Preocupações com o acúmulo de lixo plástico e seu consequente impacto ambiental levaram os cientistas e a indústria química, nas últimas décadas, a uma busca por plásticos biodegradáveis e plásticos produzidos com matérias-primas de fontes renováveis. Entre eles, encontram-se o poli(ácido lático), o poli(?-caprolactona), os poli(hidroxialcanoatos), os polímeros de amido e os polímeros sintéticos que recebem aditivos que facilitam a degradação, conhecidos como oxi-biodegradáveis. Em decorrência dos processos de produção e uso de aditivos e corantes, os plásticos podem conter constituintes que não fazem parte das moléculas do polímero. Por esta razão, o objetivo do trabalho foi determinar os elementos químicos presentes em amostras de polímeros biodegradáveis, sacolas oxi-biodegradáveis e sacolas de amido distribuídas em supermercados, empregando-se análise por ativação neutrônica instrumental (INAA) e espectroscopia de fluorescência de raios X (XRF). A identificação dos polímeros das sacolas de supermercado foi realizada por espectroscopia de absorção no infravermelho com transformada de Fourier (FTIR). Os resultados das análises químicas dos polímeros não processados evidenciaram baixas concentrações dos elementos químicos. Já os plásticos das sacolas apresentaram altas concentrações de cálcio, sódio, zinco e titânio, provenientes do uso de cargas minerais, corantes e outros aditivos. Em algumas amostras, as concentrações de zinco, cobalto, cromo, molibdênio e chumbo excederam os limites estabelecidos pela norma ABNT NBR 15448-2:2008 para polímeros biodegradáveis. As análises também indicaram que os aditivos pró-oxidantes utilizados nas sacolas oxi-biodegradáveis são baseados em compostos químicos que contêm ferro. Os resultados obtidos comprovam que os plásticos biodegradáveis podem ser utilizados de forma segura em embalagens e outras aplicações, desde que se evitem os aditivos contendo elementos químicos tóxicos e outras substâncias perigosas / Concerns about the accumulation of plastic waste and its consequent environmental impact have led scientists and chemical industry, in recent decades, to search for biodegradable plastics and plastics made with renewable raw materials. Among them are included poly (lactic acid), polycaprolactone, polyhydroxyalkanoates, starch polymers and synthetic polymers having additives which facilitate degradation, known as oxo-biodegradable. Due to production processes and use of additives and dyes, plastics may contain small amounts of chemical elements that are not part of the polymer molecules. For this reason, the objective of this study was to determine chemical elements in samples of biodegradable polymers, oxy-biodegradable and starch bags distributed in supermarkets by instrumental neutron activation analysis (INAA) and X-ray fluorescence spectroscopy (XRF). The polymers of plastic bags were identified by Fourier transform infrared spectroscopy (FTIR). Results of chemical analysis of unprocessed polymers have shown low concentrations of chemical elements. On the other hand, plastic bags have high concentrations of calcium, sodium, zinc and titanium, from the use of mineral fillers, dyes and other additives. In some bag samples, the concentration of zinc, cobalt, chromium, molybdenum and lead exceeded the limits established by the ABNT NBR 15448-2:2008 for biodegradable polymers. The analysis also indicated that the pro-oxidant additives used in the oxy-biodegradable bags are based on chemical compounds that contain iron. These results demonstrate that biodegradable plastics can be safely used in packaging and other applications, provided additives containing toxic chemical elements and other hazardous substances are avoided

O leite é classificado quimicamente como uma dispersão mista de aspecto branco com sabor levemente adocicado. Além da elevada concentração de cálcio, contém micronutrientes, aminoácidos e ácidos graxos em proporções adequadas à nutrição humana. Segundo a FAO, até o final de 2016, a produção mundial de leite bovino atingirá 817 milhões de toneladas. No Brasil, o setor lácteo apresenta-se como uma atividade de impacto socioeconômico significativo. Para atender o anseio de uma sociedade cada vez mais preocupada com a qualidade dos produtos que consome, assim como exigências internacionais, a Rede Brasileira de Laboratórios Centralizados da Qualidade de Leite (RBQL) através do Programa Nacional de Melhoria da Qualidade do Leite (PNMQL), criado pelo Ministério da Agricultura, Pecuária e Abastecimento, aprovou a Instrução Normativa nº 51 - IN51, contendo os regulamentos técnicos de produção, identidade e qualidade do leite. Milhares de medições químicas são realizadas com o propósito de tomada de decisões e regulamentações