EXTRAÇÃO ASSISTIDA POR ULTRASSOM PARA DETERMINAÇÃO COLORIMÉTRICA DE FERRO EM SOLO: UMA COMPARAÇÃO COM ESPECTROMETRIA DE MASSA COM PLASMA INDUTIVAMENTE ACOPLADO

A simple procedure for ultrasound-assisted extraction and colorimetric determination of iron in soil samples was developed. The iron concentration in the analyzed samples was determined by the colorimetric method and the results compared with inductively coupled plasma mass spectrometry (ICP-MS). Fifteen soil samples were analyzed and the iron concentration results compared with those obtained by ICP-MS using microwave-assisted sample digestion. The proposed procedure showed good efficiency for iron extraction and the results obtained by colorimetric determination exhibited good agreement with ICP-MS. Moreover, ultrasound-assisted extraction and colorimetric determination is a simple, fast and low-cost procedure for application in routine analysis.

Ion selective electrodes for determination of low and ultra low concentrations of lead (II) in natural waters

Att övervaka förekomsten av giftiga komponenter i naturliga vattendrag är nödvändigt för människans välmående. Eftersom halten av föroreningar i naturens ekosystem bör hållas möjligast låg, pågår en ständig jakt efter kemiska analysmetoder med allt lägre detektionsgränser. I dagens läge görs miljöanalyser med dyr och sofistikerad instrumentering som kräver mycket underhåll. Jonselektiva elektroder har flera goda egenskaper som t.ex. bärbarhet, låg energiförbrukning, och dessutom är de relativt kostnadseffektiva. Att använda jonselektiva elektroder vid miljöanalyser är möjligt om deras känslighetsområde kan utvidgas genom att sänka deras detektionsgränser. För att sänka detektionsgränsen för Pb(II)-selektiva elektroder undersöktes olika typer av jonselektiva membran som baserades på polyakrylat-kopolymerer, PVC och PbS/Ag2S. Fast-fas elektroder med membran av PbS/Ag2S är i allmänhet enklare och mer robusta än konventionella elektroder vid spårämnesanalys av joniska föroreningar. Fast-fas elektrodernas detektionsgräns sänktes i detta arbete med en nyutvecklad galvanostatisk polariseringsmetod och de kunde sedan framgångsrikt användas för kvantitativa bestämningar av bly(II)-halter i miljöprov som hade samlats in i den finska skärgården nära tidigare industriområden. Analysresultaten som erhölls med jonselektiva elektroder bekräftades med andra analytiska metoder. Att sänka detektionsgränsen m.hj.a. den nyutvecklade polariseringsmetoden möjliggör bestämning av låga och ultra-låga blyhalter som inte kunde nås med klassisk potentiometri. Den verkliga fördelen med att använda dessa blyselektiva elektroder är möjligheten att utföra mätningar i obehandlade miljöprov trots närvaron av fasta partiklar vilket inte är möjligt att göra med andra analysmetoder. Jag väntar mig att den nyutvecklade polariseringsmetoden kommer att sätta en trend i spårämnesanalys med jonselektiva elektroder.

Relationship between weight, age and hatching success and the concentration of heavy metals in nestling blue macaw (Anodorhynchus hyacinthinus Latham, 1790) in the Pantanal,Mato Grosso do Sul

Abstract: The concentration of heavy metals (Cr, Fe, Al, As, Cd, Cu, Pb, Mo, Ni, Se and Zn) was evaluated in the blood of nestling blue macaws (Anodorhynchus hyacinthinus) captured in the Pantanal, Mato Grosso do Sul (n=26) in 2012; this was based on the hypothesis that these birds exhibit levels of these heavy metals in their organism and that these interfere in hatching success, weight and age of the chicks. Blood samples were digested with nitric acid and hydrochloric acid and the quantification of metals was performed by ICP-OES (Optical Emission Spectroscopy and Inductively Coupled Plasma). Blood samples of nestlings showed concentrations of Cr (0.10μg/g) Fe (3.06μg/g) Al (3.46μg/g), Cd (0.25μg/g) Cu (0.74μg/g), Mo (0.33μg/g), Ni (0.61μg/g), Se (0.98μg/g), and Zn (2.08μg/g). The levels of heavy metals found were not associated with weight, age and hatching success of the chicks.

