Dissertations / Theses on the topic 'Cd absorption'

A transverse heated filter atomizer (THFA) was applied to the direct determination of Cd and Pb in urine, and its analytical performances were investigated using a PerkinElmer SIMAA 6000 atomic absorption spectrometer. Seronorm certified human urine reference materials and six realistic samples collected locally were used for the method validation. The urines were diluted ten- or five-fold with 0.2% HNO3. Cd and Pb nitrate solutions were employed as standards. Recoveries of the elements from the urine samples were investigated with the analyte addition method. Compared to the transverse heated graphite atomizer (THGA) with a platform, the THFA provided a significant reduction of spectral background and chemical interferences from the urine matrix, without the use of chemical matrix modifiers, a 1.5–2 times increase of the determination sensitivity and, therefore, a reduction of limits of detection up to 0.018 and 0.2 mg L21 for Cd and Pb, respectively. The use of a THFA collector made from carbon fiber and a tungsten wire improved recoveries of lead and cadmium in urine (¢92%). A sampling temperature 150 uC enabled us to skip the drying period, thus a significantly reduced temperature program was obtained. The accuracies of the measurements of Cd and Pb in the Seronorm urine materials were in good agreement with the recommended values: 4.1 ¡ 0.1 mg L21 of Cd (recommended 5) and 92 ¡ 1 mg L21 of Pb (recommended 85). The lifetime of the THFA for Pb determination was longer than 700 firings, with the sensitivity loss not more than 25% after 500 firings.

Cadmium (Cd) is absorbed through the lungs and the digestive tract; however, for most human non-smokers, the major route of Cd entry into the body is by ingestion. Perhaps 5% of ingested Cd is absorbed and once absorbed, Cd accumulates mostly in the liver and kidneys, where it can cause a variety of health problems. This applies equally to grazing stock. The major entry point of Cd into the food chain is therefore uptakes of traces of Cd by crop plants. This thesis focuses on Cd in vegetables. The study was conducted in an Australian context, where geogenic Cd contributions to soils are typically low. Most of the Cd in soils on Australian vegetable farms originates from materials added to boost crop production. Phosphate fertilisers were and remain the dominant Cd source. Most Australian soils are P-deficient and high rates of P fertiliser are essential for successful vegetable cropping. The P fertilisers used throughout Australia were formerly made from guano deposits mined on Pacific Islands. These contained high percentages of Cd. Current rock sources contain lower Cd concentrations. Studies showed that all the vegetable samples which contained excessive Cd concentrations were leafy vegetables, including cabbage, lettuce, silverbeet, parsley and bok choy. Cadmium impaired photosynthesis; reduced dry weight of the whole plant; slowed leaf elongation rate; decreased the length of fully expanded leaves; slowed the rate at which new leaves appeared; and altered foliar concentrations of Zn, Mn, Cu, Ca and S. These profound changes affected all parts of the plant; consequently, Cd did not affect the proportion of dry weight partitioned to the roots, stems and leaves.
Doctor of Philosophy (PhD)

The release of toxic metal species is of concern due to their detrimental effects on the environment and human health. Industrial effluents are a major source of mobilised metal species. Suitable technologies are needed to sequester toxic metal species at the point of source. Biosorption, which is based on the passive adsorption of contaminants onto biological materials, promises to offer an effective alternative or complementary step to existing treatment methods. However, to date there has been no widespread commercialisation of the technique. This is partly due to an insufficient understanding of the complex underlying mechanisms which makes it difficult to select suitable biomass for specific remediation problems and to predict process performance. This study characterised two gram-positive, thermophilic bacteria, Anoxybacillus flavithermus (BF) and Geobacillus stearothermophilus (BS), harvested at two different growth times, with regard to their acid-base and Cd�⁺ adsorption behaviour. The aim was to investigate the metal cation adsorption properties of thermophilic bacteria which has not been studied previously, and to gain a better understanding of the interactions responsible for bacterial metal cation adsorption. Experimental techniques employed in this study included microscopy to establish cell and cell wall morphology, batch acid-base and Cd�⁺ adsorption experiments to quantify proton active surface functional groups and Cd�⁺ adsorption, electrophoretic mobility measurements to assess the overall surface charge of the bacteria and in situ attenuated total reflection infrared (ATR-IR) spectroscopy to reveal the chemical identities of functional groups. Chemical equilibrium models based on batch acid-base titration and electrophoretic mobility data were developed to quantitatively describe proton active surface functional groups. These groups can also interact with metal cations. It was found that growth time was an important factor in all experiments with the differences between growth times often being more pronounced than the differences between the two bacterial strains. Microscopy revealed a gram-positive cell wall structure with different widths and staining behaviour for exponential phase cells of BF and BS. Stationary / death phase cells showed disintegrating cell walls. Acid-base titrations indicated that all cells possessed buffering capacity over the whole investigated pH range (pH 2 - 10). From electrophoretic mobility measurements, isoelectric points of ~ 3.2 for BF and < 1.8 and ~ 4.2 for exponential and stationary / death phase cells of BS respectively were estimated. Chemical equilibrium models including a Donnan electrostatic model were derived which described both the batch acid-base titration data and the electrophoretic mobility data reasonably well, although a comparison with IR data suggested room for further improvement. In situ ATR-IR spectroscopy of hydrated bacterial cells at various pH values revealed amide and carboxyl groups and a contribution from phosphate / polysaccharide moieties. Group specific interactions with Cd�⁺ were not detected, however, a partially reversible absorbance increase of all peaks suggested conformational changes in the presence of Cd�⁺. BF and BS adsorbed ~ 70 [mu]mol Cd�⁺ (g dry bacterial)⁻� at pH 5 in 0.01 M NaNO₃. Release of major cations occurred concomitantly with Cd�⁺ adsorption. The buffering and Cd�⁺-binding capacities of BF and BS were found to be comparable to those of mesophilic bacteria and ion exchange was identified as an important adsorption mechanism.

