Neste estudo foram avaliados procedimentos analíticos comparativos para o preparo de três tipos de amostras agroindustriais (rochas, cafés e antibióticos) na determinação de elementos inorgânicos pelas técnicas de espectrometria de absorção atômica em chama (FAAS), espectrometria de emissão atômica em chama (FAES) e espectrometria de absorção atômica em forno de grafite (GFAAS). Seis procedimentos de decomposição de rochas foram estudados e classificados em 3 grupos: GRUPO I: bombas de teflon; GRUPO II: bloco digestor; GRUPO III: forno de microondas convencional. Os elementos Cu, Fe, Mn e Zn foram quantificados pela técnica FAAS em duas amostras comerciais e dois materiais de referência padrão de rochas. Os melhores resultados foram obtidos para os procedimentos que empregaram forno de microondas convencional usando-se HF na mistura ácida. Os teores de 9 nutrientes foram determinados em 35 amostras de café (verde e torrado) por FAAS (Ca, Mg, Fe, Cu, Mn e Zn), FAES (Na e K) e pelo método Kjeldahl (N). As amostras foram preparadas por dois procedimentos de decomposição via úmida, um deles empregando bloco digestor e V2O5 como catalisador e o outro forno de microondas convencional. A exatidão dos métodos foi verificada pela análise de três materiais de referência padrão de folhas. Um teste foi realizado moendo-se uma das amostras de café verde em dois tipos de moinho (criogênico e tipo Willye) para avaliar possíveis contaminações. Contaminação com Fe foi observada com o uso do moinho tipo Willye. Outro teste constou da determinação desses 9 nutrientes em uma amostra de café verde com casca. Altos teores de Na, Ca, K e Fe foram encontrados na casca do café verde, confirmando assim a possibilidade de reaproveitamento desses resíduos em processos de adubação e na produção de ração animal. Análises quimiométricas aplicando-se PCA e HCA mostraram que os elementos Na, K, Ca, Mg e Fe foram os principais responsáveis pela discriminação entre as amostras de café verde e torrado. Um método foi desenvolvido para a determinação simultânea de Cd e Pb por GFAAS em antibióticos sólidos usados na fermentação da cana de açúcar. Seis amostras de antibióticos sólidos comerciais foram analisadas injetando-se 20 µL das amostras decompostas em meio ácido (forno de microondas convencional) dentro da plataforma de grafite pré-tratada com W seguido de 5 µL do modificador químico Pd 1000 mg L-1. As amostras foram solubilizadas por dois procedimentos: 1) 3 mL HNO3 conc. + 2 mL H2O2 30% (v/v) e, 2) 4 mL HNO3 20% (v/v) + 1 mL H2O2 30% (v/v). As temperaturas de pirólise e atomização do programa de aquecimento do atomizador foram fixadas em 600oC e 2200oC, respectivamente. As massas características calculadas para a determinação simultânea foram 1,6 pg Cd e 41,7 pg Pb. Limites de detecção (LOD) baseados na absorbância integrada foram 0,02 µg L-1 Cd e 0,7 µg L-1 Pb e os desvios padrões relativos (n = 10) para Cd e Pb foram 5,7% e 8,0%, respectivamente. As recuperações de Cd e Pb adicionadas às amostras digeridas variaram de 91% a 125% (Cd) e 80% a 112% (Pb). / Analytical comparative procedures for the preparation of three types of agro industrials samples (rocks, coffees and antibiotics) were evaluated in the determination of inorganic elements by flame atomic absorption spectrometry (FAAS), flame atomic emission spectrometry (FAES) and graphite furnace atomic absorption spectrometry (GFAAS) techniques. Six decomposition procedures of rocks were studied and classified in 3 groups: GROUP I: wet digestion in teflon bombs; GROUP II: wet digestion in digester heating block; GROUP III: wet digestion in conventional microwave oven system. The elements Cu, Fe, Mn and Zn were quantified by FAAS in two commercial samples and two standard reference materials of rocks. The best results were obtained for the procedures that employed conventional microwave oven system using HF in the acid mixture. The contents of 9 nutrients were determined in 35 coffee samples (green