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An Evaluation Study of the Effectiveness of Using a Reaction-Based Process for Hydrazine Remediation
Title
An Evaluation Study of the Effectiveness of Using a Reaction-Based Process for Hydrazine Remediation.
Creator
Oropeza, Cristina, Clausen, Christian, Yestrebsky, Cherie, Miles, Delbert, Elsheimer, Seth, Griffin, Timothy, University of Central Florida
Abstract / Description
Hydrazine (HZ) and monomethylhydrazine (MMH) are used extensively as hypergolic propellants at Kennedy Space Center. These highly reactive fuels are considered highly toxic, and potentially carcinogenic. Consequently, the transport, handling, and disposal of hydrazines is strictly regulated to protect personnel and the environment. Currently, KSC generates large volumes of hydrazine-laden wastewater for disposal. This waste is contained and shipped on public highways for subsequent disposal...
Show moreHydrazine (HZ) and monomethylhydrazine (MMH) are used extensively as hypergolic propellants at Kennedy Space Center. These highly reactive fuels are considered highly toxic, and potentially carcinogenic. Consequently, the transport, handling, and disposal of hydrazines is strictly regulated to protect personnel and the environment. Currently, KSC generates large volumes of hydrazine-laden wastewater for disposal. This waste is contained and shipped on public highways for subsequent disposal by incineration presenting a potentially catastrophic threat to the environment and the general public in the event of an accidental release. Other existing remediation methods include oxidative and reductive pathways as well as biodegradation in fixed film reactors. Each of these methods has associated drawbacks and limitations that make them unsuitable for industrial use. Recently, hydrazine neutralization by reaction with alpha-ketoglutaric acid (AKGA) to form the stabilized pyridazine derivatives PCA and mPCA has been explored. The applicability of this technique for use at KSC has been established and procedural considerations for implementation have been addressed.Experimental evidence based on worst case scenario decontamination processing simulations and reaction characterization has suggested that AKGA can cost effectively function as a drop-in replacement for current neutralizers with minimal modification to existing infrastructure and operating procedures. Further work will be necessary to satisfy permitting requirements and verify that the reaction product stream is non-hazardous in light of limited toxicity data.
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Date Issued
2011
Identifier
CFE0004148, ucf:49060
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0004148
Evaluation of The Biodegradability and Toxicity of PCA and mPCA
Title
Evaluation of The Biodegradability and Toxicity of PCA and mPCA.
Creator
Rueda, Juan, Randall, Andrew, Duranceau, Steven, Yestrebsky, Cherie, University of Central Florida
Abstract / Description
The main types of hypergolic propellants used at Kennedy Space Center (KSC) are hydrazine (HZ) and monomethylhydrazine (MMH). HZ and MMH are classified as hazardous materials and they are also known to be potentially carcinogenic to humans; therefore, handling these substances and their waste is strictly regulated. The wastes streams from HZ and MMH have been estimated to be the main hazardous wastes streams at KSC. Currently at KSC these wastes are first neutralized using citric acid and...
Show moreThe main types of hypergolic propellants used at Kennedy Space Center (KSC) are hydrazine (HZ) and monomethylhydrazine (MMH). HZ and MMH are classified as hazardous materials and they are also known to be potentially carcinogenic to humans; therefore, handling these substances and their waste is strictly regulated. The wastes streams from HZ and MMH have been estimated to be the main hazardous wastes streams at KSC. Currently at KSC these wastes are first neutralized using citric acid and then they are transported on public roads for incineration as hazardous materials. A new method using alpha ketoglutaric acid (AKGA) was proposed to treat HZ and MMH wastes. From the reaction of AKGA with HZ and MMH two stable products are formed, 1,4,5,6-tetrahydro-6-oxo-3-pyridazinecarboxylic acid (PCA) and l-methyl-1,4,5,6-tetrahydro-6-oxo-3-pyridazinecarboxylic acid (mPCA), respectively.The cost of purchasing AKGA is greater than the cost of purchasing citric acid; thus, AKGA can only become a cost effective alternative for the treatment of HZ and MMH wastes if the products of the reactions (PCA