Orientador: Simon Biagio Chiacchio / Banca: Roberto Calderon Gonçalves / Banca: Rogério Martins Amorim / Banca: José Giometti / Banca: Laurenil Gaste / Resumo: O objetivo do experimento foi avaliar o efeito de diferentes suplementações com selênio (Se) sobre a resposta imune humoral anti-rábica, na concentração sérica de selênio e cortisol em bovinos. Utilizou-se sessenta bovinos machos não castrados da raça Nelore, com 10 a 12 meses de idade, alimentados com pastagem de Brachiaria decumbens. Os animais foram divididos em 4 grupos (N=15) sendo que o primeiro deles não receberam suplementação (Gc) e os outros três suplementados diariamente e individualmente com concentrações de Se de 3,6 mg (G3,6), 5,4 mg (G5,4) ou 6,4 mg (G6,4). Os animais foram imunizados no dia zero com uma dose de vacina anti-rábica comercial, líquida e inativada. Nos dias zero, 15, 30, 60, 90 e 120 durante os quais submetidos ao estresse de manejo no curral e colheita de sangue. As amostras de sangue foram colhidas depois da vacinação e depois de serem submetidos ao estresse para determinação da concentração sérica de selênio, títulos de anticorpos anti-rábicos e cortisol sérico. A concentração de selênio também foi determinada nas amostras das forrageiras colhidas dos piquetes utilizados pelos bovinos. A concentração de Se na B. decumbens foi de 0,04 mg de Se/Kg de matéria seca. A concentração sérica de Se obtida no dia zero no grupo Gc era mais elevada que nos grupos G5,4 e G6,4 (P= 0,005). A concentração sérica de Se diminuiu ao longo do experimento no Gc (P<0,004), aumentou no G3,6 (P<0,000) e no grupo G5,4 (P<0,000), entretanto, no grupo G6,4 aumentou no dia 60 (P<0,002). Os títulos de anticorpos anti-rábicos não diferiram entre os grupos tratados ou não com selênio. Entretanto, 120 dias após a vacinação os títulos de anticorpos no grupo G3,6 permaneceram acima do mínimo considerado protetor (=0,5 UI/mL) (P<0,000), enquanto que nos outros grupos permaneceram baixos (P<0,05). A concentração sérica de cortisol dos bovinos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This study evaluated the effect of different concentrations of selenium (Se) supplementation on cattle antirabies humoral immune response, serum Se concentrations and cortisol levels. Sixty uncastrated male Nelore calves from 10 to 12 months grazing on Brachiaria decumbens forage were studied. The animals were assigned to one of four groups (N=15 each), which received nonsupplemented diets (Gc) or supplemented with daily and individual Se concentrations of 3.6 mg (G3.6), 5.4 mg (G5.4) or 6.4 mg (G6.4). The animals were immunized on day 0 with one dose of commercial liquid inactivated rabies vaccination. On days 15, 30, 60, 90 and 120, the cattle underwent the same stressing procedures used for vaccination in the corral. Cattle blood samples were collected after vaccination and stressing procedures to determine serum Se levels, rabies antibody titers and serum cortisol. Se levels were also determined in forage samples collected from the paddocks in which the cattle were held. Se concentration in B. decumbens was 0.04 mg of Se/Kg dry matter. Baseline Se levels obtained on day 0 were higher in Gc than in G5.4 and G6.4 (P= 0.005). Serum Se levels decreased in Gc throughout the experiment (P<0.004), increased in G3.6 (P<0.000) and G5.4 (P<0.000) and were kept high from day 60 on in group G6.4 (P<0.002). Rabies antibody titers did not differ between control and supplemented groups. However, 120 post-vaccination rabies antibody titers were kept above the protecti ve levels (=0.5 UI/mL) only in group G3.6 (P<0.00002), whereas they dropped in the other groups (P<0.05). Serum cortisol levels did not differ among the experimental groups (P=0.79), reached peak levels on day 90 and returned close to baseline levels on day 120. Se and cortisol levels were not markedly correlated. Serum cortisol and rabies antibody titers were correlated only in group G6.4, on day 60 (R=0.513; P=0.05)... (Complete abstract click electronic access below) / Doutor

