Continuous Flow Analysis Method for Determination of Dissolved Reactive Phosphorus in Ice Cores

Phosphorus (P) is an essential macronutrient for all living organisms. Phosphorus is often present in nature as the soluble phosphate ion PO43– and has biological, terrestrial, and marine emission sources. Thus PO43– detected in ice cores has the potential to be an important tracer for biological activity in the past. In this study a continuous and highly sensitive absorption method for detection of dissolved reactive phosphorus (DRP) in ice cores has been developed using a molybdate reagent and a 2-m liquid waveguide capillary cell (LWCC). DRP is the soluble form of the nutrient phosphorus, which reacts with molybdate. The method was optimized to meet the low concentrations of DRP in Greenland ice, with a depth resolution of approximately 2 cm and an analytical uncertainty of 1.1 nM (0.1 ppb) PO43–. The method has been applied to segments of a shallow firn core from Northeast Greenland, indicating a mean concentration level of 2.74 nM (0.26 ppb) PO43– for the period 1930–2005 with a standard deviation of 1.37 nM (0.13 ppb) PO43– and values reaching as high as 10.52 nM (1 ppb) PO43–. Similar levels were detected for the period 1771–1823. Based on impurity abundances, dust and biogenic particles were found to be the most likely sources of DRP deposited in Northeast Greenland.

Components of Surface Charge in Tropical Soils With Contrasting Mineralogies

Study of surface electric charges of soil colloids helps in understanding the physicochemical phenomena that influence the capacity of retaining nutrients and their availability to plants. The structural charge (sigma(0), (min)), the variable charge (sigma(q, min)), and the organic matter (OM) charge (sigma(total) (OM)) of 12 tropical soils with contrasting mineralogies were evaluated based on the difference of selectivity for Cs(+) and Li(+) between the functional ionizable surfaces groups and the mineral 2:1 siloxane surface. Soils were divided into three groups: G1, soils with a predominance of kaolinite and gibbsite in the clay fraction; G2, soils with hydroxy-interlayered 2:1 minerals; and G3, soils with smectite but without hydroxy-interlayered 2:1 minerals. The Cs absorption method was efficient for detecting the charge components in tropical soils. The mineral structural charge contributed 11% and 16%, 28% and 31%, and 52% and 59% of total soil charge of A and B horizons of soils from groups G 1, G2, and G3, respectively. On the other hand, OM contributed 53% and 37%, 48% and 41%, and 21% and 20% of total charge for the same samples, respectively, In highly weathered soils of group G I and, to a lesser extent, in soils in group G2, surface charges depended mainly on their variable components, resulting from the OM (sigma(toal) (OM)), as well as from imperfections found in 1:1 minerals (sigma(q, min)). The importance of OM in determining the magnitude of electric charges in humid tropical soils is highlighted.

Carbon dioxide efflux in a rhodic hapludox as affected by tillage systems in southern Brazil

Agricultural soils can act as a source or sink of atmospheric C, according to the soil management. This long-term experiment (22 years) was evaluated during 30 days in autumn, to quantify the effect of tillage systems (conventional tillage-CT and no-till-NT) on the soil CO2-C flux in a Rhodic Hapludox in Rio Grande do Sul State, Southern Brazil. A closed-dynamic system (Flux Chamber 6400-09, Licor) and a static system (alkali absorption) were used to measure soil CO2-C flux immediately after soybean harvest. Soil temperature and soil moisture were measured simultaneously with CO2-C flux, by Licor-6400 soil temperature probe and manual TDR, respectively. During the entire month, a CO2-C emission of less than 30 % of the C input through soybean crop residues was estimated. In the mean of a 30 day period, the CO2-C flux in NT soil was similar to CT, independent of the chamber type used for measurements. Differences in tillage systems with dynamic chamber were verified only in short term (daily evaluation), where NT had higher CO2-C flux than CT at the beginning of the evaluation period and lower flux at the end. The dynamic chamber was more efficient than the static chamber in capturing variations in CO2-C flux as a function of abiotic factors. In this chamber, the soil temperature and the water-filled pore space (WFPS), in the NT soil, explained 83 and 62 % of CO2-C flux, respectively. The Q10 factor, which evaluates CO2-C flux dependence on soil temperature, was estimated as 3.93, suggesting a high sensitivity of the biological activity to changes in soil temperature during fall season. The CO2-C flux measured in a closed dynamic chamber was correlated with the static alkali adsorption chamber only in the NT system, although the values were underestimated in comparison to the other, particularly in the case of high flux values. At low soil temperature and WFPS conditions, soil tillage caused a limited increase in soil CO2-C flux.

