparison to the non-engineered controls. Nevertheless, using this strain for fermentation of stoneless cherry mashes did not completely impede EC formation. This indicates another, as yet unidentified, source for this compound.
Abstract: So-called energy drinks with very high amounts of taurine (up to 4000 mg/l are usually granted by certificates of exemption) are increasingly offered on the market. To control the currently valid maximum limits of taurine in energy drinks, a simple and rapid analytical method is required to use it routinely in food monitoring. In this article, we describe a fast and efficient analytical method (FTIR-spectroscopy) that is able to reliably characterize and quantify taurine in energy drinks. The determination of taurine in energy drinks by FTIR was compared with amino acid analyzer (ion chromatography with ninhydrin-postcolumn derivatization). During analysis of 80 energy drinks, a median concentration of 3180 mg/l was found in alcohol-free products, 314 mg/l in energy drinks with spirits, 151 mg/l in beer-containing drinks and 305 mg/l in beverages with wine. Risk analysis of these products is difficult due to the lack of valid toxicological information about taurine and its interferences with other ingredients of energy drinks (for example caffeine and alcohol). So far, the high taurine concentrations of energy drinks in comparison to the rest of the diet are scientifically doubtful, as the advertised physiological effects and the value of supplemented taurine are unproven.
Abstract: The main components of the Southern German specialty black forest gateau (black forest cherry cake) are pastry base, filling with whipped cream or butter cream, cherries and cherry spirit as well as chocolate shavings for decoration. The cherry spirit is often added to the cream, may be contained in the filling, or is sometimes used to saturate the pastry base. The cake should contain so much cherry spirit that it distinctly tastes after the alcoholic beverage. This paper introduces a new method of determining ethanol in the cake. The method relies on fully automated steam distillation in combination with densimetry. The procedure is much faster (taking approximately 5 minutes per sample) and easier than conventional distillation methods. Validation has proved the method robust and it is also usable for other alcohol-containing bakery products or pralines. After the steam distillation, the ethanol content of the distillate may be determined using oscillation-type densimetry, enzymatic assays or headspace gas chromatography. Besides ethanol, steam distillation also separates other volatiles contained in alcoholic beverages from the sample matrix. Minor compounds derived during alcoholic fermentation can be determined directly from the cake to assure the identity and quality of the cherry spirit. Organoleptical examinations confirmed that to obtain a distinct taste of cherry spirit, the black forest gateau must contain more than 50 ml of cherry spirit per 2 kg of cake.
Abstract: 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.
Abstract: Two basic categories of the spirit drink Tequila can be distinguished according to Mexican law. For the high quality category "Tequila 100% de Agave" only pure agave juice is allowed to be fermented and distilled. Otherwise, the product is a "Mixto-Tequila", which is manufactured by adding up to 49% of sugar to the Agave wort. The sensory analysis using ranking methods showed significant differences between Tequila samples of both categories. The premium products with 100% of Agave were preferred by the test panel. Especially matured products (reposado and anejo Tequilas) had a harmonically mellow aroma and were comparable to premium fruit spirits or whiskies. The worldwide trend leading to a preference of "Tequila 100% de Agave" should be no longer ignored by the German market dominated so far by Mixto-products.
Abstract: A fully automated procedure using headspace solid-phase microextraction (HS-SPME) followed by gas chromatographic/tandem mass spectrometric (GC/MS/MS) detection was developed for the determination of the toxic contaminant ethyl carbamate (EC) in stone-fruit spirits. After addition of deuterated internal standard, the optimised HS-SPME extraction with carbowax/divinylbenzene fibres (30 min at 70 degrees C) was done applying salting out with sodium chloride in the presence of pH 7 buffer solution. For quantitative analysis the characteristic fragmentations of m/z 74>44 and m/z 62>44 for ethyl carbamate as well as m/z 64>44 for ethyl carbamate-d5 were monitored in the multiple reaction monitoring (MRM) mode using a triple quadrupole instrument. In the validation studies, ethyl carbamate exhibited good linearity with a regression coefficient of 0.998. The limits of detection and quantitation were 0.03 and 0.11 mg/l. The precision never exceeded 4.3% (intraday) and 8.2% (interday) at any of the concentrations examined. A good agreement of analysis results in comparison to conventional sample clean-up over diatomaceous earth columns was found (R = 0.956, Bias = 0.08 mg/l). The new HS-SPME/GC/MS/MS procedure is suitable for the fast, reliable and inexpensive determination of ethyl carbamate in alcoholic beverages in an automated, and therefore, convenient procedure.