La mobilité des métaux lourds est étudiée dans trois contextes de contamination, chacun à une échelle différente. Le premier est l'épandage de boues de station d'épuration sur sol forestier. Les processus sont accélérés par centrifugation, en microcosme. Malgré plusieurs mois d'évolution simulée, la migration des métaux (Cd, Ni, Pb) reste très limitée, vraisemblablement par affinité avec la matière organique accumulée en surface. Le deuxième est réalisé en mésocosme, à partir d'une terre agricole dopée en Pb. Après plusieurs mois en milieu extérieur, le Pb est retenu dans le solide. Il est adsorbé sur les particules organiques et argileuses (montmorillonite) mais reste potentiellement mobilisable. Le troisième concerne un aquifère sous un site industriel (macrocosme) pollué en Cu et H2SO4. L'acidité favorise la solubilité du Cd et du Pb. Cependant, le pouvoir tampon du solide entraîne la précipitation du Cu et du Fe; et l'immobilisation du Cd et du Pb par adsorption ou coprécipitation
The mobility of heavy metals is studied on three cases of contamination, each one at a different scale. The first one deals with spreading of sewage sludge on forest soils. Processes are accelerated under centrifugation, at microcosm scale. Despite several months of simulated evolution, migration of heavy metals (Cd, Ni, Pb) is quite limited, probably by affinity with organic matter accumulated at the surface. The second one is run at mesocosm scale, using an agricultural soil spiked with Pb. After several months outdoor, Pb is retained within the solid. It is adsorbed on organic and clay (montmorillonite) particles, but remains under a potentially soluble form. The third one corresponds to an aquifer underlying an industrial site (macrocosm) polluted by Cu and H2SO4. Acidity enhances the solubility of Cd and Pb. However, the buffer capacity of the solid induces the precipitation of Cu and Fe; and the fixation of Cd and Pb by adsorption or coprecipitation

We report the first detection of extended neutral hydrogen (H I) gas in the interstellar medium (ISM) of a massive elliptical galaxy beyond z similar to 0. The observations utilize the doubly lensed images of QSO HE 0047-1756 at z(QSO) = 1.676 as absorption-line probes of the ISM in the massive (M-star approximate to 10(11) M-circle dot) elliptical lens at z = 0.408, detecting gas at projected distances of d = 3.3 and 4.6 kpc on opposite sides of the lens. Using the Space Telescope Imaging Spectrograph, we obtain UV absorption spectra of the lensed QSO and identify a prominent flux discontinuity and associated absorption features matching the Lyman series transitions at z = 0.408 in both sightlines. The H I column density is log N(H I)= 19.6-19.7 at both locations across the lens, comparable to what is seen in 21 cm images of nearby ellipticals. The H I gas kinematics are well-matched with the kinematics of the Fe II absorption complex revealed in ground-based echelle data, displaying a large velocity shear of approximate to 360 km s(-1) across the galaxy. We estimate an ISM Fe abundance of 0.3-0.4 solar at both locations. Including likely dust depletions increases the estimated Fe abundances to solar or supersolar, similar to those of the hot ISM and stars of nearby ellipticals. Assuming 100% covering fraction of this Fe-enriched gas, we infer a total Fe mass of M-cool(Fe) similar to (5-8) x 10(4) M-circle dot in the cool ISM of the massive elliptical lens, which is no more than 5% of the total Fe mass observed in the hot ISM.