and mPCA) can be safely disposed of into the sewage system without affecting the treatment efficiency and effluent quality of the wastewater treatment plant (WWTP). In this research mPCA and PCA were analyzed for acute toxicity using fish and crustaceans as well as their effect on the wastewater treatment efficiency and viability using AS microbes, and their biodegradability by AS organisms. Acute toxicity on fish and crustaceans was investigated according to the methods for acute toxicity by USEPA (USEPA Method EPA-821-R-02-012) using Ceriodaphnia dubia (96 hours) and Pimephales promelas (96 hours) as the test organisms. The effect of mPCA and PCA in the treatment efficiency and viability were estimated from respiration inhibition tests (USEPA Method OCSPP 850.3300) and heterotrophic plate counts (HPCs). Lastly, the biodegradability of mPCA and PCA was assessed using the Closed Bottle Test (USEPA Method OPPTS 835.3110). For mPCA, the 96 hours LC50 for C. dubia was estimated at 0.77 (&)#177; 0.06 g/L (with a 95% confidence level) and the NOEC was estimated at 0.5 g/L. For P. promelas, the LC50 was above 1.5 g/L but it was noticed that mPCA had an effect on their behavior. Abnormal behavior observed included loss of equilibrium and curved spine. The NOEC on the fish was estimated at 0.75 g/L. PCA did not exhibit a significant mortality on fish or crustaceans. The LC50 of PCA in P. promelas and C. dubia was (>) 1.5 g/L and the NOEC was 1.5 g/L for both organisms. An Inhibitory effect on the heterotrophic respiration of activated sludge organisms was not observed after exposing them for 180-min to PCA and mPCA at concentrations of up to 1.5 g/L compared to the blank controls. Overall the impact of PCA and mPCA on total respiration rates was small, and only observed at 1,500 mg/L if at all. The difference was apparently caused by inhibition of nitrification rather than heterotrophic inhibition. However due to the variability observed in the measurements of the replicates, it is not possible to firmly conclude that PCA or mPCA at 1,500 mg/L was inhibitory to nitrification.Based on the results from the HPCs, mPCA and PCA did not affect the viability of heterotrophic organisms at 750 mg/L. In the BOD-like closed bottle test using a diluted activated sludge mixed liquor sample, the AS microorganisms were capable of biodegrading up to 67% of a 2 mg/L concentration of PCA (with respect to its theoretical oxygen demand, or ThOD) in 28 days. No biodegradation was observed in the samples containing 2 and 5 mg/L of mPCA after 28 days of incubation using a diluted activated sludge mixed liquor sample as inoculum.The results of this study show that mPCA is more toxic than PCA to Ceriodaphnia dubia and Pimephales promelas. However neither mPCA nor PCA had an effect on the heterotrophic respiration of an AS mixed liquor sample at 1.5 g/L and there was probably no significant inhibition of the nitrification respiration. Samples of PCA and mPCA at 2 and 5 mg/L could not be completely degraded (with respect to their total theoretical oxygen demand) by dilute AS biomass during a 28 day incubation period. mPCA did not show significant degradation in the two different biodegradation tests performed.
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Date Issued
2013
Identifier
CFE0004744, ucf:49779
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0004744
Degradation of Hydrazine and Monomethylhydrazine for Fuel Waste Streams using Alpha-ketoglutaric Acid
Title
Degradation of Hydrazine and Monomethylhydrazine for Fuel Waste Streams using Alpha-ketoglutaric Acid.
Creator
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.
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Date Issued
2014
Identifier
CFE0005493, ucf:50334
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0005493
Time and Space Efficient Techniques for Facial Recognition
Title
Time and Space Efficient Techniques for Facial Recognition.
Creator
Alrasheed, Waleed, Mikhael, Wasfy, DeMara, Ronald, Haralambous, Michael, Wei, Lei, Myers, Brent, University of Central Florida
Abstract / Description
In recent years, there has been an increasing interest in face recognition. As a result, many new facial recognition techniques have been introduced. Recent developments in the field of face recognition have led to an increase in the number of available face recognition commercial products. However, Face recognition techniques are currently constrained by three main factors: recognition accuracy, computational complexity, and storage requirements. The problem is that most of the current face...