Abstract: Habitual abuse of the wormwood spirit absinthe was described in the 19th and 20th centuries as a cause for the mental disorder "absinthism" including the symptoms hallucinations, sleeplessness and convulsions. A controversial discussion is going on if thujone, a characteristic component of the essential oil of the wormwood plant Artemisia absinthium L., is responsible for absinthism, or if it was merely caused by chronic alcohol intoxication or by other reasons such as food adulterations. To ascertain if thujone may have caused absinthism, absinthes were produced according to historic recipes of the 19th century. Commercial wormwood herbs of two different manufacturers, as well as self-cultivated ones, were used in a concentration of 6 kg/100 l spirit. In addition, an authentic vintage Pernod absinthe from Tarragona (1930), and two absinthes from traditional small distilleries of the Swiss Val-de-Travers were evaluated. A GC-MS procedure was applied for the analysis of alpha- and beta-thujone with cyclodecanone as internal standard. The method was shown to be sensitive with a LOD of 0.08 mg/l. The precision was between 1.6 and 2.3%, linearity was obtained from 0.1 to 40 mg/l (r = 1.000). After the recent annulment of the absinthe prohibition all analysed products showed a thujone concentration below the maximum limit of 35 mg/l, including the absinthes produced according to historic recipes, which did not contain any detectable or only relatively low concentrations of thujone (mean: 1.3 +/- 1.6 mg/l, range: 0-4.3 mg/l). Interestingly, the vintage absinthe also showed a relatively low thujone concentration of 1.8 mg/l. The Val-de-Travers absinthes contained 9.4 and 1.7 mg/l of thujone. In conclusion, thujone concentrations as high as 260 mg/l, reported in the 19th century, cannot be confirmed by our study. With regard to their thujone concentrations, the hallucinogenic potential of vintage absinthes can be assessed being rather low because the historic products also comply with today's maximum limits derived to exclude such effects. It may be deduced that thujone plays none, or only a minor role in the clinical picture of absinthism.
Abstract: Urine as well as head and pubic hair samples from drug abusers were analysed for opiates, cocaine and its metabolites, amphetamines, methadone and cannabinoids. Urine immunoassay results and the results of hair tests by means of gas chromatography-mass spectrometry were compared to the self-reported data of the patients in an interview protocol. With regard to the study group, opiate abuse was claimed from the majority in self-reports (89%), followed by cannabinoids (55%), cocaine (38%), and methadone (32%). Except for opiates the comparison between self-reported drug use and urinalysis at admission showed a low correlation. In contrast to urinalysis, hair tests revealed consumption in more cases. There was also a good agreement between self-reports of patients taking part in an official methadone maintenance program and urine test results concerning methadone. However, hair test results demonstrated that methadone abuse in general was under-reported by people who did not participate in a substitution program. Comparing self-reports and the results of hair analyses drug use was dramatically under-reported, especially cocaine. Cocaine hair tests appeared to be highly sensitive and specific in identifying past cocaine use even in settings of negative urine tests. In contrast to cocaine, hair lacks sensitivity as a detection agent for cannabinoids and a proof of cannabis use by means of hair analysis should include the sensitive detection of the metabolite THC carboxylic acid in the lower picogram range.
Abstract: The opiate alkaloids present in poppy seed intended for use in food recently have raised major concerns. An efficient method for routine analysis of morphine and codeine using liquid chromatography in combination with tandem mass spectrometry on a triple quadrupole instrument (LC/MS/MS) was therefore developed. The optimal sample preparation was found to be cold extraction of 10 g of unground poppy seed with 30 mL of methanol containing 0.1% acetic acid for 60 min shaken at 250 rpm. The fate of morphine during food processing was also studied. All experiments led to a significant reduction of morphine and codeine. For poppy cake only 16-50% of the morphine was recovered, and in poppy buns at the highest temperature (220 degrees C) only 3% of the original morphine content was found. Ground poppy seed showed significantly lower recoveries than untreated seed. Morphine elimination during food processing has to be taken into account in the current discussion about its maximum limits in poppy seed.
Abstract: ABSTRACT : Absinthe, a bitter spirit containing wormwood (Artemisia absinthium L.), was banned at the beginning of the 20th century as consequence of its supposed unique adverse effects. After nearly century-long prohibition, absinthe has seen a resurgence after recent de-restriction in many European countries. This review provides information on the history of absinthe and one of its constituent, thujone. Medical and toxicological aspects experienced and discovered before the prohibition of absinthe are discussed in detail, along with their impact on the current situation. The only consistent conclusion that can be drawn from those 19th century studies about absinthism is that wormwood oil but not absinthe is a potent agent to cause seizures. Neither can it be concluded that the beverage itself was epileptogenic nor that the so-called absinthism can exactly be distinguished as a distinct syndrome from chronic alcoholism.The theory of a previous gross overestimation of the thujone content of absinthe may have been verified by a number of independent studies. Based on the current available evidence, thujone concentrations of both pre-ban and modern absinthes may not have been able to cause detrimental health effects other than those encountered in common alcoholism. Today, a questionable tendency of absinthe manufacturers can be ascertained that use the ancient theories of absinthism as a targeted marketing strategy to bring absinthe into the spheres of a legal drug-of-abuse. Misleading advertisements of aphrodisiac or psychotropic effects of absinthe try to re-establish absinthe's former reputation. In distinction from commercially manufactured absinthes with limited thujone content, a health risk to consumers is the uncontrolled trade of potentially unsafe herbal products such as absinthe essences that are readily available over the internet.