da qualidade dos alimentos oferecidos à população mundial, sendo essencial existir confiabilidade nos resultados das análises químicas. Recomenda-se que os laboratórios analíticos utilizem materiais de referência certificados (MRC), provenientes de um fornecedor reconhecido e competente, que propiciem caracterização química inequívoca do material. Neste contexto, este trabalho objetivou a caracterização química de leite em pó bovino de diferentes tipos comercialmente disponíveis, com o propósito de fornecer subsídios para a produção de MRC dessa matriz alimentar. Foram adquiridas 72 amostras de leite em pó no comércio varejista, englobando os tipos integral, semidesnatado, desnatado, instantâneo e enriquecido. O método de análise por ativação neutrônica instrumental empregado permitiu a determinação dos elementos químicos essenciais Ca, Fe, K, Na e Zn, além de Br, Co, Cs e Rb. O emprego de materiais de referência certificados como controle da qualidade analítica corroborou a exatidão e a precisão dos resultados. Dentre as amostras estudadas, algumas são enriquecidas com os elementos químicos Ca e Fe. A hipótese de igualdade dos leites enriquecidos com Ca e Fe foi rejeitada para ambos, visto que observou-se a existência de diferenças estatísticas (p < 0,001) para esses elementos. A média aritmética dos leites enriquecidos com Fe foi de 167,7 mg/kg (n = 15), enquanto a média aritmética dos leites não-enriquecidos foi de 13,6 mg/kg (n = 57). A média aritmética dos leites enriquecidos com Ca foi de 22.822 mg/kg (n = 3), enquanto a média aritmética dos leites não-enriquecidos foi de 10.049 mg/kg (n = 69). De maneira geral, os leites em pó com menores quantidades de gordura (desnatado e semidesnatado) apresentaram maiores quantidades dos elementos químicos. Pela análise de agrupamento, verificou-se que a distância multivariada entre os leites em pó integrais foi menor, o que indica similaridade. Assim, entende-se como estratégica e viável a seleção deste tipo de leite em pó como candidato para a produção de material de referência certificado / Milk is chemically classified as a mixed white appearance dispersion with a slightly sweet taste. Besides the high calcium concentration, the milk contains micronutrients, amino acids and fatty acids in proportions suitable for human nutrition. According to FAO, by the end of 2016, the world production of bovine milk will reach 817 million tons. In Brazil, the dairy sector is an activity with a significant socioeconomic impact. To meet the longing of a society increasingly concerned with the quality of the products it consumes, as well as the international requirements, the Brazilian Network of Centralized Milk Quality Laboratories (RBQL) through the National Program for the Improvement of Milk Quality (PNMQL), created by the Ministry of Agriculture, Livestock and Supply, approved the Normative Instruction No. 51 - IN51, containing the technical regulations for milk production, identity and quality. Thousands of chemical measurements are performed for the purpose of making decisions and regulations of the quality of food offered to the world population, and it is essential to have reliability in the results of chemical analyses. It is recommended that analytical laboratories use certified reference materials (CRM) from a recognized and competent supplier that provides unequivocal chemical characterization of the material. In this context, this work aimed at the chemical characterization of bovine milk powder of different types commercially available, with the purpose of providing subsidies for the production of CRM of this food matrix. Seventy-two samples of milk powder were purchased in the retail market, including the integral, semi-skimmed, skimmed, instant and enriched types. Instrumental neutron activation allowed the determination of the essential chemical elements Ca, Fe, K, Na and Zn, as well Br, Co, Cs and Rb. The analytical quality control with certified reference materials corroborated the accuracy and precision of the results. Among the samples studied, some are enriched with the chemical elements Ca and Fe. The hypothesis of equality of Ca- and Fe-enriched milks was rejected for both, since there were statistical differences (p < 0.001) for these elements. The arithmetic mean of Fe-enriched milks was 167.7 mg/kg (n = 15), while the arithmetic mean of non-enriched milks was 13.6 mg/kg (n = 57). The arithmetic mean of Ca-enriched milks was 22,822 mg/kg (n = 3), while the arithmetic mean of non-enriched milks was 10,049 mg/kg (n = 69). In general, milk powder with lower amounts of fat (skimmed and semi-skimmed) had higher amounts of the chemical elements. The cluster analysis evidenced that the multivariate distance for the whole milk powder was smaller, which indicates the similarity. Thus, it is understood as strategic and viable the selection of this type of milk powder as candidate for production of certified reference material