Carbon dioxide efflux in a rhodic hapludox as affected by tillage systems in southern Brazil

Os solos agrícolas podem atuar como dreno ou fonte de C atmosférico, dependendo do sistema de manejo adotado. Este estudo foi desenvolvido em experimento de longa duração (22 anos), durante o período de 30 dias do outono, com o objetivo de avaliar o impacto de sistemas de preparo de solo (preparo convencional-PC e plantio direto-PD) nas emissões de C-CO2 de um Latossolo Vermelho distrófico, em Cruz Alta, RS. As emissões de C-CO2 do solo foram avaliadas com câmaras dinâmica (Flux Chamber 6400-09, Licor) e estática (com captação em solução alcalina), imediatamente após a colheita da soja. A temperatura e a umidade do solo foram registradas, concomitantemente com as emissões de C-CO2, por meio de sensor de temperatura e TDR manual, respectivamente, integrantes do Licor-6400. Estimou-se que, em 30 dias, uma quantidade equivalente a menos de 30 % do C aportado pelos resíduos de soja foi emitida na forma de C-CO2. As emissões de C-CO2 no solo em PD foram similares às emissões do solo em PC, independentemente do tipo de câmara utilizada. Diferenças entre sistemas de preparo quanto à emissão de C-CO2, avaliadas com a câmara dinâmica, foram verificadas somente a curto prazo (leituras diárias), com o PD apresentando maiores emissões do que o PC no início do período experimental e menores no final. A câmara dinâmica foi mais eficiente do que a estática em captar as alterações das emissões de C-CO2 em função da variação da temperatura e a porosidade preenchida por água (PPA) no solo em PD, as quais explicaram 83 e 62 % das emissões de C-CO2, respectivamente. O fator Q10, que avalia a sensibilidade da emissão de C-CO2 à temperatura do solo, foi estimado em 3,93, indicando alta sensibilidade da atividade microbiana à temperatura do solo durante o outono. As emissões de C-CO2 registradas no solo em PD com a câmara estática foram correlacionadas às da câmara dinâmica, porém com valores subestimados em relação àquela notadamente nos maiores valores de fluxo. em condições de baixa temperatura e PPA, o preparo de solo induziu limitado incremento de emissão de C-CO2.

Distúrbios nutricionais e câncer de mama: deficiência de zinco

Pós-graduação em Ginecologia, Obstetrícia e Mastologia - FMB

Studio del metodo dell'assorbimento diretto della CO2 per l'analisi del radiocarbonio

L’attuale rilevanza rappresentata dalla stretta relazione tra cambiamenti climatici e influenza antropogenica ha da tempo posto l’attenzione sull’effetto serra e sul surriscaldamento planetario così come sull’aumento delle concentrazioni atmosferiche dei gas climaticamente attivi, in primo luogo la CO2. Il radiocarbonio è attualmente il tracciante ambientale per eccellenza in grado di fornire mediante un approccio “top-down” un valido strumento di controllo per discriminare e quantificare il diossido di carbonio presente in atmosfera di provenienza fossile o biogenica. Ecco allora che ai settori applicativi tradizionali del 14C, quali le datazioni archeometriche, si affiancano nuovi ambiti legati da un lato al settore energetico per quanto riguarda le problematiche associate alle emissioni di impianti, ai combustibili, allo stoccaggio geologico della CO2, dall’altro al mercato in forte crescita dei cosiddetti prodotti biobased costituiti da materie prime rinnovabili. Nell’ambito del presente lavoro di tesi è stato quindi esplorato il mondo del radiocarbonio sia dal punto di vista strettamente tecnico e metodologico che dal punto di vista applicativo relativamente ai molteplici e diversificati campi d’indagine. E’ stato realizzato e validato un impianto di analisi basato sul metodo radiometrico mediante assorbimento diretto della CO2 ed analisi in scintillazione liquida apportando miglioramenti tecnologici ed accorgimenti procedurali volti a migliorare le performance del metodo in termini di semplicità, sensibilità e riproducibilità. Il metodo, pur rappresentando generalmente un buon compromesso rispetto alle metodologie tradizionalmente usate per l’analisi del 14C, risulta allo stato attuale ancora inadeguato a quei settori applicativi laddove è richiesta una precisione molto puntuale, ma competitivo per l’analisi di campioni moderni ad elevata concentrazione di 14C. La sperimentazione condotta su alcuni liquidi ionici, seppur preliminare e non conclusiva, apre infine nuove linee di ricerca sulla possibilità di utilizzare questa nuova classe di composti come mezzi per la cattura della CO2 e l’analisi del 14C in LSC.

