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O cádmio é um metal pesado tóxico e carcinogénico, que representa uma ameaça séria para a saúde humana. A população geral pode encontrar-se exposta ao cádmio por diversas vias e o estudo INSEF-ExpoQuim visou caracterizar a exposição da população portuguesa adulta (28-39 anos ) a este agente químico através de um estudo transversal. Este estudo incluiu 295 indivíduos, os quais reponderam a um questionário (dados sociodemográficos, de estilos de vida e possíveis vias de exposição ) e facultaram uma amostra de urina para quantificação de cádmio por espectrometria de massa com plasma indutivo acoplado ( ICP- -MS ). Observou-se uma média geométrica de 0,092 μg Cd/g creatinina [ IC ( 95%): 0,084-0,101 ], apresentando as mulheres valores mais elevados ( 0,103 vs 0,079 ), bem como os fumadores ( 0,135 vs 0,081). Cadmium is a toxic and carcinogenic heavy metal, that presents a serious threat to human health. The general population can be exposed through several pathways and the study INSEF-ExpoQuim aimed to characterise the exposure of the Portuguese adult population (28-29 years) to this chemical agent through the development of a cross-sectional study. This study has included 295 individuals, that have answered to a questionnaire (sociodemographic characteristics, lifestyle and possible exposure sources) and provided a urine sample for the quantification of cadmium by inductively coupled plasma mass spectrometry ( ICP-MS). A geometric mean of 0.092 μg Cd/g creatinine [ 95%CI: 0.084-0.101 μg Cd/g creatinine ] was observed, with females ( 0.103 vs 0.079) and smokers ( 0.135 vs 0.081) presenting higher values. O estudo INSEF-ExpoQuim foi cofinanciado no âmbito do projeto HBM4EU, que recebeu financiamento do programa de investigação e inovação Horizonte 2020 da União Europeia, ao abrigo da convenção de subvenção n.º 733032. O INSEF foi desenvolvido como parte integrante do projeto Improvement of epidemiological health information to support public health decision and management in Portugal Towards reduced inequalities, improved health, and bilateral cooperation, tendo beneficiado de um apoio financeiro de 1 500 000 euros concedido pela Islândia, Liechtenstein e Noruega, através das EEA Grants. info:eu-repo/semantics/publishedVersion

O arsénio é um elemento naturalmente presente no meio ambiente e que também pode ser libertado em resultado de atividades antropogénicas, podendo encontrar-se na forma de compostos orgânicos ou inorgânicos. O arsénio é considerado pela Organização Mundial de Saúde como um dos dez químicos de maior preocupação para a saúde pública, uma vez que o arsénio e os compostos inorgânicos de arsénio estão classificados como cancerígenos pela Agência Internacional para a Investigação do Cancro. A exposição a arsénio inorgânico ocorre principalmente por via alimentar, através do consumo de água e de alimentos contaminados. Em Portugal são escassos os dados sobre a exposição a arsénio na população geral, pelo que o objetivo do presente estudo é a caracterização da exposição da população adulta portuguesa a arsénio, utilizando amostras de urina colhidas num estudo populacional nacional ( INSEF-ExpoQuim). O presente trabalho incluiu 171 participantes no estudo INSEF-ExpoQuim que forneceram uma amostra de urina para análise da concentração de arsénio total por espectrometria de massa com plasma indutivo acoplado ( ICP-MS ). Observou-se uma média geométrica de 47,1 μg As/L [ IC95%: 41,4-53,5 ] e 8,8% dos indivíduos apresentavam valores de arsénio considerados elevados. Não se observaram diferenças nos níveis de arsénio por sexo, grupo etário, grau de urbanização da área de residência, nível de escolaridade e situação face ao trabalho. Os resultados preliminares obtidos apontam para a necessidade de monitorização dos níveis de arsénio na população portuguesa. Arsenic is an element naturally present in the environment, but it can also be released as a result of anthropogenic activities. In the environment, arsenic can be found in the form of organic compounds and in the form of inorganic compounds. Arsenic is considered by the World Health Organization as one of the ten chemicals of greatest concern for public health, since arsenic and inorganic arsenic compounds are classified as carcinogenic by the International Agency for Research on Cancer. Exposure to inorganic arsenic occurs mainly through food, through consumption of contaminated water and food. In Portugal, data on arsenic exposure in the general population are scarce, so the aim of the present study was to characterize the exposure of the Portuguese adult population to arsenic, using urine samples collected in a national population study ( INSEF-ExpoQuim). The present work included 171 participants in the INSEF-ExpoQuim study who provided a urine sample for analysis of total arsenic concentration by inductively coupled plasma mass spectrometry (ICP-MS). A geometric mean of 47.1 μg As/L [ 95% CI: 41.4-53.5 ] was observed and 8.8% of the individuals had arsenic levels considered high. No differences were observed in arsenic levels by sex, age group, degree of urbanization of the area of residence, educational level and employment situation. The obtained preliminary results point to the need to monitor the levels of arsenic in the Portuguese population. O estudo INSEF-ExpoQuim foi cofinanciado no âmbito do projeto HBM4EU, que recebeu financiamento do programa de investigação e inovação Horizonte 2020 da União Europeia, ao abrigo da convenção de subvenção n.º 733032. O INSEF foi desenvolvido como parte integrante do projeto Improvement of epidemiological health information to support public health decision and management in Portugal Towards reduced inequalities, improved health, and bilateral cooperation, tendo beneficiado de um apoio financeiro de 1 500 000 euros concedido pela Islândia, Liechtenstein e Noruega, através das EEA Grants. info:eu-repo/semantics/publishedVersion

A dieta vegetariana é um padrão alimentar que tem ganho popularidade na última década em todo o mundo, por motivos éticos, de saúde, religiosos e também ambientais. No entanto, a preocupação com a escolha desta dieta e a supressão de todas as necessidades nutricionais tem vindo a ganhar relevância. Assim, as carências nutricionais, nomeadamente de iodo, na população vegetariana, têm sido alvo de estudos no sentido de entender se a alimentação, por si só, consegue fornecer os valores diários recomendados para este elemento. Neste estudo, determinou-se o teor de iodo, por espectrometria de massa com plasma indutivo acoplado ( ICP-MS), em 37 alimentos mais consumidos pela população vegetariana. A seleção dos alimentos foi feita tendo por base o Inquérito Alimentar Nacional e de Atividade Física. Entre os alimentos analisados as algas Nori apresentam os valores mais elevados de iodo com cerca de 6511 ± 321 μg/100 g, podendo ser um alimento que se consumido na quantidade de cerca de 2,3 g/dia (equivalente a 1 folha) poderá suprir as necessidades nutricionais deste elemento. Também os lacticínios, nomeadamente os queijos (entre 53,4 ± 0,4 e 28,0 ± 0,9 μg/100 g) e os iogurtes (entre 17,2 ± 0,2 e 14,4 ± 0,1 μg/100 g), são alimentos com teores de iodo relevantes. Apenas com a alimentação, a população vegetariana e vegan poderá ter dificuldade em alcançar as necessidades diárias de iodo (150 μg/dia ), sendo assim necessário criar alternativas para aumentar os teores de iodo na alimentação. A fortificação das plantações e também dos alimentos, a utilização de sal iodado na confeção ou, se necessário, a suplementação desta população mais suscetível, são estratégias alternativas possíveis. É essencial perceber mais sobre o padrão de alimentação desta população a fim de perceber a melhor forma de mitigar este tipo de carência. The vegetarian diet is a dietary pattern that has gained popularity in the last decade around the world, due to ethical, health, religious and environmental reasons. However, the concern with the choice of this diet and the suppression of all nutritional needs has gained relevance. Nutritional deficiencies, namely iodine in this population, have been the subject of studies to understand whether diet by itself can provide the recommended daily values for this element. Thus, the iodine content was determined by inductively coupled plasma mass spectrometry ( ICP-MS ) in thirty-seven foods most consumed by the vegetarian population. The selection of foods was based on the National Food and Physical Activity Survey of Portugal. Among the analysed foods, Nori seaweeds have the highest levels of iodine with about 6511 ± 321 μg/100 g, which may be a way to meet the nutritional needs of this element, consuming about 2.3 g/day (equivalent to 1 leaf), followed by dairy products, namely cheeses (between 53.4 ± 0.4 and 28.0 ± 0.9 μg/100 g) and yoghur ts (between 17.2 ± 0.2 and 14.4 ± 0.1 μg /100 g). Just with food, the vegetarian and vegan population may have difficulty to achieve the daily iodine requirement (150 μg/day). Therefore, it is necessary to create alternatives to increase the levels of iodine in the diet, such as, for example, the fortification of crops and also of foods, the use of iodized salt in the preparation of food or, if necessary, through the supplementation of this more susceptible population. It is essential to understand more about the eating pattern of this population in order to understand the best way to mitigate this type of deficiency. info:eu-repo/semantics/publishedVersion

