The nitrate to ammonia and ceramic (NAC) process for the denitration and immobilization of low-level radioactive liquid waste (LLW)

Hazardous radioactive liquid waste is the legacy of more than 50 years of plutonium production associated with the United States' nuclear weapons program. It is estimated that more than 245,000 tons of nitrate wastes are stored at facilities such as the single-shell tanks (SST) at the Hanford Site in the state of Washington, and the Melton Valley storage tanks at Oak Ridge National Laboratory (ORNL) in Tennessee. In order to develop an innovative, new technology for the destruction and immobilization of nitrate-based radioactive liquid waste, the United State Department of Energy (DOE) initiated the research project which resulted in the technology known as the Nitrate to Ammonia and Ceramic (NAC) process. However, inasmuch as the nitrate anion is highly mobile and difficult to immobilize, especially in relatively porous cement-based grout which has been used to date as a method for the immobilization of liquid waste, it presents a major obstacle to environmental clean-up initiatives. Thus, in an effort to contribute to the existing body of knowledge and enhance the efficacy of the NAC process, this research involved the experimental measurement of the rheological and heat transfer behaviors of the NAC product slurry and the determination of the optimal operating parameters for the continuous NAC chemical reaction process. Test results indicate that the NAC product slurry exhibits a typical non-Newtonian flow behavior. Correlation equations for the slurry's rheological properties and heat transfer rate in a pipe flow have been developed; these should prove valuable in the design of a full-scale NAC processing plant. The 20-percent slurry exhibited a typical dilatant (shear thickening) behavior and was in the turbulent flow regime due to its lower viscosity. The 40-percent slurry exhibited a typical pseudoplastic (shear thinning) behavior and remained in the laminar flow regime throughout its experimental range. The reactions were found to be more efficient in the lower temperature range investigated. With respect to leachability, the experimental final NAC ceramic waste form is comparable to the final product of vitrification, the technology chosen by DOE to treat these wastes. As the NAC process has the potential of reducing the volume of nitrate-based radioactive liquid waste by as much as 70 percent, it not only promises to enhance environmental remediation efforts but also effect substantial cost savings. ^

Ecosystem responses to hydrologic change and mechanisms of nitrogen sequestration in seasonally flooded tree islands of the southern Everglades

In the Florida Everglades, tree islands are conspicuous heterogeneous elements in a complex wetland landscape. I investigated the effects of increased freshwater flow in southern Everglades seasonally flooded tree islands, and characterized biogeochemical interactions among tree islands and the marsh landscape matrix, specifically examining hydrologic flows of nitrogen (N), and landscape N sequestration capacity. I utilized ecological trajectories of key ecosystem variables to differentiate effects of increased sheetflow and hydroperiod. I utilized stable isotope analyses and nutrient content of tree island ecosystem components to test the hypothesis that key processes in tree island nitrogen cycling would favor ecosystem N sequestration. I combined estimates of tree island ecosystem N standing stocks and fluxes, soil and litter N transformation rates, and hydrologic inputs of N to quantify the net sequestration of N by a seasonally flooded tree island. ^ Results show that increased freshwater flow to seasonally flooded tree islands promoted ecosystem oligotrophy, whereas reduced flows allowed some plant species to cycle P less efficiently. As oligotrophy is a defining parameter of Everglades wetlands, and likely promotes belowground production and peat development, reintroducing freshwater flow from an upstream canal had a favorable effect on ecosystem dynamics of tree islands in the study area. Important factors influencing the stable isotopic composition of nitrogen and carbon were: (1) a contribution to soil N by soil invertebrates, animal excrement, and microbes, (2) a possible NO3 source from an upstream canal and an "open" ecosystem N cycle, and (3) greater availability of phosphorus in tree islands relative to the marsh landscape, suggesting that tree island N cycling favors N sequestration. Hydrologic sources of N were dominated by surface water loads of NO3- and NH 4+, and an important soil N transformation promoting the net loss of surface water DIN was nitrate immobilization associated with soils and surficial leaf litter. The net inorganic N sequestration capacity of a seasonally flooded tree island was 50 g yr-1 m -2. Thus, tree islands likely have an important function in landscape sequestration of inorganic N, and may reduce significant anthropogenic N loads to downstream coastal systems. ^

Importance of water source in controlling leaf leaching losses in a dwarf red mangrove (Rhizophora mangle L.) wetland

