Investigations into phosphorus removal by constructed wetlands : root bed media modifications /

A study has been conducted focusing on how the phosphorus renrx)val efficiency of a constructed wetland (CW) can be optimized through the selective enrichment of the substratum. Activated alumina and powdered iron were examined as possible enrichment compounds. Using packed glass column trials it was found that alumina was not suitable for the renx)val of ortho-phosphate from solution, while mixtures of powdered iron and quartz sand proved to be very efficient. The evaluation of iron/sand mixtures in CWs planted with cattails was performed in three stages; first using an indoor lab scale wetland, then an outdoor lab scale wetland, and finally in a small scale pilot project. For the lab scale tests, three basic configurations were evaluated: using the iron/sand as a pre-filter, in the root bed. and as a post filter. Primary lagoon effluent was applied to the test cells to simulate actual CW conditions, and the total phosphorus and iron concentrations of the influent and effluent were nfK)nitored. The pilot scale trials were limited to using only a post filter design, due to in-progress research at the pilot site. The lab scale tests achieved average renrK>val efficiencies greater than 91% for all indoor configurations, and greater than 97% for all outdoor configurations. The pilot scale tests had an average renK)val efficiency of 60%. This relatively low efficiency in the pilot scale can be attributed to the post filters being only one tenth the size of the lab scale test in terms of hydraulic loading (6 cm/day vs. 60 cm/day).

Modifications to the Suzuki reaction and mechanistic insights on the NBS mediated cleavage of benzylidene acetals /

One of the most challenging tasks for a synthetic organic chemist today, is the development of chemo, regio, and stereoselective methodologies toward the total synthesis of macromolecules. r . The objective of my thesis was to develop methodologies towards this end. The first part of my project was to develop highly functionalized chirons from D-glucose, a cheap, chiral starting material, to be utilized in this capacity. The second part of the project dealt with modifying the carbon-carbon bond forming Suzuki reaction, which is utilized quite often as a means of combining molecular sub units in total synthesis applications. As previously stated the first area of the project was to develop high value chirons from D-glucose, but the mechanism of their formation was also investigated. The free radical initiated oxidative fragmentation of benzylidene acetals was investigated through the use of several test-case substrates in order to unravel the possible mechanistic pathways. This was performed by reacting the different acetals with N-bromosuccinimide and benzoyl peroxide in chlorobenzene at 70^C in all cases. Of the three mechanistic pathways discussed in the literature, it was determined, from the various reaction products obtained, that the fragmentation of the initial benzylic radical does not occur spontaneously but rather, oxidation proceeds to give the benzyl bromide, which then fragments via a polar pathway. It was also discovered that the regioselectivity of the fragmentation step could be altered through incorporation of an allylic system into the benzylidene acetal. This allows for the acquisition of a new set of densely functionalized. chiral, valuable synthetic intermediates in only a few steps and in high yields from a-Dglucose. The second part of the project was the utilization of the phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) as an efficient reusable medium for the palladium catalyzed Suzuki cross-coupling reaction of aryl halides, including aryl chlorides, under mild conditions. The cross-coupling reactions were found to proceed in THPC containing small amounts of water and toluene using potassium phosphate and 1% Pd2(dba)3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and afforded complete conversion within 1 hour at 50 ^C. The corresponding aryl bromides also reacted under these conditions with the addition of a catalytic amount of triphenylphosphine that allowed for complete conversion and high isolated yields. The reactions involving aryl chlorides were considerably slower, although the addition of triphenylphosphine and heating at 70 ^C allowed high conversion of electron deficient derivatives. Addition of water and hexane to the reaction products results in a triphasic system in which the top hexane phase contained the biaryl products, the palladium catalyst remained fully dissolved in the central THPC layer, while the inorganic salts were extracted into the lower aqueous phase. The catalyst was then recycled by removing the top and bottom layers and adding the reagents to the ionic liquid which was heated again at 50 ^C; resulting in complete turnover of iodobenzene. Repetition of this procedure gave the biphenyl product in 82-97% yield (repeated five times) for both the initial and recycled reaction sequences.