Sodium and Potassium are essential micronutrients, considered as nutrients of public health concern. Salt consumption in Portugal almost doubles WHO recommended maximum level of intake, contributing to a significant prevalence of non-communicable diseases. Moreover, excessive Na intake leads to an increase in blood pressure, whereas K intake leads to a balance between the two ions, which contributes to the regulation of blood pressure. Thus, WHO recommends not only restrictions on Na intake but also an adequate intake of K, which corresponds to a Na/K ratio bellow 1. The aims of this work were to assess Na and K general dietary intake and evaluate Na/K ratio for food groups under study. Samples were selected according to Total Diet Study (TDS), based on foods as consumed, in Portuguese diet. Analyzed samples (n=150), constituting 11 food groups, were grouped according to food classification system FoodEx2 level 1. Sodium and potassium levels were determined using Inductively Couple Plasma Atomic Emission Spectrometry - ICP-OES. Sodium and potassium contents ranged from

A cavala é uma das espécies de peixe mais abundantes em Portugal, sendo muito rica em diversas vitaminas e micronutrientes. Entre os micronutrientes existentes neste alimento destaca-se o selénio (Se), essencial para o ser humano, mas que se pode tornar tóxico quando ingerido acima da dose diária recomendada. Sendo parte integrante de um conjunto de proteínas com ação antioxidante (as selenoproteínas) um aporte adequado de Se conduz a um melhor desempenho do sistema imunitário, com repercussões positivas no tratamento e/ou prevenção do cancro ou no retardar do desenvolvimento de doenças degenerativas, como o Alzheimer. O organismo humano não sintetiza o selénio sendo a alimentação a fonte que mais contribui para o aporte diário deste elemento. Neste estudo, pretendeu- se estudar o teor de selénio, e de outros micronutrientes, em cavalas da costa portuguesa. Esta análise foi realizada mensalmente, entre março de 2019 e fevereiro de 2020, sendo o Se determinado por espectrometria de massa acoplada a plasma indutivo (ICP-MS), e os restantes micronutrientes (Zn, Fe, Mg, Cu, K, P) por espectrometria de emissão ótica por plasma acoplado indutivamente (ICP-OES). Concluiu-se que a ordem de concentração dos elementos estudados foi estabelecida como K> P> Na> Mg> Fe> Zn. Relativamente à concentração de Se, e por utilização do teste LSD, foram identificadas algumas diferenças significativas ao longo do ano, variando esta entre 451 e 606 μg/ml, excluindo o mês de maio que foi considerado um outlier. Contudo, este resultado poderá dever-se aos hábitos alimentares da cavala e época de desova, pelo que serão necessários mais anos de estudo, de modo, a se verificarem estas conclusões preliminares. Mackerel is one of Portugal's most abundant fish species, being very rich in several vitamins and micronutrients. Among the micronutrients in this food, selenium (Se) stands out, essential for humans, but can become toxic when ingested above the recommended daily dose. As an integral part of a set of proteins with antioxidants action (selenoproteins), an adequate intake of Se leads to a better performance of the immune system, with positive repercussions in the treatment and/or prevention of cancer or in delaying the development of degenerative diseases, such as Alzheimer's. The human organism does not synthesize selenium, so the source that most contributes to this element's daily supply is food. This study intended to evaluate the content of selenium and other micronutrients in mackerel from the Portuguese coast. This analysis was carried out monthly, between March 2019 and February 2020, with the Se being determined by mass spectrometry coupled to inductive plasma (ICP-MS), and the remaining micronutrients (Zn, Fe, Mg, Cu, K, P) by inductively coupled plasma optical emission spectrometry (ICP-OES). It was concluded that the order of concentration of the studied elements was established as K> P> Na> Mg> Fe> Zn. Regarding Se content, by the LSD test, some significant differences were identified throughout the year, varying between 451 and 606 μg / ml, excluding May, which was considered an outlier. However, this result may be due to the mackerel's eating habits and spawning season. More years have to be evaluated to verify these preliminary conclusions. Os autores agradecem o apoio financeiro do Projeto NewFood4 Thought – PTDC/ASP-PLA/28350/2017. info:eu-repo/semantics/publishedVersion

Portugal é um dos países europeus onde ocorre maior número de incêndios florestais e com a mais vasta área ardida. Os incêndios ocorridos em 2017, nos concelhos de Pedrógão Grande, Castanheira de Pera e Figueiró dos Vinhos, evidenciaram o enorme impacto destas catástrofes ambientais na saúde das populações, no seu bem-estar e no seu modo de vida. Este trabalho teve como objetivo a análise de seis elementos inorgânicos, nomeadamente bromo (Br), arsénio (As), níquel (Ni), cádmio (Cd), chumbo (Pb) e cromo (Cr), em amostras de couves, batatas e ovos provenientes de hortas familiares dos três concelhos afetados, em dois períodos de tempo diferentes, após a ocorrência dos incêndios. Os resultados deste estudo foram comparados com valores obtidos para os mesmos alimentos colhidos nas mesmas áreas, antes dos incêndios (amostra controlo de couves) e com valores referidos na literatura (batatas e ovos). Quando possível, e aplicável, os resultados foram também comparados com valores limite reportados na legislação em vigor. A determinação foi realizada por Espetrometria de Massa acoplada a Plasma Indutivo (ICP-MS). Os ensaios foram realizados mediante procedimentos analíticos em conformidade com a norma ISO 17025:2005. Os resultados mostraram que as amostras de couves, colhidas após os incêndios, e a amostra controlo apresentam diferenças significativas no As, Ni, Cd, Cr e Br. Relativamente ao Pb, não foram encontradas diferenças significativas entre as amostras das duas colheitas e a amostra de controlo. Por outro lado, os elementos analisados apresentam valores abaixo dos referidos na literatura e/ou na legislação em vigor, para as três matrizes estudadas. No entanto, foram encontradas exceções para o As e Cr, nos ovos, e para o As, nas batatas da 2ª colheita, em que os valores encontrados estão acima dos referidos na literatura. Portugal is one of the European countries with the highest number of forest fires and the largest burned area. In 2017, the fires in the municipalities of Pedrógão Grande, Castanheira de Pera and Figueiró dos Vinhos, showed the enormous impact of these environmental catastrophes on the health of the population, on their well-being and on their way of life. This work aimed to analyze six inorganic elements, namely bromine (Br), arsenic (As), nickel (Ni), cadmium (Cd), lead (Pb) and chromium (Cr), in samples of cabbages, potatoes and eggs from home gardens in the three affected counties, in two different periods, after the fires occurred. The values obtained from this study were compared with values obtained for the same foods harvested in the same areas, before fires (cabbages) or with values reported in the literature (potatoes and eggs). When possible, and applicable, the results were also compared with limit values reported in the legislation. The determination was performed by Mass Spectrometry coupled to Inductive Plasma (ICP-MS). The tests were performed using analytical procedures in accordance with the ISO 17025: 2005 standard. The results showed that the cabbage samples, collected after the fires, and the control sample present significant differences in As, Ni, Cd, Cr and Br. Regarding Pb, there were no significant differences between the samples from the two harvests and the control sample. On the other hand, results showed that the analyzed elements present values below those mentioned in the literature and/or in the legislation in force, for the three matrices studied. However, exceptions were found for As and Cr in eggs and As in potatoes from the 2nd harvest, in which the values found are above those reported in the literature. Este trabalho foi financiado pelo Instituto Nacional de Saúde Doutor Ricardo Jorge, no âmbito do projeto CONFFIAR (2019DAN1611). info:eu-repo/semantics/publishedVersion

Bromine (Br) is one of the main halogens of the periodic table and has been classified as emerging contaminant due to its persistence in the environment, bio-magnification properties and risk to human health [1]. The main goal of this work was to evaluate Bromine contents in Portuguese cabbage (Brassica Oleracea var. Costata DC), in the center region of Portugal before and after forest fires. This vegetable is one of the most consumed by the Portuguese population and is recognized as an accumulator of contaminants from the air and from soils. All cabbage samples were collected in the center region of Portugal. Before forest fire 3 Portuguese cabbage were collected in 9 different zones in a total of 27 samples (Control Group-CG) and used as a control. After forest fire (AFF), 3 Portuguese cabbage were collected in 8 zones over four periods of time (first campaign in August of 2017, second campaign in December of 2017, third campaign in April of 2018 and fourth campaign in August of 2018), in a total of 96 samples. Bromine contents was determined by inductively coupled plasma mass spectrometry (ICP-MS), preceded by an alkaline extraction with 25% ammonium tetramethylhydroxide (TMAH). The results were obtained through analytical procedures that reflected the quality assurance requirements described in ISO / IEC 17025: 2005. The concentration was expressed in mg Br/kg cabbage. The amount of Br in CG (mean of 27 samples) was 2 mg/kg. Most of the cabbage samples collected after forest fire presented concentrations above CG, with the following values; the first campaign (4.8 mg/kg), the second campaign (4.0 mg/kg) and the fourth campaign (4.5 mg/kg). The only campaign AFF that presented values below CG was the third one (1.7 mg/kg). Results before forest fires (CG) and after forest fire (4 campaigns) using One Way ANOVA pointed successfully on the existing statistical differences between bromine concentrations in CG and AFFs collection (p-value < 0.05). Through the Least significant differences (LSD) test the 1st and 4th campaigns (AFF) were the only ones that evidenced significant differences with the CG. After the forest fires, the 3rd campaign showed significantly lowest values when compared with the 1st and the 4th campaigns. However, these results do not pose risk to the Portuguese population, according to the commission regulation (EC) No 839/2008, wherein the value of bromide in brassicas is 30mg/kg [2]. The authors appreciate the support of Project CONFFIAR (2019DAN1611) and the financial support of INSA. Authors also acknowledge the Portuguese Foundation for Science and Technology (FCT) for funding MARE through the strategic programme UID/MAR/04292/201. N/A

