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Determinação e quantificação de hidrocarbonetos aromáticos policíclicos em peixe fumado
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A fumagem constitui um método tradicional de processamento alimentar que, além de conferir características organoléticas distintivas, permite a conservação de diversos produtos. No entanto, durante este processamento podem formar-se hidrocarbonetos aromáticos policíclicos (HAP), alguns dos quais apresentam propriedades tóxicas, mutagénicas e carcinogénicas, constituindo uma preocupação significativa em termos de segurança alimentar.
O principal objetivo deste estudo foi determinar e quantificar os níveis dos 16 HAP prioritários da US-EPA, juntamente com o dibenzo[a,l]pireno (DB[a,l]P) e o benzo[j]fluoranteno (B[j]F) nos produtos de peixe fumado disponíveis no mercado português, avaliando a conformidade com os limites legais da legislação europeia (Regulamento (UE) 2023/915). A análise das amostras foi realizada através do método de extração QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe), seguido de cromatografia líquida de alta eficiência com deteção por arranjo de díodos e fluorescência (HPLC-DAD/FLD). Complementarmente, foi avaliado o teor de gordura total, o teor de humidade e o perfil de ácidos gordos (AG), com o objetivo de explorar possíveis correlações com os níveis de HAP. A validação do método de análise dos HAP foi realizada de acordo com o Regulamento (UE) N.º 836/2011, com resultados que demonstraram
elevada precisão, sensibilidade, recuperação adequada e conformidade com a legislação. A análise de HAP nos produtos de peixe fumado das espécies de salmão, truta, bacalhau e atum, mostrou para todas as amostras teores inferiores aos limites legais da União Europeia (UE). As concentrações de ΣHAP4 foram muito baixas, variando entre valores inferiores aos limites de quantificação (LOQ) e 0,29 μg/kg, enquanto o salmão fumado apresentou os níveis
mais elevados de ΣHAP18, com concentrações compreendidas entre 27,74 e 90,59 μg/kg. As amostras de truta também apresentaram teores consideráveis (5,02 a 53,90 μg/kg), enquanto as amostras de atum revelaram uma contaminação intermédia, com um ΣHAP18 entre 0,68 e 22,98 μg/kg. As amostras de bacalhau apresentaram a menor contaminação (1,05 a 2,59 μg/kg). Os HAP predominantes foram os de baixo peso molecular (2-3 anéis aromáticos), enquanto
os compostos de maior peso molecular e mais tóxicos como o benzo[a]pireno (B[a]P), dibenz[a,h]antraceno (DB[a,h]A) e DB[a,l]P não foram detetados, exceto o DB[a,h]A numa amostra de salmão. Na análise lipídica, o salmão e a truta apresentaram os maiores teores de gordura total em comparação com as outras espécies (atum e bacalhau). Embora tenham sido observadas correlações positivas entre o teor de gordura e os níveis de HAP, estas não foram estatisticamente significativas. A análise do perfil AG indicou uma possível relação inversa entre a percentagem de ácidos gordos polinsaturados (PUFA), particularmente ómega-3, e os níveis de ΣHAP18. Porém, a variação nas amostras impediu a identificação de uma relação descritiva entre o perfil de AG e os níveis de HAP. Em relação ao teor de humidade, não foi observada uma correlação estatisticamente significativa com as concentrações de HAP.
De forma geral, os resultados indicam que a formação e contaminação por HAP em peixe fumado é um fenómeno complexo e multifatorial, difícil de associar de forma estatística significativa a determinados fatores. Importa ainda referir que o número limitado de amostras poderá ter condicionado a significância estatística de algumas correlações observadas. Estudos futuros com maior número de amostras poderão permitir uma avaliação mais robusta das relações entre variáveis, contribuindo para a confirmação de tendências identificadas. Apesar das limitações, os resultados obtidos reforçam a conformidade dos produtos de peixe fumado disponíveis no mercado português com os requisitos legais, contribuindo para a avaliação da segurança alimentar. A predominância de compostos menos tóxicos e a ausência de HAP com maior fator de toxicidade equivalente (TEF) em quase todas as amostras foram indicadores muito favoráveis.