A hemoglobina extracelular de Glossoscolex paulistus (HbGp) possui estrutura oligomérica composta por 144 cadeias globínicas e 36 cadeias linkers, que não possuem heme, formando uma bicamada hexagonal. Estudos mostraram que a HbGp possui uma alta estabilidade á variação de pH e presença de agentes desnaturantes, tais como, surfactantes e ureia, a 25°C. Com esses conhecimentos prévios, o presente estudo tem por objetivo avaliar a estabilidade térmica da HbGp 0,5-3,0 mg/mL, nas formas oxi-, meta- e cianometa-, em diferentes valores de pH. O efeito do SDS na estabilidade térmica da oxi-HbGp 0,5 e 3,0 mg/mL, em função do pH, será investigado também. Esses estudos foram realizados usando as técnicas de absorção óptica, dicroísmo circular (CD), espalhamento de luz dinâmico (DLS) e espalhamento de raios X a baixo ângulo (SAXS). Os resultados de absorção óptica e CD revelam que o processo de desnaturação da oxi- e cianometa-HbGp, no pH 7,0, envolve a formação das espécies oxidadas aquo-meta-HbGp e hemicromo. O processo de desnaturação é próximo ao modelo de dois estados, com uma temperatura crítica (Tc) de 58-59 °C. No pH ácido, a proteína agrega a partir de 58 °C. A cinética de agregação da oxi-HbGp, no pH 7,0, é dependente da concentração de proteína e da temperatura. Os dados de DLS mostram que a meta- e cianometa-HbGp 0,5 mg/mL, pH 7,0, desnaturam a 48 ± 1 e 56 ± 1 °C, respectivamente. Em pH alcalino, a proteína dissocia parcialmente antes de desnaturar, e o aumento da concentração de proteína faz aumentar o valor de Tc para a cianometa-HbGp. Dados de SAXS mostram que a oxi- e meta-HbGp, pH 7,0, desnaturam a 60 °C, apresentando valores de Rg=143±1 Å e Dmax=450±1 Å, enquanto que a cianometa-HbGp se mantém estável, com valores de Rg=107±1 Å e Dmax=300±1 Å. As análises das curvas p(r) mostram uma porcentagem crescente de dodecâmero e tetrâmero em solução, em relação à fração de protreína íntegra e de subunidades maiores, com o aumento do pH e da temperatura. As análises baseadas no programa OLIGOMER são similares às baseadas na função p(r). A presença do SDS induz a dissociação da oxi-HbGp 0,5 mg/mL pH 7,0. Entretanto, com 3,0 mg/mL de proteína a dissociação é parcial, com a sobreposição dos processos de dissociação, desnaturação e agregação, com o aumento da temperatura. No pH 5,0, o SDS promove a agregação da oxi-HbGp em temperaturas menores. As constantes cinéticas de dissociação da oxi-HbGp 0,5 mg/mL, pH 7,0 aumentam de (0,53±0,07)x10-4 s-1 para (2,1±0,2)x10-4 s-1 na presença de 0,4 e 0,6 mmol/L de SDS a 40 °C, respectivamente. Na temperatura de 42 °C a constante aumenta 2,6 vezes, com 0,6 mmol/L de SDS, comparada a 40 °C. A oxi-HbGp 3,0 mg/ml na presença de 0,6 mmol/L de SDS, dissocia parcialmente em tempos menores com o aumento da temperatura antes de agregar. Portanto, esses estudos mostram que a estabilidade térmica da HbGp é sensível ao aumento de pH e presença de SDS. A ordem de estabilidade térmica em pH alcalino é dado por: cianometa->oxi->meta-HbGp. Alem disso, o processo de desnaturação é governado pelo valor do pH e dependente da concentração de proteína em solução.
The extracellular hemoglobin Glossoscolex paulistus of (HbGp) has an oligomeric structure composed by 144 globin chains and 36 non globin chains (named linkers), forming a hexagonal bilayer. HbGp presents a high stability reagarding pH variation and the presence of denaturing agents, such as, for example, urea and surfactant, at 25°C. In this way, the present studies aim to evaluate the thermal stability for oxy-, meta- and cyanomet-HbGp 0.5-3.0 mg/ml, at different pH values. The SDS effect on the thermal stability of oxy-HbGp 0.5 and 3.0 mg / mL is also investigated. Optical absorption, circular dichroism (CD), dynamic light scattering (DLS) and small angle X-ray scattering (SAXS) techniques were emplayed for these studies. The results based on the optical absorption and CD spectroscopies show that the denaturation process for oxy- and cyanomet-HbGp, at pH 7.0, involves the formation of oxidized species, such as aquo-met-HbGp and hemichrome. This denaturation process is very close to a two-state model, with a critical temperature (Tc) of 58-59 °C. However, in the acidic pH, the aggregation of protein occurs at 58 °C. The aggregation process kinetics for oxy-HbGp, pH 7.0, is dependent on the protein concentration and temperature. DLS data show that meta- and cyanomet-HbGp, 0.5 mg/mL, pH 7.0, undergo denaturation at 48 ± 1 and 56 ± 1 ° C, respectively. At alkaline pH, two HbGp forms undergo partial dissociation before denaturation, and at higher protein concentration, an increase of Tc values for cyanomet-HbGp is observed. SAXS results show that the denaturation of oxy-and met-HbGp occur at 60 °C, presenting Rg=143±1 Å and Dmax=450±15 Å, while cyanomet-HbGp remains stable with Rg =107±1 Å and Dmax= 300±10Å, at this temperature. The p(r) curves analysis show the increase of dodecamer and tetramer percentages in solution, with increase of pH and temperature. The results using the OLIGOMER program are similar to the p(r) data analysis. For oxy-HbGp 0.5 mg/mL pH 7.0, in the presence of SDS, oligomeric dissociation before denaturation is observed. However, with 3.0 mg/ml of protein the dissociation process is slower, showing an overlap of the dissociation, denaturation and aggregation processes in the system, with increase of temperature. At pH 5.0, SDS promotes the aggregation of oxy-HbGp at lower temperatures, as compared to the absence of surfactant. The kinetic dissociation constant values for oxy-HbGp 0.5 mg/mL increase from (0.53 ± 0.07) x10-4 s-1 to (2.1 ± 0.2) x10-4 s-1, in the presence of 0.4 and 0.6 mmol/L SDS at 40 ° C, respectively. At 42 °C the dissociation constant value increases 2.6-fold, with 0.6 mmol/L SDS, as compared to 40 °C. For oxy-HbGp 3.0 mg/ml, in the presence of 0.6 mmol/L SDS, the oligomeric dissociation is smallest occurring in shorter times with increasing temperature before aggregation. Therefore, these studies show that the thermal stability of HbGp is sensitive to the pH variation and the presence of SDS. At alkaline pH, the order of thermal stability is the following: cyanomet->oxy->met-HbGp. Furthermore, the denaturation process is governed by the pH value, being dependent on the protein concentration in solution.

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Dissertacao (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