Resumo publicado em: Acta Portuguesa de Nutrição.2019;8:63-64. Nos últimos anos, diversos estudos têm vindo a demonstrar a importância dos produtos de origem vegetal na alimentação, quer para a saúde humana quer para o ambiente. Este estudo está integrado no projecto “Avaliação da importância dos substitutos da carne na alimentação humana” e tem como objectivo a pesquisa de contaminantes químicos e microbiológicos no tempeh (alimento fermentado à base de soja), de forma a avaliar-se o risco associado ao seu consumo. Adquiriram-se, em estabelecimentos comerciais, 20 amostras de tempeh de marcas e lotes diferentes, representativas do consumo da população. As amostras foram analisadas cruas e confeccionadas de duas formas: salteadas e marinadas. Assim, cada amostra foi dividida em três sub-amostras, cada uma destinada a um tipo de confecção. Após confecção, as sub-amostras foram agrupadas obtendo-se três pools (cru, salteada e marinada), cada com 20 sub-amostras. Cada pool foi analisada em duplicado e/ou em triplicado para determinação de contaminantes químicos por ICP-MS (Arsénio, Crómio, Chumbo, Níquel, Alumínio, Cádmio e Estanho) e EAA com decomposição térmica da amostra (Mercúrio) e, para a determinação de bactérias patogénicas pelos métodos automatizado TEMPO® Biomerieux e imunoenzimático automatizado VIDAS®. Como resultados da análise química, observaram-se teores de Crómio, Níquel e Alumínio em todas as amostras, enquanto o teor de Arsénio foi superior ao limite de quantificação apenas na amostra marinada. Os restantes contaminantes inorgânicos encontravam-se abaixo dos respectivos limites de quantificação. A presença de Crómio e Níquel poderá dever-se a materiais usados no processamento, ao passo que a presença de Arsénio necessita de um estudo mais aprofundado, nomeadamente ao nível dos ingredientes utilizados na confecção. A análise microbiológica evidenciou a ausência de microrganismos patogénicos. Contudo, a contagem total de microrganismos na amostra crua mostrou que, de 5 embalagens da mesma marca e do mesmo lote, mais de 50% apresentam valores elevados, que poderá ser devido a uma contaminação da embalagem ou quebras da cadeia de refrigeração. Nas amostras pronto-a-comer (salteada e marinada), observaram-se valores aceitáveis, revelando condições higiénicas adequadas. A garantia da segurança alimentar foi efectuada por comparação com valores de referência publicados para outros produtos, surgindo assim a necessidade de criação de legislação específica. Este trabalho foi desenvolvido com o apoio da FCT. N/A

Forest fires are usually unexpected events leading to dramatic changes in all kinds of forest ecosystems, and they have a significant impact on flora. Fire mineralizes soil nutrients and returns plant-locked nutrients to the soil. Nutrients are lost from the ecosystem through the release of particulates and volatile compounds during the fire, and later through surface transport and leaching by rains1. Wildfires can play an important role in the environmental distribution of major and trace elements, including through their mobilization by fire-induced runoff and associated transport of soil and ash particles2. This study aimed to evaluate the selenium (Se), cobalt (Co), manganese (Mn), copper (Cu), lithium (Li) and zinc (Zn) content in cabbage, egg, potato and fruit samples in a total of 16 pools composed of 3 samples each at two different harvest periods. Cabbage samples from burnt zones were compared with a designated control sample from a non-burnt zone. Inductive Plasma Coupled Mass Spectrometry (ICP-MS) performed the determination of nutrient compounds. Previously, the samples underwent a heating block acid digestion with a validated time and temperature program. The analysis performed was under accordance with ISO 17025:20053 by analytical procedures. The lowest concentration founded in all nutrients was in fruits. The selenium and zinc content varied as follows: eggs> cabbage> potatoes> fruits. In the other hand, cabbage contained the highest cobalt and manganese content while eggs had lower values of copper. For lithium content, potatoes were the samples, which had lower values, than the eggs that contained higher values. The amount of the nutrients present in this study when compared to the control sample, the more pronounced increase recorded was for copper in the potato samples. Monitoring studies based on accredited methods are a powerful aid in assessing of exposure of affected populations. Este trabalho foi desenvolvido com o apoio da FCT. CONFFIAR N/A

Inductively coupled plasma mass spectrometry (ICP-MS) is one of the most suitable analytical techniques used to quantify inorganic components at trace concentrations. Being considered one of the key activities in a Quality Assurance system, the Internal Quality Control (IQC) reveals is of utmost importance when ICP-MS is used. Involving a continuous and critical assessment of the analytical methods and work routines of an analytical chemistry laboratory, the main propose of IQC is to continuously monitor the developed methodologies, as well as, to assess the reliability of the results. Within the IQC, the blank sample is an excellent tool, allowing to evaluate and monitor the quality of reagents, identify possible contaminations from the analytical processes resulting from the method and analytical processes, as well as to estimate the detection limits and the quantification limits for the trace elements analysed by ICP-MS. This study presents a methodology based on multivariate control (T2) charts for monitoring and assessing the stability of blank samples for Copper, molybdenum and lead. The proposed methodology grounds on the Statistical Process Control, where the T2 chart was designed to detect possible contaminations that may occur during the analytical method. To validate this approach, three univariate control charts, based on the Z scores, were built for each element and compared with the multivariate control chart output. The data analysis was performed using a set of blank samples collected between the years 2016 and 2018. Based on the data analysis results, the T2 chart was built and then validated through the correspondent three univariate Z charts. By comparing this set of charts it is possible to conclude that the T2 chart is in accordance with the results obtained by the three univariate charts. Although the mathematical complexity is high, this T2 chart revealed to be an appropriate IQC tool, when multi-elemental analyses are performed by ICP-MS. Este trabalho foi desenvolvido com o apoio da FCT-UNL. N/A

Verificou-se que os resultados do estudo piloto TDS em Portugal, para os contaminantes inorgânicos prioritários são semelhantes a outros estudos TDS publicados noutros países da Europa; Os valores de Cd e Pb não excedem os valores máximos para as amostras referidas na legislação; Os valores mais altos de As foram encontrados em pescado, no entanto a espécie arsenobetaína (não tóxica) é a predominante. A metodologia analítica utilizada (ICP-MS) é adequada ao estudo TDS, em particular pelos baixos limites de deteção e quantificação. Nem sempre os alimentos com teores mais elevados nutrientes/contaminantes inorgânicos, são os mais que contribuem para a ingestão/exposição. Este trabalho foi desenvolvido com o apoio da FCT. N/A

Serão apresentados cenários alternativos para monitorização da exposição a contaminantes alimentares, nomeadamente os Estudos de Dieta Total. Este trabalho foi desenvolvido com o apoio da FCT. N/A

Os incêndios florestais são fenómenos que constituem um problema ambiental com impactos adversos e diversificados nos ecossistemas atmosférico, terrestre e aquático, com repercussões económicas e sociais. Durante os incêndios florestais são libertados diferentes compostos químicos para a atmosfera resultantes da queima da madeira e da vegetação. Segundo a Direção Geral de Saúde, o fumo resultante dos incêndios florestais possui altos níveis de partículas e toxinas que podem causar doenças cancerígenas, respiratórias, oftalmológicas, cardiovasculares, neurológicas, diabetes, hipertensão, lesões de pele entre outras. As partículas suspensas contendo metais pesados e metaloides são os principais poluentes no contexto dos incêndios florestais, com impacto direto na saúde. Este trabalho foi desenvolvido com o apoio da FCT. N/A

Forest Fires can be one of the most relevant sources of environmental contamination. Few studies have dealt with the presence of heavy metals in foods cultivated on burnt soils. This work aims to evaluate the content of arsenic (As), cadmium (Cd) and lead (Pb) in Portuguese cabbage cultivated in different regions of Portugal, before and after forest fires. Este trabalho foi desenvolvido com o apoio da FCT, Projecto PRO-METROFOOD - No 739568. N/A

The adverse effects of heavy metal exposure to human health have been studied and acknowledged for many years by several international organizations such as the World Health Organization (WHO). Total Diet Studies (TDS) were adopted by several European countries as the sound scientific basis to strengthen the linkage between food consumption and food analysis with the purpose of assessing the effect of harmful substances on health. Este trabalho foi desenvolvido com o apoio da FCT, PRO-METROFOOD, No 739568 N/A

