Analysis of organomercurials in environmental and biological samples by capillary column gas chromatography with atomic fluorescence detection

The general method for determining organomercurials in environmental and biological samples is gas chromatography with electron capture detection (GC-ECD). However, tedious sample work up protocols and poor chromatographic response show the need for the development of new methods. Here, Atomic Fluorescence-based methods are described, free from these deficiencies. The organomercurials in soil, sediment and tissue samples are first released from the matrices with acidic KBr and cupric ions and extracted into dichloromethane. The initial extracts are subjected to thiosulfate clean up and the organomercury species are isolated as their chloride derivatives by cupric chloride and subsequent extraction into a small volume of dichloromethane. In water samples the organomercurials are pre-concentrated using a sulfhydryl cotton fiber adsorbent, followed by elution with acidic KBr and CuSO 4 and extraction into dichloromethane. Analysis of the organomercurials is accomplished by capillary column chromatography with atomic fluorescence detection.

Quantitative Analysis and Determination of Microcystin in water by Capillary Electrophoresis Mass Spectrometry

The presence of harmful algal blooms (HAB) is a growing concern in aquatic environments. Among HAB organisms, cyanobacteria are of special concern because they have been reported worldwide to cause environmental and human health problem through contamination of drinking water. Although several analytical approaches have been applied to monitoring cyanobacteria toxins, conventional methods are costly and time-consuming so that analyses take weeks for field sampling and subsequent lab analysis. Capillary electrophoresis (CE) becomes a particularly suitable analytical separation method that can couple very small samples and rapid separations to a wide range of selective and sensitive detection techniques. This paper demonstrates a method for rapid separation and identification of four microcystin variants commonly found in aquatic environments. CE coupled to UV and electrospray ionization time-of-flight mass spectrometry (ESI-TOF) procedures were developed. All four analytes were separated within 6 minutes. The ESI-TOF experiment provides accurate molecular information, which further identifies analytes.

Principal component analysis and assessment of language network activation patterns in pediatric epilepsy

This dissertation establishes a novel data-driven method to identify language network activation patterns in pediatric epilepsy through the use of the Principal Component Analysis (PCA) on functional magnetic resonance imaging (fMRI). A total of 122 subjects’ data sets from five different hospitals were included in the study through a web-based repository site designed here at FIU. Research was conducted to evaluate different classification and clustering techniques in identifying hidden activation patterns and their associations with meaningful clinical variables. The results were assessed through agreement analysis with the conventional methods of lateralization index (LI) and visual rating. What is unique in this approach is the new mechanism designed for projecting language network patterns in the PCA-based decisional space. Synthetic activation maps were randomly generated from real data sets to uniquely establish nonlinear decision functions (NDF) which are then used to classify any new fMRI activation map into typical or atypical. The best nonlinear classifier was obtained on a 4D space with a complexity (nonlinearity) degree of 7. Based on the significant association of language dominance and intensities with the top eigenvectors of the PCA decisional space, a new algorithm was deployed to delineate primary cluster members without intensity normalization. In this case, three distinct activations patterns (groups) were identified (averaged kappa with rating 0.65, with LI 0.76) and were characterized by the regions of: (1) the left inferior frontal Gyrus (IFG) and left superior temporal gyrus (STG), considered typical for the language task; (2) the IFG, left mesial frontal lobe, right cerebellum regions, representing a variant left dominant pattern by higher activation; and (3) the right homologues of the first pattern in Broca's and Wernicke's language areas. Interestingly, group 2 was found to reflect a different language compensation mechanism than reorganization. Its high intensity activation suggests a possible remote effect on the right hemisphere focus on traditionally left-lateralized functions. In retrospect, this data-driven method provides new insights into mechanisms for brain compensation/reorganization and neural plasticity in pediatric epilepsy.

