No description available.

High-pressure homogenization using a new flat valve homogenizer in combination with enzymatic digestion with a crude protease was investigated as a means of releasing Se compounds from zoological and botanical matrices prior to slurry introduction GF-AAS. Timed trials with four zoological certified reference materials (CRMs), three botanical reference materials (RMs), and a food crop indicated that Se release was quantitative after homogenization or became quantitative within 1 h of digestion at 60°C. / The same technique was employed on five animal feed samples. / A new model of homogenizer equipped with ceramic homogenizing valve was evaluated in terms of analyte metal contamination levels within the final sample dispersion. / Five animal feed samples and four wood pulp samples, were investigated for their content of Cu, Fe and Mn using high-pressure homogenization as the sample preparation technique prior to GF-AAS. Dispersions of dried animal feeds were sub-sampled reliably after 7 days of storage at 4°C. Trials on pulp samples indicated that pulps could be sub-sampled reliably after 1 day of storage. (Abstract shortened by UMI.)

An important task of research on trace metals in soils is to evaluate how much metals are potentially bioavailable and may cause toxic effects. In this thesis, the chemical speciation and complexation of cadmium (Cd), copper (Cu), mercury (Hg) and lead (Pb) were examined in eastern Canadian soils collected from different locations around smelters. Our goal is to be able to predict metal binding in the soil solution and on the solid phase under a wide range of field conditions. / In Chapter 2, speciation of Cd, Cu and Pb in the lysimeter soil solutions was determined using an ion exchange technique (IET) involving a resin column. The IET-speciation data were used to estimate the metal-dissolved organic carbon (DOC) binding constants using the non-ideal competitive adsorption (MICA)-Donnan model, which assumed a continuous distribution of binding affinities on the DOC molecule. The published Cd and Pb speciation data in a variety of soils (Chapter 3) were also used to test the effectiveness of two speciation models, the MICA-Donnan model and WinHumicV. Both models satisfactorily predicted the concentrations of Cd2+ and Pb2+. The two chapters of metal speciation demonstrated that the NICA-Donnan model could estimate the binding strength of organic matter in soil solutions. / Proton and metal complexation to the surface of soil particles (Chapters 4 and 5) was investigated using back-titration and batch adsorption procedures. It was shown that the surface binding of H+, Cd2+, Hg2+ and Pb2+ was significantly related to soil organic matter (SOM). Though the soil particle surface was covered by a mixture of organic and mineral components, a two-site distribution could be identified from the titration curves. With the parameters derived from the back-titration and adsorption data, the MICA-Donnan model reasonably predicted the surface complexation of proton and metals. Furthermore, the statistically significant relationships between the model parameters and soil organic matter supported the assumptions in this thesis: (1) Organic matter was the most important sorbent on the particle surface; (2) The MICA-Donnan model may be used to interpret the surface binding data in these soils.

No description available.

In the past 20 years, boron has been identified as an essential trace element for animals and humans but also as an increasingly important industrial pollutant. We examined first whether boron influenced survival of the gastrointestinal nematode Heligmosomoides bakeri. Female Balb/c mice were fed deficient (0.1 mug B/g), marginal (2.0 mug B/g) or control (12.0 mug B/g) diets, and infected with third-stage larvae. Although liver boron concentrations did not differ among diet groups, dietary boron deficiency impaired survival of the parasite and modulated a broad range of cytokines and chemokines. On the other hand, infection history altered liver mineral concentrations. Second, we examined whether elevated boron concentrations would exert toxic effects on H. bakeri in vitro. Boron toxicity was evidenced by reduced motility, fecundity, infectivity and survival. Feeding stages and free-living stages were more sensitive than non-feeding stages and parasitic stages respectively in a dose-dependent manner.

In this thesis, new approaches to direct trace metals analysis of solid samples by inductively coupled plasma spectroscopy were investigated using laser ablation and thermal vaporization systems for solid sample introduction of biological, environmental, and pharmaceutical samples. / Laser ablation with inductively coupled plasma atomic emission spectroscopy (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) was applied to pharmaceutical tablets. Precision of analysis depended on laser parameters and could be improved using signal ratios. The feasibility of using laser ablation-ICP-MS for detecting natural levels of mercury along a single human hair strand was also demonstrated. / As well, the use of an induction-heating electrothermal vaporizer (IH-ETV) coupled to an ICP-MS was successful in determining mercury concentrations in a single human hair strand. Methodologies for multielement analysis of powdered hair were also explored using IH-ETV-ICP-MS. While calibration by reference hair materials showed promise, calibration methods by liquid standards were not suitable for any element. Detection limits achieved for most elements were below natural levels found in human hair. / IH-ETV-ICP-AES was also applied to the analysis of analyze-laden chromatographic powder. This study showed potential problems that may arise due to the methodology taken to analyze such materials. Finally, recommendations for future investigations and methodologies for laser ablation and thermal vaporization are discussed.

Bioavailability of trace metals in urban contaminated soils was investigated to relate chemical extraction efficiencies with biological effects. / Results from a Collembola reproduction bioassay showed minimal toxicity suggesting limited bioavailability. Chemical extractions were carried out on these urban soils. The sodium acetate extraction was the best predictor of the biological effects of Cd while the biological effects of Zn were best explained by a water extraction. / An earthworm uptake bioassay was done to quantify the bioavailable fractions. Cadmium, Cu, Pb and Zn accumulated in Lumbricus terrestris L. The sodium acetate extraction was the best predictor of Cd uptake while calcium chloride extraction best predicted Zn uptake by earthworms. / Treatments were made to urban soils to immobilize the metals and reduce their bioavailability. The metal concentrations were so low in the soils that the effects of the treatments could not be measured. / Collembola and earthworms are good indicators of trace metal bioavailability and should be included in the evaluation of contaminated soils.

