Neste estudo foi determinado o conteúdo de metais em adoçantes dietéticos de mesa, consumidos por um número crescente de pessoas preocupadas em manter a forma física e restringir o nível calórico da dieta havendo ou não recomendação médica. Foram coletadas 26 amostras de adoçantes dietéticos distribuídos no mercado de São Paulo, em uma grande variedade de apresentações, produtos, composições e marcas. Como a composição é dependente da produção, esta análise é indispensável ao controle da qualidade e relevante à saúde do consumidor. A Espectrometria de Emissão Óptica com Fonte de Plasma Indutivamente Acoplado (ICP OES) com vista axial, mostrou-se adequada determinação dos macronutrientes Na, K, Ca, Mg e dos microelementos essenciais Fe, Cu, Zn, Cr, Mn e Se, dos potencialmente tóxicos AI, Ni, As, Cd e Pb em adoçantes sólidos e líquidos, atendendo as exigências da legislação brasileira. Assim, foi realizado um estudo comparativo entre as determinações utilizando as metodologias clássicas de pré-tratamento da amostra, como o resíduo de cinzas, a dissolução ácida com aquecimento por microondas com o procedimento sem tratamento prévio das amostras, visando facilitar a análise, uma vez que esta é a etapa que mais consome tempo e esforços. A determinação simultânea do espectro favoreceu a análise, uma vez que 74 comprimentos de onda puderam ser selecionados sem aumento no tempo ou no custo de análise, auxiliando na seleção de 36 linhas analíticas mais adequadas (livre de interferências) à determinação sem tratamento prévio da amostra. Nenhuma amostra de adoçante excedeu o valor recomendado para o somatório dos contaminantes inorgânicos (Aspartame < 10 &#181;g g-1 e Sacarina < 20 &#181;g g-1). No entanto, 6 marcas de adoçantes em pó excederam o valor limite da legislação para As (1,0 &#181;g g-1), excederam o valor para Cr total (0,1 &#181;g g-1) e 2 marcas de adoçante líquido excederam o valor para Ni (0,1 &#181;g g-1). Mostrando que os adoçantes em pó apresentam (&#8776;5 &#181;g g-1) níveis maiores de metais potencialmente tóxicos que os adoçantes líquidos (&#8776;2,O &#181;g mL-1). / The metal content in artificial sweetener usually consumed by a growing population concerned to keep body shape and to restrict the diet caloric content, by medical recommendation or not, was measured. The samples were 26 artificial sweeteners available at São Paulo\'s market, under different forms, and several suppliers, with various sweetener composition, and brands. Because the composition depends on manufacture factors, this analysis is mandatory for quality control and relevant for the user health. Inductively coupled plasma atomic emission with axial view has demonstrated to be an appropriated technique to determine the macronutrient content, such as Na, K, Ca, Mg and essential microelements such as Fe, Cu, Zn, Cr, Mn and Se, besides the potentially toxic elements such as AI, Ni, As, Cd and Pb in solid and liquid sweeteners in accordance with to the Brazilian regulation. It was also performed a comparative study of the sample preparation methodology, using classical sample pretreatment, such as burning to ashes, and acid dissolution with microwave heating and a procedure without prior sample treatment (dissolution and/or convenient dilution), aiming at facilitating the analysis of dietetic sweetener because this step is the most time and labor consuming. The analysis was simplified using the simultaneous spectra acquisition, once 74 wavelengths were selected without time or cost increase, and helping the identification of 36 appropriate analytical lines (free from interferences) to apply to the samples determination without prior treatment. None sweetener exceeded the recommended value of inorganic contaminant (for aspartame samples the value was below 10 &#181;g g-1 and for saccharine samples that was below 20 &#181;g g-1). However, 6 brands of artificial sweetener in powder exceeded the legislation limit value for As (1.0 &#181;g g-1), and other 7 brands exceeded the Cr recommended maximum value (0.1 &#181;g g-1). Other 2 brands of Iiquid sweetener exceeded the Ni recommended maximum value. Therefore, for ali samples, the artificial sweetener in powder presented higher levels of potentially toxic metais (&#8776;5&#181;g g-1) than those in a Iiquid presentation (&#8776;2.0 &#181;g mL-1).