This doctoral dissertation work strived to contribute to the ever expanding knowledge about the mechanisms of polychlorinated biphenyl (PCB) toxicity using dietary strategies. PCBs are a family of persistent environmental pollutants with a wide range of toxicity. The toxicity of PCBs is largely dependent on the congener's chlorination pattern. Of particular interest to this work was 3,3',4,4',5-pentachlorobiphenyl (PCB 126), the most potent of the dioxin-like PCB congeners. I hypothesized that in vivo PCB 126 toxicity will be ameliorated by dietary selenium supplementation, lowered dietary copper, and dietary N-acetylcysteine (NAC) supplementation. Dioxin-like PCBs are known for diminishing hepatic selenium and selenium-dependent glutathione peroxidase (SeGPx), an antioxidant enzyme. In the first study, PCB 126 caused a dose-dependent decrease in hepatic selenium and SeGPx. Supplemental dietary selenium significantly increased hepatic selenium and SeGPx, and decreased incidence of apoptosis in these rats. The results from this study support that selenium plays a protective role, and differences in liver injuries of these rats may be reflected in their selenium status. The dose-dependent increase in hepatic copper caused by PCB 126 was a subject of interest and concern in the next study. Lowering dietary copper levels without negatively affecting the function of the essential antioxidant enzyme copper zinc superoxide dismutase did not result in reduction of PCB 126-induced toxicity. Copper metabolism was unlikely a main target of PCB 126 toxicity as increasing dietary copper did not significantly increase hepatic copper levels. Hepatic copper is highly regulated and likely does not play a significant role in PCB 126-induced toxicity. The effectiveness of NAC on restoring glutathione status and reducing PCB 126 toxicity was tested in the final study. While NAC did not restore glutathione status, NAC supplemented rats had significantly reduced severity of PCB 126-induced liver status. The results of this study are consistent with the theory that NAC has a glutathione-independent effect in improving mitochondrial energy metabolism. It also suggests that PCB 126-induced mitochondrial metabolic disruption of the liver is of greater concern than oxidative stress.

The Pariette Wetlands was constructed to provide wildlife habitat in an arid environment. Elevated levels of selenium (Se) have been detected in water, soil, and biota. Selenium concentrations have ranged from below detection limit to four times the water quality criterium limit. Here we report on three interrelated research topics: 1) selenium mass balance and flux in water, 2) selenium accumulation, concentration and volatilization of water and plant tissues; and 3) selenium sorption by upland and wetlands soils. 1) Mass balance and mass water flux of selenium for the Pariette Wetlands were studied. A comparison of inlet and outlet Se fluxes was used to determine the mass of Se stored. Selenium concentrations were higher at the inlet (2.1-16.3 μg L-1) than at the outlet (2.0-14.0 μg L-1). The average amount of Se retention and/or loss was 75%. 2) Elevated levels of selenium (Se) in water, soil, and biota of the Pariette Wetlands, Utah. Twelve sample sites were selected to determine the spatial and temporal variation of Se accumulation, concentration and volatilization. At the inlet, concentrations of waterborne Se during low-flow period (winter) were significantly higher than concentrations during high-flow irrigation season (summer). Se concentrations in water at the outlet were lower during the high-flow period ranging from. In contrast, plant tissue Se concentration was lower at the inlet and higher at the outlet. Selenium volatilization results indicated that there were spatial and temporal differences among samples sites. 3) The physical and chemical properties were compared for two soils in the Pariette Draw of Utah. It appears that Se mobility is associated with the distribution of soluble salts. We surmise that soluble Se is regulated by the solubility of a sodium selenate sulfate coprecipitate.. Knowledge gained about the mass balance, storage of Se, and the associated biogeochemical processes in water, plants, and soils that contribute to the accumulation or loss of Se in the wetlands will be beneficial to future land management decisions to minimize the impact of Se exposure to wildlife.

No description available.

This thesis carefully investigates some of the limitations of existing methods for atomic spectroscopic determination of mercury, selenium and arsenic in biological and environmental materials. In particular the need for adequate sample preparation to ensure reliable atomic spectroscopic determination of these metalloids was demonstrated extensively. The thesis evaluates four most commonly used wet digestion methods for the accurate determination of mercury in biological and environmental materials by cold vapour atomic absorption spectroscopy. Excellent recovery efficiencies were obtained with this digestion mixture in fish homogenate, horse kidney, soil, canned fish and hair samples for inorganic and organic mercury. The suitability of the digestion method for the reliable determination of mercury in soil, hair and canned fish samples was also demonstrated. Mercury levels in these samples were found within normal acceptable range. The thesis outlines a new simple procedure for overcoming the loss of mercury due to sample charring. It also described a new sample ultrasound low temperature wet digestion method for biological and environmental materials. The main advantage of this approach over other conventional methods is its ability to release all mercury in inorganic form from biological and environmental samples at much lower temperatures than reported earlier / Doctor of Philosophy (PhD)