Abstract: The alcoholic beverage absinthe is recently experiencing a revival after a yearlong prohibition. This review article provides information on all aspects of this bitter spirit and its major components, especially wormwood (Artemisia absinthium L.), which contains the toxic monoterpene thujone. Over 100 references on historic and current literature are provided. The topics comprise the history of the alcoholic drink starting from its invention in the eighteenth century. Historical and modern recipes are discussed in the context of different quality categories and possibilities to reduce the content of thujone are given. The analytical techniques used to verify compliance with the maximum limit of thujone as well as further possibilities for quality control of absinthe are discussed. The toxicology of absinthe is reviewed with regard to the cause of a syndrome called "absinthism," which was described after chronic abuse of the spirit in the nineteenth century. Finally, a food regulatory and food chemical evaluation is provided and minimum requirements for absinthe are suggested. Absinthe should have a recognizable wormwood flavor and after dilution with water the characteristic clouding should arise (louche-effect). Products, which are advertized as being of premium grade should be made by distillation, should have an alcoholic strength of at least 45%vol, and should not contain artificial dye.
Abstract: Ethyl carbamate (EC) is naturally found especially in stone-fruit spirits in relatively high concentrations and has genotoxic and carcinogenic characteristics. Due to these characteristics, its concentration in stone-fruit spirits has to be minimized. To identify factors being relevant to the formation of ethyl carbamate, questionnaires have been filled in at sampling in small distilleries in Baden-Wurttemberg (Germany) since 2001. In these questionnaires, different parameters concerning the carrying out of distillation were requested. The corresponding samples were analysed in the context of official food control in Baden-Wurttemberg and the results were statistically evaluated. Special parameters should be considered in particular to minimize the formation of ethyl carbamate in production of stone-fruit spirits. Most relevant parameters are e. g. the use of automatic rinsing for stills, distillation using a catalytic converter with high copper surface, separation of tailings at an alcoholic strength of above 50% vol and the renunciation of re-using tailings for re-distillation.
Abstract: The Noni plant Morinda citrifolia L. (Rubiaceae) is sold for various conjectural nutritional and health benefits. Methods using high-performance thin-layer chromatography (HPTLC) and headspace-solid-phase microextraction/gas chromatography/mass spectrometry (HS-SPME/GC/MS) to assess the authenticity of commercial Noni juices were developed in this study, allowing differentiating between authentic and adulterated products by use of multivariate data analysis (Principal Component Analysis). Parallel to the authenticity control, the HS-SPME method employed in this paper allowed detecting the preservatives benzoic acid and sorbic acid. In comparison to standard wet-chemical determinations, the chromatographic methods are more specific for Noni and also correspond to the aroma and flavour of the fruit.
Abstract: An experimental design, in combination with oscillation-type densimetry is introduced as a novel procedure to optimise steam distillation for the determination of alcoholic strength in different types of alcoholic beverages. A central composite design was chosen to study the effects of variation in levels of receiver volume (25 and 50 ml), steam power (30-100%), distillation time (20-140 s) and sample volume (5-50 ml). Three commercial spirit drinks with different alcoholic strengths (4.9, 35.3, and 54.7% vol.) were compared on two automated steam distillation devices of different manufacturers by separately completing the experimental design for each. The models fitted for the prediction of the alcoholic strength, as indicated by an r(2) value of more than 0.93. Various surface plots were generated to describe the relationship between operating variables and predicted alcoholic strength. Optimum conditions were 50 ml receiver volume, 70% steam power, 100 s distillation time and 25 ml sample volume. Slight deviations from the optimum did not result in substantial decrease of alcoholic strength. Validation experiments carried out under predicted conditions showed excellent correspondence to the reference procedure (R=0.999).
Abstract: 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).
Abstract: BACKGROUND: Dopamine (DA)-derived tetrahydroisoquinolines (TIQs) are discussed as neurochemical factors of addiction processes in alcoholism. In a prospective study, the regional distribution of DA, (R)-salsolinol (SAL), and (S)-SAL, as well as norsalsolinol (NorSAL) was examined systematically in a large collective of human brain samples obtained by autopsy. METHODS: The material comprises 44 brains of alcoholics and 47 controls with 6 standardized specimens in each case. The analytes were determined after solid-phase extraction and enantioselective derivatization using gas chromatography-mass spectrometry. RESULTS: Levels of DA, (R/S)-SAL, and NorSAL in alcoholics did not differ significantly from those of the control group. A relationship between alcohol consumption and SAL formation could not be proved. Topical differences and no ubiquitous occurrence were encountered. Significant amounts of (R)-SAL and (S)-SAL as well as NorSAL only were found in DA-rich areas of the basal ganglia, whereas in other regions of the brain, no TIQs were detected. Especially in the nucleus caudatus, the concentrations of DA, SAL, and NorSAL decreased significantly with rising age. CONCLUSION: These findings do not support the hypothesis that one of the SAL enantiomers or NorSAL is involved in the genesis of alcoholism. However, they suggest that the concentration of the substrate DA may determine the alkaloid level during in vivo formation. The revealed data can serve as reference for other studies in humans concerning the cause of alcoholism or other neurodegenerative diseases with the involvement of TIQs.
Abstract: Beside morphological signs of hypertonic dehydration as tinting of skin, sunken eyes, dry surface of the galea or dry cutting areas of organs, a chemical profile of vitreous humor was proposed as a diagnostic tool for the diagnosis of hypertonic dehydration. The profile consists of an elevation of sodium >155 mmol/l, chloride >135 mmol/l and urea >40 mg/dl. This profile was named dehydration pattern. The value of this dehydration pattern for the diagnosis of hypertonic dehydration will be discussed by a short review of the literature and case reports. So far, the published literature on the dehydration pattern is not a sound scientific basis for the diagnosis of dehydration.
