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- Title
- The Effect of Recycled Backwash Water Operations on Fouling in a Coagulation-Ultrafiltration Process and Impact of Preozonation on Membrane Productivity.
- Creator
-
Biscardi, Paul, Duranceau, Steven, Sadmani, A H M Anwar, Lee, Woo Hyoung, Clausen, Christian, University of Central Florida
- Abstract / Description
-
This dissertation consists of research that focused on pretreatment strategies to reduce fouling of ultrafiltration (UF) membranes used for drinking water treatment, and was segmented into four key components. (1) In the first component of the work, the long-term fouling behavior of a polyethersulfone (PES) hollow-fiber UF membrane was studied at the pilot-scale for treatment of surface water over a one-year period. Pilot testing of a coagulation-flocculation-sedimentation (CFS) pretreatment...
Show moreThis dissertation consists of research that focused on pretreatment strategies to reduce fouling of ultrafiltration (UF) membranes used for drinking water treatment, and was segmented into four key components. (1) In the first component of the work, the long-term fouling behavior of a polyethersulfone (PES) hollow-fiber UF membrane was studied at the pilot-scale for treatment of surface water over a one-year period. Pilot testing of a coagulation-flocculation-sedimentation (CFS) pretreatment system revealed that chemically irreversible fouling was poorly correlated with turbidity and total organic carbon. It was also shown that recycled backwash water may have impacted membrane process performance, and that chemically irreversible fouling was responsive to changes in pretreatment configuration. (2) In the second component, pre-oxidation with ozone (preozonation) was then studied as a pretreatment process to reduce natural organic matter (NOM) fouling at the pilot-scale. This work suggested that preozonation reduced long-term chemically irreversible fouling. The chemically reversible fouling index increased by 59%, indicating that preozonation changed the characteristics of the foulants, yielding more effective chemically enhanced backwashes. (3) Bench-scale work that studied changes in NOM characteristics associated with the improved process performance were performed using fluorescent excitation-emission (EEM) spectroscopy and high-performance size-exclusion chromatography (HPSEC). Specifically, ozone was applied prior to a CFS-UF process and compared to a CFS-UF condition without ozone as the control. Although CFS reduced turbidity by 29%, ozone, when integrated with CFS increased turbidity by 58%, impacting downstream UF performance. As expected, ozone, when integrated with CFS and UF reduced filtrate true color by 40%, UV254 absorbance by 11%, and SUVA by 30%, relative to the control, indicating that preozonation changed the characteristics of the dissolved organic carbon present in the source water. (4) Follow-up bench-scale research using fluorescent EEM spectroscopy and HPSEC assessed operational strategies that impacted organic fouling. Specifically, the fate of fluorescing substances during the recycling of membrane backwash water (MBWW) ahead of CFS-UF process was investigated. Bench-scale UF membranes were used to generate MBWW from a CFS-treated surface water containing 21 mg/L dissolved organic carbon (DOC) registering a 0.95 cm-1 UV254 absorbance that had been coagulated with 100 mg/L with polyaluminum chloride. CFS settled water, when processed with UF, produced MBWW containing 9 mg/L DOC registering a 0.25 cm-1 UV254 absorbance. HPSEC with UV254 detection demonstrated an analogous UV254 reduction as measured by detector response. However, fluorescence EEM spectroscopy revealed that protein-like substances, known to be associated with irreversible fouling, had been concentrated in the MBWW. In order to evaluate recycling operations on overall DOC removal in a CFS-UF process, a blend of 30% MBWW with 70% of raw water was treated, resulting in an overall DOC removal of 73%. However, without MBWW recycle, the CFS-UF process removed less of the influent DOC (63%). In summary, this research demonstrated that NOM characteristics within MBWW should be considered when recycling backwash water in PES membrane operations, and that preozonation reduces chemically irreversible fouling when incorporated into a CSF-UF system.
Show less - Date Issued
- 2016
- Identifier
- CFE0006074, ucf:50951
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006074
- Title
- Anthropogenic Organic Chemical Removal from a Surficial Groundwater and Mass Transfer Modeling in a Nanofiltration Membrane Process.
