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The work presented in this dissertation focuses on + 4 NH in marine sediments and attempts to elucidate some of the specific pathways and processes affecting + 4 NH in coastal marine regions. The majority of work was conducted in the Laguna Madre estuary. A major feature of the estuary is the Gulf Intracoastal Waterway (GIWW) connecting the Lower Laguna Madre to Baffin Bay. Establishment of the GIWW has altered the hydrodynamics of the estuary, reduced seagrass coverage and increased sediment mobility resulting in frequent maintenance by the U.S. Army Corp of Engineers. GIWW sediment relocation associated with dredging is investigated to determine potential influence of + 4 NH release during resuspension. GIWW sediments are characterized by extremely high concentrations of porewater and exchangeable + 4 NH as well as reducing ions (millimolar HS-), and significant release hours to days after resuspension was observed during laboratory experiments. Using sediment + 4 NH porewater and exchangeable quantities, release potentials are calculated for a dredging event conducted in 1989 and results indicate that potential release from the dredging event are comparable to monthly inputs from intact GIWW and seagrass sediments. Reducing condition influence on + 4 NH adsorption dynamics was tested through resuspension experiments over a wide range of initial bulk concentrations in laboratory determined redox conditions. Significant increase in + 4 NH adsorption was observed in anoxic conditions. Calculations of the apparent partition coefficient (K*) were determined to be affected as well and implications to diagenetic models is explored. Observations in the laboratory were tested in field monitoring. Analysis of wind measurements established strong potential for interaction with sediments over the collection period. Measurements of water column + 4 NH , total suspended solids, and chlorophyll exhibited highest concentrations and correlation in areas close to the GIWW. Concentration measurements were combined with flux measurements in a model system designed to integrate field observations. Several model cases were considered including and excluding sediment resuspension. Model simulations including sediment resuspension maintained water column concentrations similar to field observations.

Mineral nutrients imported in composted dairy manure (CDM) and municipal biosolid (CMB) amendments for highway-rights-of-way and urban landscapes can pose a threat to surface water quality. Treatments were developed to evaluate recommendations for amending roadside and urban soils with compost at large volumebased rates. Texas Department of Transportation (TxDOT) recommendations were evaluated in 2002 and 2003. Municipal recommendations were evaluated in 2004. Treatments were imposed on 4 by 1.5-m field plots on a constructed soil with an 8.5% slope. Three TxDOT compost application methods were tested; incorporation at 25% by volume (CMT), topdressing over vegetation (GUC), and topdressing a 5-cm compost woodchip mix over bare soil (ECC). In 2003, a 12.5% CMT treatment was substituted for the GUC, and two contrasting composts were compared. In 2002, soil test phosphorus (STP) concentrations (mg kg-1) were 291, 360, 410, and 1921 mg kg-1 in the 0 to 5-cm layer of a course textured CMT, fine textured CMT, GUC, and ECC treatments, respectively using CDM. In 2003, STP concentrations were 264, 439, 496,623, 1115, and 2203 mg kg-1, in the 0 to 5-cm layer after incorporation of CDM and CMB at the 12.5 and 25% volume-based rates, and topdressing the 5-cm CDM- or CMB-woodchip mix over bare soil, respectively. In 2004, contrasting CMB products, relatively low or high in total phosphorus (TP) were incorporated into the soil at 12.5 and 25% by volume, or imported in transplanted sod at the 25% by volume rate. The STP concentrations were 87, 147, 180, 301, 322, and 544 mg kg-1, respective to the previously defined treatments. Runoff water from 14, 10, and 8 natural rain events was used to characterize nutrient and sediment transport in 2002, 2003, and 2004, respectively. Concentration of TDP in runoff water was highly variable for roadside treatments across rain events. Mass losses of TDP were similar after CDM or CMB were incorporated into the soil at 12.5 and 25% by volume. Compost incorporation was the most effective method for limiting TP loss in runoff. Roadway and urban soils are expected to contribute greater TP losses as P concentration increases in soils.

Six Quarter Horse yearling fillies were used in a duplicated 3 x 3 Latin square designed experiment to evaluate the technique of nitrogen retention as a response criterion for amino acid studies in the horse. The yearlings were paired by age and randomly assigned to one of three concentrates fed with a medium quality Coastal Bermudagrass hay throughout the study. Diets were fed at approximately 1.9% of horse body weight per day, divided into twice daily feedings with a 60:40 concentrate: hay ratio. With the exception of lysine and threonine, proposed amino acid requirements for yearling horses were calculated using nutrient to calorie ratios of gilts weighing 80-120 kg and gaining 325 g/d. Diet A was amino acid sufficient, as provided by a soybean meal-based concentrate. Diet B was amino acid deficient, with a cottonseed hull-based concentrate. Diet A and Diet B were isonitrogenous, containing approximately 12% crude protein. Diet C used the identical concentrate as Diet B, with synthetic essential amino acids and cysteine orally dosed to match the amino acid levels in Diet A. Nitrogen retention was not different between Diet A and Diet B. Diet C resulted in differences from Diets A and B in nitrogen retention; however, differences were a consequence of nitrogen intake. Nitrogen retained as a percent of nitrogen absorbed was lower (P < 0.05) for Diet B than for Diet A, for data not accounting for endogenous fecal and urinary losses. There were no differences in nitrogen retained as a percent of nitrogen absorbed for horses fed Diet C, when compared to either Diet A or Diet B, for data not accounting for endogenous losses. It was concluded that differences in nitrogen retained as a percent of nitrogen absorbed were observed between amino acid sufficient diets and amino acid deficient diets. However, horses fed amino acid deficient diets and orally dosed with synthetic amino acids, likely require some modified dosage level to achieve the same or higher values in nitrogen retained as a percent of nitrogen absorbed as those values for amino acid sufficient diets.