O objetivo desse trabalho foi o desenvolvimento de métodos analíticos para a determinação simultânea de Cd/Pb em cimento e Cr/Mn em alumina por espectrometria de absorção atômica com atomização eletrotérmica (SIMAAS) e amostragem de suspensão. Considerando os erros de amostragem de suspensão e as condições compromissadas impostas para a determinação simultânea, foi também objetivo do trabalho estudar a aplicação de padrão interno para corrigir erros sistemático e aleatório. A viabilidade de se usar o Tl como padrão interno foi explorada na determinação de Cd e Pb em cimento. O uso do padrão interno se baseou na hipótese de que o elemento Tl deveria adsorver quantitativamente sobre as partículas do material em suspensão. Foi feito o estudo térmico dos elementos Cd, Pb e Tl em soluções aquosas e suspensões, na presença e ausência de diferentes modificadores químicos. O melhor modificador químico (5 µg Pd + 3 µg Mg) foi escolhido com base nos gráficos de correlação. As melhores temperaturas de pirólise e atomização para a determinação simultânea de Cd e Pb foram 600°C e 2000°C, respectivamente. A preparação das amostras foi feita com suspensões contendo 30 µg L-1 de Tl em 0,1 % (v v-1) de HNO3 + 0,025 % (m v-1) de Triton X-100. A avaliação da exatidão foi feita com a determinação de Cd e Pb em cimento de construção civil e dentário com análise de solução e análise de materiais de referência de sedimento marinho (MESS1 e BCSS 1) e de rio (Buffalo River, IEAEA 356). Os resultados foram concordantes em um nível de confiança de 95% (teste t-student). Os limites de detecção (LD) obtidos foram 0,14 µg L-1 (1,4pg) para o Cd e de 1,2 µg L-1 (12 pg) para Pb. As massas características foram 1,2 pg e 25 pg para Cd e Pb, respectivamente. Na determinação simultânea de Cr e Mn em alumina não foi utilizado padrão interno. O estudo envolveu a obtenção de curvas de pirólise e atomização em presença de diferentes modificadores. Estudos de interferência mostraram que 100 mg L-1 de Al provocaram aumento nos sinais analíticos dos elementos que foi eliminado com o modificador químico NaOH (0,2 mol L-1) + HF (0,4 mol L-1) combinado com 350 µg de Nb. Nessa condição as temperaturas de pirólise e atomização foram 1400°C e 2400°C, respectivamente. As suspensões de alumina foram preparadas em 2 % (v v-1) HNO3. A avaliação da exatidão foi feita com a determinação de Cr e Mn em material de referência de alumina (Alumina Reduction Grade - 699) e os resultados foram concordantes em um nível de confiança de 95% (teste t-student). Os limites de detecção (LD), estimados a partir da variabilidade de 20 medidas consecutivas de uma solução contendo 2 % (v v-1) HNO3 foram 0,11 µg L-1 (2,2 pg) para Cr e 0,17 µg L-1 (3,5 pg) para o Mn. As massas características foram 10 pg e 1,3 pg para Cr e Mn, respectivamente.
The aim of this work was the development of analytical methods for the simultaneous determination of Cd/Pb in cement and Cr/Mn in alumina by electrothermal atomic absorption spectrometry (SIMAAS) and slurry sampling. Considering the errors of slurry sampling and the imposed compromissed conditions for the simultaneous determination, it was also the aiming of this work to study the application of internal standard for the sistematic and random errors correction. The viability of using Tl as internal standard was investigated for Cd and Pb determination in cement. The internal standard aplicability was based on the hypothesis of the element Tl would have to adsorver quantitatively on the particles of the material in suspension. The thermal behaviour of Cd, Pb and Tl in aqueous solutions and suspensions was obtained in presence and absence of different chemical modifiers. The best chemical modifier (5 mg Pd + 3 mg Mg) was chosen based on correlation graphs. The pyrolysis and atomization temperatures for the simultaneous determination of Pb were 600°C and 2000°C, respectively. The sample the preparation was made with 30 mg L-1 of Tl in 0,1% (v v-1) of HNO3 + 0.025% (m v-1 of Triton X-100. The evaluation of the accuracy was made with the determination of Cd and Pb in cement, microwave extraction in acid media and analysis of marine sediment reference materials (MESS1 and BCSS 1) and river sediment (Buffalo River, IEAEA 356). The results are concordant at 95% of confidence level using Studen\'s t-test. The detention limits (LD) was 0.14 µg L-1 (1.4 pg) for Cd and 1.2 µg L-1(12 pg) for Pb. The characteristic masses were 1.2 pg and 25 pg for Cd and Pb, respectively. The simultaneous determination of Cr and Mn in alumina was done without internal standard. Pyrolysis and atomization temperaturas were obtained in presence of different modifiers. Studies of interference shown that 100 mg L-1 of Al provoked increase in the analytical signals of Cr and Mn that was eliminated with the chemical modifier NaOH (0,2 mol L-1) + HF (0,4 mol L-1) combined with 350 mg of Nb as permanent chemical modifier. In this condition pyrolysis and atomization temperatures were 1400 °C and 2400 °C, respectively. The alumina suspensions were prepared in 2% (v v-1) HNO3. The evaluation of the accuracy was made with the determination of Cr and Mn in alumina reference material (Reduction Alumina Grating - 699) and the results were concordant at 95 % of the confidence level using Student\'s t-test. The detention limits (LD) were 0.11 µg L-1 (2.2 pg) for Cr and 0.17 µg L-1 (3.5 pg) for Mn. The characteristic masses were 10 and 1.3 pg for Cr and Mn, respectively.

Vapor generation in atomic spectrometry is a well established technique for the determination of elements that can be volatilized by chemical reactions. In-situ trapping in graphite furnaces is nowadays one of the most popular methods to increase the sensitivity. In this study, resistively heated W-coil was used as an online trap for preconcentration and revolatilization of volatile species of Bi, Cd and Pb. The collected analyte species were revolatilized rapidly and sent to a quartz Ttube atomizer for AAS measurement. Although the nature of revolatilized species of Bi and Pb are not clear, they are probably molecular since they can be transported at least 45 cm without any significant decrease in the peak height values. However, cadmium is revolatilized from the trap surface as atoms. The experimental parameters were optimized for the highest vapor generation, trapping and revolatilization efficiencies. The concentration limits of detection calculated by the 3 of blank solution were found to be 0.0027, 0.0040 and 0.015 ng/mL for Bi (18 mL), Cd (4.2 mL) and Pb (2 mL), respectively
enhancement factors in the sensitivity were 130, 31 and 20, respectively. These values are comparable with those obtained by in-situ trapping in graphite furnaces or even ICP-MS found in the literature or better. Sensitivity can be improved further for Bi and Cd using larger sample volumes, but purification of blank is required for Pb. Certified standard reference materials were analyzed for the assessment of accuracy of developed method.

