Brazil is the country with the greatest biodiversity on the planet and a major producer of food. Tropical fruits, especially natives from Brazil, may contain considerable amounts of carotenoids that have antioxidant, anti-inflammatory, provitamin A and anticancer actions, such as β-carotene and lycopene. The food structure design concept aims to manipulate the food matrix for specific purposes, e.g. the preservation and manipulation of carotenoid bioaccessibility. The aim of this thesis was to explore tropical fruits, native and exotic from Brazil in the development of delivery systems for carotenoids. A screening step was carried out with 11 fruits, among which 2 were selected, the pitanga (Eugenia uniflora) and buriti (Mauritia flexuosa) fruits that were used for the production of microemulsions. At the screening were evaluated the proximate composition, fiber contents, carotenoid profiles and bioacessibilities. The nutritional value demonstrated that these fruits have high potential as raw-materials for healthy products due to their high fiber, minerals and carotenoid contents in addition to low energy value. Analysis by HPLC-DAD allowed the identification of 14 carotenoids in the 11 fruits studied for the screening. Results demonstrated the superiority of the bioaccessibility of xanthophylls (ranging 10 % - 52 %) in relation to carotenes, and the low bioaccessibility of lycopene from pitanga (1.1 %) and average bioaccessibility of β-carotene from buriti (26 %). Pitanga and buriti had their carotenoid profiles analyzed and monitored throughout an in vitro simulation of the digestion coupled with caco-2 cell cultures. Although xanthophylls are more bioaccessible, the intestinal ephitelium absorb preferentially the provitamin A carotenoids, such β-carotene and β-criptoxanthin. In order to produce these microemulsions, high-speed homogenization (HSH) and ultrasound (US) were studied in combination with the use of surfactants (Whey Protein Isolate and Tween 80), and addition of corn oil as carotenoid carrier. The experiments have shown that the interaction of US and HSH is capable to break cell walls and release carotenoids with higher efficiency. Optical and fluorescence microscopy, as well as carotenoid analysis demonstrated that it was possible to manipulate the food matrix structure releasing the carotenoids from the plant cells and encapsulating them inside the oil droplets, what increased their retention after processing. The microemulsion were affected by time of processing and by surfactant related to their rheology, final structure, stability of emulsion and carotenoid stability to processing. Finally, a dynamic gastrointestinal system was used to compare the behavior of carotenoids from whole fruit pulps and selected microemulsions (2% Tween 80, 5% corn oil, processed by HSH-US 4 min -4 min). The results demonstrated that it was possible to increase the stability to digestion and bioaccessibility of total carotenoids, lycopene and β-carotene from the microemulsions. / O Brasil é o país detentor da maior biodiversidade do planeta e um grande produtor de alimentos. Frutas tropicais, em especial as nativas brasileiras, podem conter quantidades consideráveis de carotenoides que possuem ação antioxidante, anti-inflamatória, provitamina A e anticâncer, como β-caroteno e licopeno. O desenho estrutural dos alimentos (food structure design), visa manipular a matriz alimentar com fins específicos, por exemplo, a preservação e manipulação da bioacessibilidade de carotenoides. Na presente tese buscou-se explorar frutas brasileiras não-convencionais no desenvolvimento de sistemas de entrega de carotenoides. Foi realizada uma etapa de triagem com 11 frutas, dentre as quais, 2 foram selecionadas, a pitanga (Eugenia uniflora) e o buriti (Mauritia flexuosa), e utilizadas na produção de microemulsões. Nesta triagem foram avaliadas a composição centesimal, o teor de fibras, o perfil de carotenoides e a bioacessibilidade destes carotenoides. O valor nutricional das frutas demonstrou seu potencial para utilização em produtos saudáveis, devido a seus teores eleveados de fibras, minerais e carotenoides além do baixo teor calórico. A análise por HPLC-DAD permitiu identificar até 14 carotenoides nas amostras das 11 frutas estudadas na triagem. O estudo da bioacessibilidade dos carotenoides das 11 frutas demonstrou principalmente a superioridade da bioacessibilidade de xantofilas (variando de 10 a 52 %) em relação aos carotenos, e portanto a baixa bioacessibilidade de licopeno da pitanga (1,1%) e média bioacessibilidade de β-caroteno do buriti (26%). Pitanga e buriti tiveram o perfil de carotenoides detalhadamente acompanhados através da simulação in vitro da digestão associada à absorção intestinal por culturas de células Caco-2. Neste estudo, observou-se que embora as xantofillas sejam mais bioacessíveis, o tecido epitelial do intestino absorve preferencialmente carotenoides provitaminicos A, como o β-caroteno e a β-criptoxantina. Para produzir as microemulsões foram estudados processamentos (homogeneização de alta-velocidade - HSH e ultrassom - US) em combinação com uso de surfactantes (Whey Protein Isolate e Tween 80) e adição de óleo de milho como carreador dos carotenoides. Os experimentos mostraram que a interação entre US e HSH é capaz de romper as paredes celulares e liberarem os carotenoides com maior eficiência. Ficou demonstrado através de microscopia ótica e de fluorescência, tanto quanto pela análise de carotenoides, que foi possível manipular estruturalmente a matriz alimentar liberando os carotenoides de dentro das células vegetais e encapsulando-os dentro das gotículas de óleo, além de aumentar sua retenção após o processamento. As microemulsões obtidas sofreram efeito do tempo de processamento e do surfactante em relação à reologia, estrutura final da matriz, estabilidade ao armazenamento e estabilidade dos carotenoides ao processo. Por fim, foi utilizado um sistema dinâmico de simulação da digestão gastrointestinal para comparar o comportamento dos carotenoides oriundos das polpas integrais das frutas e das microemulsões selecionadas (Tween 80 a 2%, óleo de milho a 5% e processado por HSH-US 4 min-4 min). Os resultados demonstraram que foi possível aumentar a estabilidade à digestão e a bioacessibilidade dos carotenoides totais, do licopeno e do β-caroteno.