Achieving zero accidents—A strategic framework for continuous safety improvement in the construction industry

In the U.S., construction accidents remain a significant economic and social problem. Despite recent improvement, the Construction industry, generally, has lagged behind other industries in implementing safety as a total management process for achieving zero accidents and developing a high-performance safety culture. One aspect of this total approach to safety that has frustrated the construction industry the most has been “measurement”, which involves identifying and quantifying the factors that critically influence safe work behaviors. The basic problem attributed is the difficulty in assessing what to measure and how to measure it—particularly the intangible aspects of safety. Without measurement, the notion of continuous improvement is hard to follow. This research was undertaken to develop a strategic framework for the measurement and continuous improvement of total safety in order to achieve and sustain the goal of zero accidents, while improving the quality, productivity and the competitiveness of the construction industry as it moves forward. The research based itself on an integral model of total safety that allowed decomposition of safety into interior and exterior characteristics using a multiattribute analysis technique. Statistical relationships between total safety dimensions and safety performance (measured by safe work behavior) were revealed through a series of latent variables (factors) that describe the total safety environment of a construction organization. A structural equation model (SEM) was estimated for the latent variables to quantify relationships among them and between these total safety determinants and safety performance of a construction organization. The developed SEM constituted a strategic framework for identifying, measuring, and continuously improving safety as a total concern for achieving and sustaining the goal of zero accidents.

A model for continuous measurement of drilled shaft diameter during construction

Non-Destructive Testing (NDT) of deep foundations has become an integral part of the industry's standard manufacturing processes. It is not unusual for the evaluation of the integrity of the concrete to include the measurement of ultrasonic wave speeds. Numerous methods have been proposed that use the propagation speed of ultrasonic waves to check the integrity of concrete for drilled shaft foundations. All such methods evaluate the integrity of the concrete inside the cage and between the access tubes. The integrity of the concrete outside the cage remains to be considered to determine the location of the border between the concrete and the soil in order to obtain the diameter of the drilled shaft. It is also economic to devise a methodology to obtain the diameter of the drilled shaft using the Cross-Hole Sonic Logging system (CSL). Performing such a methodology using the CSL and following the CSL tests is performed and used to check the integrity of the inside concrete, thus allowing the determination of the drilled shaft diameter without having to set up another NDT device.^ This proposed new method is based on the installation of galvanized tubes outside the shaft across from each inside tube, and performing the CSL test between the inside and outside tubes. From the performed experimental work a model is developed to evaluate the relationship between the thickness of concrete and the ultrasonic wave properties using signal processing. The experimental results show that there is a direct correlation between concrete thicknesses outside the cage and maximum amplitude of the received signal obtained from frequency domain data. This study demonstrates how this new method to measuring the diameter of drilled shafts during construction using a NDT method overcomes the limitations of currently-used methods. ^ In the other part of study, a new method is proposed to visualize and quantify the extent and location of the defects. It is based on a color change in the frequency amplitude of the signal recorded by the receiver probe in the location of defects and it is called Frequency Tomography Analysis (FTA). Time-domain data is transferred to frequency-domain data of the signals propagated between tubes using Fast Fourier Transform (FFT). Then, distribution of the FTA will be evaluated. This method is employed after CSL has determined the high probability of an anomaly in a given area and is applied to improve location accuracy and to further characterize the feature. The technique has a very good resolution and clarifies the exact depth location of any void or defect through the length of the drilled shaft for the voids inside the cage. ^ The last part of study also evaluates the effect of voids inside and outside the reinforcement cage and corrosion in the longitudinal bars on the strength and axial load capacity of drilled shafts. The objective is to quantify the extent of loss in axial strength and stiffness of drilled shafts due to presence of different types of symmetric voids and corrosion throughout their lengths.^

Improved dynamic headspace sampling and detection using capillary microextraction of volatiles coupled to gas chromatography mass spectrometry