A baía de Sepetiba, localizada a 60 km na direção Oeste da região metropolitana do Rio de Janeiro, vem sendo submetida, nas últimas décadas, a um considerável desenvolvimento populacional e industrial, contando hoje com aproximadamente 400 indústrias (em sua maioria metalúrgicas) instaladas nas bacias de drenagem da baía, as quais lançam seus resíduos diretamente na baía ou nos corpos d'água da região. Além disso, o Porto de Sepetiba trouxe muitos investimentos industriais para a área. Toda esta expansão industrial e urbana resultou em uma série de impactos ambientais, devido ao lançamento de efluentes domésticos e industriais, os quais são ricos em metais pesados e outras substâncias potencialmente tóxicas. O objetivo deste trabalho foi avaliar a contaminação e mobilidade dos metais Cd, Cu, Ni, Pb e Zn, em sedimentos da baía de Sepetiba. Foram determinados os Sulfetos Voláteis em Ácido (AVS) e os Metais Extraídos Simultaneamente (SEM) em 65 amostras de sedimentos, coletadas de modo a cobrir toda a área da baía. Os resultados obtidos na extração ácida mostraram que os metais Cd, Cu, Pb e Zn apresentaram as mais altas concentrações extraíveis na região NE (principalmente na saídas dos rios Guandu e Canal de São Francisco), enquanto que as mais altas concentrações de Ni foram observadas na porção Oeste da baía. A comparação dos valores dos SEM com os valores guias de qualidade de sedimento (VGQS) canadenses (TEL e PEL) indicou que os metais Cd e Zn apresentaram teores nos quais é freqüente a ocorrência de efeitos negativos à biota (valores acima do PEL); já os metais Cu e Pb e Ni apresentaram concentrações que indicam uma baixa probabilidade de ocorrência de efeitos adversos aos organismos aquáticos de Sepetiba. Por outro lado, a razão S[SEM]/[AVS], ficou abaixo de 1 na porção NE, sugerindo que, apesar das altas concentrações dos metais na região, estes estão retidos no sedimento, na forma de sulfetos. Foram também determinadas as concentrações totais dos metais nos sedimentos, e observou-se que o padrão de distribuição das concentrações totais seguiu o mesmo padrão observado para os SEM, com as mais altas concentrações na porção NE da baía, classificando a área como nivel 2, com relação ao Zn, e como nível 1, com relação aos metais Cd, Cu, Pb e Ni, de acordo com a Resolução CONAMA 344/04. Apresenta-se um modelo geoestatístico, o modelo de atenuação das concentrações, que tem como proposta estimar a mobilidade de um elemento nos sedimentos. O modelo proposto mostrou os mais altos valores de atenuação para Zn, Cd, Cu e Pb na região NE, indicando que a mobilidade destes metais na região é baixa, o que está de acordo com as conclusões obtidas com o modelo S[SEM]/[AVS], indicando boas possibilidades de aplicação do modelo em estudos de contaminação de sistemas estuarinos por metais. / Sepetiba bay, located about 60 km west of the metropolitan region of Rio de Janeiro city, has undergone notable development in the last decades, with the establishment of about 400 industrial plants in its basin, basically metallurgical, which release its industrial waste either straight into the bay or through local rivers. The Sepetiba harbor also brought up a lot of industrial investment in that area. This urban and industrial expansion caused several environmental impacts, mainly due to the presence of heavy metals and other potentially toxic substances present in the effluents discharged into the bay. This work aimed to assess heavy metal (Cd, Cu, Ni, Pb e Zn) contamination and mobility in sediments from Sepetiba bay. The acid-volatile sulfides (AVS) and the concentration of simultaneously extracted metals (S[SEM) were determined in 65 sediment samples from Sepetiba bay, representing the whole area. The results obtained showed that Cd, Cu, Pb and Zn presented higher concentrations in the northeastern area (mainly in the mouth of Guandu and Canal de São Francisco rivers), while the highest concentration of Ni were observed in the western region of the bay. The comparison between SEM concentrations with the Canadian Sediment Quality Guidelines (TEL and PEL) indicated that Cd and Zn presented values which may hazard to aquatic organisms (concentration levels above PEL); the elements Cu, Pb and Ni presented concentration levels below PEL, suggesting low probability of toxicological effects to the aquatic organisms. On the other hand, the ratio S[SEM]/[AVS] was below 1 in the northeastern region, indicating that, in spite of the high concentration of the analyzed metals in this area, they are trapped in the sediment, as sulfides. The total metal concentrations in the sediments were also determined and the same distribution pattern obtained for the SEM were observed, with high concentrations in the northeastern region of the bay, classifying the area as level 2, for Zn, and as level 1, for Cd, Cu, Pb and Ni, according to the CONAMA 344/04 act. A geostatiscal approach is presented, the attenuation of concentrations model, which aims to estimate metal mobility in sediments. The proposed model showed the highest attenuation values for Zn, Cd, Cu and Pb in the northeastern region, indicating that the mobility of these metals is low in this region, suggesting low availability, which is in good agreement with the results obtained by the S[SEM]/[AVS] model. These results indicate good possibilities of applying this model in metal contamination studies in estuarine ecosystems.

Em fevereiro de 2012 um incêndio atingiu a Estação Antártica Comandante Ferraz (EACF), consumindo cerca de 70% das instalações, liberando diversos compostos para o meio ambiente. Desde então, processos de remoção de resíduos vêm sendo realizados. Com base no cenário de efeitos ambientais em um ambiente antártico, amostras de solo e sedimento foram coletadas em diferentes períodos pós-acidente a fim de se avaliar os efeitos do incêndio. As amostras foram tratadas através de digestão ácida e as concentrações parciais de metais e As foram quantificadas através de ICP-OES. O Fator de Enriquecimento foi utilizado para avaliação dos impactos causados no solo, enquanto que comparação com os valores estabelecidos pela legislação canadense (TEL e PEL) foi utilizada na avaliação do grau de contaminação do sedimento. Os resultados indicaram a introdução de Pb, Cu e Zn antropogênico em parte das amostras de solo coletadas ao redor da antiga estação antártica, cujos Fatores de Enriquecimento chegaram a, respectivamente, 208,9; 189,7 e 111,6; sendo estes presentes sob a forma de fragmentos metálicos. Também indicaram que os processos de remoção de resíduos podem ter sido tanto responsáveis pela redução nos teores de metais, como por ter reintroduzido estes elementos em outros pontos mobilizando-os durante a movimentação de resíduos. Além disso, não foram encontradas evidências de alterações significativas nos teores de Hg em solo e metais e As em sedimento marinho. / In February 2012, a fire at the Comandante Ferraz Antarctic Station (EACF) destroyed approximately 70% of the Brazilian research station. This event released many substances and residues to the region and, since then, operations for the removal of the fire wastes have been executed. Based on the scenario of environmental effects on an Antarctic environment, soil and sediment samples were collected in several different moments after the accident to study the impacts of the fire. The samples were treated through acid digestion and the partial levels of metals and As were quantified through ICP-OES. Enrichment factor was used to evaluate the impacts caused in soils, and comparisons with Canadian environmental quality guidelines (TEL and PEL) were used to assess the intensity of the sediment contamination. The results indicated the introduction of anthropogenic Cu, Pb and Zn in some of the collected soil samples around the former Antarctic station, with enrichment factors of 189.7, 208.9 and 111.6, respectively, elements those present in metallic fragments. Moreover, the analysis of the generated data showed that the procedures for wastes removal could have been responsible for the decrease in the elements\' content as well as the reintroduction of those elements due to the mobilization of the wastes in some of the sampled sites. Furthermore, there\'s no evidences of significate changes on Hg levels in soil or metal and As levels in marine sediment.