We present multisightline absorption spectroscopy of cool gas around three lensing galaxies at z = 0.4-0.7. These lenses have half-light radii r(e) = 2.6-8 kpc and stellar masses of log M-*/M-circle dot = 10.9-11.4, and therefore resemble nearby passive elliptical galaxies. The lensed QSO sightlines presented here occur at projected distances of d = 3-15 kpc (or d approximate to 1-2 r(e)) from the lensing galaxies, providing for the first time an opportunity to probe both interstellar gas at r similar to r(e) and circumgalactic gas at larger radii r >> r(e) of these distant quiescent galaxies. We observe distinct gas absorption properties among different lenses and among sightlines of individual lenses. Specifically, while the quadruple lens for HE 0435-1223 shows no absorption features to very sensitive limits along all four sightlines, strong MgII, Fe II, Mg I, and Ca II absorption transitions are detected along both sightlines near the double lens for HE 0047-1756, and in one of the two sightlines near the double lens for HE 1104-1805. The absorbers are resolved into 8-15 individual components with a line-of-sight velocity spread of Delta v approximate to 300-600 km s(-1). The large ionic column densities, log N greater than or similar to 14, observed in two components suggest that these may be Lyman limit or damped Ly a absorbers with a significant neutral hydrogen fraction. The majority of the absorbing components exhibit a uniform supersolar Fe/Mg ratio with a scatter of < 0.1 dex across the full Delta v range. Given a predominantly old stellar population in these lensing galaxies, we argue that the observed large velocity width and Fe-rich abundance pattern can be explained by SNe Ia enriched gas at radius r similar to r(e). We show that additional spatial constraints in line-of-sight velocity and relative abundance ratios afforded by a multisightline approach provide a powerful tool to resolve the origin of chemically enriched cool gas in massive haloes.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
In the last decade, the extraction magnetic solid phase (MSPE) has been intense study target in Analytical Chemistry, mainly because of its potential application in sample preparation. Recently, with the development motivation automatic analytical methods, this technique has been combined with flow systems. However, the synergistic integration of MSPE with these systems is still a challenge, especially when it involves the handling of viscous matrices. In this perspective, this thesis proposes the development of an effective automated method to perform the MSPE in aqueous and oily matrices. For be applied as magnetic adsorbent nanoparticles of Fe3O4 coated with alumina and functionalized with sodium dodecyl sulfate (SDS) and 1-(2-pyridylazo)-2-naphthol (PAN) were synthesized. The nanoparticles were characterized by diffraction analysis X-ray and scanning electron microscopy, where it was confirmed that the method used to obtain the particles was adequate. Secondly, the automatic system to run the MSPE was developed. To this end an extraction chamber was made of Teflon with a quartz window on the side, where all steps of MSPE was performed without the need for any auxiliary apparatus for immobilizing the adsorbent. For generating the magnetic field in the extraction chamber, a robotic device has been developed. After these steps, the applicability of the method was demonstrated in the extraction and preconcentration of Cd and Pb in drinking water samples and Cd in edible oils, using as detection atomic absorption spectrometry graphite furnace. Factors affecting MSPE, such as pH, the amount of adsorbent, the type and concentration of the eluent and the elution time were studied. In the best experimental conditions to the sample water, the detection limit was 0.004, and 0.043 ug L-1 for Cd and Pb, respectively. Even in this array, relative standard deviations less than 3.5% were achieved with a 15-fold enrichment factor for both analytes. In the case of determination of Cd in edible oils, detection limit (0.006 ug L-1) and standard deviation (< 3.3%) was obtained satisfactorily with a 9-fold enrichment factor. Interfering studies have been performed successfully for the two determinations, not revealing significant percentage interference in determinations. The developed automatic method is simple and robust since it does not require immobilization of the adsorbent, and was successfully applied in the determination of Cd and Pb in drinking water samples and Cd in edible oils.
Na última década, a extração em fase sólida magnética (MSPE) tem sido alvo de intenso estudo na Química Analítica, principalmente em virtude do seu potencial de aplicação no preparo de amostras. Recentemente, tendo como motivação o desenvolvimento de métodos analíticos automáticos, essa técnica vem sendo combinada aos sistemas em fluxo. Contudo, a integração sinérgica da MSPE com esses sistemas ainda é um desafio, principalmente quando envolve a manipulação de matrizes viscosas. Nessa perspectiva, a presente tese propõe o desenvolvimento de um eficiente método automático para realização da MSPE em matrizes aquosas e oleosas. Para serem aplicadas como adsorvente magnético foram sintetizadas nanopartículas de Fe3O4 revestidas com alumina e funcionalizadas com dodecil sulfato de sódio (SDS) e 1-(2-piridilazo)-2-naftol (PAN). As nanopartículas foram caracterizadas através da análise de difratometria de raios-X e da microscopia eletrônica de varredura, onde confirmou-se que o método empregado para obtenção das partículas foi adequado. Num segundo momento, o sistema automático para executar a MSPE foi desenvolvido. Para isso, uma câmara de extração foi confeccionada em Teflon, com uma janela de quartzo na lateral, onde todos os passos da MSPE foram realizados sem a necessidade de qualquer aparato auxiliar para imobilizar o adsorvente. Para geração do campo magnético, na câmara de extração, um dispositivo robótico foi desenvolvido. Depois de estabelecida essas etapas, a aplicabilidade do método foi demonstrada na extração e preconcentração de Cd e Pb em amostras de água de abastecimento e de Cd em óleos comestíveis, empregando como detecção a espectrometria de absorção atômica em forno de grafite. Fatores que afetam a MSPE, tais como o pH, a quantidade de adsorvente, o tipo e a concentração do eluente e o tempo de eluição foram estudados. Nas melhores condições experimentais, para a amostra água, o limite de detecção foi 0,004 e 0,043 μg L-1 para o Cd e o Pb, respectivamente. Ainda nessa matriz, desvios padrão relativos menores que 3,5 % foram alcançados com um fator de enriquecimento de 15 vezes para ambos os analitos. No caso da determinação de Cd em óleos comestíveis, limite de detecção (0,006 μg L-1) e desvio padrão relativo (< 3,3 %) satisfatório foi obtido com um fator de enriquecimento de 9 vezes. Os estudos de interferentes foram realizados com êxito para as duas determinações, não revelando interferência percentual significativa nas determinações. O método automático desenvolvido é simples e robusto, uma vez que não requer a imobilização do adsorvente, e foi aplicado com sucesso na determinação de Cd e Pb em amostras de água de abastecimento e de Cd em óleos comestíveis.

