Concentration and potential health risk of polycyclic aromatic hydrocarbons for consumers of chocolate in Brazil.

Chocolate is widely consumed worldwide and its market grows every year, with emerging demands for new high-quality products. However, this product is susceptible to contamination with polycyclic aromatic hydrocarbons (PAHs), representing a risk for humans. In this study, a methodology for the evaluation of benzo[a]pyrene, benzo[a]anthracene, benzo[b]fluoranthene and chrysene in chocolate by high performance liquid chromatography was validated. The occurrence, dietary exposure, and health risks of 4 PAHs in 38 commercial chocolate samples was investigated. The methodology demonstrated adequate accuracy and precision, with recovery (95.25 %-108.12 %) and relative standard deviation (0.14 %-5.83 %). Benzo[a]pyrene and the ∑4 PAHs concentrations varied between 1.09 and 10.42 µg/kg and 8.38-41.58 µg/kg, respectively. The results of risk assessment suggest low potential health risk for chocolate consumers, considering the margin of exposure (MOE) and the incremental life cancer risk (ILCR) values.

Quantification of Polycyclic Aromatic Hydrocarbons in Commonly Consumed Salami in Brazil

Polycyclic aromatic hydrocarbons (PAHs) are organic compounds that have been found in different food categories, and meat products can have high concentrations of PAHs, since the technological processes to which they are subjected, such as smoking, can produce several compounds. Considering the risk that these compounds can bring to the population's health, it is essential to develop an accurate and reliable method to evaluate the contamination of PAHs in products of animal origin. The objective of this study was to optimize and validate a method for the quantification of 4 PAHs (benz[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene) in salami. The methodology included saponification, liquid­liquid extraction, solid-phase purification, and quantification by ultra-high-performance liquid chromatography. The effects of saponification parameters were investigated by experimental design, whereas the model obtained by regression analysis was considered satisfactory with the dissolution solvent of potassium hydroxide providing the highest global sum of areas. In validation, the parameters studied were adequate and within European and INMETRO Guidelines limits. The evaluation of 22 samples indicated that 27% were contaminated with at least one of the 4 PAHs, and benz[a]anthracene being the prevalent one with content varying between < 1.00 and 17.58 µg/kg. Two samples showed PAHs contamination above the maximum tolerable limit in the European Commission Regulation.

Bioactive compounds of parsley (Petroselinum crispum), chives (Allium schoenoprasum L) and their mixture (Brazilian cheiro-verde) as promising antioxidant and anti-cholesterol oxidation agents in a food system.

This study determined the bioactive composition and antioxidant potential of parsley, chives and their mixture (Brazilian cheiro-verde). Additionally, the effect of these herbs against cholesterol oxidation in grilled sardines (Sardinella brasiliensis) was also investigated. Ultra-high Performance Liquid Chromatography-Electrospray Ionization-Mass Spectrometry (UHPLC-ESI-MS) analyses revealed the presence of phenolic acids (caffeic, chlorogenic, and ferulic acids) and flavonoids (apigenin, kaempferol, catechin) in the herbs. Higher levels of phenolics (2.10 ± 0.02 mg GAE/g) and carotenoids (205.95 ± 0.17 µg/g) were determined in parsley extracts. Moreover, parsley also presented higher antioxidant capacity by DPPH (59.21 ± 0.07 %) and ORAC (109.94 ± 18.7 µM TE/g) than the other herbs. In vivo analyses demonstrated that the herbs' extracts decreased the damage on Saccharomyces cerevisiae cells exposed to H2O2, except the chives extract at 10 µg/mL. Higher levels of cholesterol oxidation products (COPs) were determined after grilling. The total COPs increased from 61.8 ± 0.7 (raw fish) to 139.7 ± 10.1 µg/g (control). However, the addition of herbs effectively reduced cholesterol oxides formation, this effect was more pronounced in fish containing 4% parsley and 4% cheiro-verde. Promising results were found for cheiro-verde; however, it did not present synergic antioxidant effects.

Polycyclic Aromatic Hydrocarbons in Foods: Biological Effects, Legislation, Occurrence, Analytical Methods, and Strategies to Reduce Their Formation.

Polycyclic aromatic hydrocarbons (PAHs) are chemical compounds comprised of carbon and hydrogen molecules in a cyclic arrangement. PAHs are associated with risks to human health, especially carcinogenesis. One form of exposure to these compounds is through ingestion of contaminated food, which can occur during preparation and processing involving high temperatures (e.g., grilling, smoking, toasting, roasting, and frying) as well as through PAHs present in the soil, air, and water (i.e., environmental pollution). Differently from changes caused by microbiological characteristics and lipid oxidation, consumers cannot sensorially perceive PAH contamination in food products, thereby hindering their ability to reject these foods. Herein, the occurrence and biological effects of PAHs were comprehensively explored, as well as analytical methods to monitor their levels, legislations, and strategies to reduce their generation in food products. This review updates the current knowledge and addresses recent regulation changes concerning the widespread PAHs contamination in several types of food, often surpassing the concentration limits deemed acceptable by current legislations. Therefore, effective measures involving different food processing strategies are needed to prevent and reduce PAHs contamination, thereby decreasing human exposure and detrimental health effects. Furthermore, gaps in literature have been addressed to provide a basis for future studies.