The southern Everglades mangrove ecotone is characterized by extensive dwarf Rhizophora mangle L. shrub forests with a seasonally variable water source (Everglades – NE Florida Bay) and residence times ranging from short to long. We conducted a leaf leaching experiment to understand the influence that water source and its corresponding water quality have on (1) the early decay of R. mangle leaves and (2) the early exchange of total organic carbon (TOC) and total phosphorus (TP) between leaves and the water column. Newly senesced leaves collected from lower Taylor River (FL) were incubated in bottles containing water from one of three sources (Everglades, ambient mangrove, and Florida Bay) that spanned a range of salinity from 0 to 32‰, [TOC] from 710 to 1400 μM, and [TP] from 0.17 to 0.33 μM. We poisoned half the bottles in order to quantify abiotic processes (i.e., leaching) and assumed that non-poisoned bottles represented both biotic (i.e., microbial) and abiotic processes. We sacrificed bottles after 1,2, 5, 10, and 21 days of incubation and quantified changes in leaf mass and changes in water column [TOC] and [TP]. We saw 10–20% loss of leaf mass after 24 h—independent of water treatment—that leveled off by Day 21. After 3 weeks, non-poisoned leaves lost more mass than poisoned leaves, and there was only an effect of salinity on mass loss in poisoned incubations—with greatest leaching-associated losses in Everglades freshwater. Normalized concentrations of TOC in the water column increased by more than two orders of magnitude after 21 days with no effect of salinity and no difference between poisoned and non-poisoned treatments. However, normalized [TP] was lower in non-poisoned incubations as a result of immobilization by epiphytic microbes. This immobilization was greatest in Everglades freshwater and reflects the high P demand in this ecosystem. Immobilization of leached P in mangrove water and Florida Bay water was delayed by several days and may indicate an initial microbial limitation by labile C during the dry season.

Current Best Practice for Management of Medial Collateral Ligament Injury

Medical collateral ligament injuries are among the most common knee injuries for the athletic population. Immobilization once was the accepted course of treatment for MCL injuries but research has demonstrated the ineffectiveness of this approach.

Ecosystem structure, nutrient dynamics, and hydrologic relationships in tree islands of the southern Everglades, Florida, USA

Tree islands are an important structural component of many graminoid-dominated wetlands because they increase ecological complexity in the landscape. Tree island area has been drastically reduced with hydrologic modifications within the Everglades ecosystem, yet still little is known about the ecosystem ecology of Everglades tree islands. As part of an ongoing study to investigate the effects of hydrologic restoration on short hydroperiod marshes of the southern Everglades, we report an ecosystem characterization of seasonally flooded tree islands relative to locations described by variation in freshwater flow (i.e. locally enhanced freshwater flow by levee removal). We quantified: (1) forest structure, litterfall production, nutrient utilization, soil dynamics, and hydrologic properties of six tree islands and (2) soil and surface water physico-chemical properties of adjacent marshes. Tree islands efficiently utilized both phosphorus and nitrogen, but indices of nutrient-use efficiency indicated stronger P than N limitation. Tree islands were distinct in structure and biogeochemical properties from the surrounding marsh, maintaining higher organically bound P and N, but lower inorganic N. Annual variation resulting in increased hydroperiod and lower wet season water levels not only increased nitrogen use by tree species and decreased N:P values of the dominant plant species (Chrysobalanus icaco), but also increased soil pH and decreased soil temperature. When compared with other forested wetlands, these Everglades tree islands were among the most nutrient efficient, likely a function of nutrient immobilization in soils and the calcium carbonate bedrock. Tree islands of our study area are defined by: (1) unique biogeochemical properties when compared with adjacent short hydroperiod marshes and other forested wetlands and (2) an intricate relationship with marsh hydrology. As such, they may play an important and disproportionate role in nutrient and carbon cycling in Everglades wetlands. With the loss of tree islands that has occurred with the degradation of the Everglades system, these landscape processes may have been altered. With this baseline dataset, we have established a long-term ecosystem-scale experiment to follow the ecosystem trajectory of seasonally flooded tree islands in response to hydrologic restoration of the southern Everglades.

Biogeochemical Contributions of Tree Islands to Everglades Wetland Landscape Nitrogen Cycling During Seasonal Inundation

In the Florida Everglades, tree islands are conspicuous heterogeneous elements in the herbaceous wetland landscape. We characterized the biogeochemical role of a seasonally flooded tree island during wet season inundation, specifically examining hydrologically mediated flows of nitrogen (N) and N retention by the tree island. We estimated ecosystem N standing stocks and fluxes, soil and litter N transformation rates, and hydrologic fluxes of N to quantify the net ecosystem N mass flux. Results showed that hydrologic sources of N were dominated by surface water loads of nitrate (NO3) and ammonium (NH4). Nitrate immobilization by soils and surficial leaf litter was an important sink for surface water dissolved inorganic N (DIN). We estimated that the net annual DIN retention by a seasonally flooded tree island was 20.5 ± 5.0 g m−2 during wet season inundation. Based on the estimated tree island surface water DIN loading rate, a seasonally flooded tree island retained 76% of imported DIN. As such, seasonally flooded tree islands have the potential to retain 55% of DIN entering the marsh landscape via upstream canal overland flow in the wet season. By increasing reactive surface area and DOC availability, we suggest that tree islands promote convergence of elements that enhance DIN retention. Tree islands of this region are thus important components of landscape-scale restoration efforts that seek to reduce sources of anthropogenic DIN to downstream estuaries.