- Creator
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Jeffery, Samantha, Duranceau, Steven, Lee, Woo Hyoung, Sadmani, A H M Anwar, Yestrebsky, Cherie, University of Central Florida
- Abstract / Description
-
This dissertation reports on research related to trace organic compounds (TrOCs) in surficial groundwater supplies and their subsequent removal from nanofiltration (NF) membranes. The research was conducted along coastal South Florida in cooperation with the Town of Jupiter Water Utilities, Jupiter, FL (Town). The focus of the research was to determine the extent of reclaimed water impacts on surficial groundwater supplies and subsequent effects on the Town's NF water treatment plant. Routine...
Show moreThis dissertation reports on research related to trace organic compounds (TrOCs) in surficial groundwater supplies and their subsequent removal from nanofiltration (NF) membranes. The research was conducted along coastal South Florida in cooperation with the Town of Jupiter Water Utilities, Jupiter, FL (Town). The focus of the research was to determine the extent of reclaimed water impacts on surficial groundwater supplies and subsequent effects on the Town's NF water treatment plant. Routine monitoring of fourteen TrOCs in reclaimed water and at the water treatment facility revealed varying degrees of TrOC detection in the environment. Certain TrOCs, including caffeine and DEET, were detected in a majority of the water sampling locations evaluated in this work. However, subsequent dilution with highly-treated reverse osmosis (RO) permeate from alternative supplies resulted in TrOCs below detection limits in potable water at the point-of-entry (POE). Pilot testing was employed to determine the extent of TrOC removal by NF. Prior to evaluating TrOC removal, hydraulic transients within the pilot process were first examined to determine the required length of time the pilot needed to reach steady-state. The transient response of a center-port NF membrane process was evaluated using a step-input dose of a sodium chloride solution. The pilot was configured as a two-stage, split-feed, center-exit, 7:2 pressure vessel array process, where the feed water is fed to both ends of six element pressure vessels, and permeate and concentrate streams are collected after only three membrane elements. The transient response was described as a log-logistic system with a maximum delay time of 285 seconds for an 85% water recovery and 267 gallon per minute feed flowrate.Eleven TrOC pilot unit experiments were conducted with feed concentrations ranging from 0.52 to 4,500 ?g/L. TrOC rejection was well-correlated with compound molecular volume and polarizability, with coefficient of determination (R2) values of 0.94. To enhance this correlation, an extensive literature review was conducted and independent literature sources were correlated with rejection. Literature citations reporting the removal effectiveness of an additional sixty-one TrOCs by loose NF membranes (a total of 95 data points) were found to be well-correlated with molecular volume and polarizability, with R2 values of 0.72 and 0.71, respectively.Of the TrOC's detected during this research, the anthropogenic solute caffeine was selected to be modeled using the homogeneous solution diffusion model (HSDM) and the HSDM with film theory (HSDM-FT). Mass transfer coefficients, K_w (water) K_s (caffeine), and k_b (caffeine back-transport) were determined experimentally, and K_s was also determined using the Sherwood correlation method. Findings indicate that caffeine transport through the NF pilot could be explained using experimentally determined K_s values without incorporating film theory, since the HSDM resulted in a better correlation between predicted and actual caffeine permeate concentrations compared to the HSDM-FT and the HSDM using K_s obtained using Sherwood applications. Predicted versus actual caffeine content was linearly compared, revealing R2 values on the order of 0.99, 0.96, and 0.99 for the HSDM without FT, HSDM-FT, and HSDM using a K_s value obtained using the Sherwood correlation method. However, the use of the HSDM-FT and the Sherwood number resulted in the over-prediction of caffeine concentrations in permeate streams by 27 percent and 104 percent, respectively.
Show less - Date Issued
- 2016
- Identifier
- CFE0006331, ucf:51545
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006331
- Title
- Modeling Mass Transfer and Assessing Cost and Performance of a Hollow Fiber Nanofiltration Membrane Process.
- Creator
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Yonge, David, Duranceau, Steven, Sadmani, A H M Anwar, Lee, Woo Hyoung, Clausen, Christian, University of Central Florida
- Abstract / Description
-
Bench-scale water treatment testing of three next generation hollow-fiber (HF) nanofiltration (NF) membranes was conducted to characterize divalent ion rejection capabilities and investigate removal mechanisms. Existing mathematical models were investigated to describe solute transport using synthetic magnesium sulfate solutions including the size exclusion model, homogenous solution diffusion (HSD) model, dimensional analysis, and the HSD model incorporating film theory. Solute transport for...
