Effects of Simulated Drought on the Carbon Balance of Everglades Short-Hydroperiod Marsh

Hydrology drives the carbon balance of wetlands by controlling the uptake and release of CO2 and CH4. Longer dry periods in between heavier precipitation events predicted for the Everglades region, may alter the stability of large carbon pools in this wetland's ecosystems. To determine the effects of drought on CO2 fluxes and CH4 emissions, we simulated changes in hydroperiod with three scenarios that differed in the onset rate of drought (gradual, intermediate, and rapid transition into drought) on 18 freshwater wetland monoliths collected from an Everglades short-hydroperiod marsh. Simulated drought, regardless of the onset rate, resulted in higher net CO2 losses net ecosystem exchange (NEE) over the 22-week manipulation. Drought caused extensive vegetation dieback, increased ecosystem respiration (Reco), and reduced carbon uptake gross ecosystem exchange (GEE). Photosynthetic potential measured by reflective indices (photochemical reflectance index, water index, normalized phaeophytinization index, and the normalized difference vegetation index) indicated that water stress limited GEE and inhibited Reco. As a result of drought-induced dieback, NEE did not offset methane production during periods of inundation. The average ratio of net CH4 to NEE over the study period was 0.06, surpassing the 100-year greenhouse warming compensation point for CH4 (0.04). Drought-induced diebacks of sawgrass (C3) led to the establishment of the invasive species torpedograss (C4) when water was resupplied. These changes in the structure and function indicate that freshwater marsh ecosystems can become a net source of CO2 and CH4 to the atmosphere, even following an extended drought. Future changes in precipitation patterns and drought occurrence/duration can change the carbon storage capacity of freshwater marshes from sinks to sources of carbon to the atmosphere. Therefore, climate change will impact the carbon storage capacity of freshwater marshes by influencing water availability and the potential for positive feedbacks on radiative forcing.

Synthesis and electron emission properties of aligned carbon nanotube arrays

Carbon nanotubes (CNTs) have become one of the most interesting allotropes of carbon due to their intriguing mechanical, electrical, thermal and optical properties. The synthesis and electron emission properties of CNT arrays have been investigated in this work. Vertically aligned CNTs of different densities were synthesized on copper substrate with catalyst dots patterned by nanosphere lithography. The CNTs synthesized with catalyst dots patterned by spheres of 500 nm diameter exhibited the best electron emission properties with the lowest turn-on/threshold electric fields and the highest field enhancement factor. Furthermore, CNTs were treated with NH3 plasma for various durations and the optimum enhancement was obtained for a plasma treatment of 1.0 min. CNT point emitters were also synthesized on a flat-tip or a sharp-tip to understand the effect of emitter geometry on the electron emission. The experimental results show that electron emission can be enhanced by decreasing the screening effect of the electric field by neighboring CNTs. In another part of the dissertation, vertically aligned CNTs were synthesized on stainless steel (SS) substrates with and without chemical etching or catalyst deposition. The density and length of CNTs were determined by synthesis time. For a prolonged growth time, the catalyst activity terminated and the plasma started etching CNTs destructively. CNTs with uniform diameter and length were synthesized on SS substrates subjected to chemical etching for a period of 40 minutes before the growth. The direct contact of CNTs with stainless steel allowed for the better field emission performance of CNTs synthesized on pristine SS as compared to the CNTs synthesized on Ni/Cr coated SS. Finally, fabrication of large arrays of free-standing vertically aligned CNT/SnO2 core-shell structures was explored by using a simple wet-chemical route. The structure of the SnO2 nanoparticles was studied by X-ray diffraction and electron microscopy. Transmission electron microscopy reveals that a uniform layer of SnO2 is conformally coated on every tapered CNT. The strong adhesion of CNTs with SS guaranteed the formation of the core-shell structures of CNTs with SnO2 or other metal oxides, which are expected to have applications in chemical sensors and lithium ion batteries.

Numerical heat transfer analysis of carbon-based foams for use in thermal protection system

The applicability of carbon-based foams as an insulating or active cooling material in thermal protection systems (TPSs) of space vehicles is considered using a computer modeling. This study focuses on numerical investigation of the performance of carbon foams for use in TPSs of space vehicles. Two kinds of carbon foams are considered in this study. For active cooling, the carbon foam that has a thermal conductivity of 100 W/m-k is used and for the insulation, the carbon foam having a thermal conductivity of 0.225 W/m-k is used. A 3D geometry is employed to simulate coolant flow and heat transfer through carbon foam model. Gambit has been used to model the 3D geometry and the numerical simulation is carried out in FLUENT. Numerical results from this thesis suggests that the use of CFOAM and HTC carbon foams in TPS's may effectively protect the aluminum structure of the space shuttle during reentry of the space vehicle.