Potentially harmful elements (PHE) are found naturally in soils, usually in low concentrations. However, due to the intensity of the anthropic activities, the concentrations of these elements may increase and have negative effects on the environment and human health. Methods for risk assessment may predict or indicate the level of exposure to contamination of an area. In addition to the total or pseudo-total concentration of PHE, generally extracted with acidic solutions, it is possible to determine the reactive, bioavailable and bioaccessible levels of these elements in order to evaluate the degree of soil contamination. Urban soil samples located in residential areas were collected in Piracicaba, State of São Paulo (SP) and in Santo Amaro, State of Bahia, including soils collected near a primary lead smelter area (COBRAC/Plumbum), where researchers detected elevated levels of PHE. Soils samples in an old lead metallurgy plant (Usina do Calabouço / IPT), which today belongs to the Centro Integrado de Ensino Multidisciplinar (CIEM/ Companhia de Pesquisa de Recursos Minerais (CPRM) - Geological Survey of Brazil) in Apiaí, located in the Upper Ribeira Valley (SP) were also collected. In vitro methods have been used in several countries to assess the bioaccessibility of PHE in humans. In this study, procedures based on ingestion and inhalation of soils using the Unified BARGE Method (UBM) and Artificial Lysosomal Fluid (ALF) methods were used to obtain the bioaccessible concentration in the gastrointestinal and pulmonary tract, respectively. As the bioaccessible fraction does not estimate the concentration absorbed and transported into the bloodstream, the in vitro method using Caco-2 cells, which are derived from human colon adenocarcinoma, was used to assess the amount of PHE that intestinal cells can absorb. The mineralogical data was obtained, and the sequential extraction of As, Cd, Cu, Mn, Pb and Zn was carried out to evaluate their interaction with lung fluid and gastric/gastrointestinal fluids. As expected, mine tailing samples had the highest pseudo-total concentrations of PHE in comparison to soil and sediment samples, both in the bulk soil (2 mm) and in the 250 &mu;m and 10 &mu;m sizes. Both respiratory and oral bioaccessibility of PHE varied widely among matrices, indicating that they were influenced by matrices´ chemistry, physical and mineralogical characteristics. The respiratory bioaccessible fraction, calculated as a percentage of the PHE pseudo-total concentrations, ranged from 13 - 109% for As; 14 - 98% for Cd; 21 - 89% for Cu; 46 - 140% for Pb, 35 - 88% for Mn and; 21 - 154% for Zn. Gastric bioaccessibility was greater than gastrointestinal bioaccessibility, ranging from 0-33% and 0-26% for As; 0-69% and 0-40% for Cd; 18-75% and 12-89% for Cu; 24-83% and 7-50% for Pb; 43-105% and 27-97% for Mn; 14-88% and 6-46% for Zn. Pseudo-total concentration provided a good estimate of respiratory and oral bioaccessibility, but the in-vitro methods provided more accurate results. Caco-2 cell line (in vitro test) was a good model for evaluating the effect of PHE exposure, but further studies on the transport and bioavailability of PHE in intestinal cells are needed. / Elementos potencialmente nocivos (EPN), dentre eles os metais pesados, são encontrados naturalmente nos solos, geralmente em baixas concentrações. Porém, devido à intensidade das atividades antrópicas, as concentrações destes elementos podem aumentar e ocasionar efeitos negativos ao meio ambiente e à saúde humana. Métodos para a avaliação de risco podem prever ou indicar o nível da exposição de uma área à contaminação. Além do teor total ou pseudototal de EPN, geralmente extraídos com soluções ácidas, pode-se determinar os teores nas frações reativa, biodisponível, bioacessível destes elementos para avaliação do grau de contaminação do solo. Por sua vez, métodos in vitro têm sido utilizados em vários países para avaliar a bioacessibilidade de PHE em seres humanos. Neste trabalho foram utilizadas amostras de solo urbano coletadas em Piracicaba e solos coletados em áreas de uma antiga usina de metalurgia de chumbo (Usina do Calabouço/IPT) na cidade de Apiaí, ambas localizadas no Estado de São Paulo; e na cidade de Santo Amaro, Bahia, onde foram coletadas amostras de solos urbanos localizados em áreas residenciais, principalmente próximas a uma antiga área de refino de chumbo, onde foram detectados níveis elevados de EPN. Foram avaliados procedimentos baseados na ingestão e na inalação de solos coletados por meio dos métodos Unified BARGE Method (UBM) e do Artificial Lysosomal Fluid (ALF) para obtenção do teor bioacessível nos fluidos gastrointestinais e nos fluidos pulmonares, respectivamente. Como a fração bioacessível não estima a concentração absorvida e transportada para a corrente sanguínea, o