Total diet studies (TDS) provide analytical data to estimate dietary exposure and risk assessment of contaminants. TDS were adopted by several European countries as the sound scientific basis for strength the linkage between food consumption and food analysis with the purpose to assess the effect of harmful substances on health. Heavy metals have been extensively studied and their effects on human health regularly reviewed by international bodies such as the World Health Organization (WHO). Bromine is a halogen of emerging concerned and has been associated with endocrine disruption and subject to bioaccumulation in food chains. The aim of this work was to study the profile of chemical contaminants; lead chromium, cadmium. Arsenic and bromine as a contaminant of emerging concerned in foods collect in Portuguese TDS pilot study. Four hundred and eighty foods were purchased and prepared as consumed were pooled in forty laboratory samples. Then were digested with concentrated nitric acid and hydrogen peroxide in a microwave system for Pb, Cr, Cd and As, total bromine was determined using tetramethyl ammonium hydroxide (TMAH) extraction. Digested samples were analysed by inductively coupled plasma mass spectrometry (ICP-MS) and HPLC-ICP-MS for total and chemical species respectively. Analytical procedures were carried out under rigorous metrological control, laboratory performance was demonstrated through a successful participation in PT schemes runs by an accredited provider. The decreasing sequence of the mean inorganic contaminants in prioritised foods was as follows: As > Br > Cr > Pb > Cd. In Octopus was found the highest amount of As, 9138 ± 237 μg/kg, mainly arsenobetaine and in clams were detected the highest concentrations of Cd and Pb, 125 ± 17 μg/kg and 260 ± 23 μg/kg, respectively. The results of TDS Portuguese Pilot study showed that contents of inorganic chemical contaminants are similar to those published by studies carried out in other European Countries. Based on studies published we can inferred that intake of inorganic substances do not pose a risk to Portuguese population. Project PRO-METROFOOD has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 739568. N/A

Introduction: Selenium and iodine are micronutrients essential for thyroid hormone synthesis and function. There is also some evidence that low plasma selenium and iodine levels increase the risk of autoimmune thyroid diseases. Plasma levels of these oligoelements are related with dietary intake. Since foods are their main natural sources we investigated iodine and selenium content in foods as consumed collected in Portuguese TDS pilot study as representative of diet in the country. Objective: This work aims to evaluate the contents of Se and I in foods collect during the Portuguese Total Diet Study (TDS). Methodology: Samples (n=1020) were collected according to sampling plan from local markets and analyzed as pooled (n=85) of twelve samples each. The iodine and selenium contents were determined using inductively coupled plasma-mass spectrometry (ICP-MS) after alkaline (iodine) or acid (selenium) digestion assisted by microwave. To guarantee the accuracy of the laboratory results matrix matching reference materials and successfully participation in proficiency test schemes were chosen as metrological parameters. The analytical results were expressed by the average of three replicates. Cluster analysis (CA), Principal Component Analysis (PCA) and Spearman correlation were applied to evaluate the statistical significance of analytical data. Main Findings: Selenium content ranged from 109±10.85 μg/100g (fresh tuna) to 1.82±0.16 μg/100g (milk with cereals). Iodine values were found from 157±5.8 μg/100g (cockles and clams) to 0.27±0.014 μg/100g (lupine). CA classified samples into four main groups on the basis of the iodine and selenium content. PCA and CA analysis are in agreement. Spearman positive correlation (p≤ 0.05) was achieved between iodine and selenium contents. Conclusion: Application of chemometric methods to analytical data is useful to group food samples when iodine/selenium ratio is necessary to suppress iodine deficiency. This work was undertaken within Total Diet Study Exposure (www.tds-exposure.eu), which is funded by the European Commission (Grant Agreement 289108). N/A

Manganese and Copper are two essential micronutrients required for several vital functions. Recently EFSA reviewed adequate intake values for these nutrients. AIs of 1.6 mg/day for copper, and 3 mg/day for manganese were established for adults. This work aims at evaluating the contents of Mn and Cu in foods collect during the Portuguese Total Diet Study (TDS). One thousand one hundred and fifty two foods were prepared as consumed and analysed in ninety six pooled laboratory samples. Samples were digested with nitric acid and hydrogen peroxide in a microwave assisted digestion and analysed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Analytical procedures were carried out under rigorous metrological control and traceable to SI units. The following food groups were analysed: dairy products, meat, fish, cereals, pulses, bread, potatoes and juices. The lowest amounts of Mn and Cu were found in milk with 27 ± 0.9 μg/kg and 42 ± 4.5 μg/kg, respectively. The highest concentration of Mn was present in pulses 12541 ± 237 μg/kg while the maximum value of Cu was observed in cereals 2451 ± 52 μg/kg. The assessment of different food groups to overall AIs was based on combination of analytical data with consumption data from national food survey. Our results, showed that a diet including only these food groups is not sufficient to suppress the AIs of Mn or Cu for Portuguese adult population. Metrological tools were crucial to guarantee consistency conclusions. Project PRO-METROFOOD has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 739568. N/A

Este ano (2017), celebra-se o aniversário da descoberta do micronutriente selénio (Se), que foi pela primeira vez identificado pelo químico sueco Jacob Berzelius. Posteriormente, Klaus Schwarz with Foltz provaram que o Se é um nutriente essencial para o normal crescimento e reprodução dos animais e do homem. A maioria das enzimas dependentes de Se, já foram identificadas em várias funções biológicas, tal como regulação da resposta inflamatória, propriedades antioxidantes, através da regulação das espécies reativas de oxigénio (ROS) e do estado redox, e promoção da proliferação/diferenciação das células imunes. A deficiência de Se foi associada, a uma miríade de patologias, sendo de referir o aumento do risco de doenças não transmissíveis como o cancro – incluindo da tiróide – infeções e estados de imunodepressão, infertilidade masculina, diabetes, doenças de Alzheimer e Parkinson, perturbações do humor, doença de Keshan e doença de Kashin-Beck. A carência grave de Se associa-se a disfunção muscular e cardiomiopatia. Estudos no âmbito da relação do Se com o controlo glicémico, Diabetes Mellitus gestacional e hipertrofia adipocitária ainda têm resultados controversos e necessitam de mais estudos para provar a sua correlação. A interdependência entre os teores de selénio presentes nos alimentos e a redução de toxicidade do arsénio são também descritos na literatura em particular nos últimos anos. Segundo o IOM, nos EUA, e outros artigos da literatura referem que a ingestão alimentar recomendada é de 55μg/dia para um adulto. E a dose máxima admissível (UL) é o nível mais alto de ingestão diária de nutrientes suscetível de não representar qualquer risco de efeitos adversos, em quase todos os indivíduos, sendo importante que todos os indivíduos da população sejam aconselhados para não exceder esta dose – 400 μg/dia. Os alimentos são a fonte principal de selénio. Porém a biodisponibilidade deste oligoelemento está dependente da espécie química presente no alimento. Em Portugal existem poucos dados sobre o perfil de selénio nos alimentos. O objetivo deste estudo foi determinar a abundância de selenometionina (SeMet), selenito (Se IV) e selenato (SeVI) em leite e pescado como consumido pelos portugueses. As amostras foram recolhidas seguindo a metodologia adotada no projeto TDS – Exposure. Recorreu-se à técnica hifenada de HPLC-ICP-MS precedida da extração das espécies, por métodos enzimáticos, da matriz alimentar. Os ensaios foram realizados em condições de controlo da qualidade que refletem os requisitos da Norma 17025:2005. A SeMet foi a espécie predominante, em todos os alimentos analisados. No leite foram encontradas ambas as espécies inorgânicas. No pescado o Se (VI) foi a única espécie inorgânica encontrada. Este estudo foi muito importante porque possibilitou conhecer o perfil das espécies de selénio presentes em alimentos como consumidos, sendo um parâmetro que irá permitir estimar o aporte de selénio, com maior rigor. A importância das estratégias analíticas aplicadas para a quantificação e identificação das espécies de selénio serão objeto de estudos futuros. Este trabalho foi desenvolvido com o apoio da FCT. N/A

Arsenic (As), is a metalloid that can accumulate in water, plants and seafood to high levels. Depends on the chemical form it can pose a risk to human health. Inorganic arsenic (Asi) is considered a non-threshold carcinogen, and every exposure constitutes a risk. Monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) can be related with inorganic exposure and arsenobetaine (AsB) and arsenocholine (AsCh) are organic species with nontoxic effects associated. Speciation data is crucial to clarify the linkage between arsenic content and chronic diseases. A comprehensive dietary exposure assessment is required in particularly to infants and pregnant women. Fetal exposure to inorganic arsenic seems correlated with an increased risk of adverse health effects later in life. Recent advances in analytical procedures and the metrological principles applied for the identification of arsenic chemical species are discussed. HPLC-ICP-MS as the golden standard technique providing data to support a comprehensive dietary exposure assessment and to redefine risk assessment of (Asi), is presented. The contribution of Total Diet Studies as a harmonised methodology for food sampling and exposure assessment modelling to ensure comparability and consistency of arsenic data across countries is another aim of this presentation. Information about mitigation strategies to reduce exposure to arsenic is also highlighted. Este trabalho foi desenvolvido com o apoio da FCT. N/A