Show moreIn recent years, there has been an increasing interest in face recognition. As a result, many new facial recognition techniques have been introduced. Recent developments in the field of face recognition have led to an increase in the number of available face recognition commercial products. However, Face recognition techniques are currently constrained by three main factors: recognition accuracy, computational complexity, and storage requirements. The problem is that most of the current face recognition techniques succeed in improving one or two of these factors at the expense of the others.In this dissertation, four novel face recognition techniques that improve the storage and computational requirements of face recognition systems are presented and analyzed. Three of the four novel face recognition techniques to be introduced, namely, Quantized/truncated Transform Domain (QTD), Frequency Domain Thresholding and Quantization (FD-TQ), and Normalized Transform Domain (NTD). All the three techniques utilize the Two-dimensional Discrete Cosine Transform (DCT-II), which reduces the dimensionality of facial feature images, thereby reducing the computational complexity. The fourth novel face recognition technique is introduced, namely, the Normalized Histogram Intensity (NHI). It is based on utilizing the pixel intensity histogram of poses' subimages, which reduces the computational complexity and the needed storage requirements. Various simulation experiments using MATLAB were conducted to test the proposed methods. For the purpose of benchmarking the performance of the proposed methods, the simulation experiments were performed using current state-of-the-art face recognition techniques, namely, Two Dimensional Principal Component Analysis (2DPCA), Two-Directional Two-Dimensional Principal Component Analysis ((2D)^2PCA), and Transform Domain Two Dimensional Principal Component Analysis (TD2DPCA). The experiments were applied to the ORL, Yale, and FERET databases.The experimental results for the proposed techniques confirm that the use of any of the four novel techniques examined in this study results in a significant reduction in computational complexity and storage requirements compared to the state-of-the-art techniques without sacrificing the recognition accuracy.
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Date Issued
2013
Identifier
CFE0005297, ucf:50566
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0005297
CHARACTERIZATION OF NOVEL ANTIMALARIALS FROM COMPOUNDS INSPIRED BY NATURAL PRODUCTS USING PRINCIPAL COMPONENT ANALYSIS (PCA)
Title
CHARACTERIZATION OF NOVEL ANTIMALARIALS FROM COMPOUNDS INSPIRED BY NATURAL PRODUCTS USING PRINCIPAL COMPONENT ANALYSIS (PCA).
Creator
Balde, Zarina Marie G, Chakrabarti, Debopam, University of Central Florida
Abstract / Description
Malaria is caused by a protozoan parasite, Plasmodium falciparum, which is responsible for over 500,000 deaths per year worldwide. Although malaria medicines are working well in many parts of the world, antimalarial drug resistance has emerged as one of the greatest challenges facing malaria control today. Since the malaria parasites are once again developing widespread resistance to antimalarial drugs, this can cause the spread of malaria to new areas and the re-emergence of malaria in areas...
Show moreMalaria is caused by a protozoan parasite, Plasmodium falciparum, which is responsible for over 500,000 deaths per year worldwide. Although malaria medicines are working well in many parts of the world, antimalarial drug resistance has emerged as one of the greatest challenges facing malaria control today. Since the malaria parasites are once again developing widespread resistance to antimalarial drugs, this can cause the spread of malaria to new areas and the re-emergence of malaria in areas where it had already been eradicated. Therefore, the discovery and characterization of novel antimalarials is extremely urgent. A previous drug screen in Dr. Chakrabarti's lab identified several natural products (NPs) with antiplasmodial activities. The focus of this study is to characterize the hit compounds using Principal Component Analysis (PCA) to determine structural uniqueness compared to known antimalarial drugs. This study will compare multiple libraries of different compounds, such as known drugs, kinase inhibitors, macrocycles, and top antimalarial hits discovered in our lab. Prioritizing the hit compounds by their chemical uniqueness will lessen the probability of future drug resistance. This is an important step in drug discovery as this will allow us to increase the interpretability of the datasets by creating new uncorrelated variables that will successively maximize variance. Characterization of the Natural Product inspired compounds will enable us to discover potent, selective, and novel antiplasmodial scaffolds that are unique in the 3-dimensional chemical space and will provide critical information that will serve as advanced starting points for the antimalarial drug discovery pipeline.
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Date Issued
2018
Identifier
CFH2000405, ucf:45893
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFH2000405
Chemometric Applications to a Complex Classification Problem: Forensic Fire Debris Analysis
Title
Chemometric Applications to a Complex Classification Problem: Forensic Fire Debris Analysis.