método in vitro, utilizando células Caco-2, que são extraídas de adenocarcinoma do cólon humano, foi usado para avaliar a quantidade de EPN que as células intestinais podem absorver. As características mineralógicas das amostras e a extração sequencial de As, Cd, Cu, Mn, Pb e Zn foram obtidas para avaliar a interação com fluido pulmonar e do o suco gástrico e gastrointestinal. Como esperado, as amostras de rejeito de mineração apresentaram as maiores concentrações pseudototais de EPN em comparação com as amostras de solo e sedimento, tanto nas amostras < 2mm, como nas amostras de tamanho < 250 &mu;m e < 10 &mu;m. A bioacessibilidade respiratória e oral dos EPN variou amplamente entre as matrizes, indicando que foram influenciadas por características químicas, físicas e mineralógicas das matrizes. A fração bioacessível respiratória, calculada como porcentagem das concentrações de EPN pseudototal, variou de 13 a 109% para As; 14 - 98% para Cd; 21 - 89% para Cu; 46 - 140% para Pb, 35 - 88% para Mn e; 21 - 154% para Zn. A bioacessibilidade gástrica foi maior que a bioacessibilidade gastrointestinal, variando de 0 a 33% e 0 a 26% para As; 0-69% e 0-40% para Cd; 18-75% e 12-89% para Cu; 24-83% e 7-50% para Pb; 43-105% e 27-97% para o Mn; 14-88% e 6-46% para Zn. A concentração pseudototal forneceu uma boa estimativa para bioacessibilidade respiratória e oral, mas os métodos in vitro fornecem resultados mais precisos. A linhagem celular Caco-2 foi um bom modelo para avaliar o efeito da exposição ao PHE, mas são necessários mais estudos sobre o transporte e biodisponibilidade de PHE em células intestinais.

Les agrumes très consommés au niveau mondial, représente des sources de caroténoïdes tels que la β-cryptoxanthine, qui contribuent avec les flavonoïdes (hespéridine) aux effets santé de ces fruits et en particulier dans la prévention du diabète de type 2 (DT2). Le DT2 est une pathologie mondiale en croissance exponentielle. L’objectif général de ce travail est par conséquent d’étudier les propriétés nutrition-santé de concentrés de jus de clémentine, obtenus par une technologie membranaire innovante et spécifiquement enrichis en β-cryptoxanthine (βCX) et hespéridine (HES) mais également en pectines. Le devenir digestif de ces phytomicronutriments, garants de la qualité nutritionnelle des concentrés a évalué dans un premier temps en couplant le modèle de digestion in vitro aux cellules intestinales de type Caco-2. Pour une meilleure vision physiologique des mécanismes associés aux premières étapes de la digestion, des modèles de digestion, statique et dynamique, sont comparés. La bioaccessibilité et l’absorption intestinale des caroténoïdes sont fortement influencées par la teneur et structure des pectines. Dans un second temps, les activités biologiques (disglycémie, dislipidémie, inflammation) impliquées dans la prévention du DT2 sont évaluées in vivo chez le rat après administration du concentré d’agrume. L’étude a démontré qu'un aliment à base d'agrume spécifiquement enrichi en βCX et HES est efficace dans la prévention du syndrome métabolique/DT2, soulignant le rôle possible de la βCX et de sa bioconversion en rétinoïdes. Une étude in vitro complémentaire sur macrophages murins révèle des effets anti-inflammatoires synergiques des 2 phytomicronutriments. / Citrus fruits, which are widely consumed worldwide, represent sources of carotenoids such as βCX, which contribute with flavonoids (HES) to the health effects of these fruits, particularly in the prevention of type 2 diabetes (T2D). T2D is a worldwide pathology that is growing exponentially. The general objective of this work is therefore to study the nutritional and health properties of clementine juice concentrates obtained by innovative membrane technology and specifically enriched in both βCX and HES but also in pectins. The digestive behaviour of these phytomicronutrients, guarantors of the nutritional quality of the concentrates, was first assessed by coupling the in vitro digestion model with the Caco-2 intestinal cells. For a better physiological vision of the mechanisms associated with the first stages of digestion, models of static and dynamic digestion are compared. The bioavailability and intestinal absorption of carotenoids are strongly influenced by the content and structure of pectins. In a second step, the biological activities (disglycemia, dislipidemia, inflammation) involved in the prevention of T2D are evaluated in vivo in rat after administration of the citrus concentrate. The study demonstrated that a citrus food specifically enriched in βCX and HES is effective in preventing metabolic syndrome/T2D, highlighting the possible role of βCX and its retinoid bioconversion. A complementary in vitro study on murine macrophages reveals synergistic anti-inflammatory effects of the two phytomicronutrients.