[pt] Neste trabalho, métodos analíticos foram desenvolvidos para a determinação de elementos terras raras (REE, do inglês Rare Earth Elements), por espectrometria de massa e espectrometria de emissão óptica com plasma indutivamente acoplado (ICP-MS e ICP OES) numa amostra de asfalto. Foram avaliados os resultados analíticos através da análise de um material de referência certificado de rocha (GSP-1) e através da comparação dos resultados obtidos pelas duas técnicas. Dois diferentes métodos de lixiviação ácida foram empregados para o tratamento da amostra de asfalto, com HNO3 ou H2SO4, de maneira a simular os efeitos intensificados da chuva ácida. Também foi avaliada a extração da amostra com solvente orgânico e posterior lixiviação ácida, para identificar a origem (orgânica ou inorgânica) dos REE na amostra do asfalto, concluindo que eles estão presentes apenas na fração inorgânica da amostra. Os limites de detecção variaram entre 0,002 e 0,010 microgramas L elevado a menos 1 para a lixiviação com HNO3 e entre 0,001 e 0,014 microgramas L elevado a menos 1 com H2SO4, por ICP-MS, e entre 0,05 e 2,5 micrograma L elevado a menos 1 com HNO3 e entre 0,06 e 3,1 micrograma L elevado a menos 1 com H2SO4, por ICP OES. As determinações foram feitas com curvas analíticas com padrões aquosos e Rh como padrão interno. Além disso, a interferência espectral do BaO sobre Eu foi reduzida, através da precipitacao do Ba como BaSO4 quando se usou ácido sulfúrico para a lixiviacao da amostra de asfalto, reduzindo cerca de 94 porcento a concentracao de Ba em relação àquela medida no lixiviado com HNO3. As concentrações de REE variaram de 0,47 a 65,6 microgramas g menos 1, sendo que os terras raras leves (LREE) representaram 83 porcento do total de REE no asfalto investigado. O Ce foi o mais abundante dos REE no lixiviado do asfalto, seguido por Nd e La. A ordem das concentrações médias de REE no asfalto foi, em ordem decrescente: Ce maior Nd maior La maior Pr maior Sm maior Eu maior Gd maior Dy maior Er maior Yb maior Ho maior Tm maior Lu. / [en] In this study, analytical methods were developed for the determination of Rare Earth Elements by inductively coupled plasma -mass and -optical emission spectrometries (ICP-MS and ICP OES), in an asphalt sample. The analytical results were evaluated through the analysis of a rock certified reference material (GSP-1) and through the comparison of the results with the two techniques. Two different methods of acid leaching were employed for the asphalt sample treatment, with HNO3 or H2SO4, in order to simulate intensified acid rain effects. Additionally, the extraction of the sample with organic solvent and subsequent acid leaching was also evaluated to identify the origin (organic or inorganic) of REE in asphalt sample, concluding that they are present in the sample inorganic fraction. The obtained limits of detection ranged from 0.002 to 0.010 microgam L to the power of minus 1 for the leaching with HNO3 and from 0.001 to 0.014 microgram L to the power of 1 with H2SO4, by ICP-MS, and from 0.05 to 2.5 microgram L to the power of minus 1 with HNO3 and from 0.06 to 3.1 microgram L to the power of minus 1 with H2SO4, by ICP OES. The determinations were made with analytical curves with aqueous standards and Rh as internal standard. Moreover, the spectral interference by BaO on Eu was reduced, through the precipitation of Ba as BaSO4 when sulfuric acid was used for the asphalt sample leaching, decreasing about 94 percent the Ba concentration in relation to that measured in the leachate with HNO3. The concentrations of REE in the asphalt sample ranged from 0.47 to 65.6 microgran g to the power of minus 1, being the light rare earth elements (LREE) accounted for 83 percent of total REE on the asphalt investigated. Cerium was the most abundant REE in the asphalt leached, followed by Nd and La. The order of average concentrations of REE in the asphalt was, in descending order: Ce > Nd > La > Pr > Sm > Eu > Gd > Dy > Er > Yb > Ho > Tm > Lu.