Show moreBench-scale water treatment testing of three next generation hollow-fiber (HF) nanofiltration (NF) membranes was conducted to characterize divalent ion rejection capabilities and investigate removal mechanisms. Existing mathematical models were investigated to describe solute transport using synthetic magnesium sulfate solutions including the size exclusion model, homogenous solution diffusion (HSD) model, dimensional analysis, and the HSD model incorporating film theory. Solute transport for two of the membranes were described by HSD theory and were predictive of their 90% divalent ion removal. A third membrane was more accurately modeled using size exclusion and was found to be predictive of its 40% divalent ion rejection. Feed ionic strength variation was shown to significantly impact rejection. In this work, semi-empirical models were developed to describe solute transport under varying feed ionic strength conditions. Bench-scale testing of aerated groundwater confirmed the HFNF membrane divalent ion rejection capabilities. Pilot testing of a commercially available HFNF membrane was shown to remove divalent ions and dissolved organic carbon (DOC) by 10% and 25%, respectively. Financial evaluations indicated that HFNF offered cost savings over traditional spiral-wound (SW) NF, $0.60/kgal versus $0.85/kgal operating costs, respectively. Traditional SWNF membranes produced superior water quality achieving 90% divalent ion removal and 96% DOC removal but required media and membrane filtration pretreatment. When considering the costs of constructing a new 2 million gallon per day (permeate) HFNF process, conceptual cost comparisons revealed that HFNF technologies could reduce capital costs by approximately $1 million, and operating costs by $0.27/kgal for an 85% recovery plant.
Show less - Date Issued
- 2016
- Identifier
- CFE0006549, ucf:51346
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006549
- Title
- The effect of glycerol on readily biodegradable chemical oxygen demand (RBCOD) in a wastewater stream.
- Creator
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Rawut, Rojina, Sadmani, A H M Anwar, Lee, Woo Hyoung, Duranceau, Steven, University of Central Florida
- Abstract / Description
-
This study evaluated the short-term effects of glycerol addition on readily biodegradable (RB) chemical oxygen demand (COD) in a carbon limited wastewater influent. The presence of an RB fraction provides with a suitable substrate for microorganisms to produce volatile fatty acids (VFA). The oxygen utilization rate (OUR) has been used to evaluate the oxygen consumption for RB substrate in wastewater. Wastewater with low organic content contains limited RB substrate, and thus, additional...
Show moreThis study evaluated the short-term effects of glycerol addition on readily biodegradable (RB) chemical oxygen demand (COD) in a carbon limited wastewater influent. The presence of an RB fraction provides with a suitable substrate for microorganisms to produce volatile fatty acids (VFA). The oxygen utilization rate (OUR) has been used to evaluate the oxygen consumption for RB substrate in wastewater. Wastewater with low organic content contains limited RB substrate, and thus, additional carbon source is required to improve biological treatment capability. Acetate, propionate, methanol, and glycerol are the commonly available carbon sources for biological treatment process. However, the cost of acetate and propionate are relatively high, and it is not economical to use these carbon sources in the wastewater plant. The use of methanol as a carbon source inherently poses safety issues in field applications due to its toxic and flammable properties. On the other hand, crude glycerol is the byproduct of biodiesel, which is an excellent carbon source alternative. However, crude glycerol contains impurities and requires a certain degree of purification to enhance the performance. The samples for the study were collected from the Iron Bridge Wastewater Reclamation Facility (Oviedo, FL) designed for treating municipal wastewater. The total COD (TCOD) of the sample influent was in the range of 237 to 408 mg COD/L, and RBCOD value was between 38 and 80.5 mg COD/L, containing up to 10 mg COD/L of VFA. This study also demonstrates the relationship between the glycerol concentration and OURs during the diauxic growth phase from the addition of glycerol. The growth was due to the existence of RB substrate and availability of glycerol for the microorganisms. TCOD increased from 284 to 378 mg COD/L and from 284 mg COD/L to 323 mg COD/L by spiking approximately 30 and 15 mL of glycerol stock solution (6.67 g/L), respectively. RBCOD increased from 45 to 89 mg COD/L and 55 mg COD/ L by spiking 30 mL and 15 ml glycerol stock solution, respectively. The initial influent heterotrophic active biomass (ZBH) increased from 5.4 to 15.8 mg VSS/L (8 to 23.4 mg COD/L) due to the addition of glycerol, indicating that the glycerol may be an adequate carbon source. The COD of wastewater with limited VFA (e.g., 10 mg COD/L) increased up to 2,502 mg COD/L where propionic acid (2,468 mg COD/L) exists as the primary end product with a small quantity of acetic acid (34 mg COD/L). Propionic acid was the main VFA component fermented from the glycerol addition. Glycerol addition led to increased RBCOD accompanied by high VFA production. This research investigated the short-term effect of glycerol addition on existing RBCOD in wastewater. It is recommended to explore the effect of increased RBCOD by the addition of glycerol to the effluent N and P for future study.