and roasted) by FAAS (Ca, Mg, Fe, Cu, Mn and Zn), FAES (Na and K) and Kjeldahl method (N). Samples were prepared by two different wet digestion decomposition procedures; one of them employing digester heating block and the catalyst V2O5 and the other one employing a conventional microwave oven system. The accuracy of the methods was checked after analysis of three leave standard reference materials. A test was done in a green coffee sample ground in two types of mill (cryogenic and Willye) to evaluate possible contaminations. Contamination by Fe was observed with the use of Willye type mill. Another test was the determination of these 9 nutrients in an unpulped ripe cherry. High levels of Na, Ca, K and Fe were encountered in the green coffee rinds, which can be used as a complement in manuring process and for animal ration production. Chemometric analysis using PCA and HCA showed that Na, K, Ca, Mg, Cu and Fe were the principal elements to discriminate samples between green and roasted coffee. A method has been developed for the simultaneous determination of Cd and Pb in antibiotics used in sugar-cane fermentation by GFAAS. Six samples of commercial solid antibiotics were analyzed by injecting 20 µL of digested samples (closed microwave oven system) into the pretreated graphite platform with W followed by 5 µL of 1000 mg L-1 Pd chemical modifier. Samples were solubilized by two procedures: 1) 3 mL HNO3 conc. + 2 mL H2O2 30% (v/v) and, 2) 4 mL HNO3 20% (v/v) + 1 mL H2O2 30% (v/v). The pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 600oC and 2200oC, respectively. The calculated characteristic masses for the simultaneous determination were 1.6 pg Cd and 41.7 pg Pb. Limits of detection (LOD) based on integrated absorbance were 0.02 µg L-1 Cd and 0.7 µg L-1 Pb and the relative standard deviations (n = 10) for Cd and Pb were 5.7% and 8.0%, respectively. The recoveries of Cd and Pb added to the digested samples varied from 91% to 125% (Cd) and 80% to 112% (Pb).

Neste estudo foram avaliados procedimentos analíticos comparativos para o preparo de três tipos de amostras agroindustriais (rochas, cafés e antibióticos) na determinação de elementos inorgânicos pelas técnicas de espectrometria de absorção atômica em chama (FAAS), espectrometria de emissão atômica em chama (FAES) e espectrometria de absorção atômica em forno de grafite (GFAAS). Seis procedimentos de decomposição de rochas foram estudados e classificados em 3 grupos: GRUPO I: bombas de teflon; GRUPO II: bloco digestor; GRUPO III: forno de microondas convencional. Os elementos Cu, Fe, Mn e Zn foram quantificados pela técnica FAAS em duas amostras comerciais e dois materiais de referência padrão de rochas. Os melhores resultados foram obtidos para os procedimentos que empregaram forno de microondas convencional usando-se HF na mistura ácida. Os teores de 9 nutrientes foram determinados em 35 amostras de café (verde e torrado) por FAAS (Ca, Mg, Fe, Cu, Mn e Zn), FAES (Na e K) e pelo método Kjeldahl (N). As amostras foram preparadas por dois procedimentos de decomposição via úmida, um deles empregando bloco digestor e V2O5 como catalisador e o outro forno de microondas convencional. A exatidão dos métodos foi verificada pela análise de três materiais de referência padrão de folhas. Um teste foi realizado moendo-se uma das amostras de café verde em dois tipos de moinho (criogênico e tipo Willye) para avaliar possíveis contaminações. Contaminação com Fe foi observada com o uso do moinho tipo Willye. Outro teste constou da determinação desses 9 nutrientes em uma amostra de café verde com casca. Altos teores de Na, Ca, K e Fe foram encontrados na casca do café verde, confirmando assim a possibilidade de reaproveitamento desses resíduos em processos de adubação e na produção de ração animal. Análises quimiométricas aplicando-se PCA e HCA mostraram que os elementos Na, K, Ca, Mg e Fe foram os principais responsáveis pela discriminação entre as amostras de café verde e