[pt] A distribuição de elementos de terras raras (REE) é representativa das rochas e solos que originalmente os contêm e é frequentemente usada como parâmetro geoquímico ou ambiental para identificação de fontes. Este trabalho propõe um novo método de preparo de amostras para a determinação de elementos de terras raras (REE) por espectrometria de massa de plasma acoplada indutivamente (ICPMS) em amostras ambientais com altas concentrações de Ba. O método consiste na diluição das amostras, obtidas após decomposição ácida em sistema aberto, com ácido sulfúrico 10 porcento (v/v) para a separação de Ba2positive como BaSO4. A remoção da interferência sobre os isótopos de Eu (151Eu and 153Eu) foi eficiente para concentrações de Ba superiores a 0,1 mg L-1. A exatidão e a precisão foram verificadas pela análise de tres materiais certificados, rocha basáltica (NIST 688), Geological Survey (Granite G-2) e sedimento marinho (MESS-3). A metodologia proposta foi aplicada ao pavimento asfáltico, à brita e ao material de referencia certificado. Adicionalmente, todas as amostras foram decompostas por fusão alcalina e as concentrações de elementos majoritários e Eu foram determinadas por espectrometria de emissão ótica de plasma acoplada indutivamente (ICP OES). Os resultados da Eu estavam de acordo com a metodologia proposta, e os limites de detecção (LOD) para REE variaram de 0,003 mg L-1 (Lu) a 0,010 mg L-1 (Gd). A distribuição de REE foi medida em sedimentos superficiais e amostras de testemunhos coletados na Baía de Sepetiba, entre junho e setembro de 2016. A faixa de concentração de SREE foi entre 25-496 mg kg-1. Esse monitoramento é importante para avaliar o impacto da urbanização e desenvolvimento rápido e não planejado de atividades antropogênicas, comuns em muitas áreas costeiras tropicais do Brasil. / [en] The distribution of rare earth elements (REE) is representative of the rocks and soils that originally contain them and it is often used as a geochemical or an environmental parameter for source identification. This thesis proposes a new method for the determination of rare earth elements (REE), by inductively coupled plasma mass spectrometry (ICP-MS), in challenging environmental samples with high Ba concentrations. The method consists in diluting the wet sample digests, obtained after acid decomposition in an open system, with 10 porcento (v/v) sulfuric acid for the separation of Ba2+ as BaSO4. The interference removal on both Eu isotopes (151Eu and 153Eu) was efficient for Ba concentrations higher than 0.1 mg L-1. Accuracy and precision were verified by analysis of two certified materials, NIST 688 Standard Reference Material of basalt rock, Geological Survey G-2 granite and marine sediment reference material (MESS-3) provided by the National Research Council in Canada (NRC) was used to evaluate the accuracy of the REE determination in marine sediments. The proposed methodology was applied to asphalt pavement and crushed stone. Additionally, for comparison, all samples were decomposed by fusion and major elements and Eu concentrations were determined by inductively coupled plasma optical emission spectrometry (ICP OES). The Eu results were in agreement with the proposed methodology, and limits of detection (LOD) for REE varied from 0.003 mg L-1 (Lu) to 0.010 mg L-1 (Gd). The distribution of REE was also measured in surface sediments and sediment core collected in Sepetiba Bay, between June and September of 2016. The range of SREE concentrations was established between 25-496 mg kg-1. This monitoring is important to evaluate the impact of the fast and unplanned urbanization and development of anthropogenic activities, common to many tropical coastal areas in Brazil.