O tomate é a segunda hortaliça mais produzida no mundo, superada apenas pela batata, com participação efetiva na dieta humana. O seu valor como alimento traz um paradoxo. Ao mesmo tempo em que é elogiado por ser considerado um alimento funcional, com propriedades nutracêuticas, sofre críticas pela forma como é normalmente produzido, sob pesadas quantidades de fertilizantes sintéticos e pesticidas. Há muitas causas de variação que podem alterar a composição dos frutos. Neste sentido, o presente trabalho procurou coletar amostras em um universo que engloba diferentes fatores, incluindo cultivares para o consumo in natura e para o processamento industrial, sistemas de cultivo convencional e orgânico, regiões geográficas e tipos de solo. O objetivo geral foi caracterizar o tomate quanto aos elementos químicos visando a identificação daqueles de interesse agronômico ou nutricional e o estabelecimento das faixas de concentrações para frutos produzidos sob as fontes diversas de variação. Objetivos específicos envolveram estudos de representatividade amostral e de influência dos estádios de maturação e do solo na composição química dos frutos. Os tomates das cultivares AP 533, Colibri e T-92 foram coletados em propriedades localizadas em municípios do estado de São Paulo. A determinação dos elementos químicos foi feita pelo método primário de análise por ativação neutrônica instrumental (INAA). A qualidade do procedimento analítico foi verificada por meio da exatidão e da reprodutibilidade dos resultados com o emprego de materiais de referência. O estudo de representatividade amostral revelou que o número necessário de amostras para representar o tomate no campo foi inferior a 12, considerando um erro máximo admitido pelo analista de 15%. A variabilidade intra-amostral foi avaliada por meio de 12 repetições analíticas de uma mesma amostra e os resultados indicaram a homogeneidade do material. Os elementos químicos Br, Ca, Co, Cs, Fe, K, La, Na, Rb, Sr e Zn foram determinados nas amostras de polpas, sementes e solos. A análise de frutos nos estádios de maturação verde maduro e rosado indicou maiores concentrações de Ca, Fe, K, Na, Rb e Sr nos tomates rosados, enquanto Br, Co, Cs e Zn não apresentaram diferenças significativas (p < 0,05). Os solos das seis propriedades estudadas apresentaram composição química bastante diferenciada. Contudo, não foram observadas correlações das concentrações de elementos químicos encontradas nas amostras de polpa e de solo. Os resultados da caracterização química dos tomates permitiram realizar importantes inferências com relação ao comportamento dos elementos químicos. K e Ca foram os nutrientes mais abundantes na polpa e na semente. As concentrações de Br, Co, Cs, Rb e Sr na polpa diferiram significativamente (p < 0,05) tanto entre sistemas de cultivo como entre cultivares. Fe, K, Na e Zn na polpa não foram afetados pelos sistemas de cultivo, sendo as diferenças encontradas intrínsecas para cada cultivar. As polpas e as sementes dos tomates das três cultivares não apresentaram diferenças para Ca. Br permitiu a separação entre tomates orgânicos e convencionais, com concentrações maiores em tomates convencionais. Análises multivariadas revelaram que as amostras de polpa possuem uma tendência de agrupamento por categorias, tanto em termos de cultivar como de sistema de cultivo, embora esse último fator tenha apresentado resultados menos evidentes. Por outro lado, as sementes apresentaram maior tendência de agrupamento pelo fator cultivar / The tomato is the second most cultivated vegetable after the potato, having an effective participation in the human diet. Its food value remains paradoxical. At same time it is recognized as a functional food with nutraceutical properties, the tomato receives criticism due to the way it is usually cultivated, i.e. under heavy amounts of synthetic fertilizers and pesticides. There are many causes of variation that may change the fruit composition. In this aspect, the current work aimed at collecting samples in a universe that comprises different factors, including cultivars for fresh market and for processing, conventional and organic cultivation systems, geographical regions and soil types. The main objective of this work was the chemical element characterization of tomato in view of the identification of elements of agronomical and nutritional interest and establishing concentration ranges for the fruits produced under different sources of variation. The specific objectives comprehended studies of sample representativeness