The anticholesterol oxidation effects of garlic (Allium sativum L.) and leek (Allium ampeloprasum L.) in frozen fish burgers submitted to grilling.

This study determined the total phenolic content and antioxidant capacity of garlic (Allium sativum L.) and leek (Allium ampeloprasum L.), as well as evaluated their anticholesterol oxidation potential in fish burgers. The total phenolic contents were 1.1 ± 0.1 mg GAE/g FW to garlic and 1.3 ± 0.4 mg GAE/g FW for leek. Leek extract showed antioxidant activity index (1.3 ± 0.01) in DPPH and ß-carotene/linoleic acid assay (66.5 ± 1.6%); however, in ORAC assay, no statistic differences were observed (P > 0.05). Besides that, bioactive compounds of garlic and leek extracts were identified by ultra-high performance liquid chromatography-electrospray by ionization-mass spectrometry (UHPLC-ESI-MS). Fish burgers were prepared using different concentrations of leek and garlic and stored at -18 °C for 90 days. Thus, at days 0, 30, 60, and 90, the samples were grilled and analyzed as to their cholesterol and cholesterol oxidation products contents. Storage and grilling led to an increase in cholesterol oxidation products; however, addition of garlic and leek minimized cholesterol oxidation products formation. After 90 days, samples containing 3% leek + 0.5% garlic ware the most effective in inhibiting the cholesterol oxides formation during storage and showed the lowest increase in cholesterol oxidation products content (21.16%). Thus, the findings of this research indicate the potential application of garlic and leek as natural inhibitors of cholesterol oxidation in food. PRACTICAL APPLICATION: Garlic and leek have a set of bioactive compounds with a wide antioxidant capacity when used in meat foods such as fish burgers. Garlic and leek used as natural antioxidants perform well in the shelf life of fish burgers and can be substitutes for synthetic antioxidants in this type of product. The presence of both vegetables reduced the formation of prejudicial products to human health generated during the shelf life of the food.

Avaliação da presença de hidrocarbonetos policíclicos aromáticos em chocolates: exposição ao consumo e implicações à saúde / Evaluation of the presence of polycyclic aromatic hydrocarbons in chocolates: exposure to consumption and health implications

Introdução - Os hidrocarbonetos policíclicos aromáticos (HPAs) são compostos que apresentam ação potencialmente carcinogênica e mutogênica, que geram risco à saúde humana. Esses contaminantes são formados a partir da combustão incompleta de matéria orgânica, podendo ocorrer a formação durante o processamento dos alimentos em âmbito industrial (secagem, torra, pré-cozimento) e doméstico (fritar, assar e grelhar) pelo emprego de altas temperaturas. Para a produção do chocolate e outros produtos derivados do cacau, etapas como a secagem, torra e conchagem, são processos que utilizam altas temperaturas e essenciais para a produção de chocolates. Não existem estudos avaliando a presença e a exposição dietética por HPAs em chocolates no Brasil. Objetivo - Otimizar e validar a metodologia de extração e quantificação de 4 HPAs (benzo[a]antraceno (BaA), criseno (Cri), benzo[b]fluoranteno (BbF) e benzo[a]pireno (BaP)) em chocolates, quantificar sua presença em amostras de chocolates comerciais e estimar a exposição dietética aos HPAs a partir do consumo de chocolate. Métodos - As amostras de chocolate (ao leite, branco e amargo com porcentagens de cacau de 40%, 53%, 55%, 60% e 70%) foram obtidas no comércio da cidade de São Paulo. Foi realizada a otimização e validação da metodologia pelos parâmetros de linearidade, seletividade, limite de detecção, limite de quantificação, recuperação e repetibilidade. As amostras foram submetidas a extração líquido-líquido, extração em fase sólida e quantificadas por cromatógrafo líquido de alta eficiência com detector de fluorescência. A estimativa de exposição dietética (DEs) para benzo[a]pireno foi avaliada para três categorias: 1) Sexo (feminino e masculino); 2) Grupos etários: adolescentes (14 a 18 anos), adultos (19 a 59 anos) e idosos (>= 60 anos); 3) Local de residência (urbana e rural). Resultados - O método obteve faixa de linearidade entre 0,50 e 5,00 µg.kg-1 para os quatro HPAs. Com relação à seletividade, houve interferência da matriz apenas para o BaP. O método também mostrou acurácia, com recuperações médias variando entre 95,25 a 108,27% e repetibilidade mostrando valores entre 0,14 e 7,25%. Benzo[a]pireno foi encontrado em todos os chocolates, variando entre 1,58 a 4,34 µg.kg-1 de gordura. As amostras de chocolate com 53-60% cacau e chocolate 70% cacau apresentaram as maiores taxas de contaminação para BaP; já as amostras de chocolate 40% cacau e chocolate ao leite apresentaram menor contaminação. Quanto a exposição dietética, as mulheres (por gênero) e os adolescentes (por idade) apresentaram maiores DEs para BaP pelo consumo de chocolate, principalmente para o chocolate 70% cacau. Os resultados apresentaram baixa contaminação por HPAs nos chocolates analisados, no entanto, o consumo aumentado por diferentes faixas etárias pode contribuir para a DEs ao BaP. Conclusões - A metodologia padronizada foi considerada seletiva e sensível, garantindo a eficiência do ensaio. As amostras analisadas apresentaram resultados abaixo dos limites estabelecidos pelo Regulamento da Comunidade Européia No. 835/2011 para o BaP e para a soma dos 4 HPAs. Frente aos grupos analisados (sexo, idade e local de residência), os chocolates 70% cacau contribuíram para a maior exposição dietética à BaP. A presença dos quatro HPAs prioritários nos chocolates analisados demonstrou a importância de programas de monitoramento da cadeia produtiva em produtos de cacau (massa de cacau, manteiga de cacau e cacau em pó) e ingredientes adicionados (açúcar e leite em pó).