First continuous phosphate record from Greenland ice cores

A continuous and highly sensitive absorption method for detection of soluble phosphate in ice cores has been developed using a molybdate reagent and a 2m liquid waveg- uide (LWCC). The method is optimized to meet the low concentrations of phosphate in Greenland ice, it has a detection limit of around 0.1ppb and a depth resolution of approximately 2cm. The new method has been applied to obtain phosphate concen- trations from segments of two Northern Greenland ice cores: from a shallow firn core covering the most recent 120yr and from the recently obtained deep NEEM ice core in which sections from the late glacial period have been analysed. Phosphate con- centrations in 20th century ice are around 0.32ppb with no indication of anthropogenic influence in the most recent ice. In the glacial part of the NEEM ice core concentra- tions in the cold stadial periods are significantly higher, in the range of 6–24ppb, while interstadial ice concentrations are around 2ppb. In the shallow firn core, a strong cor- relation between concentrations of phosphate and insoluble dust suggests a similar deposition pattern for phosphate and dust. In the glacial ice, phosphate and dust also correlate quite strongly, however it is most likely that this correlation originates from the phosphate binding to dust during transport, with only a fraction coming directly from dust. Additionally a constant ratio between phosphate and potassium concentrations shows evidence of a possible biogenic land source.

Concentrations of heavy and precious metals in animals from hydrothermal vents of the Axial Seamount (Juan de Fuca Ridge) and Guaymas Basin (Gulf of California)

A series of samples of inhabitants of hydrothermal vents were collected during the 12-th cruise of R/V Akademik Mstislav Keldysh in Guaymas Basin (the Gulf of California) and the Axial Seamount area (Juan de Fuca Ridge). Concentrations of trace and heavy metals in the tissues of Ridgeia piscesae, Riftia pachyptila, and Paralvinella palmiformis were analyzed. Neutron-activation analysis revealed significantly higher concentrations of uranium in tissues of Paralvinella palmiformis as compared to ambient seawater. Possible reasons for such phenomenon are discussed. The data obtained by neutron-activation method are compared with those obtained by atomic-absorption method for the same tissues analyzed.

Aplicación de la celulosa bacteriana a la restauración del patrimonio bibliográfico y documental en papel

