RESUMO
Acrolein is a toxic aldehyde that can be present in various beverages, such as cachaça and other distilled spirits from sugarcane. The objective of this work was to detect and quantify acrolein in samples of cachaça produced by different processes in all regions of Brazil and to evaluate the possible routes of formation of this contaminant from the correlation with other secondary compounds present in the beverage using principal component analysis. Approximately 27.0% of the samples analyzed were outside the limit established by Brazilian legislation for this contaminant, with an average acrolein concentration of 14.01 mg 100 mL-1 anhydrous alcohol (aa). In the other samples, the average concentration was 0.97 mg 100 mL-1 aa. After selecting the variables that most closely correlated with the presence of acrolein in beverages, a positive correlation was found with the presence of butan-2-ol, propan-1-ol and volatile acids, and a slight correlation with the presence of phenolic compounds. Therefore, the presence of acrolein in cachaça can be associated with contamination of the fermentation must by bacteria of the genus Lactobacillus, as a result of the chemical degradation and enzymatic conversion of the glycerol produced during fermentation.
Assuntos
Acroleína , Glicerol , Glicerol/análise , Acroleína/análise , Bebidas Alcoólicas/análise , Bebidas/análise , Fermentação , Etanol/análiseRESUMO
Carbonyl compounds and furan derivatives may form adducts with DNA and cause oxidative stress to human cells, which establishes the carcinogenic potential of these compounds. The occurrence of these compounds may vary according to the processing characteristics of the beer. The objective of this study was, for the first time, to investigate the free forms of target carbonyl compounds [acetaldehyde, acrolein, ethyl carbamate (EC) and formaldehyde] and furan derivatives [furfural and furfuryl alcohol (FA)] during the brewing stages of ale and lager craft beers. Samples were evaluated using headspace-solid phase microextraction and gas chromatography with mass spectrometric detection in selected ion monitoring mode (HS-SPME-GC/MS-SIM). Acetaldehyde, acrolein, formaldehyde and furfuryl alcohol were found in all brewing stages of both beer types, while EC and furfural concentrations were below the LOD and LOQ of the method (0.1 and 0.01 µg L-1, respectively). Boiling and fermentation of ale brewing seem to be important steps for the formation of acrolein and acetaldehyde, respectively, while boiling resulted in an increase of FA in both types of beer. Conversely, pasteurisation and maturation reduced the levels of these compounds in both types of beer. An increase in concentration of acrolein has not been verified in lager brew probably due to the difference in boiling time between these two types of beer (60 and 90 min for ale and lager, respectively).
Assuntos
Cerveja/análise , Análise de Alimentos , Contaminação de Alimentos/análise , Acetaldeído/efeitos adversos , Acetaldeído/análise , Acroleína/efeitos adversos , Acroleína/análise , Cerveja/efeitos adversos , Fermentação , Formaldeído/efeitos adversos , Formaldeído/análise , Furanos/efeitos adversos , Furanos/análise , Humanos , Uretana/efeitos adversos , Uretana/análiseRESUMO
Compounds with toxic potential may occur in beer, such as carbonyl compounds (acetaldehyde, acrolein, ethyl carbamate [EC] and formaldehyde) and furan derivatives [furfural and furfuryl alcohol (FA)]. The objective of this study was, for the first time, to validate a method based on headspace-solid phase microextraction using a PDMS-overcoated fibre and gas chromatography with mass spectrometric detection in selected ion monitoring mode (HS-SPME-GC/MS-SIM) to investigate target carbonyl compounds and furan derivatives in beers. Analytical curves showed proper linearity with r2 ranging from 0.9731 to 0.9960 for acetaldehyde and EC, respectively. The lowest LOD was found for acetaldehyde (0.03 µg L-1), while the lowest LOQ value (1.0 µg L-1) was found for acetaldehyde and EC, formaldehyde and furfural. Recovery (90% to 105%), intermediate precision and repeatability (lower than 13%), limits of detection and quantification (values below 2.5 µg L-1) showed that the method is suitable to simultaneously quantify these compounds. EC was detected in only two samples (1 lager and 1 ale). Furfural was found in 37% and 82% of ale and lager beers, respectively. Acetaldehyde, acrolein, formaldehyde and FA were detected in all samples. However, acrolein was the only compound found in the commercial samples at a concentration capable of causing health risk. Besides furfural and FA, four other furan-containing compounds (5-methyl-2-furan methanethiol, acetylfuran, 5-methylfurfural and γ-nonalactone) were also found in beers, however, at levels low enough not to impose potential health risk.
