A hypothesis for the geochemical anomaly in the North Creek Watershed /

A regional geochemical reconnaissance by bottom stream sediment sampling, has delineated an area of high metal content in the north central sector of the North Creek Watershed. Development of a geochemical model, relating to the relative chemical concentrations derived from the chemical analyses of bottom sediments, suspended sediments, stream waters and well waters collected from the north central sector, was designed to discover the source of the anomaly. Samples of each type of material were analysed by the A.R.L. Direct Reading Multi-element Emission Spectrograph Q.A. 137 for elements: Na, K, Ca, Sr, Si, As, Pb, Zn, Cd, Ni, Ti, Ag, Mo, Be, Fe, AI, Mn, Cu, Cr, P and Y. Anomalous results led to the discovery of a spring, the waters of which carried high concentrations of Zn, Cd, Pb, As, Ni, Ti, Ag, Sr and Si. In addition, the spring waters had high concentrations of Na, Ca, Mg, 504 , alkalinity, N03' and low concentrations of K, Cl and NH3. Increased specific conductivity (up to 2500 ~mho/cm.) was noted in the spring waters as well as increased calculated total dissolved solids (up to 2047 mg/l) and increased ionic strength (up to 0.06). On the other hand, decreases were noted in water temperature (8°C), pH (pH 7.2) and Eh (+.154 volts). Piezometer nests were installed in the anomalous north central sector of the watershed. In accordance with the slope of the piezometric surface from wells cased down to the till/bedrock interface, groundwater flow is directed from the recharge area (northwest of the anomaly) towards the artesian spring via the highly fractured dolostone aquifer of the Upper Eramosa Member. The bedrock aquifer is confined by the overlying Halton till and the underlying Lower Eramosa Member (Vinemount Shale). The oxidation of sphalerite and galena and the dissolution of gypsum, celestite, calcite, and dolomite within the Eramosa Member, contributed its highly, dissolved constituents to the circulating groundwaters, the age of which is greater than 20 years as determined by tritium dating. Groundwater is assumed to flow along the Vinemount Shale and discharge as an artesian spring where the shale unit becomes discontinuous. The anomaly is located on a topographic low where bedrock is close to the surface. Thermodynamic evaluation of the major ion speciation from the anomalous spring and surface waters, showed gypsum to be supersaturated in these spring waters. Downstream from the spring, the loss of carbon dioxide from the spring waters resulted in the supersaturation with respect to calcite, aragonite, magnesite and dolomite. This corresponded with increases in Eh (+.304 volts) and pH (pH 8.5) in the anomalous surface waters. In conclusion, the interaction of groundwaters within the highly, mineralized carbonate source (Eramosa Member) resulted in the characteristic Ca*Mg*HC03*S04 spring water at the anomalous site, which appeared to be the principle effect upon controlling the anomalous surface water chemistry.

Iridium(I) complexes of phenanthroline-derived benzimidazolylidenes : synthetic, structural and catalytic studies

N-heterocyclic carbenes (NHCs) have undergone rapid development in recent years. Due to their strong a-electron donation and structural variability properties, NHCs are becoming a major class of ligands in organometallic chemistry. Compared with the other two types of NHCs (imidazolylidenes and imidazolinylidenes), benzimidazolylidenes have not been well represented. Limited synthetic approaches may impede the development ofbenzimidazolylidenes. This thesis is focused on the synthesis of phenanthroline-derived benzimidazolylidene ligands and their metal complexes. A series of benzimidazolylidene-iridium complexes were synthesized and characterized spectroscopically and crystallographic ally. All of the new complexes showed varying degrees of catalytic activity and enantioselectivity toward transfer hydrogenation and asymmetric hydrogenation. The best results were achieved in hydrogenation of methyl-2-acetamidoacrylate, which afforded (-)-(R)-methyl-2-acetamidopropanoate in 97% yield and 81 % ee.

Isolation and characterization of a chitinase-secreting mutant of mortierella pusilla with altered interaction with the mycoparasite piptocephalis virginiana

Mortierella pusilla is a susceptible host and supports good growth of the mycoparasite, Piptocephalis virginiana. Uninucleate spores of M. pusilla were sUbjected to N-methyl-N'-nitro-nitrosoguanidine (MNNG). To attain a high mutation frequency , a 1o-minute exposure to 10 mg/ml MNNG was used and lead to the survival of about 10 % of the spores. The exposed spores then were plated on chitin or milk plates. Approximately 30,000 colonies were examined after mutagenesis on the screening media. A strain, MUT23 , with abnormal slow growth morphology was found to delay parasitism by £. virginiana. The particular morphology was not due to auxotrophy, because this strain displayed normal hyphae when glucose was used as the sole carbon source. One interesting phenomenon was that MUT23 showed an extensive clearing zone around the colony on colloidal chitin agar after 20-25 d. On the same conditions, wild type strain did not show this phenotype. In addition, the MUT23 strain produced the same normal hypha as the wild type strain when it was grown on colloidal chitin agar. The MUT23 was also able to produce more spores on colloidal chitin agar than on malt-yeast extract and minimal media. The parasite germ tubes formed appressoria at the point of contact on the cell surface of wild type and MUT23 grown for 6 days cell surface but not on the cel surface of MUT23 grown for 2 days. Thus, interaction between MUT23 strain and the mycoparasite was dependent on MUT23 age. The effect of MUT23 filtrate on germination of the parasite was tested. Lysis of germinated spores of the parasite were observed in concentrated MUT23 filtered solution. MUT23 was compared to the wild type strain for their chitinase production in sUbmerged culture. The chitinase isozymes of both wild type and MUT23 were shown by immunoblotting. Eight distinct chitinase molecules were detected. MUT23 showed markedly higher chitinase activity than the wild type cultured in chitin-containing medium. Maximum chitinase activities of MUT23 were 13.5 fold higher at 20 day of the culture then that of wild type.