La preservación del patrimonio bibliográfico y documental en papel es uno de los mayores retos a los que se enfrentan bibliotecas y archivos de todo el mundo. La búsqueda de soluciones al problema del papel degradado ha sido abordada históricamente desde dos líneas de trabajo predominantes: la conservación de estos documentos mediante la neutralización de los ácidos presentes en ellos con agentes alcalinos, y su restauración mediante el método de laminación fundamentalmente con papel de origen vegetal. Sin embargo, no se ha explorado con éxito la posibilidad de reforzar la celulosa dañada, y el problema sigue sin encontrar una solución satisfactoria. Hasta el día de hoy, el desarrollo de tratamientos basados en biotecnología en la conservación del patrimonio documental ha sido muy escaso, aunque la capacidad de ciertas bacterias de producir celulosa lleva a plantear su uso en el campo de la conservación y restauración del papel. La celulosa bacteriana (CB) es químicamente idéntica a la celulosa vegetal, pero su organización macroscópica es diferente. Sus propiedades únicas (alto grado de cristalinidad, durabilidad, resistencia y biocompatibilidad) han hecho de este material un excelente recurso en diferentes campos. En el desarrollo de esta tesis se ha estudiado el uso de la celulosa bacteriana, de alta calidad, generada por Gluconacetobacter sucrofermentans CECT 7291, para restaurar documentos deteriorados y consolidar los que puedan estar en peligro de degradación, evitando así su destrucción y proporcionando al papel que se restaura unas buenas propiedades mecánicas, ópticas y estructurales. Se desarrollan asimismo protocolos de trabajo que permitan la aplicación de dicha celulosa. En primer lugar se seleccionó el medio de cultivo que proporcionó una celulosa adecuada para su uso en restauración. Para ello se evaluó el efecto que tienen sobre la celulosa generada las fuentes de carbono y nitrógeno del medio de cultivo, manteniendo como parámetros fijos la temperatura y el pH inicial del medio, y efectuando los ensayos en condiciones estáticas. Se evaluó, también, el efecto que tiene en la CB la adición de un 1% de etanol al medio de cultivo. Las capas de celulosa se recolectaron a cuatro tiempos distintos, caracterizando en cada uno de ellos el medio de cultivo (pH y consumo de fuente de carbono), y las capas de CB (pH, peso seco y propiedades ópticas y mecánicas). La mejor combinación de fuentes de carbono y nitrógeno resultó ser fructosa más extracto de levadura y extracto de maíz, con o sin etanol, que proporcionaban una buena relación entre la producción de celulosa y el consumo de fuente de carbono, y que generaban una capa de celulosa resistente y homogénea. La adición de etanol al medio de cultivo, si bien aumentaba la productividad, causaba un descenso apreciable de pH. Las capas de CB obtenidas con los medios de cultivo optimizados se caracterizaron en términos de sus índices de desgarro y estallido, propiedades ópticas, microscopía electrónica de barrido (SEM), difracción de rayos-X, espectroscopía infrarroja con transformada de Fourier (FTIR), grado de polimerización, ángulos de contacto estáticos y dinámicos, y porosimetría de intrusión de mercurio. Por otro lado hay que tener en cuenta que el material restaurado debe ser estable con el tiempo. Por ello esta misma caracterización se efectuó tras someter a las capas de CB a un proceso de envejecimiento acelerado. Los resultados mostraron que la CB resultante tiene un elevado índice de cristalinidad, baja porosidad interna, buenas propiedades mecánicas, y alta estabilidad en el tiempo. Para desarrollar los protocolos de trabajo que permitan la restauración con esta celulosa optimizada, se comienzó con un proceso de selección de los papeles que van a ser restaurados. Se eligieron tres tipos de papeles modelo, hechos con pasta mecánica, química y filtro (antes y después de ser sometidos a un proceso de envejecimiento acelerado), y tres libros viejos adquiridos en el mercado de segunda mano. Estos ejemplares a restaurar se caracterizaron también en términos de sus propiedades mecánicas y fisicoquímicas. El primer protocolo de restauración con CB que se evaluó fue el denominado laminación. Consiste en aplicar un material de refuerzo al documento mediante el uso de un adhesivo. Se seleccionó para ello la CB producida en el medio de cultivo optimizado con un 1% de etanol. Se aplicó un método de purificación alcalino (1 hora a 90 °C en NaOH al 1%) y como adhesivo se seleccionó almidón de trigo. El proceso de laminación se efectuó también con papel japonés (PJ), un material habitualmente utilizado en conservación, para comparar ambos materiales. Se concluyó que no hay diferencias significativas en las características estudiadas entre los dos tipos de materiales de refuerzo. Se caracterizó el material reforzado y, también, después de sufrir un proceso de envejecimiento acelerado. Los papeles laminados con CB mostraban diferencias más marcadas en las propiedades ópticas que los restaurados con PJ, con respecto a los originales. Sin embargo, el texto era más legible cuando el material de restauración era la CB. La mojabilidad disminuía con ambos tipos de refuerzo, aunque en los papeles laminados con CB de manera más marcada e independiente del material a restaurar. Esto se debe a la estructura cerrada de la CB, que también conduce a una disminución en la permeabilidad al aire. Este estudio sugiere que la CB mejora la calidad del papel deteriorado, sin alterar la información que contiene, y que esta mejora se mantiene a lo largo del tiempo. Por tanto, la CB puede ser utilizada como material de refuerzo para laminar, pudiendo ser más adecuada que el PJ para ciertos tipos de papeles. El otro método de restauración que se estudió fue la generación in situ de la CB sobre el papel a restaurar. Para ello se seleccionó el medio de cultivo sin etanol, ya que el descenso de pH que causaba su presencia podría dañar el documento a restaurar. El método de purificación elegido fue un tratamiento térmico (24 horas a 65 °C), menos agresivo para el material a restaurar que el tratamiento alcalino. Se seleccionó la aplicación del medio de cultivo con la bacteria mediante pincel sobre el material a restaurar. Una vez caracterizado el material restaurado, y éste mismo tras sufrir un proceso de envejecimiento acelerado, se concluyó que no hay modificación apreciable en ninguna característica, salvo en la permeabilidad al aire, que disminuye de manera muy evidente con la generación de CB, dando lugar a un material prácticamente impermeable al aire. En general se puede concluir que ha quedado demostrada la capacidad que