Smoking is a traditional food processing method that, in addition to imparting distinctive organoleptic characteristics, allows for the preservation of various products. However, during this process, polycyclic aromatic hydrocarbons (PAHs) may be formed, some of which exhibit toxic, mutagenic, and carcinogenic properties, representing a significant concern in terms of food safety. The main objective of this study was to determine and quantify the levels of the 16 priority PAHs established by the US-EPA, together with dibenzo[a,l]pyrene (DB[a,l]P) and benzo[j]fluoranthene (B[j]F), in smoked fish products available on the portuguese market, assessing their compliance with the legal limits set by European legislation (Regulation (EU) 2023/915). Sample analysis was carried out using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction method, followed by high-performance liquid chromatography with diode-array and fluorescence detection (HPLC-DAD/FLD). In addition, the total fat content, moisture content and fatty acid (FA) profile were evaluated, aiming to explore possible correlations with PAH levels. The analytical method validation for PAHs was performed in accordance with Regulation (EU) N.º 836/2011, with results demonstrating high precision, sensitivity, suitable recovery and compliance with legislation. The analysis of PAHs in smoked fish products from salmon, trout, cod, and tuna species showed that all samples had levels below the legal limits of the European Union (EU). ΣPAH4 concentrations were very low, ranging from values below the limits of quantification (LOQ) to 0.29 μg/kg, while smoked salmon showed the highest ΣPAH18 levels, with concentrations between 27.74 and 90.59 μg/kg. Trout samples also presented considerable levels (5.02-53.90 μg/kg), while tuna samples showed intermediate contamination, with ΣPAH18 between 0.68 and 22.98 μg/kg. Cod samples showed the lowest contamination (1.05-2.59 μg/kg). The predominant PAHs were those of low molecular weight (2-3 aromatic rings), while higher molecular weight and more toxic compounds such as benzo[a]pyrene (B[a]P), dibenz[a,h]anthracene (DB[a,h]A), and DB[a,l]P were not detected, except for DB[a,h]A in one salmon sample. In the lipid analysis, salmon and trout showed the highest total fat contents compared with the other species (tuna and cod). Although positive correlations were observed between fat content and PAH levels, these were not statistically significant. The FA profile analysis suggested a possible inverse relationship between the percentage of polyunsaturated fatty acids (PUFA), particularly omega-3, and ΣPAH18 levels. However, sample variability prevented the identification of a descriptive relationship between the FA profile and PAH levels. Regarding moisture content, no statistically significant correlation was observed with PAH concentrations. Overall, the results indicate that PAH formation and contamination in smoked fish is a complex and multifactorial phenomenon, difficult to associate statistically with specific factors. It should also be noted that the limited number of samples may have affected the statistical significance of some observed correlations. Future studies with a larger number of samples may allow a more robust assessment of the relationships between variables, contributing to the confirmation of the identified trends. Despite the limitations, the results obtained reinforce the compliance of smoked fish products available on the portuguese market with legal requirements, contributing to the assessment of food safety. The predominance of less toxic compounds and the absence of PAHs with higher toxic equivalency factors (TEF) in almost all samples were very favorable indicators.
Smoking is a traditional food processing method that, in addition to imparting distinctive organoleptic characteristics, allows for the preservation of various products. However, during this process, polycyclic aromatic hydrocarbons (PAHs) may be formed, some of which exhibit toxic, mutagenic, and carcinogenic properties, representing a significant concern in terms of food safety. The main objective of this study was to determine and quantify the levels of the 16 priority PAHs established by the US-EPA, together with dibenzo[a,l]pyrene (DB[a,l]P) and benzo[j]fluoranthene (B[j]F), in smoked fish products available on the portuguese market, assessing their compliance with the legal limits set by European legislation (Regulation (EU) 2023/915). Sample analysis was carried out using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction method, followed by high-performance liquid chromatography with diode-array and fluorescence detection (HPLC-DAD/FLD). In addition, the total fat content, moisture content and fatty acid (FA) profile were evaluated, aiming to explore possible correlations with PAH levels. The analytical method validation for PAHs was performed in accordance with Regulation (EU) N.º 836/2011, with results demonstrating high precision, sensitivity, suitable recovery and compliance with legislation. The analysis of PAHs in smoked fish products from salmon, trout, cod, and tuna species showed that all samples had levels below the legal limits of the European Union (EU). ΣPAH4 concentrations were very low, ranging from values below the limits of quantification (LOQ) to 0.29 μg/kg, while smoked salmon showed the highest ΣPAH18 levels, with concentrations between 27.74 and 90.59 μg/kg. Trout samples also presented considerable levels (5.02-53.90 μg/kg), while tuna samples showed intermediate contamination, with ΣPAH18 between 0.68 and 22.98 μg/kg. Cod samples showed the lowest contamination (1.05-2.59 μg/kg). The predominant PAHs were those of low molecular weight (2-3 aromatic rings), while higher molecular weight and more toxic compounds such as benzo[a]pyrene (B[a]P), dibenz[a,h]anthracene (DB[a,h]A), and DB[a,l]P were not detected, except for DB[a,h]A in one salmon sample. In the lipid analysis, salmon and trout showed the highest total fat contents compared with the other species (tuna and cod). Although positive correlations were observed between fat content and PAH levels, these were not statistically significant. The FA profile analysis suggested a possible inverse relationship between the percentage of polyunsaturated fatty acids (PUFA), particularly omega-3, and ΣPAH18 levels. However, sample variability prevented the identification of a descriptive relationship between the FA profile and PAH levels. Regarding moisture content, no statistically significant correlation was observed with PAH concentrations. Overall, the results indicate that PAH formation and contamination in smoked fish is a complex and multifactorial phenomenon, difficult to associate statistically with specific factors. It should also be noted that the limited number of samples may have affected the statistical significance of some observed correlations. Future studies with a larger number of samples may allow a more robust assessment of the relationships between variables, contributing to the confirmation of the identified trends. Despite the limitations, the results obtained reinforce the compliance of smoked fish products available on the portuguese market with legal requirements, contributing to the assessment of food safety. The predominance of less toxic compounds and the absence of PAHs with higher toxic equivalency factors (TEF) in almost all samples were very favorable indicators.
Descrição
Palavras-chave
Contamination Levels Food Safety HPLC Lipid Analysis PAH QuEChERS Análise lipídica HAP Níveis de contaminação Segurança alimentar