and studies of the influence of ripening stages and soil on the chemical composition of tomato fruits. Tomatoes from the cultivars AP 533, Colibri and T-92 were sampled in farms located in cities of São Paulo State. The determination of the chemical elements was carried out by using the primary method of measurement instrumental neutron activation analysis (INAA). The quality of the analytical procedure was evaluated by means of accuracy and reproducibility of reference materials results. The study of sample representativeness showed that the required number of 12 samples to represent the tomato in the field, considering 15% as the maximum deviation allowed by the analyst. The within-sample variability was evaluated by means of 12 analytical portions taken from one sample. The results demonstrated the homogeneity of the material. The chemical elements Br, Ca, Co, Cs, Fe, K, La, Na, Rb, Sr and Zn were determined in the samples of pulp, seeds and soils. The analysis of fruits at mature green and pink stage indicated higher concentrations of Ca, Fe, K, Na, Rb and Sr in the tomatoes at pink stage, while Br, Co, Cs and Zn did not show any significant difference (p < 0.05). The soils from the six studied farms presented different chemical compositions. However, no correlations were observed between the chemical element concentrations found in the samples of pulp and soil. The results of chemical characterization of tomatoes allowed making important inferences with relation to the chemical elements behavior. K and Ca were the most abundant nutrients in the pulp and seeds. Br, Co, Cs, Rb and Sr concentrations in the pulp showed significant differences (p < 0.05) for both cultivation systems and cultivars. Fe, K, Na and Zn concentrations in the pulp were not affected by the cultivation systems, being the differences found intrinsic to each cultivar. The pulp and seeds from the tomatoes of the three cultivars did not present any significant difference for Ca. Br allowed the discrimination of organic and conventional tomatoes, the later showing the higher concentrations. Multivariate analysis of the pulp results revealed a trend in clustering by categories, both in terms of cultivars and cultivation system, although the later showed less clear results. On the other hand, the seeds presented higher trend in clustering by the cultivar factor

abstract: There has been debate and uncertainty on two important issues in the Basin of Mexico: the formation of Epiclassic city-states following Teotihuacan state collapse (ca. A.D. 650), and the nature of the subsequent Early Postclassic Tula state expansion. I evaluate the Basin as a case of regeneration of socio-political complexity using stylistic and compositional pottery analysis to examine patterns of interaction from the Epiclassic (ca. A.D. 600/650-850) through the Early Postclassic (ca. A.D. 850-1150). I selected representative specimens of temporally diagnostic pottery from the three large settlement clusters in the northwestern Basin (Tula and the Zumpango region), the northeastern Basin (Teotihuacan Valley), and the southeastern Basin (Cerro Portezuelo, the Ixtapalapa and Chalco regions) to assess: 1) participation in regional cultural complexes, 2) direct exchange or local production of particular pottery types, 3) regional variation in the production of pottery. For certain time periods, ceramic patterns among smaller settlements clusters were distinguished. The combination of chemical and attribute analysis provided a robust method for identifying regional variation in pottery. Chemical characterization using Instrumental Neutron Activation Analysis (INAA) was used to provide fine-scaled compositional reference groups to assess regional production and exchange. Stylistic and technological attributes were used to define highly visible decorative traditions that were easily copied and low visibility production steps that were learned. Teotihuacan withdrawal from the southeastern Basin prompted reorganization and adoption of a distinctive pottery complex. Epiclassic settlement patterns throughout the Basin were reorganized into nucleated settlement clusters with unoccupied areas between them. Results indicate regional participation in the Coyotlatelco pottery tradition and a strong pattern of consumption of locally produced pottery by settlement cluster. Tula underwent significant urban growth in the Early Postclassic, while the Basin was marked by a process of "ruralization" as the Epiclassic centers dispersed and settlements filled the previously unoccupied landscape. Tula expanded its influence into the Basin with varying degrees of integration. The closest settlements in the northwestern Basin acquired the most Tula-produced pottery. The Teotihuacan Valley and Cerro Portezuelo settlements consumed mostly locally produced Tula style pottery. The southeastern settlements were least connected to Tula and initiated interactions towards Puebla-Tlaxcala. / Dissertation/Thesis / Notes authorizing use of figures. Not to be posted to public or part of publication / Ph.D. Anthropology 2011