tiene la celulosa generada por la bacteria Gluconacetobacter sucrofermentans CECT 7291 para ser utilizada como material de refuerzo en la restauración del patrimonio documental en papel. Asimismo se han desarrollado dos métodos de aplicación, uno ex situ y otro in situ, para efectuar esta tarea de restauración. ABSTRACT The preservation of bibliographic and documentary heritage is one of the biggest challenges that libraries and archives around the world have to face. The search for solutions to the problem of degraded paper has historically been focused from two predominants lines of work: the conservation of these documents by the neutralization of acids in them with alkaline agents, and their restoration by lining them with, basically, cellulose from vegetal sources. However, the possibility of strengthening the damaged cellulose has not been successfully explored, and the problem still persists. Until today, the development of biotechnology-based treatments in documentary heritage conservation has been scarce, although the ability of certain bacteria to produce cellulose takes to propose its use in the field of conservation and restoration of paper. The bacterial cellulose (BC) is chemically identical to the plant cellulose, but its macroscopic organization is different. Its unique properties (high degree of crystallinity, durability, strength and biocompatibility), makes it an excellent resource in different fields. The use of high-quality BC generated by Gluconacetobacter sucrofermentans CECT 7291 to restore damaged documents and to consolidate those that may be at risk of degradation, has been studied in this thesis, trying to prevent the document destruction, and to get reinforced papers with good mechanical, optical and structural properties. Protocols that allow the implementation of the BC as a reinforcing material were also developed. First of all, in order to select the culture medium that provides a cellulose suitable for its use in restoration, it has been evaluated the effect that the carbon and nitrogen sources from the culture medium have on the generated BC, keeping the temperature and the initial pH of the medium as fixed parameters, and performing the culture without shaking. The effect of the addition of 1% ethanol to the culture medium on BC properties was also evaluated. The cellulose layers were collected at four different times, characterizing in all of them the culture medium (pH and carbon source consumption), and the BC sheets (pH, dry weight and optical and mechanical properties). The best combination of carbon and nitrogen sources proved to be fructose plus yeast extract and corn steep liquor, with or without ethanol, which provided a good balance between the cellulose production and the consumption of carbon source, and generating BC sheets homogeneous and resistant. The addition of ethanol to the culture medium increased productivity but caused a noticeable decrement in pH. The BC layers generated with these optimized culture media, have been characterized in terms of tear and burst index, optical properties, scanning electron microscopy (SEM), X-ray diffraction, infrared Fourier transform spectroscopy (FTIR), polymerization degree, static and dynamic contact angles, and mercury intrusion porosimetry. Moreover it must be kept in mind that the restored materials should be stable over time. Therefore, the same characterization was performed after subjecting the layers of BC to an accelerated aging process. The results showed that the BC sheets obtained have a high crystallinity index, low internal porosity, good mechanical properties, and high stability over time. To develop working protocols to use this optimized BC in paper restoration, the first step was to select the samples to restore. Three types of model papers, made from mechanical pulp, chemical pulp and filter paper (before and after an accelerated aging process), and three old books purchased in the second hand market, were chosen. These specimens to be restored were also characterized in terms of its mechanical and physicochemical properties. The first protocol of restoration with BC to be evaluated is called linning. It consists on applying a reinforcing material to the document using an adhesive. The BC produced in the optimized culture medium with 1% ethanol was selected. An alkali purification method (1 hour at 90 °C in 1% NaOH) was applied, and wheat starch was selected as adhesive. The linning process was also carried out with Japanese paper (JP), a material commonly used in conservation, in order to compare both materials. It was concluded that there are no significant differences in the characteristics studied of the two types of reinforcing materials. The reinforced materials were characterized before and after undergoing to an accelerated aging. Papers lined with BC showed more marked differences in the optical properties that papers restored with JP. However, the text was more readable when BC was the reinforcing material. Wettability decreased with both types of reinforcement, although in the papers linned with BC it happened more marked and independently of the sample to restore. This is due to the closed structure of BC, which also leads to a decrement in air permeance. This study suggests that BC improves the deteriorated paper quality, without altering the information on it, and that this improvement is maintained over time. Therefore, the BC may be used as reinforcing material for linning, being more suitable than the JP to restore certain types of papers. The other restoration method to be evaluated was the in situ generation of BC over the paper to restore. For this purpose the culture medium without ethanol was selected, as the pH decrement caused by his presence would damage the document to restore. As purification method a heat treatment (24 hours at 65 °C) was chosen, less aggressive to the material to restore than the alkaline treatment. It was decided to apply the culture medium with the bacteria onto the material to restore with a brush. The reinforced material was characterized before and after an accelerated aging process. It was concluded that there was no substantial change in any characteristic, except for air permeance, which decreases very sharply after the generation of BC, getting a substantially air impermeable material. In general, it can be concluded that the ability of BC produced by Gluconacetobacter sucrofermentans CECT 7291 for its use as a reinforcing material in the restoration of paper documentary heritage, has been demonstrated. Also, two restoration methods, one ex situ and another in situ have been developed.

