The use of hyphenated spectrometric techniques for the environmental forensic assessment of non-traditional pollutants and degradates in the greater Florida Everglades

A comprehensive investigation of sensitive ecosystems in South Florida with the main goal of determining the identity, spatial distribution, and sources of both organic biocides and trace elements in different environmental compartments is reported. This study presents the development and validation of a fractionation and isolation method of twelve polar acidic herbicides commonly applied in the vicinity of the study areas, including e.g. 2,4-D, MCPA, dichlorprop, mecroprop, picloram in surface water. Solid phase extraction (SPE) was used to isolate the analytes from abiotic matrices containing large amounts of dissolved organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-) in a Quadrupole Ion Trap mass spectrometer was used to perform the characterization of the herbicides of interest. ^ The application of Laser Ablation-ICP-MS methodology in the analysis of soils and sediments is reported in this study. The analytical performance of the method was evaluated on certified standards and real soil and sediment samples. Residential soils were analyzed to evaluate feasibility of using the powerful technique as a routine and rapid method to monitor potential contaminated sites. Forty eight sediments were also collected from semi pristine areas in South Florida to conduct screening of baseline levels of bioavailable elements in support of risk evaluation. The LA-ICP-MS data were used to perform a statistical evaluation of the elemental composition as a tool for environmental forensics. ^ A LA-ICP-MS protocol was also developed and optimized for the elemental analysis of a wide range of elements in polymeric filters containing atmospheric dust. A quantitative strategy based on internal and external standards allowed for a rapid determination of airborne trace elements in filters containing both contemporary African dust and local dust emissions. These distributions were used to qualitative and quantitative assess differences of composition and to establish provenance and fluxes to protected regional ecosystems such as coral reefs and national parks. ^

The development of optimized high performance liquid chromatography systems for the analysis of improvised explosives

Existing instrumental techniques must be adaptable to the analysis of novel explosives if science is to keep up with the practices of terrorists and criminals. The focus of this work has been the development of analytical techniques for the analysis of two types of novel explosives: ascorbic acid-based propellants, and improvised mixtures of concentrated hydrogen peroxide/fuel. In recent years, the use of these explosives in improvised explosive devices (IEDs) has increased. It is therefore important to develop methods which permit the identification of the nature of the original explosive from post-blast residues. Ascorbic acid-based propellants are low explosives which employ an ascorbic acid fuel source with a nitrate/perchlorate oxidizer. A method which utilized ion chromatography with indirect photometric detection was optimized for the analysis of intact propellants. Post-burn and post-blast residues if these propellants were analyzed. It was determined that the ascorbic acid fuel and nitrate oxidizer could be detected in intact propellants, as well as in the post-burn and post-blast residues. Degradation products of the nitrate and perchlorate oxidizers were also detected. With a quadrupole time-of-flight mass spectrometer (QToFMS), exact mass measurements are possible. When an HPLC instrument is coupled to a QToFMS, the combination of retention time with accurate mass measurements, mass spectral fragmentation information, and isotopic abundance patterns allows for the unequivocal identification of a target analyte. An optimized HPLC-ESI-QToFMS method was applied to the analysis of ascorbic acid-based propellants. Exact mass measurements were collected for the fuel and oxidizer anions, and their degradation products. Ascorbic acid was detected in the intact samples and half of the propellants subjected to open burning; the intact fuel molecule was not detected in any of the post-blast residue. Two methods were optimized for the analysis of trace levels of hydrogen peroxide: HPLC with fluorescence detection (HPLC-FD), and HPLC with electrochemical detection (HPLC-ED). Both techniques were extremely selective for hydrogen peroxide. Both methods were applied to the analysis of post-blast debris from improvised mixtures of concentrated hydrogen peroxide/fuel; hydrogen peroxide was detected on variety of substrates. Hydrogen peroxide was detected in the post-blast residues of the improvised explosives TATP and HMTD.