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted into a thermal desorption probe for thermal desorption of the extracted volatile compounds into a gas chromatography-mass spectrometer (GC-MS). The performance of the CMV devices was compared with two other existing preconcentration techniques, solid phase microextraction (SPME) and planar solid phase microextraction (PSPME). Compared to SPME fibers, the CMV devices have an improved surface area and phase volume of 5000 times and 80 times, respectively. One (1) minute dynamic CMV air sampling resulted in similar performance as a 30 min static extraction using a SPME fiber. The PSPME devices have been fashioned to easily interface with ion mobility spectrometers (IMS) for explosives or drugs detection. The CMV devices are shown to offer dynamic sampling and can now be coupled to COTS GC-MS instruments. Several compound classes representing explosives have been analyzed with minimum breakthrough even after a 60 min. sampling time. The extracted volatile compounds were retained in the CMV devices when preserved in aluminum foils after sampling. Finally, the CMV sampling device were used for several different headspace profiling applications which involved sampling a shipping facility, six illicit drugs, seven military explosives and eighteen different bacteria strains. Successful detection of the target analytes at ng levels of the target signature volatile compounds in these applications suggests that the CMV devices can provide high throughput qualitative and quantitative analysis with high recovery and unambiguous identification of analytes.

Rapid inline derivatization of primary and secondary amine containing drugs by capillary electrophoresis with laser-induced fluorescence

Despite the ongoing "war on drugs" the seizure rates for phenethylamines and their analogues have been steadily increasing over the years. The illicit manufacture of these compounds has become big business all over the world making it all the more attractive to the inexperienced "cook". However, as a result, the samples produced are more susceptible to contamination with reactionary byproducts and leftover reagents. These impurities are useful in the analysis of seized drugs as their identities can help to determine the synthetic pathway used to make these drugs and thus, the provenance of these analytes. In the present work two fluorescent dyes, 4-fluoro-7-nitrobenzofurazan and 5-(4,6-dichlorotriazinyl)aminofluorescein, were used to label several phenethylamine analogues for electrophoretic separation with laser-induced fluorescence detection. The large scale to which law enforcement is encountering these compounds has the potential to create a tremendous backlog. In order to combat this, a rapid, sensitive method capable of full automation is required. Through the utilization of the inline derivatization method developed whereby analytes are labeled within the capillary efficiently in a minimum span of time, this can be achieved. The derivatization and separation parameters were optimized on the basis of a variety of experimentally determined factors in order to give highly resolved peaks in the fluorescence spectrum with limits of detection in the low µg/mL range.

Development of advanced capillary electrophoresis techniques with UV and mass spectrometry detection for forensic, pharmaceutical and environmental applications

Capillary electrophoresis (CE) is a modern analytical technique, which is electrokinetic separation generated by high voltage and taken place inside the small capillaries. In this dissertation, several advanced capillary electrophoresis methods are presented using different approaches of CE and UV and mass spectrometry are utilized as the detection methods. ^ Capillary electrochromatography (CEC), as one of the CE modes, is a recent developed technique which is a hybrid of capillary electrophoresis and high performance liquid chromatography (HPLC). Capillary electrochromatography exhibits advantages of both techniques. In Chapter 2, monolithic capillary column are fabricated using in situ photoinitiation polymerization method. The column was then applied for the separation of six antidepressant compounds. ^ Meanwhile, a simple chiral separation method is developed and presented in Chapter 3. Beta cycodextrin was utilized to achieve the goal of chiral separation. Not only twelve cathinone analytes were separated, but also isomers of several analytes were enantiomerically separated. To better understand the molecular information on the analytes, the TOF-MS system was coupled with the CE. A sheath liquid and a partial filling technique (PFT) were employed to reduce the contamination of MS ionization source. Accurate molecular information was obtained. ^ It is necessary to propose, develop, and optimize new techniques that are suitable for trace-level analysis of samples in forensic, pharmaceutical, and environmental applications. Capillary electrophoresis (CE) was selected for this task, as it requires lower amounts of samples, it simplifies sample preparation, and it has the flexibility to perform separations of neutral and charged molecules as well as enantiomers. ^ Overall, the study demonstrates the versatility of capillary electrophoresis methods in forensic, pharmaceutical, and environmental applications.^

Principal Component Analysis and Assessment of Language Network Activation Patterns in Pediatric Epilepsy