The work presented in this thesis has demonstrated that the use of elemental profiles for the quality control of herbal medicines can be applied to multiple stages of processing. A single method was developed for the elemental analysis of a variety of St John’s Wort (Hypericum perforatum) preparations using Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES). The optimised method consisted of using 5 ml of nitric acid and microwave digestion reaching temperatures of 185⁰C. Using NIST Polish tea (NIST INCT-TL- 1) the method was found to be accurate and the matrix effect from selected St John’s Wort (SJW) preparations was found to be ≤22%. The optimised method was then used to determine the elemental profiles for a larger number of SJW preparations (raw herbs=22, tablets=20 and capsules=12). Specifically, the method was used to determine the typical concentrations of 25 elements (Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Ni, Pb, Pt, Sb, Se, Sr, V, Y and Zn) for each form of SJW which ranged from not detected to 200 mg/g. To further interpret the element profiles, Principal Component Analysis (PCA) was carried out. This showed that different forms of SJW could be differentiated based on their elemental profile and the SJW ingredient used (i.e. extract or raw herb) identified. The differences in the profiles were likely due to two factors: (1) the addition of bulking agents and (2) solvent extraction. In order to further understand how the elemental profile changes when producing the extract from the raw plant, eight SJW herb samples were extracted with four solvents (100% water, 60% ethanol, 80% ethanol and 100% ethanol) and analysed for their element content. The results showed that the transfer of elements from the raw herb to an extract was solvent and metal dependent. Generally the highest concentrations of an element were extracted with 100% water, which decreased as the concentration of ethanol increased. However, the transfer efficiency for the element Cu was highest with 60% ethanol. The solvents utilised in industry (60% and 80% ethanol) were found to preconcentrate some elements; Cu (+119%), Mg (+93%), Ni (+183%) and Zn (+12%) were found to preconcentrate in 60 %v/v ethanol extracts and Cu (+5%) and Ni (+30%). PCA of the elemental profiles of the four types of extract showed that differentiation was observed between the different solvents and as the ethanol concentration increased, the extracts became more standardised. Analysis of the bioactive compounds rutin, hyperoside, quercetin, hyperforin and adhyperforin followed by subsequent Correlation Analysis (CA) displayed relationships between the elemental profiles and the molecular profiles. For example strong correlations were seen between hyperoside and Cr as well as Quercetin and Fe. This shows potential for tuning elemental extractions for metal-bioactive compounds for increased bioactivity and bioavailability; however further work in needed in this area.

As sucatas eletrônicas são hoje consideradas como matéria prima de alto valor agregado e economicamente viável, devido à presença de metais preciosos (e.g. prata, ouro, platina e paládio) em sua composição. Em geral, a comercialização é baseada no teor de metais preciosos e cobre, sendo assim, as análises químicas desempenham papel fundamental nesse ambiente de negócios. O método mais empregado para esse tipo de análise, considerado padrão é o Fire Assay, que consiste na extração dos analitos da matriz tornando determinação final praticamente livre de interferências. Entretanto o Fire Assay é um método susceptível a erros sistemáticos devido ao grande número de etapas, lento, caro e ambientalmente insustentável devido à quantidade de reagentes utilizados e resíduos gerados (e.g. chumbo). Diante dessas importantes desvantagens, o desenvolvimento de métodos que apresentem exatidão, precisão, boa frequência analítica, custo e que gere poucos resíduos se tornam necessários para a melhoria do controle de qualidade desses materiais. Sendo assim, o objetivo dessa pesquisa foi o desenvolvimento de método para a determinação simultânea de Au, Ag e Pd por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) e espectroscopia de fluorescência de raios-x por comprimento de ondas (WDSXRF), usando diferentes estratégias de preparação de amostras. As sucatas eletrônicas se caracterizam por serem heterogêneas, além disso, o material possui grande quantidade