ALa migration des métaux vers les nappes d'eau souterraines et leur transfert vers les plantes constitue un risque pour l'environnement et pour l'homme, au travers de la chaîne alimentaire. Le but de ce travail était d'évaluer la potentialité des métaux Pb, Zn, Cd et Cu à migrer dans les sols d'un secteur pollué par des retombées atmosphériques. Sachant que la migration des métaux dépend des formes physico-chimiques sous lesquelles ils sont présents, elles ont été déterminées grâce à l'application d'un schéma de spéciation constitué d'extractions chimiques sélectives. Pour répondre aux exigences de l'étude d'un vaste secteur pollué, un schéma simple mais complet, applicable à des sols différents pédologiquement a été établie. Dans ce schéma, qui comporte 5 fractions (échangeable, acido-soluble, réductible, oxydable et résiduelle), de nombreux paramètres opératoires ont été optimisés (pH, concentration, température, durée, rapport solide/liquide, nombre d'extractions). L'importance de l'ordre d'enchaînement des extractions séquentielles (place de la fraction oxydable) et des extractions parallèles a été évaluée. Une étude comparative avec le schéma de Tessier et al. (1979) couramment utilisé et celui du bureau communautaire de référence a été effectuée. Ce schéma a ensuite été appliqué aux sols du secteur étudié. Les différences de pH, de teneur en carbonates, matière organique et polluants, ainsi que de caractère rédoxique, ont permis d'évaluer le comportement de ces métaux dans des conditions très variées
The moving down of metals towards underground water and their transfer to plants constitutes a risk for both environment and human health. The aim of this work was to value Pb, Zn, Cd and Cu metals potentiality of moving in the soils of an area polluted by atmospheric dusts. As the migration of metals depends on their physico-chemical forms, these ones are determined owing to selective chemical extractions of a speciation scheme. The study of a polluted area has required the seing up of a scheme which is both simple but fiull, anal appfies to differgpt pedologic soils. In this fine fractions scheme (exchangeable, acido-soluble, reducible, oxidable and. Residual) many operating paramètres were optimised (pH, concentration, temperature, time, solid/liquid ratio, number of extractions). The importance of the sequential extractions chain order (position of the oxidable fraction) and the importance of the parallel extractions were valued. A comparative study between Tessier et al. (1979) scheme and Referencing Community Bureau's one was carried out. Then this scheme was applied to the soils of the studied area. In these soils, the differences of pH, carbonate, organic matter and pollutant contents and redoxic characteristic allowed to value the behaviour of metals in various conditions

Este trabalho avalia indicadores biológicos de exposição ocupacional de trabalhadores de incineradores de resíduos de serviços de saúde. Os elementos estudados são arsênio, berílio, cádmio, mercúrio, níquel (amostras de urina) e chumbo (amostras de sangue). Os índices obtidos são comparados com (a) os limites estabelecidos pela legislação brasileira, (b) os limites estabelecidos pela American Conference of Governmental Industrial Hygienists (ACGIH) e (c) com os mesmos índices medidos em outros trabalhadores das mesmas usinas trabalhando em diferentes áreas, funções e turnos. As determinações foram realizadas por espectrometria de absorção atômica: por forno de grafite para berílio, cádmio, níquel e chumbo; através da geração de hidreto para arsênio; por geração de vapor frio para mercúrio. Os métodos foram otimizados e validados através de material certificado e ensaios de recuperação. As amostras foram coletadas em 5 dias consecutivos, antes e após cada jornada de trabalho. As médias de concentração para os indicadores biológicos foram inferiores aos limites para exposição ocupacional para os agentes estudados. No caso do arsênio, entretanto, alguns indivíduos apresentaram valores de concentração acima do estabelecido pela legislação brasileira.
The biological occupational exposure indices of workers in medical waste incineration plants is evaluated. Arsenic, beryllium, cadmium, mercury and nickel (urine samples) and lead (blood samples) are studied. The measured indices are compared with (a) the limits imposed by Brazilian law, (b) limits established by American Conference of Industrial Governmental Hygienists and (c) the same indices measured for co-workers in different workplaces, activities and workshifts. The measurements have been carried through atomic absorption spectrometry: by graphite furnace for of beryllium, cadmium, nickel and lead; using the hidride generation for arsenic; and by cold vapor generation for Hg. The employed methods have been optimized and validated through certified samples and recovery essays. The samples were collected in 5 consecutive workdays, before and after each working shift. The measured indices are found to be below their respective occupational exposure limits when the average for each group of workers is taken. In the case of the arsenic, however, some individual workers have shown levels above the limits imposed by Brazilian law.

Ce travail montre l'intérêt, par deux aspects, des semiconducteurs semimagnétiques CdMnTe pour l'étude des propriétés structurales, magnétooptiques et électroniques des puits quantiques II-VI. La première partie est consacrée à la caractérisation des interfaces CdTe/CdMnTe dans des puits quantiques asymétriques. Le large effet Zeeman dû à l'interaction d'échange porteurs-Manganèse de la transition excitonique fondamentale, déterminé par des mesures de magnétoréflectivité et d'effet Kerr, permet une analyse précise du profil de concentration du Manganèse à proximité de l'interface. Nous mettons ainsi en évidence le mécanisme de ségrégation qui résulte l'échange d'atomes entre deux monocouches adjacentes en cours de croissance. Dans la seconde partie, l'effet Zeeman géant de la bande de conduction est utilisé pour polariser totalement le spin des électrons d'un gaz bidimensionnel de densité intermédiaire présent dans un puits quantique semimagnétique. Cette propriété permet de découpler les phénomènes dépendant et non-dépendant du spin des électrons et d'étudier ainsi les effets à N corps au sein d'un gaz d'électrons bidimensionnel. L'analyse des mesures de magnéto-transmission inter-niveaux de Landau met en évidence la création de paires électron-trou liés par l'interaction coulombienne. L'énergie de liaison de ce complexe est toutefois fortement réduite par deux mécanismes dus au gaz d'électrons : l'écrantage et le remplissage de l'espace des phases. Un autre effet à N corps est manifeste : l'interaction d'échange électron-électron qui permet d'expliquer, conjointement avec l'interaction d'échange porteurs-Manganèse, la polarisation complète du gaz à un faible champ magnétique. Un modèle au premier ordre, incluant ces trois effets, reproduit le comportement des énergies des transitions en champ.

