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Biochemical Methane Potential (BMP) Tests and Microbial Electrochemical Cells (MECs) Identify Differences in Pretreated Waste Activates Sludge (WAS) Streams

Description

Anaerobic digestion (AD), a common process in wastewater treatment plants, is traditionally assessed with Biochemical Methane Potential (BMP) tests. Hydrolysis is considered its rate-limiting step. During my research, I assessed the impact of pretreatment on BMPs and microbial electrochemical cells

Anaerobic digestion (AD), a common process in wastewater treatment plants, is traditionally assessed with Biochemical Methane Potential (BMP) tests. Hydrolysis is considered its rate-limiting step. During my research, I assessed the impact of pretreatment on BMPs and microbial electrochemical cells (MECs). In the first set of experiments, BMP tests were performed using alkaline and thermal pretreated waste activated sludge (WAS), a control group, and a negative control group as samples and AD sludge (ADS) as inoculum. The data obtained suggested that BMPs do not necessarily require ADS, since samples without inoculum produced 5-20% more CH4. However, ADS appears to reduce the initial methanogenesis lag in BMPs, as no pH inhibition and immediate CH4 production were observed. Consumption rate constants, which are related to hydrolysis, were calculated using three methods based on CH4 production, SSCOD concentration, and the sum of both, called the lumped parameter. All the values observed were within literature values, yet each provide a different picture of what is happening in the system. For the second set of experiments, the current production of 3 H-type MECs were compared to the CH4 production of BMPs to assess WAS solids' biodegradability and consumption rates relative to the pretreatment methods employed for their substrate. BMPs fed with pretreated and control WAS solids were performed at 0.42 and 1.42 WAS-to-ADS ratios. An initial CH4 production lag of about 12 days was observed in the BMP assays, but MECs immediately began producing current. When compared in terms of COD, MECs produced more current than the BMPs produced CH4, indicating that the MEC may be capable of consuming different types of substrate and potentially overestimating CH4 production in anaerobic digesters. I also observed 2 to 3 different consumption events in MECs versus 3 for BMP assays, but these had similar magnitudes, durations, and starting times in the control and thermal pretreated WAS-fed assays and not in alkaline assays. This might indicate that MECs identified the differences of alkaline pretreatment, but not between control WAS and thermal pretreated WAS. Furthermore, HPLC results suggest at least one hydrolysis event, as valerate, butyrate, and traces of acetate are observed in the reactors' effluents. Moreover, a possible inhibition of valerate-fixing microbial communities due to pretreatment and the impossibility of valerate consumption by ARB might explain its presence in the reactors' effluents.

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2017-05

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New insights into the pore development mechanism of layered hydroxides upon thermal activation

Description

Layered double hydroxides (LDHs), also known as hydrotalcite-like materials, are extensively used as precursors for the preparation of (photo-)catalysts, electrodes, magnetic materials, sorbents, etc. The synthesis typically involves the transformation to the corresponding mixed metal oxide via calcination, resulting in

Layered double hydroxides (LDHs), also known as hydrotalcite-like materials, are extensively used as precursors for the preparation of (photo-)catalysts, electrodes, magnetic materials, sorbents, etc. The synthesis typically involves the transformation to the corresponding mixed metal oxide via calcination, resulting in atomically dispersed mixed metal oxides (MMOs). This process alters the porosity of the materials, with crucial implications for the performance in many applications. Yet, the mechanisms of pore formation and collapse are poorly understood. Combining an integrated in situ and ex situ characterization approach, here we follow the evolution of porosity changes during the thermal decomposition of LDHs integrating different divalent (Mg, Ni) and trivalent (Al, Ga) metals. Variations in porous properties determined by high-resolution argon sorption are linked to the morphological and compositional changes in the samples by in situ transmission electron microscopy coupled with energy dispersive X-ray spectroscopy, which is facilitated by the synthesis of well crystallized LDHs of large crystal size. The observations are correlated with the phase changes identified by X-ray diffraction, the mass losses evidenced by thermogravimetric analysis, the structural changes determined by infrared and nuclear magnetic resonance spectroscopy, and the pore connectivity analyzed by positron annihilation spectroscopy. The findings show that the multimetallic nature of the LDH governs the size and distribution (geometry, location, and connectivity) of the mesopores developed, which is controlled by the crystallization of the MMO phase, providing key insights for the improved design of porous mixed metal oxides.

