The concentration of carbon dioxide in natural seawater is sufficient for microalgal growth, but insufficient for high algal-density culture due to limitation of photosynthesis in the artificial medium. This study was adjusted the initial pH to 5.5, 6.5 and 7.5 by adding CO2 or HCl in 1L flask cultured stagnantly with continuous illumination. The best growth of Isochrysis galbana was found in the culture (CO2-6.5i) with initial pH 6.5 using CO2 adjustment and maintaining the same during day 2 to day 5, while the worst was in CO2-5.5i. Furthermost, we adjusted the pH of cultures daily to the set values; the best growth was also found in CO2-6.5e having the cell number 221% of the blank. Initial addition of NaHCO3 with doses of 0.01 g/L, 0.05 g/L, 0.1 g/L, 0.5 g/ L and 1g/ L in the culture, showed the lowest cell number after 5 days culture is in the group of 1.0 g/L and no significant difference among the rest groups. Addition of 0.5 g/L NaHCO3 and adjusted the pH to 6.5 by HCl in the beginning promoted algal growth and resulted in the culture having 212 % cell number of the blank. Using the feedback control system, 100 L algal cultures with aeration and providing CO2 gas or HCl liquid to maintain the pH as 5.5, 6.5 and 7.5 or 7.5 individually were conducted to test the effect of pH control on the mass culture of I. galbana. Better growth was found in the culture with CO2 feedback control than HCl-control in duplicate experiments. It also showed significant difference among the groups adjusted pH between 6.5-7.5. The cell concentration could reach 1100-1400 x 104 cells/ml and was about double the amount of the blank without pH control cultured in 7 days. Meanwhile, the NO3-N concentration was nearly exhausted while the PO4-P still replete. This study reveals the high concentration and fast growth of I. galbana can be maintained under the suitable physical condition providing the carbon source in an optimal pH.

Thesis--Auburn University, 2009. / Abstract. Includes bibliographic references (p.71-87).

Thesis--Auburn University, 2010. / Abstract. Includes bibliographic references.

Thesis (Ph. D.)--York University, 2000. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references (leaves 370-416). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://wwwlib.umi.com/cr/yorku/fullcit?pNQ59143

Anthropogenic CO₂ captured from a coal-fired power plant can be used for an enhanced oil recovery (EOR) operation while mitigating the atmospheric impact of CO₂ emissions. Concern about climate change caused by CO₂ emissions has increased the motivation to develop carbon capture and sequestration (CCS) projects to reduce the atmospheric impact of coal and other fossil fuel combustion. Enhanced oil recovery operations are typically constrained by the supply of CO₂, so there is interest from oil producers to use large-volume anthropogenic (LVA) CO₂ for tertiary oil production. The intermittency of LVA CO2 emissions creates an area of concern for both oil producers and electric utilities that may enter into a CO₂ supply contract for EOR. An oil producer wants to know if intermittency from a non-standard source of CO₂ will impact oil production from the large volume being captured. Since the electric utility must supply electricity on an as-needed basis, the CO₂ emissions are inherently intermittent on a daily and seasonal basis. The electric utility needs to know if the intermittent supply of CO₂ would reduce its value compared to CO₂ delivered to the oil field at a constant rate. This research creates an experimental test scenario where one coal-fired power plant captures 90% of its CO₂ emissions which is then delivered through a pipeline to an EOR operation. Using real emissions data from a coal-fired power plant and simplified data from an actual EOR reservoir, a series of reservoir simulations were done to address and analyze potential operational interference for an EOR operator injecting large-volume, intermittent CO₂ characteristic of emissions from a coal-fired power plant. The test case simulations in this study show no significant impact to oil production from CO₂ intermittency. Oil recovery, in terms of CO₂ injection, is observed to be a function of the total pore volumes injected. The more CO₂ that is injected, the more oil that is produced and the frequency or rate at which a given volume is injected does not impact net oil production. Anthropogenic CO₂ sources can eliminate CO₂ supply issues that constrain an EOR operation. By implementing this nearly unlimited supply of CO₂, oil production should increase compared to smaller-volume or water-alternating-gas (WAG) injection strategies used today. Mobility ratio and reservoir heterogeneity have a considerable impact on oil recovery. Prediction of CO₂ breakthrough at the production wells seems to be more accurate when derived from the mobility ratio between CO₂ and reservoir oil. The degree of heterogeneity within the reservoir has a more direct impact on oil recovery and sweep efficiency over time. The volume of CO₂ being injected can eventually invade lower permeability regions, reducing the impact of reservoir heterogeneity on oil recovery. This concept should mobilize a larger volume of oil than a conventional volume-limited or WAG injection strategy that may bypass or block these lower permeability regions. Besides oil recovery, a reservoir's performance in this study is defined by its CO₂ injectivity over time. Elevated injection pressures associated with the large-volume CO₂ source can substantially impact the ability for an oil reservoir to store LVA CO₂. As CO₂, a less viscous fluid, replaces produced oil and water, the average reservoir pressure slowly declines which improves injectivity. This gradual improvement in injectivity is mostly occupied by the increasing volume of recycled CO₂. Sweep efficiency is critical towards minimizing the impact of CO₂ recycling on reservoir storage potential. Deep, large, and permeable oil reservoirs are more capable of accepting LVA CO₂, with less risk of fracturing the reservoir or overlying confining unit. The depth of the reservoir will directly dictate the injection pressure threshold in the oil reservoir as the fracture pressure increases with depth. If EOR operations are designed to sequester all the CO₂ delivered to the field, additional injection capacity and design strategies are needed. / text