L'absorption et le devenir du triticonazole dans la plante de ble ont ete etudies de l'imbibition au stade gonflement, a partir de semences traitees avec du triticonazole-14c. Durant la phase d'imbibition de la semence, des quantites importantes de triticonazole penetrent dans le caryopse. Le produit se repartir dans les teguments et l'embryon et semble par la sutie etre peu transporte dans les parties aeriennes. De la levee au stade gonflement, le triticonazole est essentiellement absorbe par les racines et transporte dans les parties aeriennes par les vaisseaux du xyleme. Le produit se repartit dans les feuilles selon un gradient de concentration decroissant des etages foliaires inferieurs vers les etages foliaires superieurs. La concentration en triticonazole dans les parties aeriennes de la plante diminue fortement du stade 2-3 feuilles au stade gonflement. Cette dilution est due a la croissance vegetale et a la metabolisation de la matiere active dans les feuilles. De plus, le chargement de matiere active dans les parties aeriennes pourrait etre limite par la position du systeme racinaire par rapport a la zone de repartition du triticonazole dans le sol. La diminution de la concentration en matiere active dans les feuilles est probablement la cause de la baisse d'efficacite du triticonazole contre differentes maladies foliaires. Les possibilites de prolonger l'efficacite du triticonazole contre les maladies foliaires par une augmentation de la dose de traitement, par l'utilisation de l'enantiomere actif seul ou par un travail sur la formulation ont ete etudiees

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Os biossorventes provenientes de materiais lignocelulósicos são alternativas de baixo custo e mais sustentável para o meio ambiente na remoção das espécies metálicas. Neste caminho, o presente trabalho descreve o uso da macrófita, Typha sp, também conhecida como taboa, para remover as espécies metálicas Cu (II), Cr (III), Cd (II) e Zn (II) em amostras aquosas. Caracterizou-se inicialmente a macrófita Typha sp utilizando as técnicas analíticas como: espectroscopia na região do infravermelho (FT-IR), análise elementar de N e Ressonância magnética nuclear (RMN) de 13C, microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva de raio X (EDS) e análise de área superficial utilizando adsorção de N2. As características adsortivas da Typha sp foram estabelecidas através de experimentos em batelada em função do pH, o tempo de contato e a concentração. As micrografias da Typha sp apresentou-se partículas com morfologia heterogênea, irregular em formato de bastão. O FT-IR e o RMN 13C confirmaram a presença de grupos funcionais como COOH, NH2 e S=C=N, que possuem pares de elétrons não ligantes e que coordenam com as espécies metálicas. A área superficial específica da Typha sp foi menor que 1 m2/g, característico de materiais não porosos. Os experimentos de adsorção mostraram que o pH 5,5 favorece a adsorção das espécies metálicas em estudo. A cinética de adsorção é rápida, sendo menor que 15 min, ajustando aos dados experimentais do modelo cinético de pseudo-segunda ordem. A capacidade máxima de adsorção determinada experimentalmente foi de 9,48, 6,55, 3,01 e 9,52 mg/g para Cr (III), Cu (II), Zn (II) e Cd (II). Respectivamente, os dados obtidos nas isotermas foram aplicados ao modelo Langmuir, cujos valores do coeficiente linear foi maior que 0,95, comprovando o bom ajuste dos dados a este modelo. A adsorção na presença de um segundo íon teve maior interferência para as espécies metálicas de Cu (II) e Zn (II) diminuindo a adsorção em 30 %. Após a determinação das caracteristica adsortivas da Typha sp, essa foi utilizada como suporte sólida na estração em fase sólida. Os parâmetros otimizados no sistema em fluxo para utilizar a Typha sp na extração em fase sólida (SPE) foram: vazão, massa, volume da amostra, concentração do ácido e o volume do eluato, obtendo uma recuperação acima de 78 %. A aplicação nas amostra do Rio Tietê e Paranapanema foram satisfatórias para as espécies Cu (II), Cd (II) e Zn (II), porém a recuperação do Cr (III) foi nula, devido a interferência da matriz. A Typha sp possui grande potencial para ser utilizada como biossorvente na adsorção das espécies metálicas em estudo, devido ao baixo custo do material e a elevada capacidade de adsorção das espécies metálicas.
Biosorbents from lignocellulosic materials are low cost alternatives and more environmentally sustainable in the removal of metal species. In this way, the present work describes the use of the macrophyte, Typha sp, also known as Taboa, to remove the Cu (II), Cr (III), Cd (II) and Zn (II) metal species in aqueous samples. Typha sp macrophyte was initially characterized using analytical techniques such as infrared spectroscopy (FT-IR), elemental analysis of N and 13C nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), energy spectroscopy dispersive X-ray diffraction (EDS) and surface area analysis using N2 adsorption. The adsorptive characteristics of Typha sp were established through batch experiments as a function of pH, contact time and concentration. The micrographs of the Typha sp presented particles with heterogeneous morphology, irregular in stick format. FT-IR and 13C NMR confirmed the presence of functional groups such as COOH, NH2 and S = C = N, which have non-binding electron pairs and coordinate with the metallic species. The specific surface area of Typha sp was less than 1 m2/g, characteristic of non-porous materials. The adsorption experiments showed that pH 5.5 favors adsorption of the metal species under study. The kinetics of adsorption is fast, being less than 15 min, adjusting to the experimental data of the kinetic model of pseudo-second order. The maximum adsorption capacity determined experimentally was 9.48, 6.55, 3.01 and 9.52 mg/g for Cr (III), Cu (II), Zn (II) and Cd (II). The data obtained in the isotherms were applied to the Langmuir model, whose linear coefficient values were greater than 0.95, confirming the good fit of the data to this model. The adsorption in the presence of a second ion had greater interference for the Cu (II) and Zn (II) metal species, reducing the adsorption by 30%. After the determination of the adsorptive characteristics of Typha sp, this was used as solid support in the solid phase separation. The optimized parameters in the flow system to use Typha sp in the solid phase extraction (SPE) were: flow, mass, sample volume, acid concentration and eluate volume, obtaining a recovery above 78%. The Cu (II), Cd (II) and Zn (II) species were satisfactory for the Tietê and Paranapanema samples, but the Cr (III) recovery was null due to matrix interference. Typha sp has great potential to be used as a biosorbent in the adsorption of the metal species under study, due to the low cost of the material and the high adsorption capacity of the metallic species.
CAPES