The major focus of this dissertation is the ancestor worship that is inferred to have been practiced in the multiethnic Middle Sicán theocratic state (AD 950-1100) that prospered on the northern North Coast of Peru. The major objective is twofold: (1) demonstrating by archaeological means that ancestors were indeed worshipped in the Middle Sicán society and (2) elucidating the nature and role of the inferred ancestor cult and associated rituals and ceremonies. Ancestor (and the veneration of it) is one of the themes that have the deepest roots in the anthropological thoughts; nevertheless, many archaeologists have uncritically invoked ancestor veneration without sufficient theoretical underpinning and empirical support, to the point that James Whitley (2002) decried "too many ancestors." This dissertation thus begins with a review of the earlier anthropological discoveries and theoretical debates on what ancestor is and who becomes an ancestor, including the cases in the Andes. Based on this review of previous studies, it is hypothesized that the select members of deceased Middle Sicán elites were transformed into an ancestor through a series of prescribed processes. This hypothesis is examined in terms of the five possible material correlates of the inferred Sicán ancestors extracted from the regional archaeological database of the study area accumulated by the Sicán Archaeological Project (SAP) for the last three decades. The role of the inferred Middle Sicán ancestor cult is approached from the ideological perspective. It is inferred that the ancestor cult was employed by the ruling group as an ideological and political means to justify the existence and extension of social hierarchies and inequalities and thus targeted at wider populations different in genealogical origins as opposed to family or lineage members. This study focuses attention on the food preparations and consumptions documented by a test excavation at the principle plaza of the Sicán capital, "Great Plaza," adjacent to the inferred ancestral tombs and hypothesizes that the commensality among the living and the dead during feasts there served not only to commemorate the inferred ancestors, but also to bring together people in different social tiers and to consolidate the highly stratified, multiethnic Middle Sicán society. Two excavations at the ceremonial core of the Middle Sicán state capital, one at the Huaca Loro West Cemetery in 2006 and the other at the Great Plaza in 2008, provide varied lines of evidence that support the above two hypotheses. The results suggest that ancestor worship was indeed practiced during the Middle Sicán Period. By maintaining and monopolizing the ritual access to the Sicán Deity through their ancestors, the Sicán elites reproduced their religious and political power and retained the legitimacy of their social status. Concurrently, the Sicán elites consciously employed their ancestor cult for social integration. After the Middle Sicán Period, these ancestors seem to have retained their spiritual viability even after the later Chimú Empire took the control of this region. If not recognized as the Sicán anymore, they were remembered and honored by the living for over four centuries. On the basis of the merits of traditional approach (e.g., the study of architecture, iconography, bioarchaeology, and ethnohistory and ethnography in the Andes), this study gives primacy to the direct focus on the material residues and relational contexts and patterns of ritual activities and studies their change and stability through time in relation to other historical contingencies. The merit of focusing on the trajectories of ritual activities themselves in a long and wide perspective is that it sheds light on the regional peculiarities and contingent nature of the inferred ancestor veneration, which may be overlooked in cross-cultural, ethnological arguments about the nature, role, and capacity of ancestors. It also provides a wealth of information not only to determine what types of activities took place, but also to explore the intangible symbolic significance behind those activities. As a result, this approach provides a practical solution to the justified criticism by Whitley (2002) and demonstrates how we should approach ancestor veneration and what evidence we would need in order to appropriately define it in archaeological record.