Role of carbon nanotube dispersion in fracture toughening of plasma sprayed aluminum oxide - carbon nanotube nanocomposite coating

Aluminum oxide (A1203, or alumina) is a conventional ceramic known for applications such as wear resistant coatings, thermal liners, heaters, crucibles, dielectric systems, etc. However applications of A1203 are limited owing to its inherent brittleness. Due to its excellent mechanical properties and bending strength, carbon nanotubes (CNT) is an ideal reinforcement for A1203 matrix to improve its fracture toughness. The role of CNT dispersion in the fracture toughening of the plasma sprayed A1203-CNT nanocomposite coating is discussed in the current work. Pretreatment of powder feedstock is required for dispersing CNTs in the matrix. Four coatings namely spray dried A1203 (A-SD), A1203 blended with 4wt.% CNT (A4C-B), composite spray dried A1203-4wt.% CNT (A4C-SD) and composite spray dried A1203-8wt.% CNT (A8CSD), are synthesized by plasma spraying. Owing to extreme temperatures and velocities involved in the plasma spraying of ceramics, retention of CNTs in the resulting coatings necessitates optimizing plasma processing parameters using an inflight particle diagnostic sensor. A bimodal microstructure was obtained in the matrix that consists of fully melted and resolidified structure and solid state sintered structure. CNTs are retained both in the fully melted region and solid-state sintered regions of processed coatings. Fracture toughness of A-SD, A4C-B, A4C-SD and A8C-SD coatings was 3.22, 3.86, 4.60 and 5.04 MPa m1/2 respectively. This affirms the improvement of fracture toughness from 20 % (in A4C-B coating) to 43% (in A4C-SD coating) when compared to the A-SD coating because of the CNT dispersion. Fracture toughness improvement from 43 % (in A4C-SD) to 57% (in A8C-SD) coating is evinced because of the CNT content. Reinforcement by CNTs is described by its bridging, anchoring, hook formation, impact alignment, fusion with splat, and mesh formation. The A1203/CNT interface is critical in assisting the stress transfer and utilizing excellent mechanical properties of CNTs. Mathematical and computational modeling using ab-initio principle is applied to understand the wetting behavior at the A1203/CNTinterface. Contrasting storage modulus was obtained by nanoindentation (~ 210, 250, 250-350 and 325-420 GPa in A-SD, A4C-B, A4C-SD, and A8C-SD coatings respectively) depicting the toughening associated with CNT content and dispersion.

Multi-objective optimization of the molecular structure of refrigerants

The aim of this work was to develop a new methodology, which can be used to design new refrigerants that are better than the currently used refrigerants. The methodology draws some parallels with the general approach of computer aided molecular design. However, the mathematical way of representing the molecular structure of an organic compound and the use of meta models during the optimization process make it different. In essence, this approach aimed to generate molecules that conform to various property requirements that are known and specified a priori. A modified way of mathematically representing the molecular structure of an organic compound having up to four carbon atoms, along with atoms of other elements such as hydrogen, oxygen, fluorine, chlorine and bromine, was developed. The normal boiling temperature, enthalpy of vaporization, vapor pressure, tropospheric lifetime and biodegradability of 295 different organic compounds, were collected from open literature and data bases or estimated. Surrogate models linking the previously mentioned quantities with the molecular structure were developed. Constraints ensuring the generation of structurally feasible molecules were formulated and used in commercially available optimization algorithms to generate molecular structures of promising new refrigerants. This study was intended to serve as a proof-of-concept of designing refrigerants using the newly developed methodology.

Chlorine Contribution to Quantitative Structure and Activity Relationship Models of Disinfection By-Products' Quantum Chemical Descriptors and Toxicities