Abstract: High-resolution nuclear magnetic resonance ( NMR) spectroscopy is introduced for the quality control and authenticity assessment of beer in official food control. Measurements were performed using a 400-MHz NMR spectrometer using flow injection technology for automatic sample changing. Only degassing and addition of buffer ( pH 5.6 in D2O for locking and 0.1% TSP for referencing) is required to prepare the beer samples. Differences in the spectral profiles of beers varying in type and origin were studied by principal component analysis ( PCA), considering the spectrum to be a characteristic fingerprint. For the first time, the high throughput of a Flow-Injection NMR system allowed a comprehensive database of beer spectra for PCA classification to be established efficiently. Beers made with barley malt could be distinguished from those made with wheat malt. Clustering of beers from the same brewing sites was observed, as well as significant discrimination of beers with deteriorated quality. Using the partial least squares ( PLS) method to correlate NMR spectra with results from reference methods, models for calculating the original gravity, ethanol and lactic acid were established. The results obtained suggest that NMR is a useful tool in the quality control of beer samples, since quantitative determination of essential compounds as well as chemometric classification are simultaneously possible. Compared to conventional methods, H-1 NMR spectroscopy is faster and requires simpler sample preparation.
Abstract: Ethyl carbamate (urethane, C(2)H(5)OCONH(2)) is a known genotoxic carcinogen of widespread occurrence in fermented food and beverages with highest concentrations found in stone-fruit spirits. Between 1986 and 2004, 631 cherry, plum or mirabelle (yellow plum) spirits were analysed for ethyl carbamate using gas chromatography in combination with mass spectrometry after extrelut extraction. The ethyl carbamate concentration of the samples ranged between 0.01 mg l(-1) and 18 mg l(-1) (mean 1.4 mg l(-1)). After exposure of the samples to UV light, significantly (p=0.001) higher concentrations between 0.01 mg l(-1) and 26 mg l(-1) (mean 2.3 mg l(-1)) were found. The ethyl carbamate concentration increased on average by 1.3 mg l(-1). A linear correlation between the year of sampling and ethyl carbamate concentration showed a statistically significant but very slight decrease (R=-0.10, p=0.024). However, if only samples which officially were non-compliant were considered exceeding the upper limit of 0.4 mg l(-1) more than twice, a significant reduction (R =-0.56, p=0.018) of the quota was evident. This shows that measures to reduce ethyl carbamate were successfully introduced in many distilleries. However, nearly 20 years after the first warnings about ethyl carbamate in spirit drinks, the problem persists especially in products derived from small distilleries. During experimental production of stone-fruit spirits using state-of-the-art technologies, it was shown that the occurrence of ethyl carbamate in stone fruit spirits is preventable. Even for small distilleries, simple possibilities like destoning exist to minimize the ethyl carbamate content.
Abstract: Ethyl carbamate (EC, urethane, C2H5OCONH2) is a known genotoxic carcinogen of widespread occurrence in fermented food and beverages with the highest concentrations being found in stone-fruit spirits. Time-consuming procedures requiring extraction and gas chromatographic-mass spectrometric determination are regarded as reference procedures for the analysis of EC in alcoholic beverages. In this study, the rapid method of Fourier transform infrared (FTIR) spectroscopy in combination with partial least-squares (PLS) regression using selected wavelength bands is applied for the first time to the screening analysis of EC in stone fruit spirits (analysis time only 2 min). Apart from the actual content of EC in the sample, additional information was available from the FTIR spectra. This included data concerning the EC precursor hydrocyanic acid (HCN) and the maximum EC concentration which could be formed during storage. The PLS procedure was validated using an independent set of samples (Q(2) = 0.71-0.76, SEP = 0.42-0.67). The method was found to lack the accuracy required for a quantitative determination; it could only be used semi-quantitatively in the context of a screening analysis. If a rejection level of 0.8 mg L(-1) is applied as cut-off, overall correct classification rates of 85-91% for the calibration set and 77-85% for the validation set were achieved. False negative results can be avoided by lowering the cut-off to 0.6 mg L(-1). Through use of FTIR screening, 60-70% of all samples can be classified as negative and removed, leaving only conspicuous analysis results exceeding cut-off to be confirmed by complex and labour-intensive reference analyses.