This research addresses group interaction and site use of the Burns Site (8BR85). Burns is a Malabar II (900-1565 AD) period site located within the Indian River Lagoon (IRL) region. The site includes a mound with spoke-like burial patterns, midden deposits, and hearth features. Through ceramic analysis, hierarchical clustering, and Instrumental Neutron Activation Analysis (INAA), this thesis explores what activities and social relationships are evident in the ceramic assemblage of the Burns Site. Formal and compositional characteristics of pottery sherds may be indicative of pottery use and movement. Descriptive statistics and correlation found no evidence of standardized local pottery production. Furthermore, the overall form and size of vessels, along with hearth features, suggests that there were no large feasting events. Instead, small meals were prepared and served at the site. To determine chemical composition and provenance, 35 sherds were subjected to INAA. These sherds were clustered into 5 chemical groups, 2 of which were nonlocal to the Indian River Lagoon Region. Nonlocal formal clusters of sherds were estimated, which provide evidence for movement of specific ceramic forms along the Atlantic coast. While there was no evidence of standardized local pottery production, certain vessel forms were being moved to the Burns Site from other regions.

Objetivou-se, com este trabalho, estudar os métodos hierárquicos de análise de agrupamentos (ligação simples, ligação completa, ligação média, centróide e de Ward com base nas distâncias Euclidiana, Euclidiana ao quadrado, Manhattan e Mahalanobis), de modo a identificar qual é o mais adequado para uma base de dados arqueológicos. Utilizou-se uma base de dados fornecida pelo Grupo de Estudos Arqueométricos do IPEN CNEN/SP, na qual foram analisadas 146 amostras de fragmentos cerâmicos de três sítios arqueológicos por análise por ativação com nêutrons instrumental, sendo determinadas as frações de massa de 24 elementos químicos: As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, U, Yb e Zn. Para a determinação do melhor método, foram avaliados os dendrogramas conjuntamente com o valor dos coeficientes de correlação cofenética (CCC), obtidos para cada método. O método da ligação média mostrou-se mais coerente na formação dos agrupamentos, apresentando também os maiores valores do CCC. Por último, um script com funções do programa estatístico R foi desenvolvido para calcular o CCC, com o intuito de auxiliar os pesquisadores a encontrar o método de agrupamento mais apropriado para sua base de dados. / The objective of this work was to study the hierarchical methods of cluster analysis (single linkage, complete linkage, average linkage, centroid and Ward with base in the Euclidean distance, Squared Euclidean distance, Manhattan and Mahalanobis) to identify which is the most appropriate in archaeological data set. It was used a data set provided by the Archaeometry Studies Group from IPEN CNEN/SP in which 146 samples of ceramic fragments from three archaeological sites analyzed by instrumental neutron activation analysis, being determined the mass fractions of 24 chemical elements: As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, U, Yb and Zn. For the determination of the best method, it was evaluated the dendrograms together with value of the cophenetic correlation coefficient (CCC) obtained for each method. The average linkage method was more coherent in formation of the clusters, and with higher CCC values. Finally, a script with functions of the R statistical software was developed to calculate the CCC with aim to be a tool for researchers find the most appropriate method of cluster analysis for their data set.