Étude de la cinétique et des dommages de gravure par plasma de couches minces de nitrure d’aluminium

Une étape cruciale dans la fabrication des MEMS de haute fréquence est la gravure par plasma de la couche mince d’AlN de structure colonnaire agissant comme matériau piézoélectrique. Réalisé en collaboration étroite avec les chercheurs de Teledyne Dalsa, ce mémoire de maîtrise vise à mieux comprendre les mécanismes physico-chimiques gouvernant la cinétique ainsi que la formation de dommages lors de la gravure de l’AlN dans des plasmas Ar/Cl2/BCl3. Dans un premier temps, nous avons effectué une étude de l’influence des conditions opératoires d’un plasma à couplage inductif sur la densité des principales espèces actives de la gravure, à savoir, les ions positifs et les atomes de Cl. Ces mesures ont ensuite été corrélées aux caractéristiques de gravure, en particulier la vitesse de gravure, la rugosité de surface et les propriétés chimiques de la couche mince. Dans les plasmas Ar/Cl2, nos travaux ont notamment mis en évidence l’effet inhibiteur de l’AlO, un composé formé au cours de la croissance de l’AlN par pulvérisation magnétron réactive et non issu des interactions plasmas-parois ou encore de l’incorporation d’humidité dans la structure colonnaire de l’AlN. En présence de faibles traces de BCl3 dans le plasma Ar/Cl2, nous avons observé une amélioration significative du rendement de gravure de l’AlN dû à la formation de composés volatils BOCl. Par ailleurs, selon nos travaux, il y aurait deux niveaux de rugosité post-gravure : une plus faible rugosité produite par la présence d’AlO dans les plasmas Ar/Cl2 et indépendante de la vitesse de gravure ainsi qu’une plus importante rugosité due à la désorption préférentielle de l’Al dans les plasmas Ar/Cl2/BCl3 et augmentant linéairement avec la vitesse de gravure.

Elemental analysis of New Zealand Nephrite Jade (pounamu) for forensic purposes

Pounamu (NZ jade), or nephrite, is a protected mineral in its natural form following the transfer of ownership back to Ngai Tahu under the Ngai Tahu (Pounamu Vesting) Act 1997. Any theft of nephrite is prosecutable under the Crimes Act 1961. Scientific evidence is essential in cases where origin is disputed. A robust method for discrimination of this material through the use of elemental analysis and compositional data analysis is required. Initial studies have characterised the variability within a given nephrite source. This has included investigation of both in situ outcrops and alluvial material. Methods for the discrimination of two geographically close nephrite sources are being developed. Key Words: forensic, jade, nephrite, laser ablation, inductively coupled plasma mass spectrometry, multivariate analysis, elemental analysis, compositional data analysis

Distribution of calcium (Ca) and magnesium (Mg) in the leaves of Brassica rapa under varying exogenous Ca and Mg supply

Background and Aims Leafy vegetable Brassica crops are an important source of dietary calcium (Ca) and magnesium (Mg) and represent potential targets for increasing leaf Ca and Mg concentrations through agronomy or breeding. Although the internal distribution of Ca and Mg within leaves affects the accumulation of these elements, such data are not available for Brassica. The aim of this study was to characterize the internal distribution of Ca and Mg in the leaves of a vegetable Brassica and to determine the effects of altered exogenous Ca and Mg supply on this distribution. Methods Brassica rapa ssp. trilocularis ‘R-o-18’ was grown at four different Ca:Mg treatments for 21 d in a controlled environment. Concentrations of Ca and Mg were determined in fully expanded leaves using inductively coupled plasma-mass spectrometry (ICP-MS). Internal distributions of Ca and Mg were determined in transverse leaf sections at the base and apex of leaves using energy-dispersive X-ray spectroscopy (EDS) with cryo-scanning electron microscopy (cryo-SEM). Key Results Leaf Ca and Mg concentrations were greatest in palisade and spongy mesophyll cells, respectively, although this was dependent on exogenous supply. Calcium accumulation in palisade mesophyll cells was enhanced slightly under high Mg supply; in contrast, Mg accumulation in spongy mesophyll cells was not affected by Ca supply. Conclusions The results are consistent with Arabidopsis thaliana and other Brassicaceae, providing phenotypic evidence that conserved mechanisms regulate leaf Ca and Mg distribution at a cellular scale. The future study of Arabidopsis gene orthologues in mutants of this reference B. rapa genotype will improve our understanding of Ca and Mg homeostasis in plants and may provide a model-to-crop translation pathway for targeted breeding.