Creator
Waddell, Erin, Sigman, Michael, Belfield, Kevin, Campiglia, Andres, Yestrebsky, Cherie, Ni, Liqiang, University of Central Florida
Abstract / Description
Fire debris analysis currently relies on visual pattern recognition of the total ion chromatograms, extracted ion profiles, and target compound chromatograms to identify the presence of an ignitable liquid according to the ASTM International E1618-10 standard method. For large data sets, this methodology can be time consuming and is a subjective method, the accuracy of which is dependent upon the skill and experience of the analyst. This research aimed to develop an automated classification...
Show moreFire debris analysis currently relies on visual pattern recognition of the total ion chromatograms, extracted ion profiles, and target compound chromatograms to identify the presence of an ignitable liquid according to the ASTM International E1618-10 standard method. For large data sets, this methodology can be time consuming and is a subjective method, the accuracy of which is dependent upon the skill and experience of the analyst. This research aimed to develop an automated classification method for large data sets and investigated the use of the total ion spectrum (TIS). The TIS is calculated by taking an average mass spectrum across the entire chromatographic range and has been shown to contain sufficient information content for the identification of ignitable liquids. The TIS of ignitable liquids and substrates, defined as common building materials and household furnishings, were compiled into model data sets. Cross-validation (CV) and fire debris samples, obtained from laboratory-scale and large-scale burns, were used to test the models. An automated classification method was developed using computational software, written in-house, that considers a multi-step classification scheme to detect ignitable liquid residues in fire debris samples and assign these to the classes defined in ASTM E1618-10. Classifications were made using linear discriminant analysis, quadratic discriminant analysis (QDA), and soft independent modeling of class analogy (SIMCA). Overall, the highest correct classification rates were achieved using QDA for the first step of the scheme and SIMCA for the remaining steps. In the first step of the classification scheme, correct classification rates of 95.3% and 89.2% were obtained for the CV test set and fire debris samples, respectively. Correct classifications rates of 100% were achieved for both data sets in the majority of the remaining steps which used SIMCA for classification. In this research, the first statistically valid error rates for fire debris analysis have been developed through cross-validation of large data sets. The error rates reduce the subjectivity associated with the current methods and provide a level of confidence in sample classification that does not currently exist in forensic fire debris analysis.
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Date Issued
2013
Identifier
CFE0004954, ucf:49586
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0004954
STATISTICAL ANALYSIS OF VISIBLE ABSORPTION SPECTRA AND MASS SPECTRA OBTAINED FROM DYED TEXTILE FIBERS
Title
STATISTICAL ANALYSIS OF VISIBLE ABSORPTION SPECTRA AND MASS SPECTRA OBTAINED FROM DYED TEXTILE FIBERS.
Creator
White, Katie, Sigman, Michael, University of Central Florida
Abstract / Description
The National Academy of Sciences recently published a report which calls for improvements to the field of forensic science. Their report criticized many forensic disciplines for failure to establish rigorously-tested methods of comparison, and encouraged more research in these areas to establish limitations and assess error rates. This study applies chemometric and statistical methods to current and developing analytical techniques in fiber analysis. In addition to analysis of commercially...
Show moreThe National Academy of Sciences recently published a report which calls for improvements to the field of forensic science. Their report criticized many forensic disciplines for failure to establish rigorously-tested methods of comparison, and encouraged more research in these areas to establish limitations and assess error rates. This study applies chemometric and statistical methods to current and developing analytical techniques in fiber analysis. In addition to analysis of commercially available dyed textile fibers, two pairs of dyes are selected for custom fabric dyeing based on the similarities of their absorbance spectra and dye molecular structures. Visible absorption spectra for all fiber samples are collected using microspectrophotometry (MSP) and mass spectra are collected using electrospray ionization (ESI) mass spectrometry. Statistical calculations are performed using commercial software packages and software written in-house. Levels of Type I and Type II error are examined for fiber discrimination based on hypothesis testing of visible absorbance spectra profiles using a nonparametric permutation method. This work also explores evaluation of known and questioned fiber populations based on an assessment of statistical p-value distributions from questioned-known fiber comparisons with those of known fiber self-comparisons. Results from the hypothesis testing are compared with principal components analysis (PCA) and discriminant analysis (DA) of visible absorption spectra, as well as PCA and DA of ESI mass spectra. The sensitivity of a statistical approach will also be discussed in terms of how instrumental parameters and sampling methods may influence error rates.
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Date Issued
2010
Identifier
CFE0003454, ucf:48396
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0003454