Este trabalho de mestrado teve como objetivo realizar a validação formal para quatro métodos de medição do Laboratório de Ativação Neutrônica (LAN) do IPEN - CNEN/SP por Análise por Ativação com Nêutrons Instrumental (INAA). Os mensurandos foram a concentração total de As em tecido de mexilhão (método-BIO-1), a concentração total de Co, Cr, Fe, Rb, Sc, Se e Zn em tecido de mexilhão (método-BIO-2), a concentração total de As e Sb em sedimento marinho (método-GEO-1) e a concentração total Co, Cr, Fe, Sc e Zn em sedimento marinho (método-GEO-2). Em um primeiro momento, foi realizado um estudo univariado para investigar a influência causada ao resultado final em diferentes configurações no preparo dos padrões sintéticos e no tempo de medição da atividade do mensurando no padrão sintético. Outras variáveis, como o tempo de medição da atividade do mensurando na amostra, distância entre amostra e detector e tempo de decaimento para medição da amostra foram estudadas em um processo multivariado, por meio da realização de um Planejamento Fatorial 23 completo (DOE). Os parâmetros de desempenho estudados para a validação dos métodos de medição em INAA foram: seletividade, exatidão (precisão e veracidade), linearidade, faixa de trabalho, seletividade, limite de detecção, limite de quantificação, robustez e incerteza de medição. Os métodos foram validados de acordo com as recomendações do Guia de validação do INMETRO DOQ-CGCRE-008. A estimativa das fontes de incertezas foi realizada de acordo com as recomendações do Guia para a expressão da incerteza de medição (ISO GUM) com o uso do método simulado. / The objective of this study was the validation of four measurement methods by Instrumental Neutron Activation Analysis (INAA) at the Neutron Activation Laboratory (LAN) of IPEN - CNEN/SP. The measurands were: mass fraction of As in biological matrix sample (método-BIO-1), mass fraction of Co, Cr, Fe, Rb, Sc, Se and Zn in biological matrix sample (método-BIO-2), mass fraction of As and Sb in geological matrix sample (método-GEO-1) and mass fraction of Co, Cr, Fe, Sc and Zn in geological matrix sample (método-GEO-2). First, a univariate method optimization was performed to investigate the influence of the the preparation of synthetic standard (monoelemental standard and/or multielemental standard) and standard measurement times. In a second step, a multivariate method optimization was carried to verify the influence of sample measurement time, sample decay time and sample distance to detector by means of a 23 full factorial design (DOE). Investigated method performance characteristics were: selectivity, accuracy (trueness and precision), linearity, work range, selectivity, limit of detection, limit of quantification, robustness and measurement uncertainty. The methods were validated according to recommendations of INMETRO DOQ-CGCRE-008 Validation Guide. The estimate of uncertainty sources was carried out according to recommendations of Guide to the expression of uncertainty in measurement (ISO GUM) using the simulated method.

Neste trabalho foram determinadas as concentrações elementares de Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sc, Sm, Ta, Tb, Th, U, Yb e Zn por meio da análise por ativação com nêutrons instrumental (INAA) em 204 fragmentos cerâmicos arqueológicos Marajoara, dos quais, 156 foram cedidos pelo Museu de Arqueologia e Etnologia da USP (MAE) e 48 cedidos pela Profª Denise Pahl Schaan, curadora do Museu do Marajó, além de 9 cerâmicas contemporâneas produzidas e comercializadas na Ilha do Marajó. Realizaram-se análises por espectroscopia de ressonância paramagnétca eletrônica (EPR) em 8 amostras arqueológicas e 1 amostra contemporânea para identificar a temperatura de queima e análises de difratometria de raio-X (XRD) em 13 amostras arqueológicas e 2 amostras contemporâneas para o estudo da composição mineralógica. O estudo das amostras discrepantes foi realizado por meio da distância Mahalanobis e o efeito do tempero adicionado à pasta cerâmica por meio do filtro modificado Mahalanobis. Os resultados foram interpretados utilizando-se a análise de conglomerados, análise de componentes principais e análise discriminante. A análise Procrustes, utilizada para o estudo de seleção de variáveis, mostrou que as variáveis Ce, Fe, Eu, Hf, K e Th são suficientes para caracterizar as amostras analisadas. O estudo comparativo entre as amostras arqueológicas e contemporâneas apresentou a formação de dois grupos bem definidos e próximos para as cerâmicas arqueológicas, e a formação de um terceiro grupo distante para as amostras contemporâneas, indicando que as amostras arqueológicas são bem diferentes das amostras contemporâneas. Tanto as análises de EPR, quanto de XRD, não apresentaram fatores relevantes para a diferenciação entre as amostras arqueológicas e contemporâneas. / In this study the elemental concentration of Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sc, Sm, Ta, Tb, Th, U, Yb and Zn were determined by instrumental neutron activation analysis (INAA) in 204 fragments of Marajoara archeological ceramics, of which 156 were provided by the Archeology and Etnology Museum of São Paulo University (MAE) and 48 were provided by Dr. Denise Pahl Schaan, Marajó Museum curator. Also, 9 contemporary ceramics produced and marketed at Marajó Island were analyzed. Electron paramagnetic resonance (EPR) analyses were performed in 8 archeological samples and 1 contemporary sample in order to identify the burning temperature of the samples. X-ray diffraction (XRD) analyses were performed in 13 archeological samples and 2 contemporary samples for the investigation of their mineralogical composition. Mahalanobis distance was used for the study of outlier while modified filter was used for the study of the temper added to the ceramic paste. Result interpretation was performed using cluster analysis, principal components analysis and discriminant analysis. Procrustes analysis was used for variable selection and it showed that the Ce, Fe, Eu, Hf, K and Th variables are adequate for the characterization of the analyzed samples. The comparative study among the archeological and contemporary ceramics showed the arrangement of two well-defined and close groups for the archeological samples and a third, distant group for the contemporary ones. This result indicates that the archeological and contemporary ceramics differ in their composition. EPR and XRD analysis were inconclusive for the differentiation of archeological and contemporaty ceramics.