Nano-grids of Yeast Cytochrome C

One innovative thought in biomolecular electronics is the exploitation of electron transfer proteins. Using nature's self assembly techniques, proteins can build highly organized edifices with retained functional activity, and they can serve as platforms for biosensors. In this research work, Yeast Cytochrome C (YCC) is immobilized with a help of a linker molecule, 3-Mercaptopropyltrimethoxysilane (3-MPTS) on a hydroxylated surface of a silicon substrate. Atomic Force Microscopy (AFM) is used for characterization. AFM data shows immobilization of one YCC molecule in between eight grids that are formed by the linker molecules. 3-MPTS monolayers are organized in grids that are 1.2 nm apart. Immobilization of 3-MPTS was optimized using a concentration of 5 mM in a completely dehydrated state for 30 minutes. The functionally active grids of YCC can now be incorporated with Cytochrome C oxidase on a Platinum electrode surface for transfer of electrons in development of biosensors, such as nitrate sensor, that are small in size, cheaper, and easier to manufacture than the top-down approach of fabrication of molecular biodevices

C-MEMS Based Micro Enzymatic Biofuel Cells

Miniaturized, self-sufficient bioelectronics powered by unconventional micropower may lead to a new generation of implantable, wireless, minimally invasive medical devices, such as pacemakers, defibrillators, drug-delivering pumps, sensor transmitters, and neurostimulators. Studies have shown that micro-enzymatic biofuel cells (EBFCs) are among the most intuitive candidates for in vivo micropower. In the fisrt part of this thesis, the prototype design of an EBFC chip, having 3D intedigitated microelectrode arrays was proposed to obtain an optimum design of 3D microelectrode arrays for carbon microelectromechanical systems (C-MEMS) based EBFCs. A detailed modeling solving partial differential equations (PDEs) by finite element techniques has been developed on the effect of 1) dimensions of microelectrodes, 2) spatial arrangement of 3D microelectrode arrays, 3) geometry of microelectrode on the EBFC performance based on COMSOL Multiphysics. In the second part of this thesis, in order to investigate the performance of an EBFC, behavior of an EBFC chip performance inside an artery has been studied. COMSOL Multiphysics software has also been applied to analyze mass transport for different orientations of an EBFC chip inside a blood artery. Two orientations: horizontal position (HP) and vertical position (VP) have been analyzed. The third part of this thesis has been focused on experimental work towards high performance EBFC. This work has integrated graphene/enzyme onto three-dimensional (3D) micropillar arrays in order to obtain efficient enzyme immobilization, enhanced enzyme loading and facilitate direct electron transfer. The developed 3D graphene/enzyme network based EBFC generated a maximum power density of 136.3 μWcm-2 at 0.59 V, which is almost 7 times of the maximum power density of the bare 3D carbon micropillar arrays based EBFC. To further improve the EBFC performance, reduced graphene oxide (rGO)/carbon nanotubes (CNTs) has been integrated onto 3D mciropillar arrays to further increase EBFC performance in the fourth part of this thesisThe developed rGO/CNTs based EBFC generated twice the maximum power density of rGO based EBFC. Through a comparison of experimental and theoretical results, the cell performance efficiency is noted to be 67%.

Preparation of an Immunosorbent and its use in the Solid Phase Extraction of Benzodiazepines

The use of capillary electrophoresis (CE) has been restricted to applications having high sample concentrations because of its low sensitivity caused by small injection volumes and, when ultraviolet (UV) detection is used, the short optical path length. Sensitivity in CE can be improved by using more sensitive detection systems, or by preconcentration techniques which are based on chromatographic and/or electrophoretic principles. One of the promising strategies to improve sensitivity is solid phase extraction (SPE). Solid Phase Extraction utilizes high sample volumes and a variety of complex matrixes to facilitate trace detection. To increase the specificity of the SPE a selective solid phase must be chosen. Immunosorbents, which are a combination of an antibody and a solid support, have proven to be an excellent option because of high selectivity of the antibody. This thesis is an exploratory study of the application of immunosorbent-SPE combined with CE for trace concentration of benzodiazepines. This research describes the immobilization and performance evaluation of an immunosorbent prepared by immobilizing a benzodiazepine-specific antibody on aminopropyl silica. The binding capacity of the immunosorbent, measured as µg of benzodiazepine/ gram of immunosorbent, was 39 ± 10. The long term stability of the prepared immunosorbent has been improved by capping the remaining aminopropyl groups by reaction with acetic anhydride. The capped immunosorbent retained its binding capacity after several uses.