de metais como Al, Cu e Fe na composição fazendo com que a comunição seja um elemento chave no método e determinante da frequência analítica. Considerando esta dificuldade as amostras foram moídas em moinho oscilatório de discos de em diferentes tempos a fim de se investigar a influencia do tamanho de partículas para estudo de representatividade e precisão além da influencia do tamanho de partículas nas determinações por WDSXRF devido ao efeito sombra. Para os analises por WDSXRF as amostras com 40 minutos de moagem e preparadas com fusão com ferro e enxofre demonstraram boas correlações quando comprados ao Fire Assay. As dissoluções das amostras para analises em ICP OES ocorreu em duas etapas, a 1&#170; com HNO3 (aquecimento em chapa) para evitar passivação do ouro e a 2&#170; com 10 ml de água régia, usando o programa do forno de micro-ondas, com rampa de 160 °C a 210 °C (30 min). Foi observado que o excesso de Cl- formou complexos que inibiram perdas de Ag+ pro precipitação. As soluções finais foram analisadas no ICP OES e as concentrações obtidas foram comparadas ao método de Fire Assay. O método proposto mostrou boa correção para todos os elementos ao método padrão. A reprodutibilidade para Au foi de 4,1% (n=15 amostras) e a recuperação média comparada ao método padrão foi de 102%. Com base nos resultados obtidos pode-se dizer que o método proposto é comparável ao Fire Assay quanto à precisão e limites de detecção, apresentando melhores respostas quanto à frequência analítica, custo e geração de resíduos / Electronic scraps are today considered as raw material of high added value and economically viable, due to the presence of precious metals (e.g. silver, gold, platinum and palladium) in your composition. In general, the marketing is based on the content of precious metals and copper, therefore, chemical analysis plays a key role in this business environment. The method employed for this kind of analysis, considered standard, is the Fire Assay, which consists of the extraction of analytes in the array, making final determination virtually free of interference. However the Fire Assay is a method susceptible to systematic errors due to the large number of steps, slow, expensive and environmentally unsustainable due to the amount of reagents used and waste generated (e.g. lead). On these important disadvantages, the development of methods which have accuracy, precision, good analytical cost and frequency that generate few residues become necessary for the improvement of the quality control of these materials. Therefore, the objective of this research was the development of method for the simultaneous determination of Au, Ag and Pd by optical emission spectrometry with inductively coupled plasma (ICP OES) and fluorescence spectroscopy for x-ray wavelengths (WDSXRF), using different sampling strategies. Electronic scraps are characterized for being heterogeneous, in addition, the material possesses large amount of metals such as Al, Cu and Fe in the composition so that the communication is a key element in determining the frequency and analytical method. Considering this difficulty the samples were ground into oscillatory grinder discs at different times in order to investigate the influence of the particle size for study of representativeness and accuracy beyond the influence of the particle size determination by WDSXRF due to the shadow effect. For the analysis by WDSXRF samples with 40 minutes of grinding and prepared with merger with iron and sulfur showed good correlations when purchased the Fire Assay. The dissolutions of the samples for analysis in ICP-OES occurred in two steps, first with HNO3 (heating plate) to avoid gold passivation and the 2nd with 10 ml of aqua regia, by using the microwave oven, with 160 °C ramp to 210 °C (30 min). It was observed that the excess of Cl-formed complex that inhibit loss of Ag+ by precipitation. The final solutions were analysed at the ICP OES and the concentrations obtained were compared to the method of Fire Assay. The proposed method showed good fix for all elements to the standard method. Reproducibility for Au was 4.1% (n = 15 samples) and the average recovery compared to the standard method was 102%. Based on the results obtained can be said that the proposed method is comparable to the Fire Assay for accuracy and limits of detection, showing best answers regarding the analytical frequency, cost and waste generation.