Abstract: Gas chromatography (GC) coupled to mass spectrometry (MS) operated in selected ion monitoring (SIM) mode is currently the method of choice for the determination of the toxic contaminant ethyl carbamate in alcoholic beverages. However, even after extensive sample cleanup over diatomaceous earth columns, the identity of ethyl carbamate often cannot be ascertained with confidence, due to inconsistent ratios of the SIM ions m/z 62, 74 and 44 because the qualifier ions are highly susceptible to interferences. Therefore, a new method combining GC and tandem MS using a triple-quadrupole instrument is introduced to determine ethyl carbamate in stone-fruit spirits. For quantitative analysis the characteristic transitions of m/z 74 --> 44 and m/z 62 --> 44 for ethyl carbamate as well as m/z 64 --> 44 for the deuterated internal standard ethyl carbamate-d5 were monitored in the multiple reaction monitoring (MRM) mode. In the validation studies, ethyl carbamate exhibited good linearity with a regression coefficient of 1.000. The limits of detection and quantitation were 0.01 and 0.04 mg/L. The recovery of the method was 100.4 +/- 9.4%. The precision never exceeded 7.8% (intraday) and 10.1% (interday) and the trueness never exceeded 11.3% (intraday) and 12.2% (interday) at any of the concentrations examined, indicating good assay accuracy. A good agreement of analytical results between a previously developed GC/MS SIM method and the GC/MS/MS MRM procedure was found (R=0.987). Regarding the validation data, the procedure is sensitive, selective and reproducible. The applicability of the developed method was demonstrated by the investigation of 70 stone-fruit spirits from commercial trade. The ethyl carbamate concentration of the samples ranged between 0.07 and 7.70 mg/L (mean 1.21 mg/L). The main advantage of the developed GC/MS/MS method is the reliability of the results without the need for time-consuming confirmatory analyses.
Abstract: In Commission Regulation (EC) No 2091/2002, an official reference method for the gas chromatographic determination of anethole in spirit drinks is given. For liqueurs that contain a large amount of sugars (e.g. Sambuca), a labour-intensive and time-consuming extraction procedure is required, because direct injection of the samples would contaminate the GC injection port. Therefore, in this study, the extraction of anethole from spirit drinks was improved. A substantially accelerated liquid-liquid extraction (LLE) procedure using n-hexane was developed. In addition, as an up-to-date alternative, headspace solid-phase microextraction (HS-SPME) was evaluated. Both LLE and HS-SPME showed very good linearities with coefficients of correlation greater than 0.99 and very good precisions between 0.8 and 4.7%. The comparison of both procedures, as well as of the reference method, revealed a significant linear correlation of the results (R > 0.95). For the first time HS-SPME/GC/MS was shown as a fast, sensitive and reliable alternative for the analysis of anethole in alcoholic beverages. In comparison to the reference method, both procedures accomplished a significantly shortened and simplified sample preparation with comparable accuracy. The fully automated HS-SPME extraction, requiring only 6 min, offered the largest advantages.
Abstract: A novel method combination using headspace solid-phase microextraction (HS-SPME) and gas chromatography (GC) was developed for the rapid determination of flavourings in sprit drinks. After addition of phosphate buffer (pH 7) and dicyclohexylmethanol as internal standard, the samples were thermically equilibrated (60 degrees C) and the analytes were extracted from the headspace for 5 min using SPME fibres coated with polydimethylsiloxane. Desorption was done in the hot injection port of the GC system at 220 degrees C. Besides of the determination of alpha-thujone and beta-thujone, HS-SPME allowed the simultaneous analysis of the flavourings pulegone, safrole, isosafrole using flame ionisation detection, and additionally beta-asarone using mass spectrometric detection. For all analytes, the method exhibited good linearity with regression coefficients higher than 0.98 and the precision resulted in ranges between 1.5 and 9.9%. The sensitivity of the method with limits of quantitation below 0.02 mg/l allowed the control of the legal maximum limits for flavourings. The comparison of the new HS-SPME/GC method with conventional extraction techniques like distillation, liquid-liquid-extraction of solid-phase extraction revealed a significant linear correlation of the results (R > 0.99). In contrast to those classical procedures, HS-SPME accomplished a significantly shortened and simplified sample preparation without the use of solvents and with minimal sample quantities, but still maintaining the same degree of sensitivity and reproducibility.
Abstract: This paper introduces a new method of determining alcoholic strength in highly viscous samples like egg liqueurs. The method relies on fully automated steam distillation in combination with oscillation-type densimetry and peristaltic pumping. The procedure is much faster (taking less than 8 min per sample) and easier than the conventional reference method (distillation, pycnometry). This makes it possible to determine alcohol content efficiently and economically, both in official food control and in spirit production. In addition, the total dry extract of the liqueur can be indirectly calculated from the density of the sample and the density of the alcoholic distillate. The parameters for the automatic steam distillation were optimised for the analysis of egg liqueur samples (100% steam power, sample weight 25 g, 130 s distillation time, 50 ml receiver). Validation has proved the method robust and precise. The relative standard deviation was below 0.56% in all cases. By analysing spirit samples under routine conditions, a high correlation (R = 0.999) with the reference method was achieved. (c) 2005 Elsevier B.V. All rights reserved.
Abstract: Absinthe is a spirit drink with a certain bitter taste, which should origin from the bitter substances of the wormwood plant (Artemisia absinthium L.). In this study, besides the principal component thujone, further characteristic components of the essential oil of wormwood are determined in absinthe and the analysis results are interpreted using multivariate statistics to authenticate the spirit drink. An efficient sample preparation using solid-phase extraction (SPE) was performed to separate the lipophilic terpenes from the alcoholic spirit matrix. Gas chromatography in combination with mass spectrometry (GC/MS) was used for separation and quantification of the analytes. The PGA scores plot of 70 absinthes showed discrimination between high-quality absinthes, which were manufactured by distillation of wormwood, and such of inferior quality, made by using small portions of wormwood extracts, macerates, oils or totally without wormwood. Quantitatively determined, 6 absinthes had a thujone content of less than 2 mg/l and in 35 products no thujone was detectable at all. In addition, the typically wormwood taste was missing and the products belonged to the inferior category "without wormwood content". The labelling of the products as "absinthe" was considered to be a deception of the consumer. Summarized, absinthe raises fewer problems in health protection than in the protection of the consumer from deception. Due to extensive control measurements of the official food control in the last years, the maximum limit of thujone is observed by all products. However, due to missing legal requirements on absinthe, a legal uncertainty exists utilised by many manufacturers selling deteriorated products.