Background and objective(s): Selenium is an essential trace element for human health. Through selenoproteins, it participates in various biological processes such as antioxidant defence, thyroid hormone production and immune responses. The role of Se in the prevention of As – induced toxicity has been documented in several studies. Se-dependent sequestration of As is suggested as a primary mechanism of interaction between Se and As toxic species. To understand the mechanisms involved in the Se/As interactions it is necessary to characterize their presence in foods as principal source of exposure. The aim of this work was to evaluate Se Methionine (SeMet), Selenite (Se (IV)) and Selenate (Se (VI)) and Arsenite (As(III)), Arsenate (As(V)), Dimethylarsinic acid (DMA) and Arsenobetaine (AsB) in fresh and cooked foods representative of the Portuguese Diet. Materials and methods: Speciation analysis was carried out by High Performance Liquid Chromatography (HPLC) coupled to Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Before analysis, samples were extracted using specific extraction procedures for As and Se. Results: More than 90% of the As present in fish samples was in the form of AsB while in rice samples results showed that 80% of the As was present as inorganic forms and 20% as DMA. SeMet was the major Se species in milk and fish samples accounting for 85-90 % of the total Se content. In cabbage Se (IV), Se (VI) and (SeMet) were found. Discussion and conclusion(s): The results showed the suitability of the analytical procedures to achieve an accurate determination of As and Se species in these complex matrices. This work was performed under the project TDS - ref. FP7- KBBE-2011-5; project HERA - ref. PTDC/SAU-ESA/100107/2008, project “ORQUE SUDOE” - Ref. SOE3/P2/F591 and project ValCAP - ref. 23290. N/A

O INSA agradece à Sociedade Portuguesa de Ciências da Nutrição (SPCNA) pela cedência dos dados de consumo alimentar utilizados neste trabalho que são originários do Estudo Alimentação e Estilos de Vida da População Portuguesa, realizado pela SPCNA ao abrigo de um protocolo de mecenato científico com a empresa Nestlé Portugal. O selénio e o iodo são micronutrientes essenciais para a síntese das hormonas da tiroide e para o seu funcionamento. Sendo a alimentação a principal fonte destes oligoelementos, o objetivo deste trabalho foi a determinação de iodo e selénio em alimentos consumidos pelos portugueses. A metodologia de amostragem seguiu as recomendações do projeto TDS-Exposure. Os mil setecentos e sessenta e quatro alimentos recolhidos foram agrupados em pools de 12 amostras e analisados por ICP-MS, em condições de controlo de qualidade acreditadas pela norma NP EN ISO/IEC 17025:2005. Em cada pool foi calculada a contribuição do selénio para a dose diária recomendada (DDR). Partindo de dados de iodo recentes obtidos nas mesmas condições, foi calculado, para cada alimento a sua contribuição para a DDR de iodo. O grupo do pescado foi onde se identificaram os alimentos mais ricos em selénio, seguido da carne, ovos e lacticínios. Em várias pools de frutas e vegetais o teor de selénio não foi quantificável estando abaixo do limite de quantificação do método analítico. Quando calculadas as contribuições dos alimentos em estudo para as doses diárias recomendadas de iodo e selénio estimou-se que uma porção de peixe magro pode contribuir com 48% da DDR de Iodo e 100% de Selénio enquanto três porções de lacticínios podem suprimir até 48% da DDR de Iodo. Com base nestes resultados que se suportam em teores obtidos em alimentos representativos da dieta portuguesa, uma alimentação rica em pescado e lacticínios pode suprir as doses diárias recomendadas para iodo e selénio, para uma população saudável. Selenium and iodine are essential micronutrients for the synthesis of thyroid hormones as well as for their functioning. Being food the main source of these trace elements the objective of this work was the determination of iodine and selenium in foods consumed by the Portuguese population. The sampling methodology followed the recommendations of the TDS-Exposure project. The one thousand seven hundred and sixty four collected foods were grouped in pools of 12 samples and analyzed by ICP-MS under conditions of quality control accredited under NP EN ISO/IEC 17025:2005. The contribution of selenium to the recommended daily intake (RDI) was calculated for each pool. Based on recent iodine data obtained under the same conditions as the present work, for the contribution of each food to iodine RDI was calculated. The fish group provided the richest foods in selenium, followed by meat, eggs and dairy products. In several fruit and vegetable pools selenium contents were not quantifiable since results were below the limit of quantification of the analytical method. When calculating the contribution of the foods under study to the RDI of iodine and selenium it was estimated that one portion of lean fish could contribute up to 48% of the RDI of iodine and 100% of selenium, while three portions of dairy products can suppress up to 48% of iodine RDI. The present results, which are based on levels of selenium and iodine obtained for foods representative of the Portuguese food consumption, evidence that for a healthy population a diet rich in fish and dairy products can fully supply the RDI for these two micronutrients. Trabalho desenvolvido no âmbito do projeto TDS-Exposure (www.tds-expure.eu) financiado pelo 7º Programa Quadro da União Europeia (Grant Agreement 289108). info:eu-repo/semantics/publishedVersion

Introdução: A toxicidade do arsénio está dependente da sua forma química sendo as espécies inorgânicas mais tóxicas que as orgânicas e, dentro destas, nem todas apresentam o mesmo nível de toxicidade. A alimentação e a água potável são a maior fonte de exposição ao arsénio inorgânico, considerado o mais carcinogénico pela EFSA[1]. A técnica hifenada de cromatografia liquida acoplada à espectrometria de massa com plasma induzido (HPLC-ICP-MS) permite a deteção e quantificação das espécies inorgânicas - As(III) e As(V) - toxicidade elevada e orgânicas - DMA, MMA, AsB, AsC, AS, AL - espécies de toxicidade baixa ou ainda desconhecida. Projeto TDS – Exposure (FP7- KBBE-2011-5), Projeto IMEKOFOODS (2013DAN851), Projeto Elementaria (2013DAN850). N/A

O níquel é um elemento natural da superfície terrestre. A alimentação é uma das principais fontes de exposição a este metal. Devido à sua acumulação no organismo pode causar efeitos nocivos para a saúde como a carcinogénese e a dermatite induzida. O principal objetivo deste trabalho foi a determinação de níquel em alimentos analisados como consumidos e representativos da dieta portuguesa. A metodologia escolhida para a quantificação deste contaminante foi a espectrometria de massa acoplada a plasma indutivo (ICP-MS) precedida por digestão ácida em vaso fechado no micro-ondas. Foram recolhidas 1560 amostras, que foram analisadas em 130 pools, contendo cada 12 alimentos idênticos. O teor de níquel variou entre 21,2 μg/kg (sumos) e 1050 μg/kg (bivalves). O limite de quantificação do método foi o parâmetro analítico considerado indicador para a avaliação da exposição. A análise comparativa entre os valores analíticos superiores ao limite de quantificação do método e os valores não quantificáveis, demonstrou que todos os pratos compostos apresentaram valores superiores ao limite de quantificação e 60% dos resultados encontrados nos laticínios eram inferiores ao limite de quantificação do método. Atendendo aos procedimentos aplicados, os resultados obtidos podem ser utilizados como fonte de informação científica para simulações da avaliação do risco de exposição ao níquel, com consequentes ganhos em saúde. Nickel is a natural element of the earth's crust. Food is one of the main sources of human exposure to this metal. Its accumulation in the body can cause harmful effects to health such as carcinogenesis or induced dermatitis. The aim of this work was the determination of nickel in foodstuffs analyzed as consumed and representative of the Portuguese diet. The methodology chosen for the quantification of this contaminant was inductively coupled plasma mass spectrometry (ICP-MS) preceded by acid digestion in closed vessel microwave digestion. In total 1560 samples were collected and then analyzed into 130 pools, each containing 12 identical foods. The nickel content varied between 21,2 μg/kg (juices) and 1050 μg/kg (bivalve). The limit of quantification of the method was the analytical parameter considered as a critical indicator to estimate the lower-bound of contamination and exposure of food. The comparative analysis between the analytical values above the limit of quantification and the unquantifiable values showed that all composites had values higher than the limit of quantification while 60% of the results found in dairy products were below that limit. Taking into account the procedures applied, the results can be used as a source of scientific information for nickel exposure risk assessment simulations, with consequent health gains.