This dissertation explores the electrochemical behavior of enzymes and their cofactors at carbon nanotube (CNT) and nitrogen-doped carbon nanotube (N-CNT) electrodes. Two common types of oxidoreductases are considered: flavin adenine dinucleotide (FAD)-dependent oxidases and nicotinamide adenine dinucleotide-dependent (NAD⁺)-dehydrogenases. Chapter 1 presents the oxygen reduction reaction (ORR) at N-CNT electrodes as a way to electrochemically measure enzymatic turnover at the electrode surface. The unique peroxide pathway at N-CNT electrodes, which catalytically disproportionates hydrogen peroxide (H₂O₂) back into oxygen, provides an increased ORR current directly proportional to the rate of enzymatic turnover for H₂O₂ producing enzymes, even in an oxygen saturated solution. Biosensing of L-lactate using the increased ORR current is demonstrated using L-lactate oxidase. Chapter 2 explores the surface bound electrochemical signal of FAD when FAD-dependent enzyme or free FAD is allowed to spontaneously adsorb onto the CNT/N-CNT surface. Specifically, the origin of the enzymatically generated FAD signal and the rate constant of the electron transfer are elucidated. Chapter 3 continues the discussion of the cofactor FAD by demonstrating its use as an informative surface specific redox probe for graphitic carbon surfaces. Primarily, FAD can be used to determine the electroactive surface area and the relative hydrophobicity/hydrophilicity of graphitic surfaces. Chapter 4 changes gears to NAD⁺-dependent dehydrogenases by investigating the electrocatalytic oxidation of NADH at N-CNTs in comparison with conventional carbon electrodes or nondoped CNTs. Biosensing of glucose through the oxidation of NADH is demonstrated using glucose dehydrogenase adsorbed onto the N-CNT surface. Chapter 5 continues the discussion of NAD⁺-dependent dehydrogenases by addressing the reaction kinetics of NADH oxidation at N-CNTs as a tool to measure the enzymatic reduction of NAD⁺.

The Electrolyte Nonrandom Two-Liquid Activity Coefficient model in Aspen PlusTM 2006.5 was used to develop a rigorous and consistent thermodynamic representation for the base sub-component systems associated with aqueous combinations of K₂CO₃, KHCO₃, MEA, and piperazine (PZ) in a mixed-solvent electrolyte system for the application of CO₂ absorption/stripping from coal fired power plants. We developed a new vapor-liquid equilibrium apparatus to measure CO₂, amine, and H2O vapor pressures at 40 and 60 oC. We found that the volatility of MEA and PZ can be approximated at 50 and 20 ppmv at 40°C for any solvent composition studied in this work, over the CO₂ partial pressure range from 0.01 to 0.1 kPa. Very few solvent compositions exhibited a greater differential capacity than 7 m MEA at 60°C; specifically 11 m MEA, 3.5 m MEA + 3.6 m PZ, 7 m MEA + 2 m PZ, 7 m MEA + 3.6 m PZ, and 5 m K+ + 7 m MEA + 3.6 m PZ. Piperazine exhibited a possible maximum differential capacity of 2.21 mole CO₂/kg-H₂O at a concentration of 7.3 m. At the Norwegian University of Science and Technology, Inna Kim determined the differential enthalpy of CO₂ absorption for aqueous combinations of K₂CO₃, KHCO₃, MEA, PZ, and CO₂, based on a consistent experimental method developed for MEA, from 40 to 120°C for use in this work. In addition, we developed a consistent method to measure the specific heat capacity for a number of similar solvent combinations. We found that the enthalpy of CO₂ absorption increased with temperature because the apparent partial heat capacity of CO₂ may be considered small. Finally, by using a differential scanning calorimeter, we determined the dissolution temperature for aqueous mixtures of unloaded piperazine, which inferred an effective operating range for solutions of concentrated piperazine, greater than 5 m PZ, over a loading range between 0.25 to 0.45 mole CO₂/2·mol PZ. Through unit cell x-ray diffraction, we were able to identify and characterize the presence of three solid phases (PZ·6H₂O, KHCO₃, and KvPZ(COO)₂) in aqueous mixture combinations of K₂CO₃, KHCO₃, PZ, and CO₂. / text

