Pentachlorophenol (PCP) is a priority environmental pollutant in North America that was widely used as a wide-spectrum biocide in the last century. Pentachlorophenol 4-monooxygenase (PcpB) is the first and rate-limiting enzyme in the PCP biodegradation pathway in <i>Sphingobium chlorophenolicum</i> ATCC 39723.<p> Pentachlorophenol 4-monooxygenase (PcpB) catalyzes the hydroxylation of pentachlorophenol in the pentachlorophenol biodegradation pathway in Sphingobium chlorophenolicum. Previous studies from two different research groups proposed oppositely that the catalytic product of PcpB was tetrachlorohydroquinone (TCHQ) and tetrachlorobenzoquinone (TCBQ). We re-examined the identity of the catalytic product of PcpB, because TCHQ and TCBQ are present in a redox-equilibrium in aqueous solutions and the chemical reagents NADPH, ethyl acetate and glutathione used for the product detection in the previous studies may shift the redox-equilibrium. In this study, we investigated the effects of NADPH, ethyl acetate and glutathione on the redox-equilibrium and product distribution. Under newly designed experimental conditions, we confirmed unambiguously that the catalytic product of PcpB is TCHQ instead of TCBQ. We also propose that TCBQ may be produced non-specifically by peroxidases within the bacterial cells and that TCBQ reductase (PcpD) might act as a self-protective rather than a PCP-degradation enzyme. <p> There is no glutathione S-transferase (GST) activity for wild type of PcpC, PcpC (C13S) mutant and a surface loop deletion mutant PcpC (LD). In the crystallization studies, PcpC (C13S), PcpB and PcpA were over-expressed and purified to >95% purity using Ni-NTA based affinity chromatography. Initial crystallization conditions have been obtained for all three enzymes from both in-house screening using the screening kits from Qiagen-Nextal and high throughput screening at the Hauptman-Woodward Institute, Buffalo, New York. Further structural determination studies will be undertaken upon obtaining large crystals suitable for X-ray diffraction data collection.

The purpose of this study was to use controlled release technology combining with in situ chemical oxidation (ISCO) and permeable reactive barrier (PRB) to remediate TCE-contaminated groundwater. In this study, potassium permanganate (KMnO4) releasing material was designed for potassium permanganate release in groundwater. The components of potassium permanganate releasing material included poly (£`-caprolactone) (PCL), potassium permanganate, and starch with a weight ratio of 2:1:0.5. Approximately 63.8% (w/w) of potassium permanganate was released from the material after 76 days of operation. The released was able to oxidize contaminant in groundwater. Results from the solid oxidation demand (SOD) experiment show that the consumption rate increased with increased contaminant concentration. TCE removal efficiency increased with the increased TCE concentration. The second-order rate law can be used to simulate the TCE degradation trend. In the column experiment, results show that the released MnO4- could oxidize TCE and TCE degradation byproducts when 95.6 pore volume (PV) of contaminated groundwater was treated. More than 95% of TCE removal can be observed in the column study. Although the concentration of manganese dioxide (MnO2) began to rise after 8.8 PV of operation, TCE removal was not affected. Results also show that low level of hexavalent chromium was detected (< 0.05 mg/L). Results from the scanning electron microscope (SEM) and energy-dispersive spectroscope (EDX) analyses show that the amounts of manganese and potassium in the materials decreased after the releasing experiment. Results indicate that the concentration of TCE and SOD need to be analyzed before the releasing materials are applied in situ. In the practical application, the releasing materials will not become solid wastes because they are decomposed after use. If this slow-releasing technology can be combined with a permeable reactive barrier system, this technology will become a more economic and environmentally-friendly green remedial system.