Show less - Date Issued
- 2016
- Identifier
- CFE0006543, ucf:51324
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006543
- Title
- Optimization of Glycerol or Biodiesel Waste Prefermentation to Improve EBPR.
- Creator
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Ghasemi, Marzieh, Randall, Andrew, Duranceau, Steven, Lee, Woo Hyoung, Jimenez, Jose, University of Central Florida
- Abstract / Description
-
The enhanced biological phosphorus removal (EBPR) process efficiency relies on different operational and process conditions especially the type of carbon source available in the wastewater. Acetic acid and propionic acid are the two major volatile fatty acids (VFAs) found in domestic wastewater which can drive biological phosphorus (P) removal to the desired level. However, often domestic wastewater does not have a sufficient amount of VFAs. Due to high acetate and propionate production-cost,...
Show moreThe enhanced biological phosphorus removal (EBPR) process efficiency relies on different operational and process conditions especially the type of carbon source available in the wastewater. Acetic acid and propionic acid are the two major volatile fatty acids (VFAs) found in domestic wastewater which can drive biological phosphorus (P) removal to the desired level. However, often domestic wastewater does not have a sufficient amount of VFAs. Due to high acetate and propionate production-cost, it is not economic to add acetate and propionate directly in full-scale wastewater treatment plants. This brought up the idea of using external carbon sources (e. g. molasses has been used successfully) in EBPR systems that can be converted to VFAs through a fermentation process. On the other hand, biodiesel fuels have been produced increasingly over the last decade. Crude glycerol is a biodiesel production major by-product that can be used as an external carbon source in wastewater treatment plant. Therefore, the main objective of this research is to optimize the glycerol/biodiesel waste fermentation process' operational conditions in pursuit of producing more favorable fermentation end-products (i. e. a mixture of acetic acid and propionic acid) by adding glycerol to a prefermenter versus direct addition to the anaerobic zone or fermentation with waste activated sludge. For this reason, different prefermenter parameters namely: mixing intensity, pH, temperature and solids retention time (SRT), were studied in a small scale fermentation media (serum bottles) and bench scale semi-continuous batch prefermenters. Experimental results revealed that glycerol/biodiesel waste fermentation resulted in a significant amount of VFAs production with propionic acid as the superior end-product followed by acetic acid and butyric acid. The VFA production was at its highest level when the initial pH was adjusted to 7 and 8.5. However, the optimum pH with respect to propionic acid production was 7. Increasing the temperature in serum bottles favored the total VFA production, specifically in the form of propionic acid. Regarding the mixing energy inconsistent results were obtained in the serum bottles compared to the bench scale prefermenters. The VFA production in mixed serum bottles at 200 rpm was higher than that of un-mixed ones. On the other hand, the unmixed or slowly mixed bench scale prefermenters showed higher VFA production than the mixed reactors. However, the serum bottles did not operate long enough to account for biomass acclimation and other long-term effects that the prefermenter experiments could account for. As a consequence one of the most important and consistently results was that VFA production was significantly enhanced by reducing mixing intensity from 100 rpm to 7 rpm and even ceasing mixing all together. This was true both for primary solids and glycerol. In addition propionate content was high under both high and low intensity, and adding glycerol also increased the fraction of primary solids that formed propionic acid instead of acetic acid. Increasing the SRT from 2 to 4 days increased the VFA production about 12% on average. In order to investigate the effect of glycerol on EBPR process efficiency two identical A2/O systems were monitored for 3 months. Experimental results suggested that glycerol addition could increase the P removal efficiency significantly. Adding glycerol to the prefermenter rather than the anaerobic zone resulted in a lower effluent soluble ortho phosphorus (SOP) (0.4 mg-P/L vs. 0.6 mg-P/L) but the difference was apparently statistically significant. Future experimentation should be done to determine if this effect is consistent, especially in carbon poor wastewaters. Also it would be desirable to conduct a longer pilot study or a full scale study to determine if this improvement in effluent SOP remains true over a range of temperature and changing influent conditions.