Abstract: To evade the new German fiscal legislation, issued to protect young people from the, dangers of alcohol consumption, novel instant beverages containing alcohol are recently sold. The food regulation of such alco-pops in powder form and the aspects regarding the law for the protection of the youth are discussed in this article. Besides deficiencies in the labeling and a significant deviation of the alcoholic strength, the composition of the products was judged as being a deception of the consumer. Ethyl acetate was determined in high contents of more than 400 g/hl of pure ethanol, being untypical for vodka or rum flavored products. Such products may lead to incalculable health consequences, because the possibility of an abusive consume of the undissolved powder cannot be eliminated.
Abstract: To evaluate the influence of stone content on spirit quality from stone fruit, cherry and plum mashes were prepared and fermented with a commercial and a diploid laboratory yeast strain. Fermentation parameters such as sugar content and ethanol production were followed. Despite an initial lag phase in cherry spirits, both yeast strains performed similarly, as substantiated by the determination of specific flavor compounds, ethyl carbamate, and methanol in the mashes and after distillation. The spirits produced were subjected to sensory analyses by trained panels of at least 25 judges. Although mashes retaining the stones could be clearly distinguished from those where the stones had been removed, no significant preference could be attributed to either spirit, indicating that qualities added by the presence of stones during fermentation are largely a matter of personal taste. Interestingly, the yeast strain used for fermentation seemed to have little influence on the spirit quality.
Abstract: A fully automated procedure using alkaline hydrolysis and headspace solid-phase microextraction (HS-SPME), followed by on-fiber derivatization and gas chromatographic-mass spectrometric (GC-MS) detection has been developed for determination of cannabinoids in hemp food samples. After addition of a deuterated internal standard, the sample was hydrolyzed with sodium hydroxide and submitted to direct HS-SPME. After absorption of analytes for on-fiber derivatization, the fiber was placed directly into the headspace of a second vial containing N-methyl- N-trimethylsilyltrifluoroacetamide (MSTFA), before GC-MS analysis. Linearity was good for Delta(9)-tetrahydrocannabinol (THC), cannabidiol, and cannabinol; regression coefficients were greater than 0.99. Depending on the characteristics of the matrix the detection limits obtained ranged between 0.01 and 0.17 mg kg(-1) and the precision between 0.4 and 11.8%. In comparison with conventional liquid-liquid extraction this automated HS-SPME-GC-MS procedure is substantially faster. It is easy to perform, solvent-free, and sample quantities are minimal, yet it maintains the same sensitivity and reproducibility. The applicability was demonstrated by analysis of 30 hemp food samples. Cannabinoids were detected in all of the samples and it was possible to differentiate between drug-type and fiber-type Cannabis sativa L. In comparison with other studies relatively low THC concentrations between 0.01 and 15.53 mg kg(-1) were determined.
Abstract: This review article provides information on all aspects of the bitter spirit, absinthe, and its major components, especially wormwood (Artemisia absinthium L.), which contains the monoterpene, thujone. In addition, the history of the alcoholic drink, from its invention in the 18th century until the recent annulment of its prohibition, is described. Historical and modern recipes are discussed in the context of different quality categories. The analytical techniques used to verify compliance with the maximum limit of thujone as well as the toxicology of absinthe are discussed. Finally, a food regulatory and food chemical evaluation is provided and minimum requirements for absinthe are suggested.
Abstract: In 1996, the prohibition of the cultivation of plants of the species Cannabis sativa L. (so-called fibre hemp) with minor content of the psychoactive Delta(9)-tetrahydrocannabinol (THC) was lifted. Nowadays, a wide variety of hemp food products is offered on the market. As a help for evaluation of such products, this review article provides the official food control with information on all aspects of hemp as foodstuff. An introduction to the botany of the hemp plant and the current law situation in Germany and the European Union is presented. In particular, the forensic-toxicological aspects regarding the influence of hemp food on drug tests are described. Furthermore, an overview of the analytic techniques used to verify compliance with the guidance values is given. Finally, suggestions for the food regulatory and food chemical evaluation of hemp food products are made.
Abstract: This paper introduces a new method of determining ethanol in spirit drinks. The method relies on fully automated steam distillation in combination with densitometry. The procedure is much faster (taking less than 5 minutes per sample) and easier than the conventional reference method (distillation, pycnometry). This makes it possible to determine alcohol content efficiently and economically, both in official food control and in spirit production. Steam distillation works particularly well for emulsion spirits, which are difficult to distil by conventional methods. Validation has proved the method robust and precise. The relative standard deviation was below 0.55% in all cases. The rapid determination has a wide linear range from 2-80%vol which makes it suitable for drinks with a low alcohol content as well as for high percentage spirits. By analysing 100 spirit samples under routine conditions, a high correspondence (R = 0.999) with the reference method was achieved.