The current work investigates the photocatalytic reduction of selenium (Se) ions, selenate Se(VI) and selenite Se(IV), from two perspectives: Se ion removal from water and wastewater and the formation of nano-Se compounds. Se ion pollution has become an environmental issue in recent years, and hence there is an urgent need for an efficient removal technique. In addition, there is increasing interest in the formation of nano-size semiconductors for niche applications. Since Se is a semiconductor, its formation onto the semiconductor TiO2 could lead to the discovery of new composite materials. The current study has successfully elucidated the mechanism of Se ions reduction by photocatalysis. Factors such as the simultaneous adsorption of the Se ions (the electron scavenger in this case) and a suitable organic compound (the hole scavenger), and the chemical properties of the hole scavenger were crucial for effective and efficient Se ions photoreduction. Optimum conditions in relation to pH, concentrations and types of hole scavenger were reported and discussed. It was also found that stoichiometric adsorption ratio of formate and selenate resulted to optimum photoreduction rate. A modified Langmuir-Hinshelwood kinetic model that considered the simultaneous adsorption of both solutes was derived. The current investigation has also seen the successful formation Se deposits of different morphologies onto the TiO2 particles. Discrete Se particles of various sizes in the nano-size range as well as a Se film were deposited onto the TiO2 particles under different initial experimental conditions. The Se-TiO2 composite semiconductor was explored for the removal of cadmium Cd2+ ions, which resulted in the formation of CdSe-TiO2 systems. The photoreduction of Se ions using silver-modified TiO2 showed the enhanced reduction of Se ions to Se2- in the form of H2Se gas. It is suggested that the H2Se gas generated from the current photoreduction process could be used as a safer and cheaper technique in the formation of Se-compounds such copper selenide, cadmium selenide and zinc selenide. All these compounds were widely used in optical and semiconducting devices.

Chronic arsenic poisoning due to arsenic contamination of groundwater is a serious public health problem in Bangladesh and neighboring countries. Severe health effects associated with chronic exposure to arsenic include melanosis and several kinds of cancer. It is now generally agreed that the arsenic contamination of groundwater in Bangladesh is of geological origin. Arsenic naturally present in aquifers may be mobilized into drinking water by microbial action.<p> The formation of a novel arsenic-selenium compound: seleno-bis (S-glutathionyl) arsinium ion, [(GS)2AsSe]-, and its subsequent excretion in rabbit bile has been demonstrated previously. This molecular basis for the in vivo antagonism between arsenic and selenium was discovered using X-ray absorption spectroscopy. There is growing evidence that, in Bangladeshi people who are suffering long term chronic lowlevel arsenic poisoning, this antagonism is causing a selenium deficiency. Administering selenium supplements might provide a simple but highly effective treatment of the Bangladeshi arsenic poisoning.<p> In order to examine the disposition of [(GS)2AsSe]-, a set of rabbits were intravenously injected with selenite, arsenite or both. Whole blood, red blood cell and plasma samples were collected at different time intervals within 2hrs after injection and cecotrope samples 24hr after injection. Samples were examined using X-ray absorption spectroscopy and both arsenic and selenium K-near edge spectra were recorded.<p> iii Speciation of arsenic and selenium will be discussed in this thesis. Results indicate that [(GS)2AsSe]- is formed in blood very rapidly after injection of both arsenite and selenite, and then is removed from blood stream within 2hrs post injection. Results also show that [(GS)2AsSe]- is assembled in red blood cells, with no [(GS)2AsSe]- detected in plasma samples. [(GS)2AsSe]- is also found in cecotrope samples after injection of both arsenite and selenite.<p> The results of this study in rabbits will contribute to the understanding of chronic arsenic poisoning in humans.

An overview of synchrotrons and synchrotron radiation is presented, along with the theory and practical considerations behind several types of X-ray spectroscopy. The theory and practical considerations of density functional theory are also given, with direct reference to some specific software packages.<p> Some synchrotron-excited X-ray spectroscopy measurements and density functional theory calculations of selenium and arsenic-doped selenium films are then outlined. The physical structure of crystalline and amorphous selenium and the electronic structure of amorphous selenium are discussed and comparison is made to the experimental results.<p> A weak feature in the conduction band is identified as a "fingerprint" of the degree of crystallization in amorphous selenium from X-ray absorption measurements. Similarly, a weak feature corresponding to lone-pairs in the valence band is identified as a "fingerprint" of the arsenic concentration from X-ray emission measurements.<p> Finally a detailed model of the structure of amorphous selenium is explained, and compared to experiment. This model is tested both by direct calculations and by a reverse Monte Carlo approach. The implications of this model with respect to the structure of amorphous and arsenic-doped amorphous selenium are discussed. Calculations suggest that simply randomizing the arrangement of "perfect" trigonal selenium is unable to reproduce the measurements of amorphous selenium; a moderate variation in the bond angle of "perfect" trigonal selenium is also necessary.