Show less - Date Issued
- 2015
- Identifier
- CFE0006310, ucf:51612
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006310
- Title
- Study of Polychlorinated Biphenyl Dechlorination by Zero Valent Magnesium With and Without Activated Carbon in Acidified Ethanol-Ethyl Lactate System.
- Creator
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Zullo, Fiona, Yestrebsky, Cherie, Clausen, Christian, Campiglia, Andres, Zou, Shengli, Duranceau, Steven, University of Central Florida
- Abstract / Description
-
Polychlorinated biphenyls (PCBs) are synthetic organic chemicals that ca de detected in the environment worldwide. PCBs were banned in the U.S in 1979 owing to their toxicity and persistence in the environment. Today PCBs are classified as human carcinogens and are among the top ten of the U.S Environmental Protection Agency's (EPA) most toxic chemicals. Many researchers have shown soil to be contaminated with PCBs at concentrations as high as 750 ppm. Given the toxicity of PCBs, there is an...
Show morePolychlorinated biphenyls (PCBs) are synthetic organic chemicals that ca de detected in the environment worldwide. PCBs were banned in the U.S in 1979 owing to their toxicity and persistence in the environment. Today PCBs are classified as human carcinogens and are among the top ten of the U.S Environmental Protection Agency's (EPA) most toxic chemicals. Many researchers have shown soil to be contaminated with PCBs at concentrations as high as 750 ppm. Given the toxicity of PCBs, there is an urgent need to extract and degrade such chemicals from contaminated soil in a cost effective way. Prior work revealed a novel method of degradation of PCBs via hydrodehalogenation with zero-valent magnesium in acidified ethanol and ethyl lactate as a solvent system. Even though this degradation method gave satisfactory results for PCB degradation, this system cannot tolerate more than 3% water in order to degrade PCBs, limiting its application to wet soil field samples. In the present work a new system of acidified ethanol and ethyl lactate with ZVMg over activated carbon was developed which shows promising results on the degradation process of PCBs even with water present in the system. A detailed study of the byproducts formed in the dechlorination process and a degradation pathway, along with the activity of the system over time, are presented in this research.Also, a study of the mechanism involved in this reaction was done via computational methods to elucidate a mechanism pathway. It was demonstrated that these reactions are exothermic and involved two transition states, the formation of the first transition state being the limiting step of this reaction.The torsion angle of the PCB congeners was also shown to be an extremely important factor in order to be able to use activated carbon as part of the remediation process. These findings allow a greater understanding of the reductive dechlorination assisted by ZVMg and will help to improve the remediation process in field samples.
Show less - Date Issued
- 2016
- Identifier
- CFE0006205, ucf:51105
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006205
- Title
- Assessing Biofiltration Pretreatment for Ultrafiltration Membrane Processes.
- Creator
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Cumming, Andrea, Duranceau, Steven, Cooper, David, Randall, Andrew, Wang, Dingbao, Yestrebsky, Cherie, University of Central Florida
- Abstract / Description
-
An engineered biological filtration (biofiltration) process treating a nutrient-enriched, low-alkalinity, organic-laden surface water downstream of conventional coagulation-clarification and upstream of an ultrafiltration (UF) membrane process was assessed for its treatment effectiveness. The impact of biofiltration pretreatment on UF membrane performance was evaluated holistically by investigating the native source water chemistry and extending the analysis into the drinking water...