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2017-05

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Characterizing Buffers to Maximize Peroxide Production in the Cathode Chamber of Microbial Fuel Cells

Description

Microbial fuel cells (MFCs) facilitate the conversion of organic matter to electrical current to make the total energy in black water treatment neutral or positive and produce hydrogen peroxide to assist the reuse of gray water. This research focuses on

Microbial fuel cells (MFCs) facilitate the conversion of organic matter to electrical current to make the total energy in black water treatment neutral or positive and produce hydrogen peroxide to assist the reuse of gray water. This research focuses on wastewater treatment at the U.S. military forward operating bases (FOBs). FOBs experience significant challenges with their wastewater treatment due to their isolation and dangers in transporting waste water and fresh water to and from the bases. Even though it is theoretically favorable to produce power in a MFC while treating black water, producing H2O2 is more useful and practical because it is a powerful cleaning agent that can reduce odor, disinfect, and aid in the treatment of gray water. Various acid forms of buffers were tested in the anode and cathode chamber to determine if the pH would lower in the cathode chamber while maintaining H2O2 efficiency, as well as to determine ion diffusion from the anode to the cathode via the membrane. For the catholyte experiments, phosphate and bicarbonate were tested as buffers while sodium chloride was the control. These experiments determined that the two buffers did not lower the pH. It was seen that the phosphate buffer reduced the H2O2 efficiency significantly while still staying at a high pH, while the bicarbonate buffer had the same efficiency as the NaCl control. For the anolyte experiments, it was shown that there was no diffusion of the buffers or MFC media across the membrane that would cause a decrease in the H2O2 production efficiency.

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2016-05

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Continuous Hydrogen Peroxide Production using Microbial Electrochemical Cells

Description

Alternative ion exchange membranes for implementation in a peroxide production microbial electrochemical cel (PP-MEC) are explored through membrane stability tests with NaCl electrolyte and stabilizer EDTA at varying operational pHs. PP-MEC performance parameters \u2014 H2O2 concentration, current density, coulombic efficiency

Alternative ion exchange membranes for implementation in a peroxide production microbial electrochemical cel (PP-MEC) are explored through membrane stability tests with NaCl electrolyte and stabilizer EDTA at varying operational pHs. PP-MEC performance parameters \u2014 H2O2 concentration, current density, coulombic efficiency and power input required \u2014 are optimized over a 7 month continuous operation period based on their response to changes in HRT, EDTA concentration, air flow rate and electrolyte. I found that EDTA was compatible for use with the membranes. I also determined that AMI membranes were preferable to CMI and FAA because it was consistently stable and maintained its structural integrity. Still, I suggest testing more membranes because the AMI degraded in continuous operation. The PP-MEC produced up to 0.38 wt% H2O2, enough to perform water treatment through the Fenton process and significantly greater than the 0.13 wt% batch PP-MEC tests by previous researchers. It ran at > 0.20 W-hr/g H2O2 power input, ~ three orders of magnitude less than what is required for the anthraquinone process. I recommend high HRT and EDTA concentration while running the PP- MEC to increase H2O2 concentration, but low HRT and low EDTA concentration to decrease power input required. I recommend NaCl electrolyte but suggest testing new electrolytes that may control pH without degrading H2O2. I determined that air flow rate has no effect on PP-MEC operation. These recommendations should optimize PP-MEC operation based on its application.

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2016-05

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Direct Flame Solid Oxide Fuel Cells for Use in Remote Powering Applications

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In this Honors thesis, direct flame solid oxide fuel cells (DFFC) were considered for their feasibility in providing a means of power generation for remote powering needs. Also considered for combined heat and fuel cell power cogeneration are thermoelectric cells

In this Honors thesis, direct flame solid oxide fuel cells (DFFC) were considered for their feasibility in providing a means of power generation for remote powering needs. Also considered for combined heat and fuel cell power cogeneration are thermoelectric cells (TEC). Among the major factors tested in this project for all cells were life time, thermal cycle/time based performance, and failure modes for cells. Two types of DFFC, anode and electrolyte supported, were used with two different fuel feed streams of propane/isobutene and ethanol. Several test configurations consisting of single cells, as well as stacked systems were tested to show how cell performed and degraded over time. All tests were run using a Biologic VMP3 potentiostat connected to a cell placed within the flame of a modified burner MSR® Wisperlite Universal stove. The maximum current and power output seen by any electrolyte supported DFFCs tested was 47.7 mA/cm2 and 9.6 mW/cm2 respectively, while that generated by anode supported DFFCs was 53.7 mA/cm2 and 9.25 mW/cm2 respectively with both cells operating under propane/isobutene fuel feed streams. All TECs tested dramatically outperformed both constructions of DFFC with a maximum current and power output of 309 mA/cm2 and 80 mW/cm2 respectively. It was also found that electrolyte supported DFFCs appeared to be less susceptible to degradation of the cell microstructure over time but more prone to cracking, while anode supported DFFCs were dramatically less susceptible to cracking but exhibited substantial microstructure degradation and shorter usable lifecycles. TECs tested were found to only be susceptible to overheating, and thus were suggested for use with electrolyte supported DFFCs in remote powering applications.