Abstract: Using a solid-phase extraction procedure, an enantioselective derivatization and a gas chromatographic-mass spectrometric method, the levels of dopamine (DA) and of the dopamine-derived tetrahydroisoquinoline alkaloids (R)/(S)-salsolinol (SAL) and norsalsolinol (NorSAL) were determined in human brain samples. A complex pre-analytical synthesis of reference substances as well as deuterated internal standards allowed the standardized and reproducible analysis. In this study, to our best knowledge for the first time, the regional distribution of (R)-SAL and (S)-SAL, as well as NorSAL is examined systematically in a large collective of human brain samples obtained by autopsy. The material comprises 91 brains and 8 standardized specimens in each case. Anatomical concentration differences and no ubiquitous occurence were encountered. Significant amounts of (R)-SAL, (S)-SAL and NorSAL were only found in dopamine-rich areas of the basal ganglia, whereas in other regions of the brain no tetrahydroisoquinolines were detected. These findings suggest that the concentration of the substrate dopamine may determine the alkaloid level during in vivo formation. In our opinion, non-enzymatic formation of SAL via the Pictet-Spengler reaction reveals both the SAL enantiomers. An additional enzymatic synthesis of only (R)-SAL could explain the predominant occurrence of this enantiomer. Especially in the nucleus caudatus, the concentrations of DA, SAL and NorSAL decreased significantly with rising age, which may be consistent with apoptotic effects of ageing. Our data can serve as reference for other studies in humans concerning the etiology of alcoholism or other neurodegenerative diseases with the involvement of tetrahydroisoquinolines.
Abstract: In Germany, the substitution of methadone for heroin abusers has arisen recently and has resulted in various medicolegal problems. Normally, these concern methadone-associated deaths, or the prescription of methadone resulting in criminal prosecutions concerning physicians. Not to be forgotten is the problem of driving while taking methadone.In the years 1997-2001, we detected methadone in the blood of 398 cases that were analysed by the Institute of Legal Medicine, Bonn. Methadone was the only drug in only 18 cases. In most of the cases, up to five additional drugs were also being taken: benzodiazepines (61%), ethanol (40%), morphine (39%), cannabinoids (35%), cocaine (28%), anti-depressants (3%), and amphetamines (2%).
Abstract: This article describes a fully automated procedure for detecting cannabinoids in human hair samples. The procedure uses alkaline hydrolysis and headspace solid-phase dynamic extraction (HS-SPDE), followed by on-coating derivatization and gas chromatography-mass spectrometry (GC-MS). SPDE is a further development of solid-phase microextraction (SPME), based on an inside needle capillary absorption trap. It uses a hollow needle with an internal coating of polydimethylsiloxane as extraction and pre-concentration medium.Ten mg of hair were washed with deionised water, petroleum ether and dichloromethane. After adding deuterated internal standards, the sample was hydrolyzed with sodium hydroxide and directly submitted to HS-SPDE. After absorption of analytes for an on-coating derivatization procedure, the SPDE-needle was directly placed into the headspace of a second vial containing N-methyl-N-trimethylsilyl-trifluoroacetamide before GC-MS analysis. The limit of detection was 0.14 ng/mg for Delta(9)-tetrahydrocannabinol, 0.09 ng/mg for cannabidiol, and 0.12ng/mg for cannabinol. Absolute recoveries were in the range of 0.6 to 8.4%. Linearity was verified over a range from 0.2 to 20 ng/mg, with coefficients of correlation between 0.998 and 0.999. Intra- and inter-day precision were determined at two different concentrations and resulted in ranges between 2.3 and 6.0% (intra-day) and 3.3 and 7.6% (inter-day). Compared with conventional methods of hair analysis, this automated HS-SPDE-GC-MS procedure is substantially faster. It is easy to perform without using solvents and with minimal sample quantities, and it yields the same sensitivity and reproducibility. Compared to SPME, we found a higher extraction rate, coupled with a faster automated operation and greater stability of the device.
Abstract: A new method combination, headspace solid-phase dynamic extraction coupled with gas chromatography/tandem mass spectrometry (HS-SPDE/GC/MS/MS), is introduced to determine drugs of abuse in hair samples. This highly automated procedure utilizes SPDE for pre-concentration and on-coating derivatization as well as GC and triple quadrupole MS/MS for selective and sensitive detection. All these steps, apart from washing and cutting of the hair samples, are performed without manual intervention on a robot-like autosampler.SPDE is a solventless extraction technique related to solid-phase microextraction (SPME). The analytes are absorbed from the sample headspace directly into a hollow needle with an internal coating of polydimethylsiloxane by repeated aspirate/dispense cycles.The HS-SPDE/GC/MS/MS procedure was applied to the analysis of methadone, the trimethylsilyl derivatives of cannabinoids and the trifluoroacetyl derivatives of amphetamines and designer drugs. The method was shown to be sensitive with detection limits between 6 and 52 pg/mg hair matrix and precision between 0.4 and 7.8% by the use of an internal standard technique. Linearity was obtained from 0.1-20 ng/mg with coefficients of correlation between 0.995 and 0.999.Compared with conventional methods of hair analysis, HS-SPDE/GC/MS/MS is easier to use, substantially faster, with the degree of sensitivity and reproducibility demanded in clinical and forensic toxicology. The main advantage of the SPDE technique in relation to SPME is the robustness of the capillary.