Show moreAn engineered biological filtration (biofiltration) process treating a nutrient-enriched, low-alkalinity, organic-laden surface water downstream of conventional coagulation-clarification and upstream of an ultrafiltration (UF) membrane process was assessed for its treatment effectiveness. The impact of biofiltration pretreatment on UF membrane performance was evaluated holistically by investigating the native source water chemistry and extending the analysis into the drinking water distribution system. The biofiltration process was also compared in treatment performance to two alternative pretreatment technologies, including magnetic ion exchange (MIEX(&)#174;) and granular activated carbon (GAC) adsorption.The MIEX(&)#174;, GAC adsorption, and biologically active carbon (BAC) filtration pretreatments were integrated with conventional pretreatment then compared at the pilot-scale. Comparisons were based on collecting data regarding operational requirements, dissolved organic carbon (DOC) reduction, regulated disinfection byproduct (DBP) formation, and improvement on the downstream UF membrane operating performance. UF performance, as measured by the temperature corrected specific flux or mass transfer coefficient (MTC), was determined by calculating the percent MTC improvement relative to the existing conventional-UF process that served as the control. The pretreatment alternatives were further evaluated based on cost and non-cost considerations.Compared to the MIEX(&)#174; and GAC pretreatment alternatives, which achieved effective DOC removal (40 and 40 percent, respectively) and MTC improvement (14 and 30 percent, respectively), the BAC pretreatment achieved the lowest overall DOC removal (5 percent) and MTC improvement (4.5 percent). While MIEX(&)#174; relies on anion exchange and GAC relies on adsorption to target DOC removal, biofiltration uses microorganisms attached on the filter media to remove biodegradable DOC.Two mathematical models that establish an empirical relationship between the MTC improvement and the dimensionless alkalinity to substrate (ALK/DOC) ratio were developed. By combining the biofiltration results from the present research with findings of previous studies, an empirical relationship between the MTC improvement versus the ALK/DOC ratio was modeled using non-linear regression in Minitab(&)#174;. For surface water sources, UF MTC improvement can be simulated as a quadratic or Gaussian distribution function of the gram C/gram C dimensionless ALK/DOC ratio. According to the newly developed empirical models, biofiltration performance is optimized when the alkalinity to substrate ratio is between 10 and 14. For the first time a model has thus been developed that allows for a predictive means to optimize the operation of biofiltration as a pretreatment prior to UF membrane processes treating surface water.
Show less - Date Issued
- 2015
- Identifier
- CFE0005595, ucf:50260
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005595
- Title
- Degradation of Hydrazine and Monomethylhydrazine for Fuel Waste Streams using Alpha-ketoglutaric Acid.
- Creator
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Franco, Carolina, Yestrebsky, Cherie, Clausen, Christian, Rex, Matthew, Harper, James, Duranceau, Steven, University of Central Florida
- Abstract / Description
-
Alpha-ketoglutaric acid (AKGA) is an organic acid important for the metabolism of essential amino acids as well as for the transfer of cellular energy. It is a precursor of glutamic acid which is produced by the human body during the Krebs Cycle. AKGA has a specific industrial interest as it can be taken as a dietary supplement and is also widely used as a building block in chemical synthesis.Collectively termed as hydrazine (HZs), hydrazine (HZ) and monomethylhydrazine (MMH) are hypergolic...
Show moreAlpha-ketoglutaric acid (AKGA) is an organic acid important for the metabolism of essential amino acids as well as for the transfer of cellular energy. It is a precursor of glutamic acid which is produced by the human body during the Krebs Cycle. AKGA has a specific industrial interest as it can be taken as a dietary supplement and is also widely used as a building block in chemical synthesis.Collectively termed as hydrazine (HZs), hydrazine (HZ) and monomethylhydrazine (MMH) are hypergolic fuels that do not need an ignition source to burn. Because of the particular HZs' characteristics the National Aeronautics and Space Administration (NASA) at Kennedy Space Center (KSC) and the US Air Force at Cape Canaveral Air Force Station (CCAFS) consistently use HZ and MMH as hypergolic propellants. These propellants are highly reactive and toxic, and have carcinogenic properties. The handling, transport, and disposal of HZ waste are strictly regulated under the Resource Conservation and Recovery Act (RCRA) to protect human health and the environment. Significant quantities of wastewater containing residuals of HZ and MMH are generated at KSC and CCAFS that are subsequently disposed off-site as hazardous waste. This hazardous waste is shipped for disposal over public highways, which presents a potential threat to the public and the environment in the event of an accidental discharge in transit. NASA became aware of research done using AKGA to neutralize HZ waste. This