Carbon sequestration is a method of capturing and storing excess anthropogenic CO₂ in the subsurface. When CO₂ is injected, the temperature and pressure at depth turn it into a supercritical (SC) fluid, where density is that of a liquid, but viscosity and compressibility resemble a gas. Ultimately the SC CO₂ is trapped at depth either by low permeability sealing layers, by reactions with minerals, or by dissolving into fluids. The injected CO₂ is buoyant and initially exists as a non-aqueous hydrophobic layer floating on top of the subsurface brine, up against the upper sealing formation, but over time it will dissolve into the brine and potentially react with minerals. The details of that initial dissolution reaction, however, are only poorly understood, and I address three basic questions for this research: What is the fundamental kinetics of SC CO₂ dissolution into water? How fast does dissolved CO₂ diffuse away from the source point? And what geochemical conditions influence the dissolution rate? To answer these questions I employed a high pressure flow-through approach using a column packed with coarse quartz sand. The system was both pressure and temperature controlled to have either liquid or SC CO₂ present, and was typically run at 100 Bar, 0.5 to 2.5 mls/min, and 28-60°C. After establishing the hydraulic parameters for the column using two conservative tracers (Br, As), injections (5 and 20 [mu]l) were made either as aqueous solutions equilibrated to high pressure CO₂, or as pure liquid or SC CO₂ into 0.1 mmol NaOH. For all experiments the pH of the system was monitored, and [CO₂] over time was calculated from those data. For injections of brine with dissolved CO₂, transport was conservative and was nearly identical to the conservative tracers. The CO₂ quickly mixes in the column and does not react with the quartz. The liquid and SC CO₂ injections, however, do not act conservatively, and have a very long tailing breakthrough curve that extends to tens of pore volumes. I hypothesize that the SC CO₂ is becoming trapped as a droplet or many droplets in the pore spaces, and the long breakthrough tail is related either to the rate of dissolution into the aqueous phase, the diffusion of dissolved CO₂ away from the phase boundary, or the reaction with the NaOH, limited to the narrow contact zones in the pore throats. Because of the speed at which acid-base reactions occur (nanosecond kinetics), I infer that the rate limiting step is either surface dissolution or diffusion. From plots of ln[CO₂] v. time I obtained values for k, the specific rate of the dissolution reaction R=-k[CO₂]. No trend for k was seen with respect to changes in temperature, but k did show a trend with respect to changing flow rate. k increased from an average value of 3.05x10⁻³ at 0.5 ml/min to an average value of 3.38x10⁻³ at 1.6 ml/min, and then held constant at the higher flow rates, up to 2.5 ml/min. I interpret these data to show that at low flow rates, the reaction is diffusion limited; the fluid nearest the contact zone becomes saturated with dissolved CO₂. At higher flow rates, the fluid is moving fast enough that saturation cannot occur, and the kinetics of the dissolution reaction dominate. Simple geometric models indicate that the CO₂/water interface is shaped like a spherical cap, indicating that the snapped-off CO₂ is forming a meniscus in the pore throat, limiting the surface area across which dissolution can occur. / text

No description available.

Total organic carbon (TOC) and chemical oxygen demand (COD) are two methods used for measuring organic pollutants in wastewater. Both methods are widely used but the COD method results in production of hazardous wastes, including mercury.The purpose of this study was to validate the method TOC that will replace COD and find a factor to convert TOC to COD. In this study 26 samples were analyzed from four sewage treatment plant in the municipality of Enköping.The results show that the COD method could be replaced by the TOC method.The factor for COD/TOC was between 3.1 - 3.3. Both methods will be used in parallel until 2013 when it will be forbidden to use the COD analysis.