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2014-05

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Augmenting Protocols for In-situ Separation of Biocompounds.

Description

In our modern world the source of for many chemicals is to acquire and refine oil. This process is becoming an expensive to the environment and to human health. Alternative processes for acquiring the final product have been developed but

In our modern world the source of for many chemicals is to acquire and refine oil. This process is becoming an expensive to the environment and to human health. Alternative processes for acquiring the final product have been developed but still need work. One product that is valuable is butanol. The normal process for butanol production is very intensive but there is a method to produce butanol from bacteria. This process is better because it is more environmentally safe than using oil. One problem however is that when the bacteria produce too much butanol it reaches the toxicity limit and stops the production of butanol. In order to keep butanol from reaching the toxicity limit an adsorbent is used to remove the butanol without harming the bacteria. The adsorbent is a mesoporous carbon powder that allows the butanol to be adsorbed on it. This thesis explores different designs for a magnetic separation process to extract the carbon powder from the culture.

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2015-05

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The Effect of pH, Acetate, and Buffer Concentration on Anode Biofilms of Geobacter sulfurreducens PCA Using Advanced Electrochemical Methods

Description

The mechanisms of extracellular respiration in Geobacter sulfurreducens, commonly considered to be a model organism for anode respiration, are yet to be completely understood. The interplay between electron and proton transport especially could be a key to gaining further insights.

The mechanisms of extracellular respiration in Geobacter sulfurreducens, commonly considered to be a model organism for anode respiration, are yet to be completely understood. The interplay between electron and proton transport especially could be a key to gaining further insights. One way to investigate the mechanisms of extracellular respiration under varying environmental conditions is by analyzing the electrochemical response of the biofilm with respect to pH, buffer concentrations, and acetate concentrations. I seek to increase the understanding of the electrochemical response of the G. sulfurreducens biofilm through electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques in concert with chronoamperometry. I used Geobacter sulfurreducens PCA biofilms in single-chamber electrochemical cells (approximately 100 mL volume) with a small gold working electrode (3.14 mm2). I observed limitations in the initial methods used for media replacement. I tracked changes in the CV data, such as EKA (midpoint potential), as a function of pH and buffer concentration. The media replacement method developed demonstrates success in pH experiments that will be transferrable to other environmental conditions to study electron transport. The experiments revealed that the clarity of data collected is dependent on the quality of the biofilm. A high quality biofilm is characterized by a high current density and normal growth behavior. The general trends seen in these experiments are that as pH increases the potential decreases, and as buffer concentration increases the potential decreases and pH increases. Acetate-free conditions in the reactor were unable to be achieved as characterized by non-zero current densities in the acetate-free experiments.

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2016-05

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Synthesis and stability of ceramic-carbonate dual-phase membrane for carbon dioxide separation

Description

Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and

Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and microporous inorganic membranes to separate CO2. These membranes, however, have limitations at high temperature resulting in poor permeation performance. To address these limitations, the use of a dense dual-phase membrane has been studied. These membranes are composed of conductive solid and conductive liquid phases that have the ability to selectively permeate CO2 by forming carbonate ions that diffuse through the membrane at high temperature. The driving force for transport through the membrane is a CO2 partial pressure gradient. The membrane provides a theoretically infinite selectivity. To address stability of the ceramic-carbonate dual-phase membrane for CO2 capture at high temperature, the ceramic phase of the membrane was studied and replaced with materials previously shown to be stable in harsh conditions. The permeation properties and stability of La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF)-carbonate, La0.85Ce0.1Ga0.3Fe0.65Al0.05O3-δ (LCGFA)-carbonate, and Ce0.8Sm0.2O1.9 (SDC)-carbonate membranes were examined under a wide range of experimental conditions at high temperature. LSCF-carbonate membranes were shown to be unstable without the presence of O2 due to reaction of CO2 with the ceramic phase. In the presence of O2, however, the membranes showed stable permeation behavior for more than one month at 900oC. LCGFA-carbonate membranes showed great chemical and permeation stability in the presence of various conditions including exposure to CH4 and H2, however, the permeation performance was quite low when compared to membranes in the literature. Finally, SDC-carbonate membranes showed great chemical and permeation stability both in a CO2:N2 environment for more than two weeks at 900oC as well as more than one month of exposure to simulated syngas conditions at 700oC. Ceramic phase chemical stability increased in the order of LSCF < LCGFA < SDC while permeation performance increased in the order of LCGFA < LSCF < SDC.