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.
Abstract: The technique of automated headspace solid-phase dynamic extraction (SPDE) coupled with gas chromatography-mass spectrometry was evaluated for the determination of amphetamines and synthetic designer drugs in hair samples. Headspace SPDE is a novel method for the solventless extraction of organic compounds in aqueous samples. In a so-called inside needle capillary absorption trap a hollow needle with an internal coating of polydimethylsiloxane is used as extraction and preconcentration medium. Sampling is performed on the solution headspace by passing the gas through the device actively by a syringe. Analytes present in the sample are sorbed onto the deposited stationary phase. The syringe needle is placed into the injection port of a GC and rapid heating of the metal needle induces the desorption of analytes. For the determination of amphetamine, methamphetamine, 3,4-methylendioxyamphetamine (MDA), 3,4-methylendioxymethamphetamine, 3,4-methylendioxyethylamphetamine (MDEA), 3,4-methylendioxyphenyl-2-butanamine and N-methyl-1-(3,4-methylendioxyphenyl)-2-butanamine in human hair samples, 10 mg of hair were hydrolysed with sodium hydroxide. After absorption of analytes for an on-coating derivatization procedure the SPDE needle was directly placed into the headspace of a second vial containing N-methyl-bis(trifluoroacetamide). A validation procedure revealed absolute analyte recoveries between 10.2 and 16.7%. Linearity was obtained from 0.1 to 20 ng/mg with coefficients of correlation between 0.992 and 0.999. Intra- and inter-day precision were determined at two different concentrations and resulted in ranges between 1.4 and 4.1% (intra-day) and 4.2-14.6% (inter-day). Limits of detection between 0.03 ng/mg (MDA) and 0.19 ng/mg (MDEA) were achieved. Results indicated that SPDE is a rapid and sensitive method for the analysis of biological samples. Compared to solid-phase microextraction we found a higher extraction rate coupled with a faster automated operation.
Abstract: This paper describes a fully automated procedure using alkaline hydrolysis and headspace solid-phase microextraction (HS-SPME) followed by on-fiber derivatization and gas chromatographic-mass spectrometric (GC-MS) detection of cannabinoids in human hair samples. Ten milligrams of hair was washed with deionized water, petroleum ether, and dichloromethane. After the addition of deuterated internal standards the sample was hydrolyzed with sodium hydroxide and directly submitted to HS-SPME. After absorption of analytes for an on-fiber derivatization procedure the fiber was directly placed into the headspace of a second vial containing N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA) before GC-MS analysis. The limit of detection was 0.05 ng/mg for delta9-tetrahydrocannabinol (THC), 0.08 ng/mg for cannabidiol (CBD), and 0.14 ng/mg for cannabinol (CBN). Absolute recoveries were in the range between 0.3 and 7.5%. Linearity was proved over a range from 0.1 to 20 ng/mg with coefficients of correlation from 0.998 to 0.999. Validation of the whole procedure revealed excellent results. In comparison with conventional methods of hair analysis this automated HS-SPME-GC-MS procedure is substantially faster. It is easy to perform without use of solvents and with minimal sample quantities, but with the same degree of sensitivity and reproducibility. The applicability was demonstrated by the analysis of 25 hair samples from several forensic cases. The following concentration ranges were determined: THC 0.29-2.20 (mean 1.7) ng/mg, CBN 0.55-4.54 (mean 1.2) ng/mg, and CBD 0.53-18.36 (mean 1.3) ng/mg. 11-nor-Delta9-tetrahydrocannabinol-9-carboxylic acid could not be detected with this method.
Abstract: This study describes a fully automated procedure using alkaline hydrolysis and headspace (HS) solid-phase microextraction (SPME) followed by on-fiber derivatization and gas chromatographic (GC)-mass spectrometric (MS) detection of amphetamine, methamphetamine, methylendioxyamphetamine, methylendioxymethamphetamine, methylendioxyethylamphetamine, methylendioxyphenylbutanamine, and methylmethylendioxyphenylbutanamine in human hair samples. Ten milligrams of hair is washed with deionized water, petroleum ether, and dichloromethane. After the addition of deuterated internal standards the sample is hydrolyzed with sodium hydroxide and directly submitted to HS-SPME. After the absorption of analytes for an on-fiber derivatization procedure the fiber is directly placed into the HS of a second vial containing N-methyl-bis(trifluoroacetamide) before GC-MS analysis. The limits of detection are determined between 0.01 and 0.17 ng/mg. Absolute analyte recoveries are in the range between 0.3% and 7.5%. Linearity is proven over a range from 0.1 to 50 ng/mg with coefficients of correlation from 0.998 to 1. In comparison with conventional methods of hair analysis, this fully automated HS-SPME-GC-MS procedure is substantially faster and easier to perform without using solvents. It uses minimal sample amounts and has the same degree of sensitivity and reproducibility.
