Photocatalytic decomposition of organophosphonates and fluorophenols in irradiated titanium dioxide suspensions

Dimethyl methyl phosphonate (DMMP), diethyl methyl phosphonate (DEMP), and fluorophenols undergo rapid decomposition upon TiO$\sb2$ catalyzed photooxidation in air saturated aqueous solution. The degradation rates of DMMP were determined over a range of temperatures, under solar and artificial irradiation with and without simultaneous sonication. Solar illumination is effective for the degradation and the use of low energy of sonication increases the rate of mineralization. The surface area and the type of TiO$\sb2$ dramatically affect the photoactivity of the catalyst. A number of intermediate products are formed and ultimately oxidized to phosphate and carbon dioxide. Possible reaction mechanisms and pathways for DMMP and DEMP are proposed. The Langmuir-Hinshelwood kinetic parameters for the photocatalysis of fluorophenols suggest modestly different reactivity for each isomer. The adsorption constant is largest for the ortho isomer consistent with the adsorption onto TiO$\sb2$ through both hydroxyl and fluoride groups to form a chelated type structure. ^

Photocatalytic decomposition of organophosphonates fluorophenols in irradiated titanium dioxide suspensions

Dimethyl methyl phosphonate (DMMP), diethyl methyl phosphonate (DEMP), and fluorophenols undergo rapid decomposition upon TiO2 catalyzed photooxidation in air saturated aqueous solution. The degradation rates of DMMP were determined over a range of temperatures, under solar and artificial irradiation with and without simultaneous sonication. Solar illumination is effective for the degradation and the use of low energy of sonication increases the rate of mineralization. The surface area and the type of TiO2 dramatically affect the photoactivity of the catalyst. A number of intermediate products are formed and ultimately oxidized to phosphate and carbon dioxide. Possible reaction mechanisms and pathways for DMMP and DEMP are proposed. The Langmuir- Hinshelwood kinetic parameters for the photocatalysis of fluorophenols suggest modestly different reactivity for each isomer. The adsorption constant is largest for the ortho isomer consistent with the adsorption onto TiO2 through both hydroxyl and fluoride groups to form a chelated type structure.

Structure of international cooperation in trade, investment and environment

This dissertation analyzes the obstacles against further cooperation in international economic relations. The first essay explains the gradual nature of trade liberalization. I show that existence of asymmetric information between governments provides a sufficient reason for gradualism to exist. Governments prefer starting small to reduce the cost of partner’s betrayal when there is sufficient degree of information asymmetry regarding the partner’s type. Learning about partner’s incentive structure enhances expectations, encouraging governments to increase their current level of cooperation. Specifically, the uninformed government’s subjective belief for the trading partner being good is improved as the partner acts cooperatively. This updated belief, in turn, lowers the subjective probability of future betrayal, enabling further progress in cooperation. The second essay analyzes the relationship between two countries facing two policy dilemmas in an environment with two way goods and capital flows. When issues are independent and countries are symmetric, signing separate agreements for tariffs (Free Trade Agreements-FTA) and for taxes (Tax Treaties-TT) provides the identical level of enforcement as signing a linked agreement. However, linkage can still improve the joint welfare by transferring the slack enforcement power in a case of asymmetric issues or countries. I report non-results in two cases where the policy issues are interconnected due to technological spillover effect of FDI. Moreover, I show that linking the agreements actually reduces enforcement when agreements are linked under a limited punishment rule and policy variables are strategic substitutes. The third essay investigates the welfare/enforcement consequences of linking trade and environmental agreements. In the standard literature, linking the agreements generate non-trivial results only when there is structural relation between the issues. I focus on institutional design of the linkage and show that even if environmental aspects of international trade are negligible linking the agreements might still have some interesting welfare implications under current GATT Rules. Specifically, when traded goods are substitutes in consumption, linking the environmental agreement with trade agreement under the Withdrawal of Equivalent Concession Rule (Article XXVIII) will reduce the enforcement. However, enforcement in environmental issue increases when the same rule is implemented in the absence of linkage.

S12C water control structure near SRS-1a, Shark River Slough

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.