A study of some constituents in human female saliva

Changes in the concentration of some constituents in women's saliva during the menstrual cycle were studied. Saliva was used because it is easier to collect than other body fluids and is continuously available for analysis. Glucose, the enzyme 17-Acetyl-D-glucosaminidase (NAG) and Calcium which are saliva constituents and belong to three different chemical groups were selected for the study. Several analytical techniques were investigated. The fluorometric assay procedure was found to be the best because of its specificity and sensitivity for the estimation of these constituents. resides the fluorametric method a spectrophotometric method was used in the NAG determination and an atomic absorption method in the calcium estimation. Glucose was estimated by an enzymatic method. This is based on the reaction of glucose with the enzymes glucose oxidase and peroxidase to yield hydrogen peroxide, which in turn oxidises a non-fluorescent substrate, p-hydroxyphenylacetic acid, to a highly fluorescent product. The saliva samples in this determination had to be centrifuged at high speed, heated in a boiling water bath, centrifuged again and then treated with a mixture of cation and anion resins to remove the substances that inhibited the enzyme system. In the determination of the NAG activity the saliva samples were diluted with citric acid/phosphate buffer, and then centrifuged at high speed. The assay was based on the enzymic hydrolysis of the non-fluorescent substrate 4-Methyl-umbelli1eryl-p-D-glucosaminide to the highly fluorescent 4-Methyl-umbelliferone• Calcium was estimated by a fluorometric procedure based upon the measurement of the fluorescence produced by the complex formed between calcein blue and calcium, at pH 9 - 13. From the results obtained from the analysis of saliva samples of several women it was found that glucose showed a significant increase in its level around the expected time of ovulation. This was found in seven cycles out of ten. Similar results were found with the enzyme NAG. No significant change in the calcium levels was observe& at any particular time of the cycle. The levels of the glucose, the activity of the enzyme NAG and the concentration of the calcium were found to change daily, and to differ from one subject to another and in the same subject from cycle to cycle. The increase observed it salivary glucose levels and the enzyme NAG activity could be monitored to predict the time of ovulation.