Introdução: O café é a segunda bebida mais consumida do mundo. O grão de café é uma das mais importantes \"commodities\" alimentares, sendo o principal produto de exportação agrícola. A produção mundial de café na safra 2016-2017 alcançou 153,869 milhões de sacas de 60 quilos. A bebida de café é consumida sob diversos métodos e preparações e a adição de açúcar e/ou leite são as mais comuns. O crescente consumo de cápsula de café expresso vem ganhando os lares da população brasileira com aumento de 29 % de 2010 a 2015, com estimativa de crescimento na ordem de 18 % de 2015 até 2020. A busca por diferentes tipos de café está relacionada com os efeitos sensoriais que o café pode exercer para os humanos. Entretanto, o café é considerado uma bebida bioativa com efeito antioxidante que atua como anticancerígeno, anti-obesidade, antidiabético, anti-hipertensivo e hepatoprotetor. Deste modo faz-se necessário avaliar a atividade antioxidante das cápsulas de café expresso de acordo com sua intensidade (torra) e avaliar o efeito da adição de ingrediente sobre os compostos fenólicos, a atividade antioxidante e sua bioacessibilidade. Objetivo: Avaliar o efeito de diferentes intensidades de torra e da adição de ingrediente sobre os compostos fenólicos e a atividade antioxidante das cápsulas de café expresso e sua bioacessibilidade. Material e Métodos: O presente projeto foi dividido em dois ensaios. O primeiro ensaio contou com quatorze cápsulas comerciais de café expresso, sendo treze tradicionais e uma descafeinada. O segundo ensaio contou com três cápsulas, sendo duas tradicionais e uma descafeinada. Todas foram adquiridas em estabelecimentos comerciais da cidade de São Paulo. No primeiro ensaio as bebidas foram preparadas como descrito na embalagem usando uma cafeteira doméstica e água. No segundo ensaio, às bebidas (preparadas de acordo ao primeiro ensaio), foram adicionados 40 mL leite e/ou 5 g de açúcar. A atividade antioxidante foi investigada pelo ensaio de eliminação de radicais ABTS, pela capacidade de absorção de radicais peroxila de oxigênio pelo (ORAC) e a capacidade de eliminação de radicais DPPH. O teor total de fenólicos foi determinado pelo método de Folin-Ciocalteau, as melanoidinas foram avaliadas pela absorbância a 420 nm e a digestão in vitro foi realizada por hidrólise assistida por enzimas digestivas. O perfil fenólico foi avaliado por CLAE/DAD. A capacidade de inibição da peroxidação lipídica foi determinada pela medição de substâncias reativas ao ácido tiobarbitúrico (TBARS). Resultados: No primeiro ensaio, todas as bebidas de café em cápsula apresentaram atividade antioxidante de acordo os métodos ORAC, DPPH e ABTS, variando de acordo a intensidade (torra) de cada cápsula. O teor de fenólicos variou de 191,41 a 374,36 mg equivalentes de ácido clorogênico/dose de café e as melanoidinas variaram entre 0,197 nm e 0,372 nm. No segundo ensaio, os fenólicos totais variaram de 129,40 a 541,81 mg equivalentes de ácido clorogênico/dose nas bebidas digeridas e não digeridas, respectivamente. A atividade antioxidante foi maior nas bebidas com adição de leite. O teor total de fenólicos foi maior nas amostras não digeridas. O perfil fenólico encontrado nas amostras não digeridas e digeridas, foi cafeína, ácido clorogênico, ácido cafeico, ácido p-cumárico e ácido ferúlico. Após a digestão in vitro, os ácidos fenólicos e a cafeína estavam mais bioacessíveis nas bebidas de café com adição leite e com leite e açúcar em comparação com as bebidas de café puras. As bebidas não digeridas apresentaram menor produção de TBARS em relação àquelas digeridas. Conclusão: Todas bebidas de café expresso em cápsulas estudadas apresentaram atividade antioxidante. A maior intensidade da torra pode influenciar a quantidade de fenólicos totais e atividade antioxidante. O conteúdo de ácidos fenólicos e cafeína e a atividade antioxidante das bebidas dependem dos ingredientes adicionado à preparação. Os compostos são mais bioacessíveis em bebidas com leite com açúcar e com leite, em comparação com bebidas puras. Os resultados sugerem que existem interações entre ácidos fenólicos e componentes do leite por meio de interação hidrofóbicas e/ou hidrofílicas que afetam a biodisponibilidade de ambos. / Introduction: Coffee is the second most consumed drink in the world. Coffee beans are one of the most important food \"commodities\" being the main agricultural export product. World coffee production in the 2016-2017 harvest reached 153,869 million bags of 60 kilos. The coffee drink is consumed of several methods and preparations, the addition of sugar and / or milk is the most common. The increasing consumption of espresso capsules has been gaining the homes of the Brazilian population with a 29% increase from 2010 to 2015, with an estimated growth of around 18% from 2015 to 2020. The search for different types of coffee is related to the sensory effects that coffee can exert on humans. However, coffee is considered a bioactive beverage with antioxidant effect that acts as anticancer, anti-obesity, antidiabetic, antihypertensive and hepatoprotective Thus, it is necessary to evaluate the antioxidant activity of the espresso capsules according to their intensity (roast) and to evaluate the effect of the addition of the ingredient on the phenolic compounds, the antioxidant activity and its bioacessibilide. Objective: To evaluate the effect of different roast intensities and the addition of the ingredient on the phenolic compounds and the antioxidant activity of the espresso capsules and its bioaccessibility. Material and Methods: The present project was divided into two trials. The first trial included: Fourteen commercial