Aerial photo of SRS-1a, the S12c water control structure, and the surrounding area, Shark River Slough

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.

Aerial photo of SRS-1a, the S12c water control structure, and the surrounding area, Shark River Slough

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.

Aerial photo of SRS-1a, the S12c water control structure, and the surrounding area, Shark River Slough

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.

Aerial photo of SRS-1a, the S12c water control structure, and the surrounding area, Shark River Slough

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.

Microteaching Lesson Study: Mentor interaction structure and its relation to elementary preservice mathematics teacher knowledge development

This study investigated Microteaching Lesson Study (MLS) and three possible MLS mentor interaction structures during the debriefing sessions in relation to elementary preservice teacher development of knowledge for teaching. One hundred three elementary preservice teachers enrolled in five different sections of a mathematics methods course at a southern urban university were part of the study. This included 72 participants who completed MLS across three different mentor interaction structures as part of their course requirements and 31 elementary preservice teachers who did not complete MLS as part of their methods course and served as a comparison group for a portion of the study. A sequential mixed-methods research design was used to analyze the relationship between MLS mentor interaction structure and growth in preservice teachers' mathematics teacher knowledge. Data sources included pre and post assessments, group developed lesson plans and final reports, a feedback survey with Likert-type and open-ended questions, and transcripts of audio-recorded debriefing sessions. The pre and post assessments were analyzed using Analysis of Variance (ANOVA) and descriptive statistics were used to analyze the Likert-type feedback survey questions. Group MLS lesson plans, final reports, and transcripts of debriefing sessions along with the open-ended questions from the feedback survey were coded in a three-step process as described by Miles and Huberman (1994). In alignment with findings from M. Fernandez (2005, 2010), elementary preservice teachers participating in MLS grew in content knowledge related to MLS topics taught by one another. Results from the analysis of pre and post content knowledge assessments revealed that participants grew in their understanding of the mathematics topics taught during MLS irrespective of their mentor interaction structure and when compared to the participants who did not complete MLS in their methods course. Findings from the analysis of lesson plans for growth in pedagogical content knowledge revealed the most growth in this area occurred for participants assigned to the interaction structure in which the MLS mentor participated in the first two debriefing sessions. Analysis of the transcripts of the discourse during the debriefing sessions and the feedback surveys support the finding that the elementary preservice teachers assigned to the interaction structure in which the MLS mentor participated in the first and second debriefing sessions benefited more from the MLS experience when compared to elementary preservice teachers assigned to the other two interaction structures (MLS mentor participated in only the first debriefing session and MLS mentor participated in only the last debriefing session).

Developing a high density platinum/alumina hermetic feedthrough

Typically, hermetic feedthroughs for implantable devices, such as pacemakers, use a alumina ceramic insulator brazed to a platinum wire pin. This combination of material has a long history in implantable devices and has been approved by the FDA for implantable hermetic feedthroughs. The growing demand for increased input/output (I/O) hermetic feedthroughs for implantable neural stimulator applications could be addressed by developing a new, cofired platinum/alumina multilayer ceramic technology in a configuration that supports 300 plus I/Os, which is not commercially available. Seven platinum powders with different particle sizes were used to develop different conductive cofire inks to control the densification mismatch between platinum and alumina. Firing profile (ramp rate, burn- out and holding times) and firing atmosphere and concentrations (hydrogen (wet/dry), air, neutral, vacuum) were also optimized. Platinum and alumina exhibit the alloy formation reaction in a reduced atmosphere. Formation of any compound can increase the bonding of the metal/ceramic interface, resulting in enhanced hermeticity. The feedthrough fabricated in a reduced atmosphere demonstrated significantly superior performance than that of other atmospheres. A composite structure of tungsten/platinum ratios graded thru the via structure (pure W, 50/50 W/Pt, 80/20 Pt/W and pure Pt) exhibited the best performance in comparison to the performance of other materials used for ink metallization. Studies on the high temperature reaction of platinum and alumina, previously unreported, showed that, at low temperatures in reduced atmosphere, Pt 3Al or Pt8Al21 with a tetragonal structure would be formed. Cubic Pt3Al is formed upon heating the sample to temperatures above 1350 °C. This cubic structure is the equilibrium state of Pt-Al alloy at high temperatures. The alumina dissolves into the platinum ink and is redeposited as a surface coating. This was observed on both cofired samples and pure platinum thin films coated on a 99.6 Wt% alumina and fired at 1550 °C. Different mechanisms are proposed to describe this behavior based on the size of the platinum particle