Líquidos iônicos (LIs) são sais que se encontram no estado líquido em temperaturas menores que 100ºC e que vêm ganhando protagonismo na área chamada química verde, prometendo: substituir solventes nocivos ao meio ambiente, aprimorar componentes eletrônicos, favorecer biocatálises dentre outros. Sua alta estabilidade e baixa toxicidade são frequentemente afirmadas, porém, devem ainda ser melhor investigadas. Com o objetivo de implementar o entendimento da interação dos líquidos iônicos com sistemas de relevância biológica, realizamos um estudo sistemático acerca da interação de 3 diferentes líquidos iônicos anfifílicos de mesma cabeça polar e diferentes caudas carbônicas ([C10mim][Cl], [C12mim][Cl] e [C14mim][Cl]) com 3 diferentes proteínas modelo, através das técnicas de absorção óptica, fluorescência, dicroísmo circular (CD) e espalhamento de raios-X a baixos ângulos (SAXS). Para Tanto, utilizamos as proteínas BSA e HSA (Albuminas de Soro Bovino e Humano, respectivamente) além da lisozima. Observamos a supressão da fluorescência das proteínas em todos os casos analisados, onde a diminuição da intensidade correspondeu a, para as proteínas BSA, HSA e lisozima, respectivamente, (55±3)%, (16.1±0.8)% e (4.1±0.2)%, em presença de 0.6mM de [C14mim][Cl], (38±2)%, (13.2±0.7)% e (0.6±0.1)% em presença de 0.6mM de [C12mim][Cl] e (11.0±0.5)%, (9.2±0.5)% e (0.0±0.1)% em presença de 0.6mM de [C10mim][Cl]. Os espectros de absorbância e fluorescência de todos os sistemas nos indicam uma interação de contato entre as proteínas e os líquidos iônicos. Constatamos também o deslocamento do pico de fluorescência, das proteínas BSA e HSA, para menores comprimentos de onda (blue-shift), na medida em que a concentração de LI era aumentada. O máximo deslocamento () alcançado correspondeu a (21±1)nm para ambas albuminas, enquanto que a lisozima não apresentou deslocamento significativo. O blue-shift pode ser explicado pela aproximação das cadeias carbônicas e formações de pontes de hidrogênio nas proximidades dos triptofanos. De acordo com a técnica de SAXS, evidenciamos o aumento do raio de giro das proteínas, na medida em que adicionamos LIs. O raio de giro da BSA, da HSA e lisozima em ausência de LI são (29±1)Å, (30±1)Å e (15±1)Å, respectivamente, e passam para (46±1)Å, (44±1)Å e (20±1)Å respectivamente, em presença de 0.6mM de [C14mim][Cl]. As curvas de SAXS também apresentaram o indício da formação de estruturas micelares a partir de uma dada concentração. Além da alteração em sua estrutura terciária, os dados de CD indicam uma leve perda de estrutura secundária de ambas as albuminas (BSA e HSA), passando de 80 para 65% de -hélice em ausência e presença de 0.6mM de [C14mim][Cl], respectivamente. Sugerimos que as interações das proteínas com os líquidos iônicos, embora inicialmente movidas por forças eletroestática, possuem como principal fator o efeito hidrofóbico, portanto quanto maior a cadeia carbônica do LI maior é sua interação com a proteína. Tal interação causa o desenovelamento das proteínas e formação de um complexo e estruturas micelares a altas concentrações de LI. Acreditamos que este trabalho traz novas informações acerca da interação dos LIs com proteínas modelo, indicando sua capacidade de alterar a conformação das mesmas.
Ionic liquids (ILs) are salts that are liquid at temperatures smaller than 100 ° C and are gaining prominence in the so-called green chemistry, promising: replace harmful solvents to the environment, improve electronic components, and favor biocatalysis, among others. Its high stability and low toxicity are often asserted; nevertheless, they are ascribed to ILs due to its small volatility. With the aim of improving the understanding of the interaction of ILs with biological relevant systems, we conducted a systematic study of the interaction of three different ionic liquids of the same polar head and different paraffinic tails ([C10mim][Cl], [C12mim][Cl] and [C14mim][Cl]) with three different model proteins, through the techniques of optical absorption, fluorescence, circular dicrhoism (CD) and small angle X-ray scattering (SAXS). To do so, we use BSA and HSA proteins (Bovine Serum Albumin and the Human Serum Albumin, respectively) and lysozyme. We observed fluorescence quenching, of all studied proteins, where the decrease in the fluorescence was (for BSA, HAS and lysozyme, respectively): (55 ± 3)%, (16.1 ± 0.8)% to (4.1 ± 0.2 )% in the presence of 0.6mm [C14mim][Cl], (38 ± 2)%, (13.2 ± 0.7)% to (0.6 ± 0.1)% in the presence of 0.6mm [C12mim][Cl] and ( 11.0 ± 0.5)% (9.2 ± 0.5)% and (0.0 ± 0.1)% in the presence of 0.6mm [C10mim][Cl]. UV-vis absorbance spectra and fluorescence indicate all systems in a contact interaction between proteins and ionic liquids. We also note the shift of the fluorescent peak of BSA and HSA proteins for shorter wavelengths (blue-shift), as the IL content was increased. The maximum shift () achieved corresponded to (21 ± 1) nm for both albumins, whereas no significant displacement was observed for lysozyme. The blue-shift can be explained by the approach of carbon chains and formation of hydrogen bonds in the vicinity of tryptophan. SAXS data indicate an increasing in the proteins radius of gyration value as ILs was added in the solution. The turning radius of BSA, HSA and lysozyme in the absence of IL are (29 ± 1) Å, (30 ± 1) Å and (15 ± 1) Å, respectively, and go to (46 ± 1) Å, ( 44 ± 1) Å and (20 ± 1) Å, respectively, in the presence of 0.6mm [C14mim][Cl]. The SAXS curves also show evidence of the formation of micellar structures from a given concentration. Besides the change in its tertiary structure, the CD data indicates a slight loss of secondary structure of both albumins (BSA and HSA), from 80 to 65% of -helix in the absence and presence of 0.6mm [C14mim][Cl], respectively. We suggest that the interactions of the protein with the ionic liquid, although initially driven by electrostatic forces, have a major factor hydrophobic effect and thus the higher the carbon chain of greater IL is its interaction with the protein. This interaction causes unfolding of the protein and formation of a micellar structures at high concentrations of IL. We believe this work provides new information about the interaction of ILs with model proteins, indicating its ability to alter the conformation of the same.

L'etude de l'eclatement zeeman par des mesures magneto-optiques, et l'aimantation en fonction de la temperature dans les semiconducteurs semimagnetiques cd#1##xmn#xte et zn#1##xmn#xte a permis de mettre en evidence une forte decroissance des inegalites d'echange (-) lorsque t decrit pour 1. 8