Assuntos
Cerveja/análise , Contaminação de Alimentos/análise , Microextração em Fase Sólida , Acetaldeído/análise , Acroleína/análise , Formaldeído/análise , Furanos/análise , Cromatografia Gasosa-Espectrometria de Massas , Estrutura Molecular , Medição de Risco , Uretana/análiseRESUMO
This work evaluated the presence of contaminants in stored rainwater in 36 polyethylene tanks installed in two rural communities of the semiarid of Bahia, Brazil. Carbonyl compounds were analyzed by High Performance Liquid Chromatography (HPLC-UV), BTEX (Benzene, Toluene, Ethylbenzene and Xylenes) by gas chromatoghaphy (GC-FID), and trace elements by inductively coupled plasma optical emission spectrometry (ICP-OES). Seven carbonyl compounds were quantified including acrolein (<3-115⯵gâ¯L-1), which is considered a potent mutagenic agent, above the potability limit in 75% of the cases. Trace elements such as copper, zinc, barium, aluminum and lead, more frequently found, were also quantified, and lead (<0,56-99⯵gâ¯L-1) was above the tolerable limit for drinking water of 10⯵gâ¯L-1 in 73% of the cases. The results show that the stored water in polyethylene cisterns in the Brazilian semiarid region does not present satisfactory conditions for human consumption.
Assuntos
Água Potável/análise , Polietileno , Poluentes Químicos da Água/análise , Acroleína/análise , Benzeno/análise , Derivados de Benzeno/análise , Brasil , Cromatografia Gasosa/métodos , Cromatografia Líquida de Alta Pressão/métodos , Água Potável/química , Armazenamento de Alimentos/instrumentação , Armazenamento de Alimentos/métodos , Metais/análise , Análise Espectral/métodos , Tolueno/análise , Xilenos/análiseRESUMO
The objective of this research was to estimate for the first time the transformations that the free form of some target carbonyl compounds may undergo during winemaking and assess the exposure risk to these compounds through the consumption of the Merlot commercial wines under study. Acrolein and furfural were found in grapes and the respective wines, although levels were observed to decline throughout the winemaking process. Formaldehyde was found in all stages of wine production in levels lower than the limit of quantification of the method and ethyl carbamate was not found in samples. Acetaldehyde seems to be a precursor of acetoin and 2,3-butanediol, since the levels of this aldehyde decreased along winemaking and the formation of the ester and alcohol was verified. Furfural levels decreased, while the occurrence of furan-containing compounds increased during winemaking. The formation of acetaldehyde during alcoholic fermentation and the potential environmental contamination of grapes with acrolein and furfural are considered as the critical points related to the presence of toxic carbonyl compounds in the wine. Acrolein was found in the samples under study in sufficient quantities to present risk to human health, while other potentially toxic carbonyl compounds did not result in risk. This study indicated for the first time the presence of acrolein in grapes suggesting that environmental pollution can play an important role in the levels of this aldehyde detected in wines. Reduction of the emission of this aldehyde to the environment may be achieved by replacing wood burning by another heat source in fireplaces or wood stones, and abandoning the practice of burning garbage and vegetation.
Assuntos
Acetaldeído/administração & dosagem , Acetaldeído/análise , Acroleína/administração & dosagem , Acroleína/análise , Ingestão de Líquidos , Furaldeído/administração & dosagem , Furaldeído/análise , Vinho/análise , Fermentação , Humanos , Medição de Risco , Vitis/químicaRESUMO
Acrolein is a pollutant released daily to the indoor environment from different sources. The present study reports the development of a simple and sensitive cold fiber solid phase microextraction sampling method for the determination of acrolein in exhaled air and indoor air by gas chromatography mass spectrometry. O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine was used as derivatizing agent supported on a 65-µm polydimethylsiloxane-divinylbenzene SPME fiber. An acrolein permeation tube at 326.25 ng min-1 rate was used to generate gaseous standards. The method shows good results for main validation parameters. The limits of detection and quantification were 2.88 and 5.08 µg m-3, respectively, for indoor analysis; and 2.40 and 3.79 µg m-3, respectively, for exhaled air analysis. The precision showed standard deviation ranges from 6.00 to 8.00% for intra-assay analyses and from 8.00 to 10.00% for inter-assay analyses. After optimizing the conditions, analyses of real samples were performed on indoor environments contaminated by cigarette smoke, or heated oil, including pastry shops, restaurants, churros stands, and closed parking cars located in the city of Belo Horizonte, Brazil. Acrolein breaths of exposed people were also determined. A good Pearson correlation coefficient (r = 0.901) was observed between the concentration of acrolein in indoor air and exhaled air, allowing to propose acrolein breath as environmental exposure biomarker. Graphical Abstract Cold fiber solid phase microextraction gas chromatography/mass spectrometry.