Muitos estudos têm sido realizados para determinar elementos essenciais nos alimentos, dentre eles o vinho, devido aos seus importantes papéis nutricionais em funções do corpo humano. Estudos apontam que o consumo diário e moderado de vinho contribui de forma significativa para as necessidades dos elementos essenciais para o corpo humano, tais como Ca, Co, Cr, Fe, K, Mg, Mn, Zn, V, entre outros, bem como traz benefícios para a saúde como a prevenção de inúmeras doenças e maior expectativa de vida, relacionados em particular com a ingestão de antioxidantes como os compostos polifenólicos. Por outro lado, outros elementos são bons indicadores da origem do vinho e as suas concentrações podem ser utilizadas como critério para garantir a autenticidade e a qualidade do vinho, bem como avaliar se os limites de tolerância estabelecidos pela lei foram respeitados durante todo o processo de produção. Todavia, embora a indústria do vinho no Brasil esteja entre as 15 maiores do mundo, ainda são poucos os estudos analíticos dos elementos no vinho se comparado a outros grandes produtores. Neste sentido este estudo teve como objetivo avaliar alguns procedimentos para preparação de amostras de vinho para determinar elementos essenciais por Análise por Ativação Neutrônica Instrumental (INAA) e comparar os resultados com a técnica de Espectrometria de Emissão Atômica por Plasma de Argônio Acoplado Indutivamente (ICP OES). Três procedimentos de preparação da amostra foram estudados: liofilização, evaporação e calcinação. Os parâmetros estudados foram precisão, exatidão e limite de detecção. Foram aplicados testes estatísticos de ANOVA e Tukey Kramer para verificar as diferenças estatísticas entre as médias obtidas pelos três procedimentos de preparação do vinho para INAA com as médias obtidas por ICP OES. Foi observado que cerca de 60% dos resultados obtidos por liofilização foram concordantes com aqueles obtidos por ICP OES. / Several studies have been carried out for determining essential elements in foodstuffs, including wine, due to its important nutritional role in human body functions. It was shown that daily consumption of wine in moderation contributes significantly to the needs of essential elements in human body such as Ca, Co, Cr, Fe, K, Mg, Mn, Zn, V, among others, and has health benefits in the prevention of numerous diseases and longer life expectancy, related in particular to the intake of antioxidants such as polyphenolic compounds. Trace elements are good indicators of origin of wines and their concentrations can be used as criteria to ensure authenticity, quality and show that the tolerance limits established by law were respected throughout the production process. However, although Brazilian wine industry is among the 15 largest in the world, analytical studies for organic and inorganic compounds of wine content are still small when compared to other major producers. In this sense, this study aimed to evaluate some procedures of wine sample preparation to determine essential elements by Instrumental Neutron Activation Analysis (INAA) and compare the results with those determined by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP OES). Three sample preparation procedures were studied: freeze-drying, evaporation and dry ashing. The parameters studied were precision, accuracy and detection limit. ANOVA and Tukey-Kramer tests were applied to verify the statistical differences between the mean values obtained by the three wine preparation procedures for INAA with those means obtained by ICP OES. It was noticed that about 60% of results obtained by freeze-drying agreed with those obtained by ICP OES.