Aplicação da tecnologia eletroquímica para a remoção e monitoramento de metais pesados em efluentes aquosos

Heavy metals are present in industrial waste. These metals can generate a large environmental impact contaminating water, soil and plants. The chemical action of heavy metals has attracted environmental interest. In this context, this study aimed to test t he performance of electrochemical technologies for removing and quantifying heavy metals. First ly , the electroanalytical technique of stripping voltammetry with glassy carbon electrode (GC) was standardized in order to use this method for the quantificatio n of metals during their removal by electrocoagulation process (EC). A nalytical curves were evaluated to obtain reliability of the determin ation and quantification of Cd 2+ and Pb 2+ separately or in a mixture. Meanwhile , EC process was developed using an el ectrochemical cell in a continuous flow (EFC) for removing Pb 2+ and Cd 2+ . The se experiments were performed using Al parallel plates with 10 cm of diameter (  63.5 cm 2 ) . The optimization of conditions for removing Pb 2+ and Cd 2+ , dissolved in 2 L of solution at 151 L h - 1 , were studied by applying different values of current for 30 min. Cd 2+ and Pb 2+ concentrations were monitored during electrolysis using stripping voltammetry. The results showed that the removal of Pb 2 + was effective when the EC pro cess is used, obtaining removals of 98% in 30 min. This behavior is dependent on the applied current, which implies an increase in power consumption. From the results also verified that the stripping voltammetry technique is quite reliable deter mining Pb 2+ concentration , when compared with the measurements obtained by atomic absorption method (AA). In view of this, t he second objective of this study was to evaluate the removal of Cd 2+ and Pb 2+ (mixture solution) by EC . Removal efficiency increasing current was confirmed when 93% and 100% of Cd 2+ and Pb 2+ was removed after 30 min . The increase in the current promotes the oxidation of sacrificial electrodes, and consequently increased amount of coagulant, which influences the removal of heavy metals in solution. Adsortive voltammetry is a fast, reliable, economical and simple way to determine Cd 2+ and Pb 2+ during their removal. I t is more economical than those normally used, which require the use of toxic and expensive reagents. Our results demonstrated the potential use of electroanalytical techniques to monitor the course of environmental interventions. Thus, the application of the two techniques associated can be a reliable way to monitor environmental impacts due to the pollution of aquatic ecosystems by heavy metals.

Fabrication and optimizing of metal nano silicate as toxic metal absorbent from sea water

Pure Water, is a crucial demand of creature life. Following industrial development, extra amount of toxic metals such as chromium enters the environmental cycle through the sewage, which is considered as a serious threat for organisms. One of the modern methods of filtration and removal of contaminants in water, is applying Nano-technology. According to specific property of silicate materials, in this article we try to survey increased power in composites and various absorption in several morphologies and also synthesis of Nano-metal silicates with different morphologies as absorbent of metal toxic ions. At first, we synthesize nano zink silicate with three morphologies considering context and the purpose of this survey. 1) Nano synthesis of zink silicate hollow cavity by hydrothermal method in mixed solvent system of ethanol/glycol polyethylene. 2) Zink nano wires silicate in a water-based system by controlling the amount of sodium silicate. 3) Synthesis of nano zink silicate membrane. After synthesizing, we measured the cadmium ion absorbance by synthesized nano zink silicates. Controlling PH, is the applied absorption method. Next step, we synthesized nano zink-magnesium silicate composite in two various morphologies of nanowires and membrane by different precent of zink and magnesium, in order to optimize synthesized nano metal silicate. We used zink nitrate and magnesium nitrate and also measured cadmium absorption by synthesized nano metal silicates in the same way of PH control absorption. In the 3rd step, in order to determine the impact of the type of metal in nano metal silicate, we synthesized nano magnesium silicate and compared its absorption with nano zink silicate. Furthermore, we calculated the optimal concentration in one of synthesizes. Optimal concentration is the process which has the maximum absorption. While applying two methods of absorption in the test, finally we compared the effect of absorption method on the absorption level. Below you find further steps of synthesis: 1) Using IR, RAMAN, XRD spectroscopy to check the accuracy of synthesis. 2) Checking the dispersion of nano particles in ethanol solution by light microscope. 3) Measuring and observing particles with scanning electron microscope (SEM). 4) Using atomic absorption device for measuring the cadmium concentration in water-based solutions. The nano metal silicates were synthesized successfully. All of synthesized nano absorbents have the cadmium ion absorbency. The cadmium absorption via nano absorbents depend on various factors such as kind of metal in nano silicate and percent of metal in nano metal silicate composite. Meanwhile the absorption and PH control of medium containing the absorbent and solution would affect the cadmium absorption.