This dissertation establishes a novel data-driven method to identify language network activation patterns in pediatric epilepsy through the use of the Principal Component Analysis (PCA) on functional magnetic resonance imaging (fMRI). A total of 122 subjects’ data sets from five different hospitals were included in the study through a web-based repository site designed here at FIU. Research was conducted to evaluate different classification and clustering techniques in identifying hidden activation patterns and their associations with meaningful clinical variables. The results were assessed through agreement analysis with the conventional methods of lateralization index (LI) and visual rating. What is unique in this approach is the new mechanism designed for projecting language network patterns in the PCA-based decisional space. Synthetic activation maps were randomly generated from real data sets to uniquely establish nonlinear decision functions (NDF) which are then used to classify any new fMRI activation map into typical or atypical. The best nonlinear classifier was obtained on a 4D space with a complexity (nonlinearity) degree of 7. Based on the significant association of language dominance and intensities with the top eigenvectors of the PCA decisional space, a new algorithm was deployed to delineate primary cluster members without intensity normalization. In this case, three distinct activations patterns (groups) were identified (averaged kappa with rating 0.65, with LI 0.76) and were characterized by the regions of: 1) the left inferior frontal Gyrus (IFG) and left superior temporal gyrus (STG), considered typical for the language task; 2) the IFG, left mesial frontal lobe, right cerebellum regions, representing a variant left dominant pattern by higher activation; and 3) the right homologues of the first pattern in Broca's and Wernicke's language areas. Interestingly, group 2 was found to reflect a different language compensation mechanism than reorganization. Its high intensity activation suggests a possible remote effect on the right hemisphere focus on traditionally left-lateralized functions. In retrospect, this data-driven method provides new insights into mechanisms for brain compensation/reorganization and neural plasticity in pediatric epilepsy.

Computer program for the analysis of non-prismatic beams

One of the major problems in the analysis of beams with Moment of Inertia varying along their length, is to find the Fixed End Moments, Stiffness, and Carry-Over Factors. In order to determine Fixed End Moments, it is necessary to consider the non-prismatic member as integrated by a large number of small sections with constant Moment of Inertia, and to find the M/EI values for each individual section. This process takes a lot of time from Designers and Structural Engineers. The object of this thesis is to design a computer program to simplify this repetitive process, obtaining rapidly and effectively the Final Moments and Shears in continuous non-prismatic Beams. For this purpose the Column Analogy and the Moment Distribution Methods of Professor Hardy Cross have been utilized as the principles toward the methodical computer solutions. The program has been specifically designed to analyze continuous beams of a maximum of four spans of any length, integrated by symmetrical members with rectangular cross sections and with rectilinear variation of the Moment of Inertia. Any load or combination of uniform and concentrated loads must be considered. Finally sample problems will be solved with the new Computer Program and with traditional systems, to determine the accuracy and applicability of the Program.

Development of Advanced Capillary Electrophoresis Techniques with UV and Mass Spectrometry Detection for Forensic, Pharmaceutical and Environmental Applications

Capillary electrophoresis (CE) is a modern analytical technique, which is electrokinetic separation generated by high voltage and taken place inside the small capillaries. In this dissertation, several advanced capillary electrophoresis methods are presented using different approaches of CE and UV and mass spectrometry are utilized as the detection methods. Capillary electrochromatography (CEC), as one of the CE modes, is a recent developed technique which is a hybrid of capillary electrophoresis and high performance liquid chromatography (HPLC). Capillary electrochromatography exhibits advantages of both techniques. In Chapter 2, monolithic capillary column are fabricated using in situ photoinitiation polymerization method. The column was then applied for the separation of six antidepressant compounds. Meanwhile, a simple chiral separation method is developed and presented in Chapter 3. Beta cycodextrin was utilized to achieve the goal of chiral separation. Not only twelve cathinone analytes were separated, but also isomers of several analytes were enantiomerically separated. To better understand the molecular information on the analytes, the TOF-MS system was coupled with the CE. A sheath liquid and a partial filling technique (PFT) were employed to reduce the contamination of MS ionization source. Accurate molecular information was obtained. It is necessary to propose, develop, and optimize new techniques that are suitable for trace-level analysis of samples in forensic, pharmaceutical, and environmental applications. Capillary electrophoresis (CE) was selected for this task, as it requires lower amounts of samples, it simplifies sample preparation, and it has the flexibility to perform separations of neutral and charged molecules as well as enantiomers. Overall, the study demonstrates the versatility of capillary electrophoresis methods in forensic, pharmaceutical, and environmental applications.