torrado. Um método foi desenvolvido para a determinação simultânea de Cd e Pb por GFAAS em antibióticos sólidos usados na fermentação da cana de açúcar. Seis amostras de antibióticos sólidos comerciais foram analisadas injetando-se 20 µL das amostras decompostas em meio ácido (forno de microondas convencional) dentro da plataforma de grafite pré-tratada com W seguido de 5 µL do modificador químico Pd 1000 mg L-1. As amostras foram solubilizadas por dois procedimentos: 1) 3 mL HNO3 conc. + 2 mL H2O2 30% (v/v) e, 2) 4 mL HNO3 20% (v/v) + 1 mL H2O2 30% (v/v). As temperaturas de pirólise e atomização do programa de aquecimento do atomizador foram fixadas em 600oC e 2200oC, respectivamente. As massas características calculadas para a determinação simultânea foram 1,6 pg Cd e 41,7 pg Pb. Limites de detecção (LOD) baseados na absorbância integrada foram 0,02 µg L-1 Cd e 0,7 µg L-1 Pb e os desvios padrões relativos (n = 10) para Cd e Pb foram 5,7% e 8,0%, respectivamente. As recuperações de Cd e Pb adicionadas às amostras digeridas variaram de 91% a 125% (Cd) e 80% a 112% (Pb). / Analytical comparative procedures for the preparation of three types of agro industrials samples (rocks, coffees and antibiotics) were evaluated in the determination of inorganic elements by flame atomic absorption spectrometry (FAAS), flame atomic emission spectrometry (FAES) and graphite furnace atomic absorption spectrometry (GFAAS) techniques. Six decomposition procedures of rocks were studied and classified in 3 groups: GROUP I: wet digestion in teflon bombs; GROUP II: wet digestion in digester heating block; GROUP III: wet digestion in conventional microwave oven system. The elements Cu, Fe, Mn and Zn were quantified by FAAS in two commercial samples and two standard reference materials of rocks. The best results were obtained for the procedures that employed conventional microwave oven system using HF in the acid mixture. The contents of 9 nutrients were determined in 35 coffee samples (green and roasted) by FAAS (Ca, Mg, Fe, Cu, Mn and Zn), FAES (Na and K) and Kjeldahl method (N). Samples were prepared by two different wet digestion decomposition procedures; one of them employing digester heating block and the catalyst V2O5 and the other one employing a conventional microwave oven system. The accuracy of the methods was checked after analysis of three leave standard reference materials. A test was done in a green coffee sample ground in two types of mill (cryogenic and Willye) to evaluate possible contaminations. Contamination by Fe was observed with the use of Willye type mill. Another test was the determination of these 9 nutrients in an unpulped ripe cherry. High levels of Na, Ca, K and Fe were encountered in the green coffee rinds, which can be used as a complement in manuring process and for animal ration production. Chemometric analysis using PCA and HCA showed that Na, K, Ca, Mg, Cu and Fe were the principal elements to discriminate samples between green and roasted coffee. A method has been developed for the simultaneous determination of Cd and Pb in antibiotics used in sugar-cane fermentation by GFAAS. Six samples of commercial solid antibiotics were analyzed by injecting 20 µL of digested samples (closed microwave oven system) into the pretreated graphite platform with W followed by 5 µL of 1000 mg L-1 Pd chemical modifier. Samples were solubilized by two procedures: 1) 3 mL HNO3 conc. + 2 mL H2O2 30% (v/v) and, 2) 4 mL HNO3 20% (v/v) + 1 mL H2O2 30% (v/v). The pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 600oC and 2200oC, respectively. The calculated characteristic masses for the simultaneous determination were 1.6 pg Cd and 41.7 pg Pb. Limits of detection (LOD) based on integrated absorbance were 0.02 µg L-1 Cd and 0.7 µg L-1 Pb and the relative standard deviations (n = 10) for Cd and Pb were 5.7% and 8.0%, respectively. The recoveries of Cd and Pb added to the digested samples varied from 91% to 125% (Cd) and 80% to 112% (Pb).