Cardiovascular disease (CVD) is the leading cause of death in the United States. Analysis of vascular reactivity (VR) in response to brachial artery occlusion is used to estimate arterial health and to determine the likelihood of future cardiovascular complications. Development of a sensitive technique to assess VR is fundamental to the field of preventive cardiology. The conventional technique to study VR is by monitoring arterial diameter changes during hyperemia following occlusion using ultrasound based methods. Such measurements require highly qualified technicians and expensive equipment; and are complicated by signal noise introduced by motion and posture among others. It is well known that tissue temperature changes are a direct response to variations in blood flow, and it has been observed in small clinical studies that variations in fingertip temperature during brachial artery occlusion and subsequent hyperemia is a simple surrogate for the measurement of vascular reactivity and endothelial dysfunction. Given the promising nature of thermal monitoring to study VR, this thesis focuses on the analysis of the underlying physics affecting fingertip temperature during vascular occlusion and subsequent hyperemia. I will quantify the contribution of hemodynamic, anatomical and environmental factors over digit temperature changes, which will serve to determine the sensitivity of the digital thermal monitoring (DTM) technique. I have quantified the effect of several contributing factors to fingertip temperature and DTM results. The aims of this thesis focus on: (1) creation of a mathematical model of heat transfer at baseline, during, and after a reactive hyperemia test; and (2) validation of the model and experimental analysis of thermal and flow parameters in healthy volunteers. The proposed project is an innovative study that intends to show and quantify the relationship between VR and digital thermal reactivity, translating mathematical models based on the physics of heat transfer and fluid mechanics to clinical application. The parametric studies performed with the zeroth order model served to separate the contribution of environment and blood flow over the temperature curves measured during brachial artery occlusion. The thermal models developed were able to reproduce the trend of the temperature response observed experimentally at the fingertip.

This work presents a modeling and control study of a reactive distillation column used for hydrogenation of benzene. A steady state and a dynamic model have been developed to investigate control structures for the column. The most important aspects of this control problem are that the purity of the product streams regarding benzene need to be met. At the same time as little toluene as possible should be converted. The former is a constraint imposed by EPA regulations while the latter is tied to process economics due to the high octane number of toluene. It is required to satisfy both of these objectives even under the influence of disturbances, as the feed composition changes on a regular basis. The dynamic model is used for developing transfer function models of two potential control structures. Pairing of inputs and outputs is performed based upon the Relative Gain Array (RGA) and PI controllers were designed for each control structure. The controller performance was then compared in simulation studies. From our results, control structure 2 performed better than control structure 1. The main advantage of CS2 over CS1 is noticed in the simulation of feed composition disturbance rejection, where CS2 returns all variables back to steady state within 3 hrs while it take CS1 more than 20 hrs to return the temperature variables back to steady state.

Reactive chemicals are presented widely in the chemical and petrochemical process industry. Their chemical reactivity hazards have posed a significant challenge to the industries of manufacturing, storage and transportation. The accidents due to reactive chemicals have caused tremendous loss of properties and lives, and damages to the environment. In this research, three classes of reactive chemicals (unsaturated hydrocarbons, self-reacting chemicals, energetic materials) were evaluated through theoretical and experimental methods. Methylcyclopentadiene (MCP) and Hydroxylamine (HA) are selected as representatives of unsaturated hydrocarbons and self-reacting chemicals, respectively. Chemical reactivity of MCP, including isomerization, dimerization, and oxidation, is investigated by computational chemistry methods and empirical thermodynamic–energy correlation. Density functional and ab initio methods are used to search the initial thermal decomposition steps of HA, including unimolecular and bimolecular pathways. In addition, solvent effects are also examined using water cluster methods and Polarizable Continuum Models (PCM) for aqueous solution of HA. The thermal stability of a basic energetic material, Nitroethane, is investigated through both theoretical and experimental methods. Density functional methods are employed to explore the initial decomposition pathways, followed by developing detailed reaction networks. Experiments with a batch reactor and in situ GC are designed to analyze the distribution of reaction products and verify reaction mechanisms. Overall kinetic model is also built from calorimetric experiments using an Automated Pressure Tracking Adiabatic Calorimeter (APTAC). Finally, a general evaluation approach is developed for a wide range of reactive chemicals. An index of thermal risk is proposed as a preliminary risk assessment to screen reactive chemicals. Correlations are also developed between reactivity parameters, such as onset temperature, activation energy, and adiabatic time to maximum rate based on a limited number, 37 sets, of Differential Scanning Calorimeter (DSC) data. The research shows broad applications in developing reaction mechanisms at the molecular level. The methodology of reaction modeling in combination with molecular modeling can also be used to study other reactive chemical systems.