The electronic properties of amorphous materials are greatly affected by the density of localized states in the mobility gap of these materials. The exact shape of the density of states (DOS) distribution in amorphous selenium (a-Se) is still unresolved despite decades of research. One of the most commonly employed methods to investigate charge transport properties in high resistivity materials is time-of-flight (TOF) transient photoconductivity experiment. The TOF transient photoconductivity technique is used to measure the induced photocurrent in the external circuit when the sample is photoexcited. Information pertaining to carrier mobility and other carrier parameters are deduced from the shape of the photocurrent. The investigation of the charge transport phenomenon is well known to be a complicated task. Monte Carlo (MC) simulation method has become a standard method for carrier transport studies in amorphous materials. The purpose of this research work is to develop a Monte Carlo simulation model for charge transport in typical TOF transient photoconductivity experiment to investigate the DOS distribution in a-Se. The MC simulations were first performed for relatively simpler models for which theoretical and analytical solutions were available. The MC model developed here is based on simulating the drift of carriers resulting from photogeneration, subject to the influence of an applied electric field and multiple trapping events. The free drift time of photocarriers and their dwell time in the traps are stochastic in nature, in accordance with the probabilities of these events. Electron time-of-flight transient photocurrents were calculated in amorphous selenium as a function of the electric field. The distribution of localized states (DOS) in a-Se has been investigated by comparing the experimentally measured and calculated transient photocurrents. The analysis of multiple-trapping transport has been done by the discretization of a continuous DOS. The DOS distribution has been optimized to produce the best agreement between the calculated and measured transient photocurrents. The resulting DOS has distinct features: A first peak at ~0.30 eV below Ec with an amplitude ~1017 eV1 cm3, a second small peak (or shoulder) at 0.450.50 eV below Ec with an amplitude 10141015 eV1 cm3, and deep states with an integral concentration 10111014 cm3 lying below 0.65 eV, whose exact distribution could not be resolved because of the limitations of the available experimental data. The density of states (DOS) distribution in the vicinity of the valence band mobility edge in vacuum coated a-Se films has been investigated by calculating the MC hole transient photocurrents at different temperatures, and also the dependence of the drift mobility on the temperature and field. The calculated TOF transient photocurrents were compared with experimental data published elsewhere. It is shown that, analogous to electron transport in a-Si:H, the DOS near Ev is a featureless, monotonically decreasing distribution in energy up to Ev + 0.4 eV, without the 0.28 eV peak near the valence band which was thought to control the hole drift mobility. Such a DOS was able to account for hole TOF data reported previously by several authors to date.

The main objective of this study was to investigate small-bodied fish caging as an approach to evaluate selenium (Se) bioaccumulation and speciation in native fish species inhabiting lakes influenced by uranium (U) milling effluent in northern Saskatchewan, Canada. In contaminated environments freshwater fish show a high propensity to accumulate Se beyond levels needed for normal physiological function. Maternal transfer of elevated Se concentrations to offspring can cause deformities and reduced survival in fry, and in certain cases negatively impact the sustainability of native fish populations. This research included a caging validation study using wild, naïve (i.e., collected from a reference lake) lake chub (Couesius plumbeus) and spottail shiner (Notropis hudsonius), and three field based 21-day caging studies to investigate the dominance of the feeding pathway with respect to Se uptake and speciation in wild populations of northern small-bodied fish exposed to a gradient of Se. Three feeding regimes were used: an in situ benthic diet, a basal Se diet of Chironomus dilutus (1.5 µg Se/g dry weight) and a Se-spiked diet of C. dilutus (5.5 µg Se/g dry weight). Lake chub were identified as more suitable candidates for caging due to higher survival and condition factor at the completion of the in situ 21-day trial. The resulting Se bioaccumulation was compared among treatments as well as to wild small-bodied fish populations from the study area. Results from the caging experiments showed that caged lake chub exposed to natural and controlled diets with elevated Se had significantly greater whole-body Se concentrations after 21 days compared to fish caged in the reference lake. The results also showed that whole-body Se concentrations exceeded conservative Se thresholds, and approached the currently proposed USEPA regulatory threshold (7.91 µg/g dry weight) designed to protect fish species in only three weeks. The use of stable carbon (C), nitrogen (N), and sulphur (S) isotope ratios indicated that alternate benthic food sources native to the exposure lake were consumed in conjunction with the controlled diets. Stable isotope analysis of both wild and caged lake chub indicated that the N and S isotopic signatures decreased with increasing Se exposure, representing differences in isotopic signatures of the food sources. Speciation results from caged lake chub indicated that Se substituted for S in methionine (i.e. selenomethionine) was the dominant Se species found in caged lake chub exposed to dietary sources of elevated Se. Overall, this research demonstrates that using caged native lake chub represents a useful biomonitoring approach to investigate patterns of Se bioaccumulation and speciation in fish.