espresso capsules, thirteen traditional and one decaffeinated. The second trial had three capsules, two traditional and one decaffeinated. Both were purchased at food stores in the city of São Paulo. In the first assay the beverages were prepared as described on the package using a domestic kettle and water. In the second assay, the beverages were prepared according to the first test, but 40 ml of milk and / or 5 g of sugar. The antioxidant activity was investigated by the ABTS radical scavenging assay, oxygen radical scavenging ability (ORAC) and the DPPH radical scavenging ability. The total phenolic content was determined by the Folin-Ciocalteau method, as melanoidins were evaluated for absorbance at 420 nm and an in vitro digestion was performed by digestive enzyme assisted hydrolysis. The phenolic profile was evaluated by HPLC / DAD. Lipid peroxidation was determined by the action of thiobarbituric acid reactive substances (TBARS). Results: In the first trial, all capsule coffee beverages presented antioxidant activity according to the ORAC, DPPH and ABTS methods, varying according to the intensity (roast) of each capsule. The phenolic range ranged from 191.41 to 374.36 mg of chlorogenic acid equivalent / mL of coffee and the melanoidins ranged from 0.197 nm to 0.372 nm. In the second assay, total phenolics ranged from 129.40 to 541.81 mg equivalents of chlorogenic acid / dose in the digested and undigested beverages, respectively. The antioxidant activity was higher in beverages with milk addition. The total phenolic content was higher in the undigested samples. The phenolic profile found in the undigested and digested samples was caffeine, chlorogenic acid, caffeic acid, p-coumaric acid and ferulic acid. After in vitro digestion, phenolic acids and caffeine were more bioaccessible in coffee drinks with added milk and with milk and sugar compared to pure coffee beverage. Undigested beverages presented lower TBARS production in relation to those digested. Conclusions: All espresso drinks in capsules studied have antioxidant activity. The intensity can influence the amount of total phenolics and antioxidant activity. The content of phenolic acids and caffeine and the antioxidant activity of the beverages depend on the ingredients added to the preparation. The compounds are more bioavailable in milk and sugar milk beverages compared to pure beverages. The results suggest that there are interactions between phenolic acids and milk components through hydrophobic and / or hydrophilic interaction that affects the bioavailability of both.

Orientador: Marcelo Alexandre Prado / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-21T19:36:01Z (GMT). No. of bitstreams: 1 Mazon_ElaineMarradeAzevedo_D.pdf: 2626954 bytes, checksum: 7cc1b7c8e92de797976754431156c2af (MD5) Previous issue date: 2013 / Resumo: O consumo de vinhos no Brasil aumentou cerca de 20% na última década, e sua comercialização vem se difundindo, principalmente, pelo aumento da oferta, aumento do poder aquisitivo da população brasileira, aumento da produção e pelos benefícios à saúde que lhe são atribuídos. A análise de elementos traço nos vinhos é de grande importância para o controle da qualidade, autenticidade, biodisponibilidade de metais e estudo da toxicidade, visando garantir a segurança alimentar para os consumidores. Este trabalho descreve o desenvolvimento de um método empregando a espectrometria de absorção atômica com forno de grafite para a determinação de arsênio (As), cádmio (Cd), cobre (Cu) e chumbo (Pb) em amostras de vinhos brasileiros. A digestão ácida preliminar não foi necessária no preparo de amostra. O programa de aquecimento, empregado no forno de grafite foi otimizado para os diferentes tipos de vinhos e as amostras foram diluídas na proporção de 1:3 com ácido nítrico (65% v/v) e peróxido de hidrogênio (30% m/m). A curva analítica foi preparada em meio aquoso e alguns modificadores foram investigados para cada elemento. As determinações foram realizadas nas seguintes faixas lineares 10-100 µg L-1 Cu; 5,0 - 60 µg L-1 Pb; 0,5 - 2,0 µg L-1 Cd; 10 - 60 µg L-1 As. Os limites de quantificação obtidos foram 11,5; 2,5; 0,22 e 5,0 µg L-1, respectivamente. As recuperações obtidas variaram de 92-103% (vinho tinto) e 99-106% (vinho branco) para o Cu, 97-107% (vinho tinto) e 95-101% (vinho branco) para o Pb, 89-102% (vinho tinto) e 98-106% (vinho branco) para o Cd, e 103-106% (vinho tinto) e 99-107% (vinho branco) para o As. Foram analisadas 45 amostras de vinhos nacionais adquiridos no comércio de Campinas/SP de diversas regiões do Brasil. Foram determinados os teores de As, Cd, Cu e Pb nas amostras de vinho e os valores encontrados estavam abaixo dos teores estabelecidos pela legislação brasileira. Foram calculadas as contribuições dos vinhos estudados na dieta de um adulto, com relação a ingesta destes elementos e os valores demonstraram que os vinhos estudados apresentaram baixa contribuição. Também foram determinados os valores de pH e os teores de polifenóis totais nos vinhos, as amostras apresentaram valores compatíveis com os relatados na literatura com valores médios para polifenóis em vinhos de mesa de 2046,0 mg L-1, vinhos tinto 1443,0 mg L-1 e espumantes 1606,0 mg L-1. Os valores de pH variaram de 2,8 a 3,8 entre os vinhos. Foi feito o estudo da acessibilidade e da fração dialisável pelo método in vitro dos elementos As, Cd, Cu e Pb nos vinhos e os resultados demonstraram para todos os elementos que a fração solúvel foi maior que 37% e a dialisável, maior que 43%, indicando alta capacidade de acessibilidade. Quanto aos dizeres de rotulagem foi observada uma necessidade de complementação da atual legislação