The influence of pH on metal extractability from two sacrificial soils that received large amounts of biosolids was studied in four separate trials. The soils (Soil 1: gravelly sandy loam; Soil 2: sandy clay loam) were collected from different water treatment plants in Gauteng. Both soils had undergone significant changes in physical (organic carbon content) and chemical characteristics (pH, metal and nutrient content) due to the prolonged disposal of biosolids. A preliminary pot trial was conducted where large quantities of lime were added to the soils. Results indicated that the soils had high pH buffer capacities due to low pH and high organic matter content. An unexpected increase in the metals extracted with NH4EDTA after intensive liming lead to the performing of three further trials to shed light on the phenomenon. In the second trial lime was added to the soils at four rates (0, 12, 24, 36 tons ha-1). An increase in most NH4EDTA extractable metals was found and this was correlated with increasing absorbance values (at 465 nm) of the extracting solutions (indicating increased extractability of organic matter). In the third trial limed (27 ton ha-1) and unlimed samples were incubated over a period of 20 weeks with regular sampling intervals. The NH4NO3 extractable metals decreased significantly in the lime treated soils but the NH4EDTA extractable metals generally increased. A fourth trial was conducted due to concern regarding the increased EDTA extractable metals after liming and a possible correlation with plant metal bioavailability. The soils were incubated in pots with four lime rates (0, 12, 24, and 36 ton ha-1) and wheat and spinach grown for two months. Although similar trends as for the previous trials were obtained in terms of metal extractability, plant metal content was best correlated with NH4NO3 extraction levels. The results indicate that liming is a safe option for sacrificial soils and that NH4NO3 extractable and plant metal levels decrease with liming. The use of EDTA in metal guidelines or in soil metal content studies is discouraged due to its increased metal extractability with liming and poor correlation with plant metal content. / Thesis (PhD)--University of Pretoria, 2005. / Plant Production and Soil Science / Unrestricted

Bioremediation was studied in soils containing high concentrations of formulated chlorpyrifos (5 mg kg-1 Dursban® 4E) and atrazine (5 mg kg-1 AAtrex® 4L) using amendments including lignocellulosic sorbents, microbial nutrients (vegetable oil, corn meal and fertilizers), and microbial extracts from organic media previously exposed to these pesticides (chlorpyrifos and atrazine, respectively). Radiolabeled atrazine was used to examine the various dissipation routes in contaminated soil, also amended with lignocellulosic sorbents and microbial nutrients. Both chlorpyrifos and atrazine dissipation from contaminated soils was enhanced by organic-based material amendments. The half-lives of chlorpyrifos based on extractability for soils unamended and amended with vegetable oil and peat moss were 87 and 52 days, respectively. The half-lives of atrazine in unamended and amended soil (vegetable oil, peat moss and fertilizers) were 175 and 40 days, respectively. The leachability of chlorpyrifos from contaminated soil was dramatically reduced by 82% during the first 30 days of incubation in treatments amended with vegetable oil and peat moss while only a 28% of reduction in leachability occurred in the corresponding unamended controls. Only a slight reduction of atrazine leachability was detected in amended treatments after 120 days of incubation. Differences were found in the leachability of chlorpyrifos and atrazine when they were applied to soil either as technical grade or formulated material. The presence of surfactants and other adjuvants in formulated chlorpyrifos (Dursban® 4E) reduced chlorpyrifos leachability in contaminated soil. Chlorpyrifos leachability was reduced by 43% in the formulated chlorpyrifos treatments, whereas there was a negligible decrease in technical chlorpyrifos treated soil during the first 3 days after contamination. Atrazine extractability and leachability was not affected by its formulation (AAtrex® 4L). Amendments with lignocellulosic sorbents and nutrients decreased atrazine®s volatility from contaminated soils. After 16 weeks of incubation, less than 1% of 14C-atrazine was volatilized from incubated soils. Overall, after 16 weeks of incubation less than 4% of 14C-atrazine was mineralized and more radioactivity was recovered from amended treatments than unamended treatments as 14CO2. The major portion of radioactivity (62%) was associated with physisorbed atrazine represented by the ethylacetate extract I from unamended treatments while only 28% of initial applied radioactivity was recovered in the corresponding amended treatments. Based on the sum of radioactivity in humic and fulvic acids, approximately 14% of radioactivity was incorporated or chemisorbed atrazine and its metabolites in both unamended and amended treatments. Forty-five percent of the initially applied radioactivity was associated with alkali insoluble fraction in amended treatments but only 17% of the initially applied radioactivity was detected in the corresponding unamended treatments. Less than 2 % of initial activity associated with physisorbed portions of fulvic acids and alkaline insoluble fraction indicated as the radioactivity in methylene chloride and ethylacetate extract II . Over time, more radioactivity was associated with polar atrazine hydroxylated degradation products. / Ph. D.