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2013

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Metabolic engineering for the biosynthesis of styrene and its derivatives

Description

Metabolic engineering is an extremely useful tool enabling the biosynthetic production of commodity chemicals (typically derived from petroleum) from renewable resources. In this work, a pathway for the biosynthesis of styrene (a plastics monomer) has been engineered in Escherichia coli

Metabolic engineering is an extremely useful tool enabling the biosynthetic production of commodity chemicals (typically derived from petroleum) from renewable resources. In this work, a pathway for the biosynthesis of styrene (a plastics monomer) has been engineered in Escherichia coli from glucose by utilizing the pathway for the naturally occurring amino acid phenylalanine, the precursor to styrene. Styrene production was accomplished using an E. coli phenylalanine overproducer, E. coli NST74, and over-expression of PAL2 from Arabidopsis thaliana and FDC1 from Saccharomyces cerevisiae. The styrene pathway was then extended by just one enzyme to either (S)-styrene oxide (StyAB from Pseudomonas putida S12) or (R)-1,2-phenylethanediol (NahAaAbAcAd from Pseudomonas sp. NCIB 9816-4) which are both used in pharmaceutical production. Overall, these pathways suffered from limitations due to product toxicity as well as limited precursor availability. In an effort to overcome the toxicity threshold, the styrene pathway was transferred to a yeast host with a higher toxicity limit. First, Saccharomyces cerevisiae BY4741 was engineered to overproduce phenylalanine. Next, PAL2 (the only enzyme needed to complete the styrene pathway) was then expressed in the BY4741 phenylalanine overproducer. Further strain improvements included the deletion of the phenylpyruvate decarboxylase (ARO10) and expression of a feedback-resistant choristmate mutase (ARO4K229L). These works have successfully demonstrated the possibility of utilizing microorganisms as cellular factories for the production styrene, (S)-styrene oxide, and (R)-1,2-phenylethanediol.

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Date Created
2014

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A novel handheld real-time carbon dioxide analyzer for health and environmental applications

Description

The accurate and fast determination of carbon dioxide (CO2) levels is critical for many health and environmental applications. For example, the analysis of CO2 levels in exhaled breath allows for the evaluation of systemic metabolism, perfusion, and ventilation, and provides

The accurate and fast determination of carbon dioxide (CO2) levels is critical for many health and environmental applications. For example, the analysis of CO2 levels in exhaled breath allows for the evaluation of systemic metabolism, perfusion, and ventilation, and provides the doctors and patients with a non-invasive and simple method to predict the presence and severity of asthma, and Chronic Obstructive Pulmonary Disease (COPD). Similarly, the monitoring of CO2 levels in the atmosphere allows for assessment of indoor air quality (IAQ) as the indoor CO2 levels have been proved to be associated with increased prevalence of certain mucous membrane and respiratory sick building syndrome (SBS) symptoms. A pocket-sized CO2 analyzer has been developed for real-time analysis of breath CO2 and environmental CO2. This CO2 analyzer is designed to comprise two key components including a fluidic system for efficient gas sample delivery and a colorimetric detection unit integrated into the fluidic system. The CO2 levels in the gas samples are determined by a disposable colorimetric sensor chip. The sensor chip is a novel composite based sensor that has been optimized to provide fast and reversible response to CO2 over a wide concentration range, covering the needs of both environmental and health applications. The sensor is immune to the presence of various interfering gases in ambient or expired air. The performance of the sensor in real-time breath-by-breath analysis has also been validated by a commercial CO2 detector. Furthermore, a 3D model was created to simulate fluid dynamics of breath and chemical reactions for CO2 assessment to achieve overall understanding of the breath CO2 detection process and further optimization of the device.

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2014