In this study, a reproducible spectrophotometric method was established and applied to measure reductive capacity of various nanomaterials. Reductive capacity had been implicated in the toxicity of nanomaterials, but a standardized measurement method had been lacking until this work. The reductive capacity of nanoparticles was defined as the mass of iron reduced from Fe3 to Fe2 by unit mass of nanoparticles, in an aqueous solution that initially contained ferric ions. To measure the reductive capacity, the nanomaterials were incubated in a ferric aqueous solution for 16 hours at 37 degrees C, and the reductive capacity of the nanoparticles was determined by measuring the amount of Fe3 reduced to Fe2 using a spectrophotometric method. The reagents 1,10-phenanthroline and hydroquinone were used as a Fe2 indicator and a reducing agent respectively for the assay. To standardize this method, various experiments were carried out. For the initial ferric solution, various Fe salts were tested, and Iron(III) sulfate was chosen as Fe salt for the standard method. The measured reductive capacity of nanoparticles was found to vary with the measurement conditions; the measured reductive capacity increased with increasing the Fe/nanoparticle ratio; the measured reductive capacity increased with incubation time and leveled off after 8 hours of incubation. For hydrophobic materials, the surfactant Tween-20 was added so that the particles could be wetted and suspended in the ferric aqueous solution. After incubation, the particles were removed from the solution by either filtration or centrifugation before applying the spectrophotometric method. In addition, optimal pH and minimum time to reach ultimate color intensity were also found. Carbon-based nanomaterials, standard reference material and metal oxides were measured for their reductive capacities with this method and characterized by transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDS), x-ray diffraction (XRD), BET measurement and Raman spectroscopy. For some nanoparticles, the reductive capacity was measured for both the pristine form and the form treated by oxidization or grinding. All carbon-based nanomaterials, except for pristine C60, have a significant reductive capacity while reductive capacity of metal oxides is very low. And it was found that reductive capacity can be increased by surface functional groups or structural defects and reduced by oxidization or heating (graphitization). The reductive capacity of a material can play an important role in its toxicology by synergistic toxic effects in the presence of transition metal ions through the Fenton reaction. Moreover, even without transition metal ions, the ability of a material to donate electrons can be involved in toxicity mechanisms via generation of reactive oxygen species.

Abstract A novel process of combining electrokinetic remediation and nano-sized iron wall was used for studying its effectiveness of treating nitrate-containing soil. Nitrates and nitrites are commonly found in surface water and groundwater. These substances, in general, could pose a threat to both organisms in the water bodies and human health. Traditionally, nitrogen oxides in various water bodies are treated by biological denitrification processes. However, it would take a longer time to yield a satisfactory result as compared with physicochemical processes. In recent years, permeable reactive barriers (PRBs) using zero-valent iron have been successfully used for degradation of various compounds including nitrates. Electrokinetic processing (EK) also is considered as an effective in-situ technology for removing both inorganic and organic substances from the treatment zone. In this work, the synthesized nano-scale iron particles were incorporated into a PRB, which was further combined with EK to form a novel process for the degradation of nitrates. Various operating parameters were studied in this work. The nano-sized iron particles were determined to be ranging from 50-80nm in size and having specific surface area of 37.83m2. The isoelctric point of these nanoparticles was found to be at pH 7.3. Experimental results have shown that the best location of the iron wall was 5cm from the anode reservoir. Also, the optimal treatment time would be six days in this study. The treatment efficiency was found to increase with increasing dose of nano-sized iron particles in the PRB. Operating with the polarity reverse would slightly increase the overall treatment efficiency as compared with the case of no polarity reverse (92.38% versus 88.34%). An electric gradient of 1.5V/cm was determined to be the optimal electric field strength in this study. In this work, it was also found that 2.5g nano-scale iron particles outperformed 20g micro-scale iron particles (75-150&#x00B5;m) in terms of nitrate degradation. In a study of using an extended treatment time up to 20 days, the black colored iron wall would fade away becoming a rusty plume toward the cathode as the treatment time elapsed. Furthermore, the Fe2+ concentration was elevated throughout the soil column after the 20-day treatment. Therefore, it is evident that nano-sized iron particles would migrate when they are subjected to EK. Based on the research findings obtained, the novel process employed in this study was found to be an effective one for in-situ treatment of nitrate-containing soil.