No description available.

O sangue é uma suspensão de células contidas num líquido complexo chamado plasma. O termo sangue total refere-se a amostras de sangue com a totalidade de seus constituintes, parte sólida e líquida. Sendo os elementos químicos responsáveis por funções essenciais, como regulação osmótica, frequência cardíaca e contratibilidade, coagulação sanguínea e excitabilidade neuromuscular. A determinação de elementos químicos em fluidos corporais como sangue, soro, plasma, tecido e urina é usada como monitor de parte ou de todo o organismo. Nesse trabalho, utilizou-se a técnica de fluorescência de raios X (EDXRF) para análise de amostras de sangue total humano e animal, hamsters da espécie dourada (Mesocricetus auratus) e cavalos da raça crioula (Equus caballus). Nas amostras de sangue humano, foram determinados intervalos de referência de Na (1788 - 1826 μg g-1), Mg (63 - 75 μg g-1), P (602 - 676 μg g-1), S (1519 - 1718 μg g-1), Cl (2743 - 2867 μg g-1), K (1508 - 1630 μg g-1), Ca (214 - 228 μg g-1), Cu (4 - 6 μg g-1) e Zn (1 - 3 μg g-1). Foram determinados intervalos de referência de Na (1714 - 1819 μg g-1), Mg (51 - 79 μg g-1), P (970 - 1080 μg g-1), S (1231 - 1739 μg g-1), Cl (2775 - 2865 μg g-1), K (1968 - 2248 μg g-1), Ca (209 - 257 μg g-1), Cu (4 - 6 μg g-1) e Zn (3 - 5 μg g-1) para amostras de sangue de hamster dourado. As amostras de sangue de cavalo da raça crioula apresentaram os intervalos de: Na (1955 - 2013 μg g-1), Mg (51 - 75 μg g-1), P (443 - 476 μg g-1), S (1038 - 1140 μg g-1), Cl (2388 - 2574 μg g-1), K (1678 - 1753 μg g-1), Ca (202 - 213 μg g-1), Cu (4,1 - 4,5 μg g-1) e Zn (2,0 - 2,2 μg g-1). Estudo comparativo dos resultados entre as técnicas de análise por ativação neutrônica (NAA) e EDXRF indica a igualdade de desempenho das técnicas analíticas na análise de matrizes biológicas. Os resultados contribuem no estabelecimento de intervalos de referência para a população brasileira saudável e para as referidas espécies de animais. / Blood is a suspension of cells contained in a complex liquid called plasma. The term whole blood refers to samples with both solid and liquid parts. Inorganic elements are responsible for essential functions, such as osmotic regulation, cardiac frequency and contractibility, blood clotting and neuromuscular excitability. The determination of inorganic elements in corporeal fluids such as blood, serum, plasma, tissue and urine is used as a monitor for a part or the whole organism. In this work, the X-Ray fluorescence technique (EDXRF) was used for the determination of inorganic elements in whole blood samples from humans and animals (golden hamsters, Mesocricetus auratus and crioula breed horses, Equus caballus). The reference intervals of Na (1788 - 1826 μg g-1), Mg (63 - 75 μg g-1), P (602 - 676 μg g-1), S (1519 - 1718 μg g-1), Cl (2743 - 2867 μg g-1), K (1508 - 1630 μg g-1), Ca (214 - 228 μg g-1), Cu (4 -6 μg g-1) e Zn (1 - 3 μg g-1) were determined for human blood. The reference intervals, for golden hamster blood were found to be: Na (1714 - 1819 μg g-1), Mg (51 - 79 μg g-1), P (970 - 1080 μg g-1), S (1231 - 1739 μg g-1), Cl (2775 - 2865 μg g-1), K (1968 - 2248 μg g-1), Ca (209 - 257 μg g-1), Cu (4 - 6 μg g-1) e Zn (3 -5 μg g-1). The reference intervals, for crioula breed horse blood, showed to be: Na (1955 - 2013 μg g-1), Mg (51 - 75 μg g-1), P (443 - 476 μg g-1), S (1038 - 1140 μg g-1), Cl (2388 - 2574 μg g-1), K (1678 - 1753 μg g-1), Ca (202 - 213 μg g-1), Cu (4,1 - 4,5 μg g-1) e Zn (2,0 - 2,2 μg g-1). Comparative study between NAA and EDXRF, both techniques showed the same performance for the analyses of biological matrices. The results contribute for the establishment of reference intervals for the Brazilian healthy population and the referred animal species.