The work presented in this dissertation focuses on + 4 NH in marine sediments and attempts to elucidate some of the specific pathways and processes affecting + 4 NH in coastal marine regions. The majority of work was conducted in the Laguna Madre estuary. A major feature of the estuary is the Gulf Intracoastal Waterway (GIWW) connecting the Lower Laguna Madre to Baffin Bay. Establishment of the GIWW has altered the hydrodynamics of the estuary, reduced seagrass coverage and increased sediment mobility resulting in frequent maintenance by the U.S. Army Corp of Engineers. GIWW sediment relocation associated with dredging is investigated to determine potential influence of + 4 NH release during resuspension. GIWW sediments are characterized by extremely high concentrations of porewater and exchangeable + 4 NH as well as reducing ions (millimolar HS-), and significant release hours to days after resuspension was observed during laboratory experiments. Using sediment + 4 NH porewater and exchangeable quantities, release potentials are calculated for a dredging event conducted in 1989 and results indicate that potential release from the dredging event are comparable to monthly inputs from intact GIWW and seagrass sediments. Reducing condition influence on + 4 NH adsorption dynamics was tested through resuspension experiments over a wide range of initial bulk concentrations in laboratory determined redox conditions. Significant increase in + 4 NH adsorption was observed in anoxic conditions. Calculations of the apparent partition coefficient (K*) were determined to be affected as well and implications to diagenetic models is explored. Observations in the laboratory were tested in field monitoring. Analysis of wind measurements established strong potential for interaction with sediments over the collection period. Measurements of water column + 4 NH , total suspended solids, and chlorophyll exhibited highest concentrations and correlation in areas close to the GIWW. Concentration measurements were combined with flux measurements in a model system designed to integrate field observations. Several model cases were considered including and excluding sediment resuspension. Model simulations including sediment resuspension maintained water column concentrations similar to field observations.

The active center of copper proteins can divide into Type I, Type II and Type III categories according to their copper coordinated environment. The synthesis and characterization of thiol ligands, NSC2SN(1c): N1,N2-bis(2-mercaptoethyl)-N1,N2-bis-(2-pyridinylmethyl)- 1,2-ethanediamine and NSC4SN(1d): N1,N4-bis(2-mercaptoethyl)-N1,N4- bis(2-pyridinylmethyl)-1,4-butane-diamine to mimic that active center of copper proteins are described. Those new types of ligands (1c and 1d) react with [Cu(CH3CN)4]ClO4 afford the mononuclear copper complexes. On the other hand, the synthesis of the known tripodal ligand TNPA(4b): 2,2¡¦2,¡¨-nitrilotris(N-(pyridine-2-yl)acetamide) and new tripodal ligand TNPMA(4c): 2,2¡¦2¡¨-nitrilotris(N-(pyridin-2-ylmethyl)acetamide) are also characterized. The reactivity of [Cu(CH3CN)4]BF4 of two tripodal ligands are described.

Nitrogen fixation is an ecologically important microbial process that can contribute bioavailable combined N to habitats low in N. Shipworms, or wood-boring bivalves, host N2-fixing and cellulolytic symbiotic bacteria in gill bacteriocytes, which have been implicated as a necessary adaptation to an N-poor C-rich (wooden) diet. Shipworm symbionts are known to fix N within the gill habitat and newly fixed N is subsequently incorporated into non-symbiont containing host tissue. The presence of N2-fixation in gill bacteriocytes presents a conundrum because N2-fixation is tightly regulated by oxygen in most other diazotrophic microbes. Also, the direct evidence of new N being incorporated into the host tissue indicates that there are potentially complex nutrient cycles in this symbiosis, which have not been investigated. We used the cultivated symbiont Teredinibacter turnerae, which has been isolated from many shipworm species, as a model organism to elucidate controls on N2-fixation and N release in the shipworm symbiosis. Our results indicate that headspace oxygen concentration does not control biomass specific N2-fixation and respiration activity in T. turnerae, but it does influence the magnitude of the growth rate and timing of culture growth. Also, we examined the controls of oxygen on inorganic nutrient uptake rates, and documented a small amount of dissolved inorganic nitrogen release. While the N budget is only partially balanced, we provide indirect evidence for the allocation of fixed N to the excretion of exopolymeric substances and dissolved organic nitrogen; future studies that measure these additional N sinks are necessary to close the N budget. Although there are limitations of using pure cultures to investigate a complex symbiotic system, this study provides direct experimental evidence that T. turnerae has adaptations that are conducive to N2-fixation in gill bacteriocytes.

Thesis (Ph. D.)--Lehigh University, 2000. / Includes bibliographical references and vita.

Thesis (Ph. D.)--University of Chicago, Dept. of Molecular Genetics and Cell Biology, June 2001. / Includes bibliographical references. Also available on the Internet.

Thesis (M.S. in crop science)--Washington State University, December 2009. / Title from PDF title page (viewed on Jan. 13, 2010). "Department of Crop and Soil Sciences." Includes bibliographical references.