Currently in Taiwan¡¦s textile-dying industry, sodium hypochlorite (NaOCl) is popularly used as a decolorization oxidant. In order to surely meet the effluent color regulation of 550 ADMI (American Dye Manufactures Institute), excessive dosage of sodium hyperchlorite is commonly used, which results in the increase of residual chloride and the accumulation of toxic chlorinated compound in the environment. This study probes into the characteristics of substitute oxidant for sodium hypochlorite to avoid the production of toxic products. The study includes decolorization efficiency evaluation, economical analysis and feasibility of commercial application. This study adopts ozone as an oxidant and ultraviolet light as the oxidant enhancer for the purpose of preventing the occurrence of secondary pollution products like trihalomethane from the sodium hyperchlorite application. Literature review indicates that there are several studies for reaction mechanisms of oxidation and disinfection of ozone and ultraviolet light for decolorization and the conclusions reveal much promising results. There are three topics in this study, which are: Topic 1: Feasibility study. This study focuses on whether the effluent color concentration of the treatment process meets the color effluent standard or not. A 3.5 L volume reactor was used in this section. Topic 2: Influencing factor analysis. A 14 L volume reactor was adopted for analyzing the influencing factors for decolorization and for comparing the differences in treatment efficiencies between a dye finishing plant effluent and two commercial dyestuff samples. Topic 3: Economic analysis. The analysis focuses on economic comparison between NaOCl and UV/Ozone processes for effluent decolorization. Analysis results of the investment cost, operation/maintenance expense, and investment return duration are presented in this section. A 50 L volume reactor was used to achieve the evaluation for this part. First topic of this study examined some operating parameters for treating effluent from the biological and chemical coagulation units of a dye-finishing wastewater treatment plant using the UV/Ozone technique to meet an effluent regulation of 550 ADMI values could be reduced from approximately 4,000 to 200 ADMI in an hour using the UV/Ozone technique. The results show that higher color removal efficiency could be achieved at pH values around 3 as compared with higher pH values of around 7 and 10. This might be due to the fact that the predominant ozone molecules at lower pH values are more selective to certain chromophore molecules in wastewater, despite the fact that hydroxyl radicals are predominant at higher pH values and have a stronger oxidation capability than ozone. The UV light used in this study emitted from the experimental lamp can excite oxygen and water molecules to produce ozone molecules and hydroxyl radicals that can then increase decolorization rate. The findings of this investigation reveal that the proposed UV/Ozone treatment scheme has potential for development into an environmentally friendly decolorization approach for dye finishing wastewater treatment. The second topic is to investigate the feasibility of applying UV/Ozone techniques to reduce color content caused by two commercial reactive dyes (Orange-13 and Blue-19). Bench experiments were performed using a 14-L reactor. Controlling factors including pH value, dosage of ozone, reaction time, and UV intensity were evaluated to obtain the optimal operating parameters. Results from this study show that the ozone dosage and pH value dominated the effects on the decolorization process. However, UV intensity shows relatively insignificant effects. Results also indicate that the color content could be reduced from 2,000 to 200 ADMI within a reaction time of 30 minutes with a total ozone dosage of 100 mg/L. This study shows that pH values of approximately 3 and 10 favored the decolorization of the studied Dye Blue-19 and Orange-13, respectively. This was due to the effects that molecular ozone and hydroxyl radicals had significant oxidative power at low and high pH, respectively. Moreover, molecular ozone was more selective to certain dye structures during its oxidation process. This also caused the effect that pH value played an important role on color removal. Kinetic analyses show that the decolorization reactions of Dye Orange-13 and Blue-19 followed a first-order decolorization model. Experimental results also indicate that the degree of decolorization was primarily proportional to the ozone dosage. Results from this study provide us an insight into the characteristics and mechanisms of decolorization by UV/ozone technique. Results will also aid in designing a system for field application of dye finishing plants. According to the results from the third topic, for a dye finishing plant of wastewater flow rate of 800CMD (m3/day), the capital cost of equipment and related establishment as well as amendment is about US$ 116,300, and the monthly operation and maintenance cost is US$ 4,030. In this study, ozone was used as a substitute decolorizing oxidant to treat the effluent from the secondary biological and physical/chemical treatment plant. Because the current cost for the decolorization oxidant (NaOCl) is approximately US$ 5,700 per month, the monthly saving, adopting the decolorization system using UZ/Ozone, will be US$ 1,670. The investment return period will be over 7 years and is not attractive to the plant owners. However, to prevent the accumulated toxicity of chloride compounds in the environment and to promote the desires of investment on the advanced decolorization technique, a favorable tax deduction policy needs to be applied.