específica para vinhos, com a finalidade de melhorar a qualidade das informações oferecidas ao consumidor através dos rótulos dos vinhos / Abstract: Wine consumption in Brazil has been increasing in 20% in the last decade, and its sales have been disseminating mainly due to offer and production increase, and to health benefits attributed to it. The analysis of trace elements in wine is of great importance for quality control, authenticity, metal bioavailability and toxicity study, aiming at granting safety to consumers. This paper describes the development of a method which employs atomic absorption spectrometry with graphite oven in order to determine arsenic, cadmium, copper and lead in Brazilian wines samples. A preliminary acid digestion has not been necessary in the sample preparation. The heating program employed to the graphite oven has been optimized for the different types of wine and the samples have been diluted in proportion of 1:3 with nitric acid (65% v/v) and hydrogen peroxide (30% m/m). The analytical curve has been prepared in aqueous medium and some modifiers have been investigated for each element. The determinations have been performed in the following linear ranges 10-100 µg L-1 Cu; 5,0 - 60 µg L-1 Pb; 0,5 - 2,0 µg L-1 Cd; 10 - 60 µg L-1 As. The qualification limits obtained were 11,5; 2,5; 0,22 e 5,0 µg L-1, respectively. The recoveries obtained ranged from 92-103% (red wine) and 99-106% (white wine) for Cu, 97-107% (red wine) and 95-101% (white wine) for Pb, 89-102% (red wine) and 98-106% (white wine) for Cd, and 103-106% (red wine) and 99-107% (white wine) for As. Brazilian wines, about 45 samples from Campinas/SP local market have been analyzed at several Brazilian regions. The contents of As, Cd, Cu and Pb have been determined in the samples and the amounts found out were below the contents established by the Brazilian legislation. The contribution of those elements on the diet of an adult have been calculated, and the amounts have shown that the studied wines presented low contribution. The pH levels and the total polyphenols contents have also been determined, the samples presented compatible rates according to the literature, with average rates for polyphenol in table wines at 2046,0 mg L-1, red wines 1443,0 mg L-1 and sparking 1606,0 mg L-1. The pH rates varied from 2,8 to 3,8 among the wines. The accessibility and the dialysis fraction through the in vitro method have also been studied for the elements As, Cd, Cu and Pb in the wines. The results show that for all elements soluble fractions greater than 37% and higher than 43% dialyzable indicating high capacity accessibility. As for labeling was observed a need complement the current legislation for wine in order to improve the quality of information offered to consumers through wine labels / Doutorado / Ciência de Alimentos / Doutora em Ciência de Alimentos

Des pollutions des sols (péri)urbains et urbaines fortement peuplées en métaux et metalloïdes persistants (éco)toxiques sont couramment observées à l’échelle globale. Certains éléments (Se, Cu…) ont des rôles biologiques et par contre d’autres (Pb, Cd…) ont uniquement un impact (éco)toxique qui peut être influencé par leur spéciation et compartimentation qui modifient leurs transferts et biodisponibilité. Dans une optique de gestion des sols et d’alimentation durables, des questions scientifiques pluridisciplinaires sont à creuser concernant : (i) les mécanismes en jeu dans la biodisponibilité et l’impact sur les organismes vivants des éléments inorganiques en lien avec leur spéciation ; (ii) la co-gestion des risques environnement-santé induits par des installations industrielles classées : ICPE en France (ex. usine de recyclage de batteries) avec les riverains qui cultivent des potagers ou les employés. Dans ce contexte, ont été étudiés : (i) le transfert des métaux entre phase solide et solution du sol sous l’influence des vers de terre sur un site ICPE; (ii) le transfert et la bioaccessibilité du Se en conditions contrôlées pour 2 formes chimiques; (iii) le risque sanitaire pour les riverains d’un site ICPE qui jardinent, et les facteurs influant les plombémies des professionnels (étude statistique des données). Une review bibliographique de la qualité du manioc en lien avec les pratiques culturales et culinaires et les caractéristiques de l’environnement a finalement été réalisée pour compléter la démarche « Sciences et Société » de la thèse. L’analyse des différents isotopes du plomb dans les sols aux alentours de l’usine de recyclage a permis de conclure que 84 à 100% du plomb des sols de surface est d’origine anthropique. Un comportement d’évitement des zones les plus polluées en plomb a été observé pour l’espèce de vers de terre A. caliginosa. Le transfert racinaire, la translocation du sélénium vers le maïs et sa bioaccessibilité dans le grain sont plus élevés dans le cas du séléniate (facteur de translocation de 1.1, et bioaccessibilité humaine de 89,3%) par rapport au sélénite (0.13, et bioaccessibilité de 82,7%). L’étude de la qualité des cultures des jardins proches de l’usine (à Bazoches), en relation avec la qualité du sol (faible contamination, pH basique et teneur élevée en matières organiques qui réduisent les transferts) et de l’atmosphère a mis en évidence un transfert atmosphère-plante qui dépend du métal (le Cd est le plus biodisponible) et du végétal. Les concentrations en Pb et Cd suivent respectivement les séquences : [laitue>poireau>céleri>carotte] et [laitue>céleri>carotte>poireau]. Pour réduire l’exposition des populations, un lavage soigneux des productions avant la consommation est préconisé. / Pollution of (peri)urban