TDS provide analytical data to estimate dietary exposure of chemical contaminants. In this work was studied Pb, As, Cr and Cd profile in foods from Portuguese TDS Pilot Study. Nine hundred and twenty four foods were pooled in two hundred and thirty one laboratory samples and analysed by ICP-MS under rigorous metrological control. The highest amount (µg/kg) obtained for each chemical substance was: As 9138 ± 237 (Octopus); Pb 282 ± 5.5 (snails); Cr 605 ± 28 (Cured meat); Cd 248 ± 5 (snails). These levels of potential harmful substances do not pose a risk to population. N/A

Selenium and iodine are micronutrients essential for thyroid hormone synthesis and function. There is also some evidence that low plasma selenium and iodine levels increase the risk of autoimmune thyroid diseases. Plasma levels of these oligoelements are related with dietary intake. Since foods are their main natural sources we investigated iodine and selenium content in foods as consumed collected in Portuguese TDS pilot study as representative of diet in the country. Samples (n=492) were collected according to sampling plan from local markets and analyzed as pooled (n=41) of twelve samples each. The iodine and selenium contents were determined using inductively coupled plasma-mass spectrometry after alkaline (iodine) or acid (selenium) digestion assisted by microwave. To guarantee the accuracy of the laboratory results matrix matching reference materials and successfully participation in proficiency test schemes were chosen as metrological parameters. The analytical results were expressed by the average of three replicates. Cluster analysis and Spearman correlation were applied to evaluate the statistical significance of analytical data. Selenium content ranged from 109±10.85 µg/100g (fresh tuna) to 1.82±0.16 µg/100g (milk with cereals). Iodine values were found from 157±5.8 µg/100g (cockles and clams) to 0.27±0.014 µg/100g (lupine). Cluster analysis classified samples into four main groups on the basis of the iodine and selenium content. Spearman positive correlation (p≤ 0.05) was achieved between iodine and selenium contents. Application of chemometric methods to analytical data is useful to group food samples when iodine/selenium ratio is necessary to suppress iodine deficiency through dietary intake. This work was undertaken within Total Diet Study Exposure (www.tds-exposure.eu), which is funded by the European Commission (Grant Agreement 289108) N/A

A couve Portuguesa (Brassica oleracea L. var. costata DC.) é o vegetal mais cultivado em Portugal não sujeito a agricultura intensiva, o mais consumido pela população rural e muito apreciado pela população em geral. As hortícolas folhosas são acumuladoras de metais pesados e sinalizadoras de contaminantes ambientais. Com a realização deste trabalho pretendeu-se avaliar, por ICP-MS, a concentração de 10 elementos traço em couves portuguesas cultivadas em todos os distritos de Portugal Continental e Ilhas. Foram analisadas couves com origem em 20 locais de Portugal Continental e Ilhas. Para cada local foi realizada uma pool com 3 folhas exteriores de 3 couves diferentes. Como procedimento de preparação de amostras, as folhas foram lavadas, liofilizadas, trituradas e digeridas por microondas em vaso fechado. Os resultados, expressos pela média de 3 réplicas, foram analisados estatisticamente através da análise de clusters e de redes neuronais. Concluiu-se que as couves analisadas não continham cádmio e chumbo acima dos valores legislados, 50 e 100 µg/kg, respetivamente [1, 2]. O arsénio é o elemento determinante para caraterizar o local de origem deste vegetal, pois é o que apresenta maior variabilidade entre as regiões estudadas. Este fator poder-se-á atribuir à diferença de contaminantes presentes nos solos e águas das diferentes regiões. Futuramente, tendo por base este trabalho, pretende-se publicar um artigo científico e fazer a avaliação da exposição continuada. [1] Regulamento EU nº 488/2014 da Comissão de 12 de Maio de 2014. Jornal Oficial da União da União Europeia [2] Regulamento EU nº 1881/2006 da Comissão de 19 de Dezembro de 2006. Jornal Oficial da União da União Europeia Este trabalho foi realizado com suporte financeiro através do projeto SOE3/P2/F591 - Observatório de Investigação para a Qualidade Ambiental do Sudoeste Europeu – ORQUE SUDOE.

O níquel é um elemento natural da superfície terrestre. A alimentação é uma das principais fontes de exposição deste metal na população não fumadora. Devido à sua acumulação no organismo pode causar efeitos nocivos para a saúde como a carcinogénese e a dermatite endógena. O principal objetivo deste trabalho foi a determinação de níquel em alimentos analisados como consumidos e representativos da dieta portuguesa. A metodologia escolhida para a quantificação deste contaminante foi a espectrometria de massa acoplada a plasma indutivo (ICP-MS) precedida por digestão ácida em vaso fechado no micro-ondas. Foram recolhidas 1560 amostras, que foram analisadas em 130 pools, contendo cada 12 alimentos idênticos. O teor de níquel variou entre 21,2 µg/kg (sumos) e 1050 µg/kg (bivalves). O limite de quantificação do método foi o parâmetro analítico considerado indicador para a avaliação da exposição. A análise comparativa entre os valores analíticos superiores ao limite de quantificação do método e os valores não quantificáveis, demonstrou que todos os compósitos apresentaram valores acima do limite de quantificação e 60% dos resultados encontrados nos lacticínios estavam abaixo do limite de quantificação. Atendendo aos procedimentos aplicados os resultados obtidos podem ser utilizados como fonte de informação científica para simulações da avaliação de risco de exposição ao níquel, com consequentes ganhos em saúde. Este trabalho foi desenvolvido no âmbito do projeto TDS-Exposure financiado pela Comissão Europeia (Grant Agreement 289108). N/A

Prémio do melhor poster. Selénio (Se) é um oligoelemento essencial para a saúde humana, sendo os alimentos a sua principal fonte de aborção. A ingestão diária recomendada (RDA) para adultos é de 55 µg Se/dia em que esta depende dos seus níveis de concentração nos alimentos e da quantidade de alimentos consumidos. A deficiência de Se pode causar a redução de respostas imunitárias como reduzir a proteção contra doenças crónicas. Em doses superiores a 250 µg Se/dia pode causar lesões na pele e queda de cabelo e unhas. A avaliação do teor de selénio na dieta requer informações sobre o Se total mas também das espécies bioaccessíveis presentes nas amostras. O objetivo deste trabalho foi avaliar em alimentos representativos do consumo nacional, a concentração de Se total e suas espécies, selenometionina (SeMet), selenito (Se(IV)) e selenato (Se(VI)). A determinação do Se total foi realizada por Espetrometria de Massa acoplado a Plasma Indutivo (ICP-MS) e as espécies de Se foram identificadas por Cromatografia Líquida de Alta Eficiência (HPLC) acoplada ao ICP-MS equipado com célula de reação dinâmica (HPLC-DRC-ICP-MS). Precedidas por digestão em microondas (selénio total) e hidrólise enzimática, hidrólise ácida e extração com água (especiação). Para garantir o controlo de qualidade do método foram avaliados os parâmetros de reprodutibilidade, repetibilidade e exatidão utilizando materiais de referência certificados (MRC) e amostras com concentração de padrão conhecida. Os resultados obtidos dos MRC estavam em concordância com os valores certificados e a recuperação de padrão com um critério de aceitação entre 80 e 120 %. Os resultados mostraram que os métodos foram adequados na determinação de Se total nas amostras analisadas variando entre 67 ± 3 ug.kg-1 (couve) e 161 ± 16 ug.kg-1 (leite). SeMet e Se(VI) foram as espécies mais abundantes nas amostras analisadas representando 85 - 90 % do teor de Se total. Este trabalho foi realizado com suporte financeiro através do projeto SOE3/P2/F591 - Observatório de Investigação para a Qualidade Ambiental do Sudoeste Europeu – ORQUE SUDOE

The main objective of this study was to study the levels of strontium, total arsenic and inorganic arsenic present in nectars, fruit juices and waters consumed in Portugal. A second objective was to evaluate the reliability of pooled versus single samples to derive consistent estimates of exposure assessment to inorganic contaminants. Twenty four samples of juices and nectars representative of the domestic market were acquired in May 2014 in the Lisbon region. Samples of representative brands were collected randomly in supermarkets of national implementation in accordance with consumer preference. Afterwards these were analyzed both as single units and as two pools, one of nectars and the other of juices, composed by 12 samples each. Prior to analysis samples were digested by high pressure closed vessel microwave digestion using only ultrapure reagents. An ICP-MS was used to quantify the levels of Strontium and Arsenic present in samples. Whenever the concentration obtained for arsenic was equal or above 5 µg.l-1 samples were signalized for speciation studies. These were carried out by coupling an HPLC to the ICP-MS, and enabled the determination of two inorganic arsenic species, As(III) and As(V), as well as two other organic species, AsB and DMA. Extraction of arsenic from samples was based on previously published work [1] and consisted on a dilution and a filtration steps previously to introducing the samples to the HPLC. Arsenic was found above the LQ (LQ=2 µg.l-1) in almost half the samples under study which shows that arsenic speciation is crucial to clarify the toxicity of arsenic present in foodstuffs. The speciation study proved that most of this arsenic, whether in juices, nectars or waters, is present as As(III) and As(V). However, there is no European legislation for arsenic in fruit juice. Inconsistent results were obtained for arsenic between pooled and single samples. Also, the present work provided a clear example of how, due to a dilution factor, pooling might mask the presence of a contaminant and therefore underestimate exposure assessments. References [1] S. D. Conklin and P. E. Chen, “Quantification of four arsenic species in fruit juices by ion-chromatography–inductively coupled plasma–mass spectrometry,” Food Additives & Contaminants: Part A, vol. 29. pp. 1272–1279, 2012. The research leading to these results has received partial funding from the European Union’s Seventh Framework Program for research, technological development and demonstration under grant agreement n° 289108.