Method for cadmium and lead longitudinal profiles determination in hair by solid sampling graphite furnace atomic absorption spectrometry

This paper describes methods for the direct determination of Cd and Pb in hair segments (c.a. 5 mm similar to 80 mu g) by solid sampling graphite furnace atomic absorption spectrometry, becoming possible longitudinal profiles in a single strand of hair. To distinguish endogenous and exogenous content. strands of hair were washed by using two different procedures: IAEA protocol (acetone + water + acetone) and the combination of IAEA protocol with HCl washing (acetone + water + acetone + 0.1 mol l(-1) HCl). The concentration of Cd and Pb increased from the root Until the tip of hair washed according to IAEA protocol. However, when the strand of hair was washed using the combination of IAEA protocol and 0.1 mol l(-1) HCl, Cd concentrations decreased in all segments, and Pb concentrations decreased drastically near to the root (5 to 12 mm) and was systematically higher ill the end. The proposed method showed to be useful to assess the temporal variation to Cd and Pb exposure and call be Used for toxicological and environmental investigations. The limits of detection were 2.8 ng g(-1) for Cd and 40 ng g(-1) for Pb. The characteristic masses based oil integrated absorbance were 2.4 pg for Cd and 22 pg for Pb.

Method development and optimization for the determination of selenium in bean and soil samples using hydride generation electrothermal atomic absorption spectrometry

The present investigation is the first part of an initiative to prepare a regional map of the natural abundance of selenium in various areas of Brazil, based on the analysis of bean and soil samples. Continuous-flow hydride generation electrothermal atomic absorption spectrometry (HG-ET AAS) with in situ trapping on an iridium-coated graphite tube has been chosen because of the high sensitivity and relative simplicity. The microwave-assisted acid digestion for bean and soil samples was tested for complete recovery of inorganic and organic selenium compounds (selenomethionine). The reduction of Se(VI) to Se(IV) was optimized in order to guarantee that there is no back-oxidation, which is of importance when digested samples are not analyzed immediately after the reduction step. The limits of detection and quantification of the method were 30 ng L(-1) Se and 101 ng L(-1) Se, respectively, corresponding to about 3 ng g(-1) and 10 ng g(-1), respectively, in the solid samples, considering a typical dilution factor of 100 for the digestion process. The results obtained for two certified food reference materials (CRM), soybean and rice, and for a soil and sediment CRM confirmed the validity of the investigated method. The selenium content found in a number of selected bean samples varied between 5.5 +/- 0.4 ng g(-1) and 1726 +/- 55 ng g(-1), and that in soil samples varied between 113 +/- 6.5 ng g(-1) and 1692 +/- 21 ng g(-1). (C) 2011 Elsevier B.V. All rights reserved.

Biomonitoring method for the simultaneous determination of cadmium and lead in whole blood by electrothermal atomic absorption spectrometry for assessment of environmental exposure

The aim of this work is to propose a biomonitoring method for the simultaneous determination of Cd and Pb in whole blood by simultaneous electrothermal atomic absorption spectrometry for assessment of environmental levels. A volume of 200 mu L of whole blood was diluted in 500 mu L of 0.2% (w v(-1)) Triton(R) X-100 + 2.0% (v v(-1)) HNO3. Trichloroacetic acid was added for protein precipitation and the supernatant analyzed. A mixture of 250 mu g W + 200 mu g Rh as permanent and 2.0% (w v(-1)) NH4H2PO4 as co-injected modifiers were used. Characteristic masses and limits of detections (n = 20, 3s) for Cd and Pb were 1.26 and 33 pg and 0.026 mu g L-1 and 0.65 mu g L-1, respectively. Repeatability ranged from 1.8 to 6.8% for Cd and 1.2 to 1.7% for Pb. The trueness of method was checked by the analysis of three Reference Materials: Lyphocheck(R) Whole Blood Metals Control level 1 and Seronorm(TM) Trace Elements in Whole Blood levels 1 and 2. The found concentrations presented no statistical differences at the 95% confidence level. Blood samples from 40 volunteers without occupational exposure were analyzed and the concentrations ranged from 0.13 to 0.71 mu g L-1 (0.32 +/- 0.19 mu g L-1) for Cd and 9.3 to 56.7 mu g L-1 (25.1 +/- 10.8 mu g L-1) for Pb. (C) 2007 Elsevier B.V. All rights reserved.