Use of Metals and Anion Species with Chemometrics Tools for Classification of Unprocessed and Processed Coconut Waters

Coconut water is a natural isotonic, nutritive, and low-caloric drink. Preservation process is necessary to increase its shelf life outside the fruit and to improve commercialization. However, the influence of the conservation processes, antioxidant addition, maturation time, and soil where coconut is cultivated on the chemical composition of coconut water has had few arguments and studies. For these reasons, an evaluation of coconut waters (unprocessed and processed) was carried out using Ca, Cu, Fe, K, Mg, Mn, Na, Zn, chloride, sulfate, phosphate, malate, and ascorbate concentrations and chemometric tools. The quantitative determinations were performed by electrothermal atomic absorption spectrometry, inductively coupled plasma optical emission spectrometry, and capillary electrophoresis. The results showed that Ca, K, and Zn concentrations did not present significant alterations between the samples. The ranges of Cu, Fe, Mg, Mn, PO (4) (3-) , and SO (4) (2-) concentrations were as follows: Cu (3.1-120 A mu g L(-1)), Fe (60-330 A mu g L(-1)), Mg (48-123 mg L(-1)), Mn (0.4-4.0 mg L(-1)), PO (4) (3-) (55-212 mg L(-1)), and SO (4) (2-) (19-136 mg L(-1)). The principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied to differentiate unprocessed and processed samples. Multivariated analysis (PCA and HCA) were compared through one-way analysis of variance with Tukey-Kramer multiple comparisons test, and p values less than 0.05 were considered to be significant.

Hydrochemical evaluation of different spring waters for bottling

This investigation was carried out within the Parana sedimentary basin in São Paulo and Mato Grosso do Sul States, Brazil, and involved the sampling of different spring water samples with the purpose of evaluating their quality for bottling Several methods were utilized for acquiring the hydrochemical data, such as methyl orange end-point titration, potentiometry, ion selective electrodes, spectrophotometry, atomic absorption spectrophotometry and inductively coupled plasma spectrometry The results obtained for the analyzed samples were compared with the guideline values established by the São Paulo State and Brazilian Health Ministry legislations for defining the potable water standards The Brazilian Code for Mineral Waters that was established by Register 7841 published on 8 August 1945 was also taken into account for verifying if the spring waters are mineralized The hydrochemical data allowed the identification of anthropogenic and geogenic inputs of some constituents in most of the samples, which affected the water quality and did not allow them to be utilized for commercial purposes (bottling) The waters of these springs can only become appropriate for human consumption after previous chemical treatment

Potencialidades analíticas do dietilditiofosfato de amônio em espectrometria de massas com plasma indutivamente acoplado empregando extração em fase sólida e sistemas de injeção em fluxo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Decomposição de argilas em forno de microondas e determinação simultânea dos seus constituintes principais por espectrometria de emissão óptica em plasma indutivamente acoplado

ANALYSIS OF CLAYS BY INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROMETRY AFTER CLOSED-VESSEL MICROWAVE-ASSISTED ACID DECOMPOSITION. In this work a closed-vessel microwave-assisted acid decomposition procedure for clays was developed. Aluminum, Ca, Fe, K, Mg, Na, Si, and Ti were determined in clay digestates by inductively coupled plasma optical emission spectrometry. The most critical parameter for total decomposition of clays was the composition of the reagent mixture. The applied power and the heating time exerted a less critical influence. Best decomposition conditions were attained using a reagent mixture containing 4 mL aqua regia plus 3 mL HF and the heating program was implemented in 12 min. The accuracy of the results was demonstrated using two standard reference materials and a paired t-test showed a good agreement between determined and certified values at a 95% confidence level.