Objective: The main objectives of the present work were 1) to study the inorganic contaminants present in nectars and fruit juices consumed in Portugal and 2) to evaluate the reliability of pooled versus single samples to derive consistent estimates of exposure assessment to inorganic contaminants. Methodology: Twenty four samples of juices and nectars representative of the domestic market were acquired in May 2014 in the Lisbon region. Samples of representative brands were collected randomly in supermarkets of national implementation in accordance with consumer preference. Afterwards these were analyzed both as single units and as two pools, one of nectars and the other of juices, composed by 12 samples each. The work focused on the determination of Copper, Manganese, Cobalt, Selenium, Zinc, Arsenic, Cadmium, Chromium and Lead using ICP-MS. Element determination was preceded by high pressure closed vessel microwave digestion. Speciation studies for the determination of inorganic arsenic were carried out through HPLC-ICP-MS. Results: Cadmium was present in concentrations above the limit of quantification (LQ) only in one sample. Arsenic was found above the LQ (LQ=2 µg/L) in almost half the samples under study. The speciation study proved that most of this arsenic is present in the inorganic forms (As III and As V). However, there is no European legislation for arsenic in fruit juice. Inconsistent results were obtained for arsenic between pooled and single samples. Conclusions: In the nectars and fruit juices studied metals and metalloids of known toxicity were found in levels below legislated limits for water intended for human consumption. In light of the obtained results arsenic speciation is crucial to clarify the toxicity of arsenic present in foodstuffs. Also, the present work provided a clear example of how, due to a dilution factor, pooling might mask the presence of a contaminant and therefore underestimate exposure assessments. The research leading to these results has received partial funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement n° 289108.

Objetivo: Caracterizar o teor de macronutrientes e de componentes inorgânicos da quinoa (Chenopodium quinoa), utilizando metodologias validadas que assentam em pressupostos de controlo da qualidade rigorosos, permitindo a sua inclusão na tabela de composição de alimentos portugueses e nas restantes bases de dados que aderiram à plataforma EuroFIR. Este trabalho foi realizado no âmbito do projeto de investigação “Desarrollo de Alimentos andinos procesados: una alternativa para la conservación de la biodiversidad” (PICT-nº 2245), financiado pelo Ministerio de Ciencia y Tecnología de Argentina e do protocolo de colaboração cientifica assinado entre o INSA e o Universidade Nacional de Jujuy.

Objetivo: Descrever as tarefas acometidas ao INSA e o trabalho laboratorial realizado no Laboratório de Materiais de Referência do Departamento de Alimentação e Nutrição, no âmbito do projeto ORQUE SUDOE.

A quinoa (Chenopodium quinoa), amaranto (Amaranthus caudatus), milho roxo (Zea mays L.) e trigo-sarraceno (Fagopyrum esculentum) têm ganho cada vez mais atenção da comunidade científica, especialmente devido ao seu alto valor nutricional e benefícios para a saúde. O seu perfil mineral pode variar com a origem geográfica, ou com as condições de cultivo, sendo por isso aconselhável o uso de metodologias validadas que assentem em pressupostos de controlo de qualidade rigorosos. A preparação prévia da amostra para a determinação de minerais é uma etapa crítica de ensaio devido às possíveis contaminações e perdas de analito que podem ocorrer. A destruição da matéria orgânica e disponibilização dos analitos, para posterior determinação dos minerais, pode ser efetuada por diferentes métodos (digestão por via seca, digestão ácida a baixa e a alta temperatura e digestão por microondas). O objetivo deste trabalho foi comparar os resultados de teor de minerais em pseudocereais (quinoa, amaranto e trigo mourisco) e milho roxo obtidos por Espectrometria de Emissão Atómica com Plasma acoplado indutivamente (ICP-OES) quando três métodos digestão diferentes – digestão por via seca, sistema de aquecimento por bloco de grafite (DigiPREP) e digestão por microondas - foram utilizados. Os teores de minerais obtidos com os três procedimentos foram comparados e o desempenho dos métodos foi avaliado usando materiais de referência certificados apropriados. Estatisticamente, não houve evidência de que os três métodos de digestão diferentes tenham influenciado os resultados finais, (P

publicado: Zappa, G. and Zoani, C. (editors) 1st IMEKOFOODS: metrology promoting objective and measurable food quality & safety, Rome, October 12-15, 2014. Roma: ENEA: 118 (P30). Disponível em: http://imekofoods.enea.it/sites/default/files/docs/Abstract_Book_1st-IMEKOFOODS_.pdf Total diet studies complement traditional monitoring and surveillance by providing a scientific basis for population dietary exposure to contaminants, with potential impact on public health. This should be achieved by using quality assurance procedures and specifically by applying analytical methods where performance criteria have been established in compliance with metrological requirements. The aim of this study is to determine the amounts of minerals and trace elements in 24 types of fruit juices, obtained from various kinds of fruits, available in the Portuguese market and representative of consumption by Portuguese population. Inductively coupled plasma optical emission spectrometry (ICP-OES) technique was employed for determination of the elements Sodium, Potassium, Calcium, Phosphorus, Magnesium, Manganese, Iron, Copper, Zinc, and ICP-MS for the trace elements, Chromium, Nickel, Molybdenum, Strontium, Tin, Cobalt, Selenium, Arsenium, Cadmium and Lead. In orange juice high Potassium and Phosphorus content were observed. High concentration of Sodium 6,9 % was determined in apple juice and Arsenic was found below limit of quantification for majority of samples under analysis. All the results have been achieved in agreement with rigorous metrological procedures as previous defined. This information will be used for dietary exposure assessment which combines food consumption data with data on the concentration of chemicals in food. The resulting dietary exposure estimate may then be compared with the relevant health based guidance value for the food chemical of concern, if available, as part of the risk characterization. Metrological procedures reveal a crucial tool to guarantee fiability of measurement results used in risk assessment associated with the consumption of fruit juice. This work was completed on behalf of the INSA (Project Elementaria 2013DAN850)

A Food and Drug Administration (FDA) publicou recentemente orientações sobre o teor de arsénio inorgânico em sumos de fruta e no arroz. Assim, é expectável que tanto nos Estados Unidos como em todos os países que seguem as recomendações da FDA seja exigido a apresentação de certificados de análise que evidenciam a conformidade dos produtos, com as recomendações da FDA. Nesta comunicação é feita a apresentação dos métodos analíticos que permitem determinar o teor de arsénio inorgânico e de outros metais pesados em produtos hortícolas e frutícolas. Assim, faz-se uma descrição dos requisitos da FDA e das condições de ensaio exigidas por esta instituição, Norte Americana. O método requerido é um método em que, recorrendo à técnica hifenada de HPLC-ICP-MS, identifica e quantifica as espécies químicas de arsénio presentes em produtos alimentares. No caso do arsénio esta técnica é de extrema importância porque é a única reconhecida pela FDA que permite identificar quais as espécies tóxicas e as espécies não tóxicas presentes. Serão assim discutidas as diferenças entre as técnicas que determinam o teor de arsénio total e aquela como a HPLC-ICP-MS que identifica o teor de arsénio inorgânico de toxicidade elevada e o teor de espécies químicas de arsénio sem toxicidade conhecida. São apresentados alguns exemplos que ilustram estas diferenças e a necessidade de as evidenciar, bem como, as condições laboratoriais existentes em Portugal, que podem ser postas à disposição das entidades exportadoras.

Recent data shows that Portugal has a rice consume of 15.8 kg/capita/year, the largest in Europe. The Sado estuary, located in the West Coast of Portugal, is a major area for rice production in Portugal. Although this area is partially classified as a natural reserve, it is also threatened by many sources of anthropogenic pressure and runoff from agriculture grounds, originating a moderately contaminated estuary in some hot-spot areas. The present work aims at evaluating the level of inorganic contaminants present in different rice varieties including whole grain, white rice, husk and bran. A total of 33 samples were obtained from Sado region and from distribution stores. Contents in manganese, copper, zinc, vanadium, chromium, cobalt, nickel, arsenic, selenium, strontium, cadmium and lead, were evaluated using an ICP-MS. Samples with the highest content of arsenic, were analyzed for arsenic speciation by coupling an HPLC to the ICP-MS. Samples were analyzed in compliance with the internal quality criteria established by the laboratory. In most samples levels of lead, cadmium, cobalt, and vanadium were below or near to the LOQ. Arsenic content varies between 98 and 250 µg/kg. Speciation data, showed that the species present were mainly arsenite (AsIII), representing about 80% of total arsenic, and dimethylarsinic acid (DMA). After comparing this data with other analytical results used in risk assessment studies we can infer that inorganic contaminants in samples are not a matter of concern. This study also shows the need of powerful analytical techniques with very low detection limits to measure inorganic contaminants in foods. This work was completed on behalf of project “23290 – ValCAP” funded by the Portuguese Innovation Agency (ADI) and project “ORQUE SUDOE”, Ref. SOE3/P2/F591. Sandra Gueifão acknowledges the financial support from the project “ORQUE SUDOE” in the frame of students Exchange.