Comparison of community structure of mangrove and riprap rock habitats along urban coastlines of south Florida

Globally, mangrove ecosystems have substantially declined, largely a result of human impacts. Mangroves provide a number of ecosystem services such as shoreline stabilization and nursery habitat for fish species. As declines continue, many of these ecosystem services are lost or altered. The need for shoreline stabilization has become increasingly apparent when chronic erosion wear away coastlines once mangroves are removed. Limestone boulders called riprap have been employed to offset continued erosion associated with mangrove clearing. In urban coastal areas adjacent to Biscayne Bay, Florida, as much as 80 percent of mangroves have been lost. More recently, riprap has been used in conjunction with mangroves to restore wetlands throughout the Bay. This riprap-mangrove habitat provides structure for marine organisms to colonize. However, fish assemblages and benthic composition could vary between this hybridized habitat and natural mangrove systems. Comparisons of fish and benthic community structure were made, to determine if abundance, species richness, and overall diversity differed between the two habitat types. Visual census and benthic quadrat surveys were conducted in vi mangrove and mangrove-riprap sites within two regions of Biscayne Bay. Total fish abundance was greater in mangroves, but the effect of habitat type on species richness varied between regions. The community structure of fishes and benthic composition differed significantly between mangroves and riprap habitats. Because species composition is so distinct, it is likely that the two communities do no function in the same manner. In areas with cleared shorelines, it may be important to consider the function of added anthropogenic structure for ecological communities.

Incorporating variable peak -to -daily ratios in the equilibrium traffic assignment procedure of the Florida Standard Urban Transportation Modeling Structure (FSUTMS)

The standard highway assignment model in the Florida Standard Urban Transportation Modeling Structure (FSUTMS) is based on the equilibrium traffic assignment method. This method involves running several iterations of all-or-nothing capacity-restraint assignment with an adjustment of travel time to reflect delays encountered in the associated iteration. The iterative link time adjustment process is accomplished through the Bureau of Public Roads (BPR) volume-delay equation. Since FSUTMS' traffic assignment procedure outputs daily volumes, and the input capacities are given in hourly volumes, it is necessary to convert the hourly capacities to their daily equivalents when computing the volume-to-capacity ratios used in the BPR function. The conversion is accomplished by dividing the hourly capacity by a factor called the peak-to-daily ratio, or referred to as CONFAC in FSUTMS. The ratio is computed as the highest hourly volume of a day divided by the corresponding total daily volume. ^ While several studies have indicated that CONFAC is a decreasing function of the level of congestion, a constant value is used for each facility type in the current version of FSUTMS. This ignores the different congestion level associated with each roadway and is believed to be one of the culprits of traffic assignment errors. Traffic counts data from across the state of Florida were used to calibrate CONFACs as a function of a congestion measure using the weighted least squares method. The calibrated functions were then implemented in FSUTMS through a procedure that takes advantage of the iterative nature of FSUTMS' equilibrium assignment method. ^ The assignment results based on constant and variable CONFACs were then compared against the ground counts for three selected networks. It was found that the accuracy from the two assignments was not significantly different, that the hypothesized improvement in assignment results from the variable CONFAC model was not empirically evident. It was recognized that many other factors beyond the scope and control of this study could contribute to this finding. It was recommended that further studies focus on the use of the variable CONFAC model with recalibrated parameters for the BPR function and/or with other forms of volume-delay functions. ^

Left to right: Sharon Ewe and Peter Lenaker assessing mangrove forest structure, Shark River Slough

This material is based upon work supported by the National Science Foundation through the Florida Coastal Everglades Long-Term Ecological Research program under Cooperative Agreements #DBI-0620409 and #DEB-9910514. This image is made available for non-commercial or educational use only.