A Simple Method Based on ICP-MS for Estimation of Background Levels of Arsenic, Cadmium, Copper, Manganese, Nickel, Lead, and Selenium in Blood of the Brazilian Population

Throughout the world, biomonitoring has become the standard for assessing exposure of individuals to toxic elements as well as for responding to serious environmental public health problems. However, extensive biomonitoring surveys require rapid and simple analytical methods. Thus, a simple and high-throughput method is proposed for the determination of arsenic (As), cadmium (Cd), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb), and selenium (Se) in blood samples by using inductively coupled plasma-mass spectrometry (ICP-MS). Prior to analysis, 200 l of blood samples was mixed with 500 l of 10% v/v tetramethylammonium hydroxide (TMAH) solution, incubated for 10 min, and subsequently diluted to 10 ml with a solution containing 0.05% w/v ethylenediamine tetraacetic acid (EDTA) + 0.005% v/v Triton X-100. After that, samples were directly analyzed by ICP-MS (ELAN DRC II). Rhodium was selected as an internal standard with matrix-matching calibration. Method detection limits were 0.08, 0.04, 0.5, 0.09, 0.12, 0.04, and 0.1 g//L for As, Cd, Cu, Mn, Ni, Pb, and Se, respectively. Validation data are provided based on the analysis of blood samples from the trace elements inter-\comparison program operated by the Institut National de Sante Publique du Quebec, Canada. Additional validation was provided by the analysis of human blood samples by the proposed method and by using electrothermal atomic absorption spectrometry (ETAAS). The method was subsequently applied for the estimation of background metal blood values in the Brazilian population. In general, the mean concentrations of As, Cd, Cu, Mn, Ni, Pb, and Se in blood were 1.1, 0.4, 890, 9.6, 2.1, 65.4, and 89.3 g/L, respectively, and are in agreement with other global populations. Influences of age, gender, smoking habits, alcohol consumption, and geographical variation on the values were also considered. Smoking habits influenced the levels of Cd in blood. The levels of Cu, Mn, and Pb were significantly correlated with gender, whereas Cu and Pb were significantly correlated with age. There were also interesting differences in Mn and Se levels in the population living in the north of Brazil compared to the south.

Hydrochemical evaluation of bottled mineral waters and spring at Corumbataí city, São Paulo State, Brazil

This investigation was carried out within São Paulo State, Brazil, and involved the sampling of well-known mineral bottled waters for performing a comparative hydrochemical study and of a spring occurring at Corumbataí city, in order to evaluate its suitability for bottling. Several methods were utilized for acquiring the hydrochemical data like the methyl orange end-point titration, potentiometry, ion selective electrode, colorimetry, flame photometry and inductively-coupled plasma spectrometry. The results obtained for the analyzed samples were compared with the guideline values established by the National Commission of Rules and Standards for Food of the Brazilian Health Ministry published in 1976. The Brazilian Code for Mineral Waters that was established by Register 7841 published on 8 August 1945 was also taken into account for verifying if the spring waters are mineralized. The hydrochemical data allowed identify some constituents impoverishing the water quality, thus, implying on its nonutilization for commercial purposes (bottling). In one specific case, the spring water only can become appropriate for human consumption after previous chemical treatment. © 201 WIT Press.

Classification of honeys from Pará State (Amazon region, Brazil) produced by three different species of bees

Vinte e sete amostras de mel, produzidas em dez cidades do Estado do Pará (Região Amazônica, norte do Brasil) por três espécies diferentes de abelhas (Apis mellifera, Melipona fasciculata e Melipona flavoneata), foram analisadas em seus teores de elementos minerais (Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Sr e Zn) e alguns parâmetros fisicoquímicos (cor, umidade, densidade, pH, sólidos insolúveis e solúveis totais, cinzas, condutividade elétrica, índice de formol, acidez livre, hidroximetilfurfural, açúcares redutores e totais e sacarose). Os teores minerais foram determinados via espectrometria de emissão atômica por plasma acoplado indutivamente (ICP OES) e as análises dos parâmetros físico-químicos seguiram metodologias oficiais. Os resultados das análises físico-químicas apresentaram-se de acordo com a legislação nacional e internacional, bem como com outros trabalhos similares ao redor do mundo. A análise estatística multivariada (análise por agrupamento hierárquico (HCA) e por componentes principais (PCA)) foi aplicada aos resultados dos teores metálicos e aos parâmetros físico-químicos, sendo possível a separação das amostras de mel conforme a espécie produtora.

Determinação de 'SB' e 'PB' em embalagens de poli(tereftalato) de etileno (PET) por espectrometria de absorção atômica com fonte contínua e de alta resolução em forno de grafite empregando amostragem direta de sólidos

Pós-graduação em Química - IQ

Chemical Modification of Palm Fibres Surface with Zirconium Oxychloride

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)