To assess the risks associated with the consumption of arsenic-containing foodstuffs, the determination of total arsenic is not sufficient since the toxicity of arsenic is highly dependent on its chemical form. Inorganic species, such as arsenite (AsIII) and arsenate (AsV), are more toxic than monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) and therefore represent a higher potential health risk. Organic arsenic compounds, such as arsenobetaine (AsB), which is the major species found in seafood, are non-toxic and can be consumed without health concerns [1]. The present work aimed at analysing the total arsenic content and its species in fish, rice and baby food samples. Rice is of paramount importance since it is a staple food for many populations and the main contributed for arsenic exposure. Also rice is the dominant carbohydrate source to babies up to one year. Since infants have low body weight they are more exposed to arsenic toxicity than adults. Therefore rice varieties intended to be consumed by infants must be carefully monitored for arsenic content. Fish samples from different species (gilthead sea bream, meagre, salmon and oyster), were subjected to different cooking methods: boiling, grilling and roasting. Arsenic content was determined on both raw and cooked fish samples, by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). For all three matrices speciation studies were carried out by coupling a High Performance Liquid Chromatographer (HPLC) to an ICP-MS. To guaranty the quality of results samples were analyzed in duplicate and a reference material was used for total concentration determination and for speciation studies complying with metrological requirements. The obtained results for total arsenic in fish were between 710 µg.kg-1 and 5978 µg.kg-1. The lowest value was observed in the samples from raw meagre and the highest in grilled gilthead sea bream. Speciation studies revealed that, even though fish samples presented a high content of arsenic, more than 90% of the arsenic present was in the form of AsB. Apparently, the culinary treatment does not enhance the inter-conversion of species. Total arsenic content in rice and baby foods, were between 29 µg.kg-1 and 1143 µg.kg-1. The higher value was referred to the bran of the rice and the lowest to the baby foods. Speciation results showed that 80% of arsenic was present as inorganic and 20% as DMA in rice and rice baby foods.

The Sado estuary, located in the West Coast of Portugal, is partially classified as a natural reserve, but is threatened by many sources of anthropogenic pressure and runoff from agriculture grounds, originating a moderately contaminated estuary in some hot-spot areas. The small fishermen community of the Carrasqueira Village is located on the south margin of the Sado Estuary where previous epidemiological studies confirmed several human exposure routes to Sado estuary contaminants namely trough occupation, water and food consumption. The aim of this work is to evaluate the contamination and mineral profile from local farming as an important food intake of the Carrasqueira community. Another population VNMF, established near a pristine estuary, (the Mira Estuary) was surveyed as reference. According to a food frequency questionnaire conducted in the exposure population, the most frequent vegetables are tomato, lettuce, cabbage and potatoes. Samples of these vegetables, as well as soil and water were collected from three backyards in each population and analysed by ICP-MS and ICP-OES . Contents in phosphorus, calcium, iron, magnesium, potassium, chromium, manganese, nickel, copper, zinc, arsenic, selenium, cadmium ,lead, were evaluated. The obtained results show that tomatoes and lettuces grown in Carrasqueira farms present the highest content of copper (676±6.45 µg.kg-1 and 255±3.62 µg.kg-1 respectively). Trace amounts of selenium were detected in vegetables from different farms (5-9 µg.kg-1). The highest amount of zinc was found in lettuce grown in Carrasqueira 2 (4604±30.74 µg.kg-1). The lowest content of strontium was found in lettuce grown in VNMF (559±21.38 µg.kg-1). In all analysed samples the observed values for cadmium and lead were below levels set by European legislation. The results show that nutritional quality of local farming vegetables near pollution sources should be accessed taking into account not only nutrients but also contaminants analysis for food safety. FCT PTDC/SAL-ESA/100107/2008

Chemical speciation in foodstuffs is of uttermost importance since it is nowadays recognized that both toxicity and bioavailability of an element depend on the chemical form in which the element is present. Regarding arsenic, inorganic species are classified as carcinogenic while organic arsenic, such as arsenobetaine (AsB) or arsenocholine (AsC), is considered less toxic or even non-toxic. Fish samples, from 3 different species (gilthead sea bream, meagre and salmon), were subjected to three different cooking methods: boiling, grilling and roasting. Arsenic content was determined on both raw and cooked samples by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Speciation studies were carried out by coupling a High Performance Liquid Chromatographer (HPLC) to an ICP-MS. To guaranty the quality of results samples were analyzed in duplicates and a reference material was used for total concentration determination and for speciation studies complying with metrological requirements. The obtained results for total arsenic were between 265 µg.kg-1 and 7585 µg.kg-1. The lowest value was observed in the samples from boiled meagre and the highest in grilled gilthead sea bream. The speciation studies revealed that, even though fish samples presented a high content of arsenic, more than 90% of the arsenic present was in the form of arsenobetaine. Apparently, the culinary treatment does not enhance the interconversion of species. FCT PTDC/SAU-ESA/103825/2008 e ORQUE SUDOE Ref. SOE3/P2/F591

nº 794, publicado no book of abstract editado por Hamit KOKSEL no EUROFOODCHEM XVII Purple corn (Zea mays L.), quinoa (Chenopodium Quinoa) and amaranth (Amaranthus caudatus) are a cereal and pseudocereals of Andean origin, largely consumed in North of Argentina. Buckwheat (Fagopyrum esculentum) is a pseudocereal with an important role in food diets around the world, especially in Asia and Eastern Europe. They gained increasing attention of scientific community, specially due to their high nutritional value and health benefits. Mineral concentrations in cereals and pseudocereals can differ with genotype, type of soil, fertilizer application, region’s mineral composition and treatments applied, that can even cause the loss of some minerals. Analytical values must be obtained by applying high quality criteria, such as criteria on sample handling, appropriate sample preparation and subsequent analytical method and, an effective internal and external quality control program. Inductively Couple Plasma Atomic Emission Spectrometry – ICP-OES is a high specific technique which allows a rapid and simultaneous multi-elemental analysis of several elements, in a numerous and wide scale of sample matrices, with good detection limits. A previous sample decomposition through its dissolution is required which can be undertaken by different methods, namely microwave digestion, dry-ashing, wet digestion. The destruction of organic matter is a slow step of overall analytical process largely dependent on the content of major components. The purpose of this work was to compare the performances of microwave and dry-ashing digestion procedures, including the optimization of microwave conditions to assist ICP-OES analysis. The optimized digestion method was applied on determination, of copper, manganese, iron, zinc, magnesium, calcium, phosphorus, sodium and potassium contents in purple corn, quinoa, amaranth, buckwheat and rice. Samples were dry ashed within platinum capsules in a furnace at 470 ºC during 40 h and microwave digested using a closed-vessel system digestion with a mixture of concentrated acid nitric, hydrogen peroxide and deionised water. The accuracy of analytical procedure was verified by analyzing a NIST 1548a reference material. Mineral profiles of purple corn, pseudocereals and rice were compared. Copper ranged from 0.07 mg/100g (rice) to 0.59 mg/100g (quinoa), manganese ranged from 0.64 mg/100g (purple corn) to 1.73 mg/100g (quinoa), iron ranged from 0.2 mg/100g (rice) to 8.8 mg/100g (amaranth), zinc ranged from 1 mg/100g (rice) to 5.1 mg/100g (amaranth), magnesium ranged from 27 mg/100g (rice) to 211 mg/100g (amaranth), calcium ranged from < 10 mg/100g (rice) to 154 mg/100g (amaranth), phosphorus ranged from 105 mg/100g (rice) to 480 mg/100g (amaranth), potassium ranged from 90 mg/100g (rice) to 587 mg/100g (quinoa). By comparing purple corn and pseudocereals with rice, pseudocereals presented the highest mineral content as expected. Also, for almost all minerals, purple corn showed higher mineral amounts than rice. These results showed that purple corn and pseudocereals understudy can be added to diets, with already known improved nutritional benefits. Statistically there was no evidence that the two different digestion methods applied have influenced final results, as P value was considered to be not significant (P > 0.05). However, microwave digestion enabled a more effective control of contamination or losses than dry-ashing, with less time consuming dispended.

Honey is natural product that gain popularity in food industry as no processed sweetener. Honey composition is highly influenced by the types of flowers used by the bees as well as regional and climatic conditions. Honey composition profile gained special attention by scientific community due to high nutritional value and health claims. In this work proximal and mineral profile of multi-floral honey from Argentina, Portugal and Mozambique were determined and reported for the first time. Therefore the nutrient analysis and chemical properties with the purpose to be included in national Food Composition Databank and disseminated through EuroFIR e-search platform was carried out. Ash, Moisture, and Protein content, °Brix sugar, pH and electrical conductivity were determined by AOAC methods and Calcium, Copper, Iron, Sodium, Potassium, Phosphorus, Magnesium, were analyzed by or ICP-OES and Selenium by ICP-MS. The values were obtained applying quality criteria as defined by EuroFIR guidelines for laboratory analysis. This required criteria on sample handling, an appropriate analytical method in terms of precision and accuracy, limit of quantification selectivity, and an effective internal and external quality control program including appropriate use of Certified Reference Materials and participation in adequate Proficiency Testing Schemes carried out by laboratories hold ISO/EN 17025. Guidelines for laboratory performance are paramount to guarantee the acceptability of values in EuroFIR and others Food Data Organizations. This provides the necessary information to the users of Food Composition Databanks who wish to have an overview of the parameters, which influence the estimation of nutrient intake, and may affect the diet-disease relationship.