research indicated that AKGA transformed HZ in an irreversible reaction potentially leading to the disposal of the hypergols via the wastewater treatment facility located at CCAFS eliminating the need to transport most of the HZ waste off-site.New Mexico Highlands University (NMHU) has researched this transformation of HZ by reaction with AKGA to form stabilized pyridazine derivatives. NMHU's research suggests that the treatment of HZ and MMH using AKGA is an irreversible reaction; once the reaction takes place, HZ and/or MMH cannot re-form from the byproducts obtained. However, further knowledge relating to the ultimate end products of the reaction, and their effects on human health and the environment, must still be addressed. The known byproduct of the AKGA/HZ neutralization reaction is 6-oxo-1,4,5,6-tetrahydro-pyridazine-3-carboxylic acid (PCA), and the byproduct of the AKGA/MMH reaction is 1-methyl-6-oxo-4,5-dihydro-pyridazine-3-carboxylic acid (mPCA).This research addressed several primary areas of interest to further the potential use of AKGA for HZ and MMH neutralization: 1) isolation of the end-product of the MMH-AKGA degradation process, 1-methyl-6-oxo-4,5-dihydro-pyridazine-3-carboxylic acid (mPCA), and determination of several physical properties of this substance, 2) evaluation of the kinetics of the reaction of AKGA with HZ or MMH, 3) verification of the chemical mechanism for the reaction of the individual hypergols with AKGA, 4) determination of whether the addition of a silicone-based antifoaming agent (AF), citric acid (CA) and/or isopropyl alcohol (IPA) to the AKGA and HZ or MMH solution interferes with the degradation reaction, 4) application of laboratory bench scale experiments in field samples, and 5) determination of the reaction enthalpy of these reactions.
Show less - Date Issued
- 2014
- Identifier
- CFE0005493, ucf:50334
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005493
- Title
- Photo-induced Protonation of Polyaniline Composites and Mechanistic Study of the Degradation of Polychlorinated Biphenyls with Zero-Valent Magnesium.
- Creator
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Kirkland, Candace, Yestrebsky, Cherie, Campiglia, Andres, Clausen, Christian, Frazer, Andrew, Duranceau, Steven, University of Central Florida
- Abstract / Description
-
As technology advances, a need for non-metal, conductive materials has arisen for several types of applications. Lithographic techniques are helpful to develop some of these applications. Such techniques require materials that are insulating and become conductive after irradiated. Composites of polyaniline in its emeraldine base form (PANI-EB) doped with photo-acid generators (PAG) become conductive upon photo-irradiation. This increase in conductivity is due to the protonation of PANI-EB....
Show moreAs technology advances, a need for non-metal, conductive materials has arisen for several types of applications. Lithographic techniques are helpful to develop some of these applications. Such techniques require materials that are insulating and become conductive after irradiated. Composites of polyaniline in its emeraldine base form (PANI-EB) doped with photo-acid generators (PAG) become conductive upon photo-irradiation. This increase in conductivity is due to the protonation of PANI-EB. Such materials may be utilized to fabricate conducting patterns by photo-irradiation; however, the conductivity obtained by direct irradiation of PANI-EB/PAG composites is normally quite low ((<)10-3 S/cm) due to aggregation of highly loaded PAG. In this work, poly(ethylene glycol) (PEG), a proton transfer polymer, was added to PANI-EB/PAG. Results showed the addition of low molecular weight (MW) (550) PEG significantly enhanced the photo-induced conductivity to a level comparable to that of PANI-salt synthesized by oxidizing aniline in the presence of an acid. High MW (8000) PEG is less effective than PEG 550, and composites of PANI-EB and N-PEG-PANI showed conductivity as high as 102 S/cm after treatment with HCl vapor. The photo-induced conductivity of the N-PEG-PANI/PANI-EB/PAG composite reached 10-2-10-1 S/cm. Polychlorinated biphenyls (PCBs) are a class of chemicals with 209 different congeners, some of which are known carcinogens, and are persistent organic pollutants in the environment. After its synthesis, it was seen as a phenomenal additive in a multitude of different applications leading to the wide spread use of PCBs and a need for a safe, effective, and inexpensive remediation technique. While it is known that magnesium can degrade PCBs, the mechanism of this reaction was not well-understood. In order for magnesium to be broadly used as a remediation tool, it is necessary to fully understand how the reaction is taking place and if the PCBs are able to be fully dechlorinated into biphenyl. This research focuses on the hydrodechlorination of PCBs with zero-valent magnesium in acidified ethanol. The degradation pathways of 2, 2', 3, 5, 5', 6- hexachlorobiphenyl were investigated to determine the identity of the daughter PCBs produced, how and if they continue to be dechlorinated into biphenyl. The proton source for this hydrodehalogenation reaction was also studied using both deuterated solvent and acid to give more detail to the mechanism of this reaction.