O sangue é uma suspensão de células contidas num líquido complexo chamado plasma. O termo sangue total refere-se a amostras de sangue com a totalidade de seus constituintes, parte sólida e líquida. Sendo os elementos químicos responsáveis por funções essenciais, como regulação osmótica, frequência cardíaca e contratibilidade, coagulação sanguínea e excitabilidade neuromuscular. A determinação de elementos químicos em fluidos corporais como sangue, soro, plasma, tecido e urina é usada como monitor de parte ou de todo o organismo. Nesse trabalho, utilizou-se a técnica de fluorescência de raios X (EDXRF) para análise de amostras de sangue total humano e animal, hamsters da espécie dourada (Mesocricetus auratus) e cavalos da raça crioula (Equus caballus). Nas amostras de sangue humano, foram determinados intervalos de referência de Na (1788 - 1826 μg g-1), Mg (63 - 75 μg g-1), P (602 - 676 μg g-1), S (1519 - 1718 μg g-1), Cl (2743 - 2867 μg g-1), K (1508 - 1630 μg g-1), Ca (214 - 228 μg g-1), Cu (4 - 6 μg g-1) e Zn (1 - 3 μg g-1). Foram determinados intervalos de referência de Na (1714 - 1819 μg g-1), Mg (51 - 79 μg g-1), P (970 - 1080 μg g-1), S (1231 - 1739 μg g-1), Cl (2775 - 2865 μg g-1), K (1968 - 2248 μg g-1), Ca (209 - 257 μg g-1), Cu (4 - 6 μg g-1) e Zn (3 - 5 μg g-1) para amostras de sangue de hamster dourado. As amostras de sangue de cavalo da raça crioula apresentaram os intervalos de: Na (1955 - 2013 μg g-1), Mg (51 - 75 μg g-1), P (443 - 476 μg g-1), S (1038 - 1140 μg g-1), Cl (2388 - 2574 μg g-1), K (1678 - 1753 μg g-1), Ca (202 - 213 μg g-1), Cu (4,1 - 4,5 μg g-1) e Zn (2,0 - 2,2 μg g-1). Estudo comparativo dos resultados entre as técnicas de análise por ativação neutrônica (NAA) e EDXRF indica a igualdade de desempenho das técnicas analíticas na análise de matrizes biológicas. Os resultados contribuem no estabelecimento de intervalos de referência para a população brasileira saudável e para as referidas espécies de animais. / Blood is a suspension of cells contained in a complex liquid called plasma. The term whole blood refers to samples with both solid and liquid parts. Inorganic elements are responsible for essential functions, such as osmotic regulation, cardiac frequency and contractibility, blood clotting and neuromuscular excitability. The determination of inorganic elements in corporeal fluids such as blood, serum, plasma, tissue and urine is used as a monitor for a part or the whole organism. In this work, the X-Ray fluorescence technique (EDXRF) was used for the determination of inorganic elements in whole blood samples from humans and animals (golden hamsters, Mesocricetus auratus and crioula breed horses, Equus caballus). The reference intervals of Na (1788 - 1826 μg g-1), Mg (63 - 75 μg g-1), P (602 - 676 μg g-1), S (1519 - 1718 μg g-1), Cl (2743 - 2867 μg g-1), K (1508 - 1630 μg g-1), Ca (214 - 228 μg g-1), Cu (4 -6 μg g-1) e Zn (1 - 3 μg g-1) were determined for human blood. The reference intervals, for golden hamster blood were found to be: Na (1714 - 1819 μg g-1), Mg (51 - 79 μg g-1), P (970 - 1080 μg g-1), S (1231 - 1739 μg g-1), Cl (2775 - 2865 μg g-1), K (1968 - 2248 μg g-1), Ca (209 - 257 μg g-1), Cu (4 - 6 μg g-1) e Zn (3 -5 μg g-1). The reference intervals, for crioula breed horse blood, showed to be: Na (1955 - 2013 μg g-1), Mg (51 - 75 μg g-1), P (443 - 476 μg g-1), S (1038 - 1140 μg g-1), Cl (2388 - 2574 μg g-1), K (1678 - 1753 μg g-1), Ca (202 - 213 μg g-1), Cu (4,1 - 4,5 μg g-1) e Zn (2,0 - 2,2 μg g-1). Comparative study between NAA and EDXRF, both techniques showed the same performance for the analyses of biological matrices. The results contribute for the establishment of reference intervals for the Brazilian healthy population and the referred animal species.