A procedure was developed for the extraction of rennet from fresh frozen vells. Frozen vells were minced in a Model VCM-25 Hobart Vertical Cutter/Mixer. Dry sodium chloride was added until the salt concentration in the moisture of the tissue was 10%. Salted tissue was placed in galvanized steel cells and heated in a water bath to 49, 54, 57 and 60 C for 0, 15, 30, 45 and 60 minutes. The heated tissue was dried to about 4% moisture at ambient temperature with the aid of an electric fan. The dried salted tissue was extracted with a sodium chloride solution adjusted to give a salt concentration of 10% in the extraction solution. Salted vell tissue heated to 49 C for 60 minutes and to 54 C for 30 minutes prior to drying produced 82 and 55%, respectively, more recoverable enzyme activity than unheated salted tissue. However, tissue which was salted, heated and not dried prior to extraction produced less recoverable activity than unheated samples. Unsalted vell tissue which was heated to 49, 54, 57 and 60 C for 15, 30, 45 and 60 minutes and extracted without being dried yielded lower recoverable activity than unheated samples. Heating unsalted vell tissue to 54, 57 and 60 C for 15, 30, 45 and 60 minutes prior to drying did not increase recoverable enzyme activity over unheated samples. Unsalted tissue heated to 49 C produced a slightly higher recovery than unheated samples.

L'objectif de la thèse est de contribuer à l'explicitation du lien au terroir, dans le cas de vins d'Appellation d'Origine Contrôlée. À ce lien au terroir correspond une typicité, qui correspond à des propriétés remarquables et partagées pour un groupe humain de référence. Le lien causal entre typicité et terroir a été étudié en prenant comme élément d'étude le chantier de vendange et les vinifications associées. La composition phénolique des vendanges, et leur aptitude à être extraits lors de la vinification ont permis de mieux interpréter le lien causal étudié. La représentation conceptuelle de la typicité, qui engendre des choix techniques, a été mise en évidence, du point de vue des critères sensoriels d'appartenance et des critères sensoriels de distinction. Cette représentation conceptuelle est en générale consensuelle, et les principaux facteurs du terroir, explicatifs du lien, correspondent au milieu physique. La représentation perceptuelle a été étudiée, permettant de mettre en évidence des descripteurs d'appartenance et de distinction, et de les hiérarchiser vis à vis de la perception globale de la typicité. Cette représentation est moins consensuelle. Les principaux facteurs du terroir, explicatifs du lien, correspondent aux actes techniques, en particulier la date de vendanges et la durée de cuvaison.Une évolution de la composition de la vendange en fonction du niveau de maturité a été mise en évidence d'un point de vue histologique, mais son interprétation est incomplète. L'aptitude des proanthocyanidines à être extraits, en fonction du niveau de maturité des baies est fortement corrélé à la perception globale de la typicité. Dans le cas de vins revendiquant un lien au terroir, certaines représentations de la typicité sont partagées, et engendrent des choix techniques (date de vendange, durée de cuvaison). L'importance de ces choix peut être démontré par l'étude de la composition de la vendange en composés phénoliques. Cependant, il existe un écart entre la typicité en tant que concept et la typicité telle qu'elle est sensoriellement perçue. / The aim of this work is to contribute to highlight the terroir effect, in the case of wines from delimited origin. The typicality is the result of the terroir effect and corresponds, to remarkable and shared properties for a human group of reference. The causal link between typicality and terroir was studied by taking into account the harvest date and the associated wine makings. The phenolic composition of the grape at harvest, and their extractability during the wine making made it possible to better interpret the studied causal link. The conceptual representation of the typicality, which generates technical choices, was highlighted, from the point of view of the sensory criteria of similarity and of distinction. This conceptual representation is in general consensual, and the main factors of the terroir, which explain the causal link, correspond to the soil and climate. The perceptual representation was studied, descriptors of similarity and distinction were highlighted, and theses descriptors were organized with respect to the global perception of the typicality. This representation is less consensual than conceptual one. The main factors of the terroir, which explain the causal link, correspond to the technical acts, particularly the harvest date and the vatting duration.Composition of the harvest, according to the level of maturity was highlighted from a histological point of view, but its interpretation was unfinished. The aptitude of the proanthocyanidins for being extracted, according to the level of maturity is strongly correlated for the global perception of the typicality. For wines related to terroir, some typicality representations are shared, and lead to technical choices (harvest date, duration of vatting). These choices are explained by the harvest composition. However, there is a difference between the typicality as a concept and the typicality as sensory perception.

TNT (2,4,6-trinitrotoluene) readily and predominantly transforms to 2ADNT (2-amino-4,6-dinitrotoluene) and 4ADNT (4-amino-2,6-dinitrotoluene) in environmental matrixes and tissues. Solid phase microextraction (SPME) was used to extract ADNTs (amino-dinitrotoluenes) from tissue as a potential method to investigate the recalcitrance of metabolically-generated ADNTs versus absorbed ADNTs. Tubifex tubifex was allowed to metabolize TNT into ADNTs in 24-hr static non-renewal exposure test followed by 24-hr depuration in clean reconstituted hard water. Polyacrylate-coated (PA) SPME fibers were then deployed and agitated in tissue homogenates containing metabolically-generated ADNTs for 48 hr to provide a measure of available ADNTs. Extractability of ADNTs from T. tubifex tissue containing metabolically-generated ADNTs was significantly less than extractability of ADNTs from T. tubifex tissue containing absorbed ADNTs: 50-60% and 81-90% of expected extractability based on fiber-water partition ratio. The lower SPME extractability of metabolically-generated ADNTs may stem from the unavailability of metabolically-generated ADNTs sequestered in tissue or bound to tissue macromolecules during metabolism of TNT to ADNT. Tissue extractions using SPMEs may be able to estimate such bound organic residues in tissue and serve as potential indicators of toxicological bioavailability and biomagnification potential of tissue-associated organic compounds.