The current study investigated application of natural adsorbents in brine treatment. Brines are hypersaline waters generated in power stations and mining industries rich in Mg2+, K+, Ca2+, Na+, SO4 2- , Cl- and traces of heavy metals, thus there is a need for these brines to be treated to recover potable water and remove problematic elements. Natural adsorbents have been successfully used in waste water treatment because of their high surface area and high adsorptive properties when they are conditioned with acid or base. The investigation of pH showed that natural adsorbents did not perform well at low pH of 4 and 6. The adsorbents were able to work efficiently at the natural pH of 8.52 of the brine solution. These results show that natural adsorbents hold great potential to remove cationic major components and selected heavy metal species from industrial brine wastewater. Heterogeneity of natural adsorbents samples, even when they have the same origin, could be a problem when wastewater treatment systems utilizing natural clinoptilolite and bentonite are planned to be developed. Therefore, it is very important to characterize the reserves fully in order to make them attractive in developing treatment technologies.

The factors affecting the accumulation of nitrate in kikuyu grass pastures and the effect of elevated nitrate levels upon digestion in the ruminant were investigated. A high potassium level in the soil seems to be the major factor stimulating the accumulation of excessive amounts of nitrate in kikuyu grass, when the nitrate content of the soil is also high. The continuous elongation of kikuyu grass tillers allows constant exposure of high nitrate containing stem tissue to the grazing ruminant. Digestibility studies in vitro showed that nitrite, formed during the assimilatory reduction of nitrate to ammonia, reduces cellulose digestion, but the degree of reduction also depends upon the presence of readily available carbohydrates and protein in the digest. Studies in vivo showed that the microbial population can adapt to metabolise high concentrations of nitrate (500 mg% N, m/m) in fresh kikuyu grass, without the accumulation of nitrite in the rumen. However, introduction into the rumen of nitrite in excess of the capacity of the nitrite reducing microbes, causes nitrite accumulation. Nitrite has no direct effect upon rumen cellulase activity. Due to the affinity of rumen carbohydrases for the substrate, attempts to isolate these enzymes by means of isoelectric focusing and other separation techniques met with limited success. Nitrite strongly reduces the xylanolytic, total and cellulolytic microbial numbers with a concomitant decrease in xylanase and cellulase activity of the digest. Decreased microbial numbers could not be .attributed to a less negative redox potential of the digest in the presence of nitrite, nor could the effect upon the cellulolytic microbes be attributed to an effect of nitrite on branched chain fatty acid synthesis required for cellulolytic microbial growth. A study of the effect of nitrite upon the specific growth rate of pure cultures of the major cellulolytic bacteria, Ruminococcus flavefaciens strain FDI, Butyrivibrio fibrisolvens strain Ce 51, Bacteroides succinogenes strain S 85 and Ruminococcus albus strain 22.08.6A and the non-cellulolytic bacterium Selenomonas ruminantium strain ATCC 19205 revealed the extreme sensitivity to nitrite of some of these bacteria and the relative insensitivity of others. Growth inhibition seems to depend primarily upon the extent to which these microbes derive their energy from electron transport-mediated processes. / Thesis (Ph.D.)-University of Natal, Pietermaritzburg, 1985.

Carbonatites are igneous rocks comprising more than 50 modal percent of carbonate minerals and characterized by highly variable modal compositions. The majority of carbonatites are confined to intra-continental rifts, whereas occurrences associated with plate margins and orogenic settings are less common. Petrogenesis of carbonatites has been a matter of intense debate for several decades. The possible genetic models include crystallisation from a primary carbonatite magma, liquid immiscibility and crystal fractionation from carbonate-rich silicate magma. In contrast to the voluminous bulk-rock trace-element data and major-element analyses of minerals from carbonatites available in the literature, there has been no systematic study concerned with the trace-element signatures of the most common constituents of these rocks. This work is the first comprehensive study of the interrelations between the trace-element chemistry of the most common constituents of carbonatites, the geochemistry of these rocks, and their tectonic setting. The rock samples examined represent 21 different localities worldwide. The extent of major- and trace-element substitutions in amphibole, clinopyroxene, trioctahedral micas, dolomite, magnetite and perovskite is investigated in detail. The silicate minerals from carbonatites exhibit much larger compositional diversity than previously recognized. They can incorporate significant amounts of such petrogenetically important elements as Sr, REE, Zr, Nb and Ta. The majority of studied clino-amphibole- and clinopyroxene-group minerals exhibit previously unrecognized a bimodal distribution patterns of REE, which can be explained in terms of crystal chemistry of these phases. The trace-element signature of phlogopite from carbonatites, particularly Nb, Mn, Ni and Cr, is distinctly different from that of phlogopite from kimberlites, and can be used as a reliable petrogenetic indicator. Compositional variations in dolomite reflect magmatic and subsolidus processes in carbonatites. Magnetite from carbonatites follows a well-defined magmatic and previously unrecognized reaction trend. Contrary to prior studies, this mineral is only a minor host of HFSE in carbonatitic rocks. The U-Pb age data, trace-element and Sr-isotopic composition of perovskite from the Afrikanda carbonatite and clinopyroxenite suggest that the two rocks are not related by crystal fractionation. This study underlines the importance of a systematic approach in petrogenetic studies based on trace-element distribution.