The first of a series of mass mortalities of Nile crocodiles in the Olifants and Letaba rivers in the Kruger National Park (KNP) was reported in the winter of 2008. The present study investigated the levels and possible effects on eggshell thickness of inorganic elements and organic pollutants in Nile crocodile eggs from these rivers, and comparing them with eggs from a reference crocodile farm and a reference dam inside the KNP. The egg contents were analyzed for chlorinated organic compounds and brominated flame retardants. Eggshells and egg contents were analyzed for inorganic elements. The elemental concentrations in the eggshells and contents were low when compared with previous studies. The highest concentrations were found in the eggs from the reference crocodile farm. The eggs from the reference dam and the crocodile farm had thicker shells, and the eggs from the Olifants and Letaba rivers had thinner shells. Not all eggs in a female develop at the same rate, while eggshell formation presumably occurs at the same time for all eggs. As a result, the elemental profile of egg contents may differ between eggs of the same clutch, but less so for the shells. Weak or no associations were found between the elemental concentrations of the content and eggshells and eggshell thinning. A possible organic pollutant–induced eggshell thinning effect was found. The compounds found were not at levels that could have caused the mortalities, but may affect the sex ratios through endocrine disruption. Further studies are therefore required. / Thesis (M.Sc (Environmental Science))--North-West University, Potchefstroom Campus, 2011.

The first of a series of mass mortalities of Nile crocodiles in the Olifants and Letaba rivers in the Kruger National Park (KNP) was reported in the winter of 2008. The present study investigated the levels and possible effects on eggshell thickness of inorganic elements and organic pollutants in Nile crocodile eggs from these rivers, and comparing them with eggs from a reference crocodile farm and a reference dam inside the KNP. The egg contents were analyzed for chlorinated organic compounds and brominated flame retardants. Eggshells and egg contents were analyzed for inorganic elements. The elemental concentrations in the eggshells and contents were low when compared with previous studies. The highest concentrations were found in the eggs from the reference crocodile farm. The eggs from the reference dam and the crocodile farm had thicker shells, and the eggs from the Olifants and Letaba rivers had thinner shells. Not all eggs in a female develop at the same rate, while eggshell formation presumably occurs at the same time for all eggs. As a result, the elemental profile of egg contents may differ between eggs of the same clutch, but less so for the shells. Weak or no associations were found between the elemental concentrations of the content and eggshells and eggshell thinning. A possible organic pollutant–induced eggshell thinning effect was found. The compounds found were not at levels that could have caused the mortalities, but may affect the sex ratios through endocrine disruption. Further studies are therefore required. / Thesis (M.Sc (Environmental Science))--North-West University, Potchefstroom Campus, 2011.