Introduction - Polycyclic aromatic hydrocarbons (PAHs) are compounds that have a potentially carcinogenic and mutogenic action, which generate risk to human health. These contaminants are formed from the incomplete combustion of organic matter, which can occur during industrial (drying, roasting, pre-cooking) and domestic (frying, roasting and grilling) processing of food by the use of high temperatures. For the production of chocolate and other products derived from cocoa, steps such as drying, roasting and conching are processes that use high temperatures and are essential for the production of chocolates. There are no studies evaluating the presence and dietary exposure to PAHs in chocolates in Brazil. Objective - To optimize and validate the methodology for the extraction and quantification of 4 PAHs (benzo[a]anthracene (BaA), chrysene (Chr), benzo[b]fluoranthene (BbF) and benzo[a]pyrene (BaP)) in chocolates, quantify the presence in commercial chocolate samples and estimate dietary exposure to PAHs from the consumption of chocolate. Methods - Chocolate samples (milk, white and dark with cocoa percentages of 40%, 53%, 55%, 60% and 70%) were obtained from commercial stores in the city of São Paulo. The methodology was optimized and validated by the parameters of linearity, selectivity, limit of detection, limit of quantification, recovery and repeatability. The samples were subjected to liquid-liquid extraction, solid-phase extraction and quantified by a High Performance Liquid Chromatograph with fluorescence detector. The dietary exposure estimate (DEs) for benzo[a]pyrene was assessed for three categories: 1) Gender (female and male); 2) Age groups: adolescents (14 to 18 years), adults (19 to 59 years) and elderly (>= 60 years); 3) Place of residence (urban and rural). Results - The method obtained a linearity range between 0.50 and 5.00 µg.kg-1 for the four PAHs. Regarding selectivity, there was interference from the matrix only for BaP. The method also showed accuracy, with average recoveries ranging from 95.25 to 108.27% and repeatability showing values between 0.14 and 7.25%. Benzo[a]pyrene was found in all chocolates, ranging from 1.58 to 4.34 µg.kg-1 of fat. Chocolate samples with 53-60% cocoa and chocolate 70% cocoa showed the high contamination for BaP; the 40% cocoa and milk chocolate samples showed low contamination. As for dietary exposure, women (by gender) and adolescents (by age) had higher DEs for BaP due to chocolate consumption, especially for 70% cocoa chocolate. The results showed low contamination by PAHs in the analyzed chocolates, however, the increased consumption by different age groups can contribute to DEs to BaP. Conclusions - The standardized methodology was considered selective and sensitive, ensuring the efficiency of the test. The analyzed samples showed results below the limits established by the European Community Regulation No. 835/2011 for the BaP and for the sum of the 4 PAHs. In view of the groups analyzed (gender, age and place of residence), chocolates 70% cocoa contributed to the greater dietary exposure to BaP. The presence of the four priority PAHs in the analyzed chocolates demonstrated the importance of programs to monitor the production chain in cocoa products (cocoa mass, cocoa butter and cocoa powder) and ingredients used in chocolate formulation (sugar and powdered milk).