By integrating Nanotechnology and MEMS technology, this thesis aims to research a flexural-plate wave (FPW) sensor for testing Immunoglobulin E (IgE) concentration in blood serum, a significant index for the diagnosis of allergies. The traditional methods of blood assay are time-consuming and costly, and its average accuracy of only 60-70 percent. After compare the major four kinds of acoustic sensor, the FPW sensor demonstrates a high accuracy, high sensitivity, low operation frequency, low diagnosis time and low cost. This thesis utilizes a reactive RF sputter system to deposite the piezoelectric ZnO thin film. To obtain the high C-axis orientation (002) characteristic of ZnO membrane, many parameters such as substrate temperature, Ar/O2 ratio and RF power have been adjusted and optimized during the sputtering process. The effects of varied parameters will be investigated and analysis by using SEM or XRD facilities. In this study, we combined the high figure-of-merits ZnO deposition techniques and single-side anisotropic silicon etch process to implement the process integration of FPW device. Finally, this research has demonstrated a 50-60MHz center frequency can be extracted from such silicon-based FPW microsensor.

This study was to prepare nanoscale MgO using the homogeneous precipitation process and to investigate its destructive adsorption with dye wastewater of reactive black-5 and reactive blue-19. In addition, UV-vis Spectrophotometer, Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry (MALDI-TOF/MS) and Gas Chromatograph/Mass Spectrometer (GC/MS) were used to analyze the intermediates resulting from destructive adsorption. Based on the results obtained, the destructive adsorption mechanisms for the treatment of dye wasterwater by nanoscale MgO were proposed in this study. In this work, the optimal operating conditions for nanoscale MgO synthesis were determined to be the following: (1) a chemical reaction time of 7 hr, (2) reaction temperature of 125¢J, (3) molar ratio of 9 for urea/MgCl2¡D6H2O, (4) water addition of 250 mL, (5) mixing intensity of 90 strokes per min, (6) calcination at 450¢J for 4 hr, (7) reflux time of 24 hr, (8) freeze-drying method, (9) two stage calcinations. Using these operating conditions one is able to prepare 2-D nanoscale MgO of hexagonal platelets with a thickness of 20-30 nm and BET surface area of 120-125 m2/g. The adsorption model of nanoscale MgO for RB-5 and RB-19 was fitted to the Langmuir equation and their adsorption capacity were 196.08 mg/g and 163.93 mg/g, respectively. Both of them were fitted to the pseudo-second-order kinetic model equation. The optimal operating conditions of nanoscale MgO for destructive adsorption of both dyes were determined to be the following: (1) an initial dye concentration of 1000 mg/L, (2) a nanoscale MgO dose of 15 g/L, (3) a vigorous mixing of 30 min, (4) no need of system pH adjustment. Under such conditions, chemical oxygen demand (COD) and American Dye Manufacturers Institute (ADMI) of RB-5 and RB-19 were lower than the textile effluent standards. According to the UV-vis spectrophotometer scanning results, the color removal of nanoscale MgO for RB-5 and RB-19 was good. At the same time, the absorbance of their second maximal peaks was decreased and some peaks were observed. Therefore, it proved that the model dyes were destroyed. Experimental results have shown that nanoscale MgO has a better performance of destructive adsorption on RB-5 than that of RB-19. This might be ascribed to the following reasons: (1) a greater molecular weight, (2) a longer molecule structure, (3) more sulfate ethyl sulfone groups for RB-5, and (4) a hard to be destroyed structure of anthraquinone for RB-19. The destructive adsorption of dye wastewater by nanoscale MgO presumably took place mainly on the surface active sites of nanoscale MgO, including anion/cation vacancies, superoxide anion, edge, corner, isolated OH, lattice bound OH and assiocited-OH groups. According to the results of MALDI-TOF/MS and GC/MS analysis, the relevant reaction mechanism for RB-5 could be divided into three stages: (1) adsorption and water-soluble groups exfoliation stage, (2) chromophor decomposition and decolorization stage, and (3) further degradation stage for light-color intermediates. On the other hand, the relevant reaction mechanism for RB-19 might involve only the adsorption and auxochrome exfoliation stage and chromophor decomposition and decolorization stage.