A Model for Continuous Measurement of Drilled Shaft Diameter During Construction

Non-Destructive Testing (NDT) of deep foundations has become an integral part of the industry’s standard manufacturing processes. It is not unusual for the evaluation of the integrity of the concrete to include the measurement of ultrasonic wave speeds. Numerous methods have been proposed that use the propagation speed of ultrasonic waves to check the integrity of concrete for drilled shaft foundations. All such methods evaluate the integrity of the concrete inside the cage and between the access tubes. The integrity of the concrete outside the cage remains to be considered to determine the location of the border between the concrete and the soil in order to obtain the diameter of the drilled shaft. It is also economic to devise a methodology to obtain the diameter of the drilled shaft using the Cross-Hole Sonic Logging system (CSL). Performing such a methodology using the CSL and following the CSL tests is performed and used to check the integrity of the inside concrete, thus allowing the determination of the drilled shaft diameter without having to set up another NDT device. This proposed new method is based on the installation of galvanized tubes outside the shaft across from each inside tube, and performing the CSL test between the inside and outside tubes. From the performed experimental work a model is developed to evaluate the relationship between the thickness of concrete and the ultrasonic wave properties using signal processing. The experimental results show that there is a direct correlation between concrete thicknesses outside the cage and maximum amplitude of the received signal obtained from frequency domain data. This study demonstrates how this new method to measuring the diameter of drilled shafts during construction using a NDT method overcomes the limitations of currently-used methods. In the other part of study, a new method is proposed to visualize and quantify the extent and location of the defects. It is based on a color change in the frequency amplitude of the signal recorded by the receiver probe in the location of defects and it is called Frequency Tomography Analysis (FTA). Time-domain data is transferred to frequency-domain data of the signals propagated between tubes using Fast Fourier Transform (FFT). Then, distribution of the FTA will be evaluated. This method is employed after CSL has determined the high probability of an anomaly in a given area and is applied to improve location accuracy and to further characterize the feature. The technique has a very good resolution and clarifies the exact depth location of any void or defect through the length of the drilled shaft for the voids inside the cage. The last part of study also evaluates the effect of voids inside and outside the reinforcement cage and corrosion in the longitudinal bars on the strength and axial load capacity of drilled shafts. The objective is to quantify the extent of loss in axial strength and stiffness of drilled shafts due to presence of different types of symmetric voids and corrosion throughout their lengths.

Improved Dynamic Headspace Sampling and Detection using Capillary Microextraction of Volatiles Coupled to Gas Chromatography Mass Spectrometry

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted into a thermal desorption probe for thermal desorption of the extracted volatile compounds into a gas chromatography-mass spectrometer (GC-MS). The performance of the CMV devices was compared with two other existing preconcentration techniques, solid phase microextraction (SPME) and planar solid phase microextraction (PSPME). Compared to SPME fibers, the CMV devices have an improved surface area and phase volume of 5000 times and 80 times, respectively. One (1) minute dynamic CMV air sampling resulted in similar performance as a 30 min static extraction using a SPME fiber. The PSPME devices have been fashioned to easily interface with ion mobility spectrometers (IMS) for explosives or drugs detection. The CMV devices are shown to offer dynamic sampling and can now be coupled to COTS GC-MS instruments. Several compound classes representing explosives have been analyzed with minimum breakthrough even after a 60 min. sampling time. The extracted volatile compounds were retained in the CMV devices when preserved in aluminum foils after sampling. Finally, the CMV sampling device were used for several different headspace profiling applications which involved sampling a shipping facility, six illicit drugs, seven military explosives and eighteen different bacteria strains. Successful detection of the target analytes at ng levels of the target signature volatile compounds in these applications suggests that the CMV devices can provide high throughput qualitative and quantitative analysis with high recovery and unambiguous identification of analytes.