soils by (eco)toxic metal(loid)s is commonly observed on a global scale. Some elements (Se, Cu ...) have biological roles and other (Pb, Cd ...) only have an (eco)toxic impact influenced by their speciation and compartmentalization that can change their transfers and bioavailability. With the perspective of sustainable management of soil and food, multidisciplinary scientific questions are digging for: (i) the mechanisms involved in the bioavailability and impact on living organisms of inorganic elements related to speciation; (ii) the co-management of environmental-health risks from industrial regulated plants (ICPE in France, such as former battery recycling plant) with residents who grow vegetable gardens or employees. In this context, were studied: (1) the transfer of metals between solid phase and soil solution under the influence of earthworms on a ICPE site; (2) the transfer and bioavailability of Se in controlled conditions for two chemical forms; (3) the health risk for the residents with gardening activities near ICPE plant and factors influencing blood lead of professionals (statistical analysis of data). A literature review of the quality of cassava in connection with the cultivation and culinary practices and characteristics of the environment was finally performed to complete the "Science and Society" process of the thesis. From the analysis of different isotopes of lead in the soil around the recycling plant it was concluded that 84 to 100% of lead in surface soils has anthropogenic origin. Avoidance behavior in the most lead polluted areas was observed for A. caliginosa earthworm species. The selenium root transfer, translocation to corn and its bioavailability in the grain are higher in the case of selenate (translocation factor of 1.1, and human bioavailability of 89.3%) compared to selenite (0.13 and bioaccessibility 82.7%). The study of crops quality in the gardens near the ICPE plant (in Bazoches), in relation to atmosphere and soil quality (low Pb contamination, alkaline pH and high organic content that reduce pollutants transfers) highlighted an atmosphere-plant transfer which depends on the metal (Cd is the most bioavailable) and plant species. Pb and Cd concentrations follow respectively the sequences: [lettuce> Leek> celery> carrot] and [lettuce> celery> carrot> leek]. To reduce population exposure, thorough washing of productions before consumption is recommended.

Chaque année, 65 millions de m3 de sédiments sont extraits par dragage des ports, des canaux, des rivières et des fleuves français. Ces matériaux sont souvent contaminés par des métaux lourds, pesticides et autres polluants organiques accumulés au cours du temps, et doivent être stockés à terre. La valorisation des sédiments contaminés est encadrée par des guides techniques et par la réglementation en vigueur. Ces guides proposent une méthodologie d’évaluation et des valeurs seuils protectrices pour la santé humaine et l’environnement, utilisant les teneurs totales en composé organique hydrophobe (COH). Ce travail évalue le comportement environnemental à long terme de sédiments contaminés et précise quels sont les paramètres et les mécanismes contrôlant la mobilité des polluants organiques, afin de passer dans les études du danger au risque. 5 sédiments de natures différentes ont été suivis au laboratoire pendant 18 mois, et diverses méthodes de mesure des fractions solides, colloïdales et dissoutes ont été pratiquées. La matière organique des sédiments est hétérogène et possède une multitude de sites de sorption. La présence d’origine exogène de suie et de matières organiques condensées (Black Carbon) et d’hydrocarbures est responsable de la forte rétention des COH dans le sédiment (coefficients de partage Kd élevés et cinétiques de désorption très lentes).Une modélisation à partir des coefficients de partage, même avec des estimations très fines, peut largement sous-évaluer le risque environnemental (facteur 1000) car la mobilité des COH au travers des colloïdes ou macromolécules dissoutes n’est pas prise en compte dans les modèles d’émission et de transport classiques. / Each year, 65 million m3 of sediment are removed by dredging of harbors, canals, rivers and French rivers. These materials are often contaminated with heavy metals, pesticides and other organic pollutants accumulated over time, and should be stored ashore. The re-use of contaminated sediments under various scenarii is supervised by technical guidelines and regulations. These guides offer an evaluation methodology and thresholds for protecting human health and the environment, using the total solid concentrations of hydrophobic organic compound (HOC). This work evaluates the long-term environmental behavior of contaminated sediments and precisely what are the parameters and mechanisms controlling the mobility of organic pollutants, to assess risk rather than hazard. 5 sediments were monitored in the laboratory for 18 months, and various methods of measuring solid, colloidal and dissolved fractions were performed. The organic matter in sediments is heterogeneous and has a multitude of sorption sites. The presence of exogenous origin of soot and condensed organic matter (Black Carbon) and hydrocarbons is responsible for the high retention of HOC in the sediment (high partition coefficients Kd and very slow desorption kinetics). Classical modeling of the dissolved phase by partition coefficients, even refined, may significantly under-estimate the environmental risk (factor up to 1000) because the mobility of COH through colloids or dissolved macromolecules is not taken into account in the conventional transmission and transport models.