This research aims to understand the organization of activities across a prehispanic urban center at the Formative period site of Tlalancaleca (800 BC- AD 100), located in Puebla, Mexico. This study analyzes soil samples at the central civic-ceremonial complex of Cerro Grande in an attempt to understand the use of space. This work is a part of the larger Proyecto Arqueológico Tlalancaleca, Puebla (PATP), which is focused on understanding the socio-political organization at Tlalancaleca that led to this site of early urbanism. Soil samples from Tlalancaleca are analyzed using three chemical methods to perform a cross-comparison of analytical methods. These three methods are inductively coupled plasma-optical emission spectrometry (ICP-OES), Mehlich 3 soil phosphorus colorimetry, and portable X-ray fluorescence (pXRF) spectrometry. The final results of this soil analysis confirm that the Cerro Grande Complex was an actively used space, with areas maintained for specific uses and areas where activities changed over time. In the comparison of methods, ICP-OES was found to be the most comprehensive, precise, and accurate method to use, while pXRF and Mehlich colorimetry were found to show differing information with regards to available and natural concentrations of the different elements. An analytical examination of phosphorus, strontium, calcium, and barium revealed evidence of construction of monumental buildings, a cache, and possible separate feasting areas, indicating that physical spaces and constructions were likely attached to social and political organizations.

The purpose of this research is to develop a rapid determination method for heavy metals in soil. Using X-ray fluorescence to obtain soil metals decision limit (CC£\) and detection capability (CC£]), to establish the scope of soil metal concentration selection. Then aqua regia digestion digestion and ICP-OES analysis of Pb, Cd, Zn, Ni, Cr, Cu area to check the accuracy of screening. Operating conditions; First, the soil standard samples for the Establishment and assessment of the applicability of the standard. Finally,using of the soil near the control standard establish methods and explore ways to establish the applicability and potential impact. I hope this research can provide a fast, accurate, and sensitivity of soil heavy metal screening, to achieve savings of cost. The results show that the standard reference soil Cu: screening rate was 79.7%, sensitivity was 43.6% and an specificity of 87.7%; reference standard soil Pb: screening rate was 91.5%, a sensitivity of 8.3% specificity 91.5%;reference standard soil Cr:screening rate was 100%, sensitivity was 0%, 100% specificity; reference standard soil Ni: screening rate was 96.1%, sensitivity was 0%, specificity 92.4%; reference standard soil Zn: screening rate was 82.4%, sensitivity was 69.2%, specificity 87.1%; reaching control values of soil Cu: screening rate was 83.0%, sensitivity was 30.8%, specificity of 84.3%. Screening rate and specificity with 80%, the sensitivity poor areas, water was the major disturbance factor.

Glass has been used to make a variety of artifacts including bottles, drinking cups, vessels, window glasses, beads and bracelets. Although occasional glass bracelets were dated back to 2000 BC, large scale manufacture of glass bracelets was encountered in Central Europe in the last centuries of 1000BC. During the excavations of Mezraa H&ouml / y&uuml / k (Birecik-Sanliurfa) in 2000-20002, a number of glass bracelets were unearthed that belongs to 13th century AD. On going excavations of Mersin Yumuktepe also give quite a lot of 11th-12th centuries Byzantine glass bracelets. In this study a group of those bracelets was started to be examined. After technical drawings, color identification had been carried out by using Munsell color chart. Thin sections of some samples of Mezraa H&ouml / y&uuml / k have been prepared and then observed by an optical microscope in Mineral Research and Exploration (MTA). Observation of thin sections showed the amorphous structure of glass with some impurities and gas bubbles. On some samples deteriorated surface layers were present. XRD traces of those layers showed the typical amorphous background of glass in which no crystalline phase is present. Elemental analysis of the samples has been done using ICP-OES method in METU Central Laboratory. In the analysis major (except SiO2), minor and some trace elements were determined. ICP-OES data showed that glass bracelet samples studied are of soda-lime-silica glass. But percentage of Na2O is less than expected from typical composition of soda-lime-silica glass / being 10.5 wt % as average. This might be due to removal of Na ions from the glass network because of leaching under burial conditions. Concentration of Al2O3 in the samples of Mezraa H&ouml / y&uuml / k is almost same. This may be due to the using one type of quartz sand in bracelet production. Color producing elements seem to be Fe, Mn and Cu.