Quantitative Structure-Activity Relationship (QSAR) has been applied extensively in predicting toxicity of Disinfection By-Products (DBPs) in drinking water. Among many toxicological properties, acute and chronic toxicities of DBPs have been widely used in health risk assessment of DBPs. These toxicities are correlated with molecular properties, which are usually correlated with molecular descriptors. The primary goals of this thesis are: 1) to investigate the effects of molecular descriptors (e.g., chlorine number) on molecular properties such as energy of the lowest unoccupied molecular orbital (ELUMO) via QSAR modelling and analysis; 2) to validate the models by using internal and external cross-validation techniques; 3) to quantify the model uncertainties through Taylor and Monte Carlo Simulation. One of the very important ways to predict molecular properties such as ELUMO is using QSAR analysis. In this study, number of chlorine (NCl) and number of carbon (NC) as well as energy of the highest occupied molecular orbital (EHOMO) are used as molecular descriptors. There are typically three approaches used in QSAR model development: 1) Linear or Multi-linear Regression (MLR); 2) Partial Least Squares (PLS); and 3) Principle Component Regression (PCR). In QSAR analysis, a very critical step is model validation after QSAR models are established and before applying them to toxicity prediction. The DBPs to be studied include five chemical classes: chlorinated alkanes, alkenes, and aromatics. In addition, validated QSARs are developed to describe the toxicity of selected groups (i.e., chloro-alkane and aromatic compounds with a nitro- or cyano group) of DBP chemicals to three types of organisms (e.g., Fish, T. pyriformis, and P.pyosphoreum) based on experimental toxicity data from the literature. The results show that: 1) QSAR models to predict molecular property built by MLR, PLS or PCR can be used either to select valid data points or to eliminate outliers; 2) The Leave-One-Out Cross-Validation procedure by itself is not enough to give a reliable representation of the predictive ability of the QSAR models, however, Leave-Many-Out/K-fold cross-validation and external validation can be applied together to achieve more reliable results; 3) ELUMO are shown to correlate highly with the NCl for several classes of DBPs; and 4) According to uncertainty analysis using Taylor method, the uncertainty of QSAR models is contributed mostly from NCl for all DBP classes.

Ecosystem structure in disturbed and restored subtropical seagrass meadows

Shallow seagrass ecosystems frequently experience physical disturbance from vessel groundings. Specific restoration methods that modify physical, chemical, and biological aspects of disturbances are used to accelerate recovery. This study evaluated loss and recovery of ecosystem structure in disturbed seagrass meadows through plant and soil properties used as proxies for primary and secondary production, habitat quality, benthic metabolism, remineralization, and nutrient storage and exchange. The efficacy of common seagrass restoration techniques in accelerating recovery was also assessed. Beyond removal of macrophyte biomass, disturbance to seagrass sediments resulted in loss of organic matter and stored nutrients, and altered microbial and infaunal communities. Evidence of the effectiveness of restoration actions was variable. Fill placement prevented additional erosion, but the resulting sediment matrix had different physical properties, low organic matter content and nutrient pools, reduced benthic metabolism, and less primary and secondary production relative to the undisturbed ecosystem. Fertilization was effective in increasing nitrogen and phosphorus availability in the sediments, but concurrent enhancement of seagrass production was not detected. Seagrass herbivores removed substantial seagrass biomass via direct grazing, suggesting that leaf loss to seagrass herbivores is a spatially variable but critically important determinant of seagrass transplanting success. Convergence of plant and sediment response variables with levels in undisturbed seagrass meadows was not detected via natural recovery of disturbed sites, or through filling and fertilizing restoration sites. However, several indicators of ecosystem development related to primary production and nutrient accumulation suggest that early stages of ecosystem development have begun at these sites. This research suggests that vessel grounding disturbances in seagrass ecosystems create more complex and persistent resource losses than previously understood by resource managers. While the mechanics of implementing common seagrass restoration actions have been successfully developed by the restoration community, expectations of consistent or rapid recovery trajectories following restoration remain elusive.

Enhanced 3-Dimensional Carbon Nanotube Based Anodes for Li-ion Battery Applications

A prototype 3-dimensional (3D) anode, based on multiwall carbon nanotubes (MWCNTs), for Li-ion batteries (LIBs), with potential use in Electric Vehicles (EVs) was investigated. The unique 3D design of the anode allowed much higher areal mass density of MWCNTs as active materials, resulting in more amount of Li+ ion intake, compared to that of a conventional 2D counterpart. Furthermore, 3D amorphous Si/MWCNTs hybrid structure offered enhancement in electrochemical response (specific capacity 549 mAhg-1). Also, an anode stack was fabricated to further increase the areal or volumetric mass density of MWCNTs. An areal mass density of the anode stack 34.9 mg/cm2 was attained, which is 1,342% higher than the value for a single layer 2.6 mg/cm2. Furthermore, the binder-assisted and hot-pressed anode stack yielded the average reversible, stable gravimetric and volumetric specific capacities of 213 mAhg-1 and 265 mAh/cm3, respectively (at 0.5C). Moreover, a large-scale patterned novel flexible 3D MWCNTs-graphene-polyethylene terephthalate (PET) anode structure was prepared. It generated a reversible specific capacity of 153 mAhg-1 at 0.17C and cycling stability of 130 mAhg-1 up to 50 cycles at 1.7C.