Show less - Date Issued
- 2014
- Identifier
- CFE0005513, ucf:50308
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005513
- Title
- Magnesium and Acidified Ethanol Based Treatment Systems for the Extraction and Dechlorination of Polychlorinated Biphenyls from Contaminated Oils, Paints, and Soils.
- Creator
-
Novaes-Card, Simone, Yestrebsky, Cherie, Clausen, Christian, Elsheimer, Seth, Frazer, Andrew, Duranceau, Steven, University of Central Florida
- Abstract / Description
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Polychlorinated biphenyls (PCBs) are a class of environmentally persistent halogenated organic compounds that were once used as stabilizers to improve the properties of a variety of materials such as lubricants, heat transfer fluids, paints, and caulking materials. PCBs are also capable of migration through processes such as spillage into soils, leaching into groundwater, and volatilization into the atmosphere. Although banned in 1979 over health concerns, PCBs persist in these materials to...
Show morePolychlorinated biphenyls (PCBs) are a class of environmentally persistent halogenated organic compounds that were once used as stabilizers to improve the properties of a variety of materials such as lubricants, heat transfer fluids, paints, and caulking materials. PCBs are also capable of migration through processes such as spillage into soils, leaching into groundwater, and volatilization into the atmosphere. Although banned in 1979 over health concerns, PCBs persist in these materials to this day because they are resistant to biotic degradation and natural weathering processes. The wide variety of contaminated materials means that many existing treatment options cannot be used across all media. This research focuses on the adaptation of a reductive dehalogenation system for dechlorination of PCBs from machine oils, paints, sludges, and soils. The system utilizes magnesium, glacial acetic acid, and ethanol in order to remove the chlorine atoms from the biphenyl backbone, which is less toxic and can be broken down biotically.A treatment plan was devised for machine oil contaminated with PCBs, involving sorption of PCBs onto a column of super activated alumina followed by desorption into hexane and treatment of the hexane with magnesium and acidified ethanol to dechlorinate the PCBs. In a small-scale study, 98.5% of PCBs from an oil sample were sorbed to the column, and the PCBs that were subsequently desorbed were dechlorinated to below detectable levels within one day of magnesium and acidified ethanol treatment. Information from small-scale studies was used to design larger sorption columns intended for use at a field site.A field study was conducted to compare the effectiveness of two different treatment system pastes at removing PCBs from painted surfaces. These pastes were formulated with bulking and viscosity control agents in order to cling to vertical surfaces, and contained either acidified ethanol and magnesium (Activated Metal Treatment System, AMTS) or acidified ethanol only (Non-Metal Treatment System, NMTS). AMTS was capable of 64.8% average removal of PCBs from paint, while NMTS demonstrated 89.5% average removal but required a second step to dechlorinate the extracted PCBs. This system allows for treatment of surfaces without demolishing the structure. AMTS was also studied for in situ dechlorination of PCBs in soils, and NMTS enclosed in a polyethylene barrier was studied for extraction of PCBs from sludges.A two-step system was devised for the ex situ treatment of PCB-contaminated soils. Solvent extraction with ethanol or an ethanol/ethyl lactate cosolvent is followed by dechlorination using magnesium and glacial acetic acid. Studies included the optimization of extraction solvent, cosolvent ratio, cost, and reuse of magnesium or extraction solvent. Surface analysis of magnesium particles used in dechlorination showed a precipitate occluding part of the surface, which was thought to be a combination of magnesium ethoxide and magnesium hydroxide. This precipitate is thought to come from the reaction of magnesium ethoxide formed during the PCB dechlorination process with pore water extracted from the soil.
Show less - Date Issued
- 2013
- Identifier
- CFE0005222, ucf:50630
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005222