Assuntos
Acroleína/análise , Poluição do Ar em Ambientes Fechados/análise , Testes Respiratórios/métodos , Monitoramento Ambiental/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Microextração em Fase Sólida/métodos , Acroleína/química , Humanos , Metais/química , Reprodutibilidade dos Testes , Sensibilidade e EspecificidadeRESUMO
A method was developed for the extraction and UFLC-DAD-ESI-MS analysis of carbonyl compounds (CCs) in oils heated to 180°C. Different parameters were evaluated, and the best results were 1.5ml of acetonitrile as the extraction solvent, manual stirring for 3min and 30min of sonication time. The method was validated using soybean oil samples spiked with CCs at concentration levels ranging from 0.2 to 10.0µg.mL-1. The average recoveries in the lowest concentration level ranged from 70.7% to 85.0%. Detection limits ranged from 0.03 to 0.1µg.mL-1, and the quantification limit was 0.2µg.mL-1 for all compounds. When the method was applied to samples of heated oil, the CCs identified were 4-hydroxy-2-nonenal, 2,4-decadienal, 2,4-heptadienal, 4-hydroxy -2-hexenal, acrolein, 2-heptenal, 2-octenal, 4,5-epoxy-2-decadal, 2-decenal, and 2-undecenal, with the first three mentioned presenting the highest mean concentrations after heating, specifically 36.9, 34.8 and 22.6µg.g-1 of oil, respectively.
Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Óleo de Soja/análise , Espectrometria de Massas por Ionização por Electrospray/métodos , Acroleína/análise , Aldeídos/análise , CalefaçãoRESUMO
The present study aimed to develop a methodology using capillary electrophoresis for the determination of sinapaldehyde, syringaldehyde, coniferaldehyde, and vanillin in whiskey samples. The main objective was to obtain a screening method to differentiate authentic samples from seized samples suspected of being false using the phenolic aldehydes as chemical markers. The optimized background electrolyte was composed of 20 mmol L(-1) sodium tetraborate with 10% MeOH at pH 9.3. The study examined two kinds of sample stacking, using a long-end injection mode: normal sample stacking (NSM) and sample stacking with matrix removal (SWMR). In SWMR, the optimized injection time of the samples was 42 s (SWMR42); at this time, no matrix effects were observed. Values of r were >0.99 for the both methods. The LOD and LOQ were better than 100 and 330 mg mL(-1) for NSM and better than 22 and 73 mg L(-1) for SWMR. The CE-UV reliability in the aldehyde analysis in the real sample was compared statistically with LC-MS/MS methodology, and no significant differences were found, with a 95% confidence interval between the methodologies.
Assuntos
Bebidas Alcoólicas/análise , Eletroforese Capilar/métodos , Contaminação de Alimentos/análise , Acroleína/análogos & derivados , Acroleína/análise , Bebidas Alcoólicas/classificação , Benzaldeídos/análiseRESUMO
The frying of foods in the home can be a cause of indoor pollution due to the formation of acrolein. The emission of acrolein formed during frying in soybean, corn, canola, sunflower and palm oils was studied. A GC/MS method has been developed to determine acrolein in French fries using SPME as the sampling technique after derivatization with 2,4-dinitrophenylhydrazine (DNPH). Optimum SPME conditions included desorption at 250°C for 2min after an adsorption time of 10min at room temperature. The method presented good resolution, repeatability, detection and quantification limits, and linearity of response. French fries were prepared in five different oils with four frying steps. The results showed that changes in acrolein concentration occurred after frying potatoes in different types of oil and at different frying cycles. Potatoes fried in soybean oil contained the lowest concentration of acrolein. Shoestring potatoes contained a lower concentration of acrolein than potato chips and French fries, respectively, because of the higher surface/volume ratio.
Assuntos
Acroleína/análise , Culinária/métodos , Fast Foods/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Solanum tuberosum/química , Microextração em Fase Sólida/métodos , Acroleína/metabolismo , Temperatura Alta , Hidrazinas , Óleos de Plantas/química , Reprodutibilidade dos Testes , Cloreto de Sódio , ViscosidadeRESUMO
Acrolein is an alpha,beta-unsaturated aldehyde with enormous capacity of reaction, occurs in the air like a pollutant, but it is (we know now) an important lipid peroxidation product as well. The compound is one of the several aldehydes produced from fatty acid oxidation, although it is particularly important because it constitutes the major electrophyle aldehyde derived from lipid oxidation. Acrolein can be formed actively from oxidized fatty acids and undergo aldolic condensation in alkaline pH; this is a particular characteristic that we have used in its process of separation with capillary electrophoresis. We have shown that the oxidation of unsaturated fatty acids forms acrolein, and that the use of capillary electrophoresis to be a powerful, sensitive, and attractive method for separation, identification, and quantization of this and other aldehydes from in vitro lipid peroxidation.