L'utilisation des engrais chimiques phosphatés, et les usines de fertilisants, ayant comme matière première la roche phosphate et rejetant du phosphogypse, contribuent à l’élévation des teneurs des radionucléides naturels et des éléments traces métalliques dans l’environnement. Ces contaminations risquent d’affecter l’écosystème et la santé humaine.Cette étude évalue l’impact sanitaire des radionucléides naturels émetteurs gamma des séries de désintégration de 238U, 232Th, de l’élément naturel radioactif 40K et du Pb, présents dans la matière première et les produits d’une usine de fertilisants au Liban.L’objectif principal est de caractériser la contamination diffuse de ces polluants dans une optique d’évaluation du risque sanitaire dans 9 sites résidentiels, non-cultivés autour de l’usine. Un focus est spécifiquement porté sur l’évaluation quantitative du risque sanitaire lié à la consommation de la plante sauvage Dittrichia viscosa et l’ingestion accidentelle de poussières de sol pour les habitants de la zone étudiée. La notion de bioaccessibilité du Pb des sols et des plantes est intégrée dans ces évaluations. Des extractions chimiques par EDTA et le Physiologically Based Extraction Test (PBET) ont été utilisés pour une estimation in vitro, des fractions disponibles et bioaccessibles du Pb. Ces dernières ont été intégrées dans les calculs des risques. Les risques radiologiques relatifs aux rayonnements ionisants gamma des radionucléides ont également été estimés via les paramètres radiologiques.L’ensemble des travaux a montré que l’usine de fertilisants engendre une contamination diffuse qui augmente les niveaux de radionucléides et du Pb dans l’environnement proche, plus précisément dans les sols (pour 238U, 226Ra et leurs descendants 214Pb, 212Pb et 210Pb, ainsi que pour Pb), et dans les parties aériennes des plantes Dittrichia viscosa (pour Pb et 210Pb). L’étude de la distribution du 210Pb et les fractions PbEDTA apportent des informations complémentaires pour caractériser l’apport en Pb dû à l’activité de l’usine. Les résultats ont montré que les valeurs moyennes des concentrations d’activité des radionucléides dans les échantillons de sol étaient légèrement supérieures à ceux déterminés dans d'autres régions libanaises et aux valeurs moyennes mondiales. D’après les paramètres radiologiques, aucun risque significatif n’a été identifié pour la population fréquentant la zone.Les concentrations en Pb pseudo-total de sol ont été inférieures aux seuils applicables. Des dépassements de seuil ont été constatés pour les teneurs en Pb dans les feuilles de Dittrichia viscosa.Deux schémas d’évaluation de risque sanitaire du Pb ont été étudiés : un premier schéma classique basé sur l’hypothèse de l’ingestion des teneurs totales en Pb dans les sols et les plantes ; un deuxième schéma où seulement les fractions pouvant atteindre la circulation systémique ont été évaluées et considérées dans les calculs de risque. Ces deux schémas ont été appliqués à deux scénarios de terrain à forte exposition. La prise en compte des concentrations de Pb bioaccessible dans les calculs réduit considérablement (au moins d’un facteur de 10) le risque potentiel pour les deux scénarios alors que les calculs du risque selon le schéma classique montrent un risque significatif pour les enfants. Quel que soit le schéma de calcul de risque retenu, l’ingestion des plantes reste la voie principale d’exposition pour les deux scénarios maximalistes. / The use of phosphate fertilizers and phosphate rock as raw material by fertilizer plants, and the by-product phosphogypsum, contribute in increasing the levels of natural radionuclides and trace metals in the environment. This may affect the ecosystem and human health.This study evaluates the radiological impact of natural gamma-emitting radionuclides, mainly 238U, 232Th and their decay product, and 40K. As well as, it evaluates the health impact of Pb, present in the raw material and fertilizers produced by a fertilizer plant in Lebanon.The main objective is to characterize the diffuse contamination of these pollutants with a view to assess the health risk in 9 non-cultivated residential sites around the plant. A focus on the quantitative assessment of the health risk is specifically linked to the consumption of the wild plant Dittrichia viscosa and the accidental ingestion of soil dust for the inhabitants of the study area. The concept of bioaccessibility of soil and plant Pb is integrated into these assessments. Chemical extractions using EDTA and the Physiologically Based Extraction Test (PBET) were used for in vitro estimation of available and bioaccessible Pb fractions. These were incorporated into the risk calculations. The radiological risks related to gamma ionizing radiation from radioelements were also estimated via radiological parameters.All of the work has shown that the fertilizer plant generates diffuse contamination that increases the levels of radionuclides and Pb in the near environment, specifically in soils (for 238U, 226Ra and their decay products 214Pb, 212Pb and 210Pb, as well as for Pb), and in the aerial parts of Dittrichia viscosa plants (for Pb and 210Pb). The study of the distribution of 210Pb and PbEDTA fractions provide additional information to characterize the Pb contribution due to the activity of the plant. The results showed that the mean values of activity concentrations of radioelements in soil samples were slightly higher than those determined in other Lebanese regions and worldwide average values. Based on the radiological parameters, no significant risk has been identified for the population frequenting the area.The pseudo-total soil Pb concentrations were below the applied thresholds. Threshold exceedances were observed for Pb levels in Dittrichia viscosa leaves.Two health risk assessment schemes for Pb were studied: a first classical scheme based on the hypothesis of the total ingestion of total Pb levels in soils and plants; a second scheme where only fractions reaching the systemic circulation have been measured and considered in risk calculations. These two schemes were studied for two high-exposure field scenarios. Taking into account the bioaccessible Pb concentrations in the calculations greatly reduces (at least by a factor of 10) the potential risk for both scenarios, whereas the classical risk calculations show a significant risk for the children. Whatever the chosen risk calculation scheme, ingestion of plants remains the main route of exposure for the two maximalist scenarios.

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