Design optimization of modern machine drive systems for maximum fault tolerant and optimal operation

Modern electric machine drives, particularly three phase permanent magnet machine drive systems represent an indispensable part of high power density products. Such products include; hybrid electric vehicles, large propulsion systems, and automation products. Reliability and cost of these products are directly related to the reliability and cost of these systems. The compatibility of the electric machine and its drive system for optimal cost and operation has been a large challenge in industrial applications. The main objective of this dissertation is to find a design and control scheme for the best compromise between the reliability and optimality of the electric machine-drive system. The effort presented here is motivated by the need to find new techniques to connect the design and control of electric machines and drive systems. ^ A highly accurate and computationally efficient modeling process was developed to monitor the magnetic, thermal, and electrical aspects of the electric machine in its operational environments. The modeling process was also utilized in the design process in form finite element based optimization process. It was also used in hardware in the loop finite element based optimization process. The modeling process was later employed in the design of a very accurate and highly efficient physics-based customized observers that are required for the fault diagnosis as well the sensorless rotor position estimation. Two test setups with different ratings and topologies were numerically and experimentally tested to verify the effectiveness of the proposed techniques. ^ The modeling process was also employed in the real-time demagnetization control of the machine. Various real-time scenarios were successfully verified. It was shown that this process gives the potential to optimally redefine the assumptions in sizing the permanent magnets of the machine and DC bus voltage of the drive for the worst operating conditions. ^ The mathematical development and stability criteria of the physics-based modeling of the machine, design optimization, and the physics-based fault diagnosis and the physics-based sensorless technique are described in detail. ^ To investigate the performance of the developed design test-bed, software and hardware setups were constructed first. Several topologies of the permanent magnet machine were optimized inside the optimization test-bed. To investigate the performance of the developed sensorless control, a test-bed including a 0.25 (kW) surface mounted permanent magnet synchronous machine example was created. The verification of the proposed technique in a range from medium to very low speed, effectively show the intelligent design capability of the proposed system. Additionally, to investigate the performance of the developed fault diagnosis system, a test-bed including a 0.8 (kW) surface mounted permanent magnet synchronous machine example with trapezoidal back electromotive force was created. The results verify the use of the proposed technique under dynamic eccentricity, DC bus voltage variations, and harmonic loading condition make the system an ideal case for propulsion systems.^

Elemental analysis of biological matrices by laser ablation high resolution inductively coupled plasma mass spectrometry (LA-HR-ICP-MS) and high resolution inductively coupled plasma mass spectrometry (HR -ICP -MS)

The need for elemental analysis of biological matrices such as bone, teeth, and plant matter for sourcing purposes has emerged within the forensic and geochemical laboratories. Trace elemental analyses for the comparison of materials such as glass by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS has been shown to offer a high degree of discrimination between different manufacturing sources. Unit resolution ICP-MS instruments may suffer from some polyatomic interferences including 40Ar16O+, 40Ar 16O1H+, and 40Ca 16O+ that affect iron measurement at trace levels. Iron is an important element in the analysis of glass and also of interest for the analysis of several biological matrices. A comparison of the analytical performance of two different ICP-MS systems for iron analysis in glass for determining the method detection limits (MDLs), accuracy, and precision of the measurement is presented. Acid digestion and laser ablation methods are also compared. Iron polyatomic interferences were reduced or resolved by using dynamic reaction cell and high resolution ICP-MS. MDLs as low as 0.03 μg g-1 and 0.14 μg g-1 for laser ablation and solution based analyses respectively were achieved. The use of helium as a carrier gas demonstrated improvement in the detection limits of both iron isotopes (56Fe and 57Fe) in medium resolution for the HR-ICP-MS and with a dynamic reaction cell (DRC) coupled to a quadrupole ICP-MS system. ^ The development and application of robust analytical methods for the quantification of trace elements in biological matrices has lead to a better understanding of the potential utility of these measurements in forensic chemical analyses. Standard reference materials (SRMs) were used in the development of an analytical method using HR-ICP-MS and LA-HR-ICP-MS that was subsequently applied on the analysis of real samples. Bone, teeth and ashed marijuana samples were analyzed with the developed method. ^ Elemental analysis of bone samples from 12 different individuals provided discrimination between individuals, when femur and humerus bones were considered separately. Discrimination of 14 teeth samples based on elemental composition was achieved with the exception of one case where samples from the same individual were not associated with each other. The discrimination of 49 different ashed plant (cannabis) samples was achieved using the developed method. ^

The Development of High Performance Liquid Chromatography Systems for the Analysis of Improvised Explosives

Existing instrumental techniques must be adaptable to the analysis of novel explosives if science is to keep up with the practices of terrorists and criminals. The focus of this work has been the development of analytical techniques for the analysis of two types of novel explosives: ascorbic acid-based propellants, and improvised mixtures of concentrated hydrogen peroxide/fuel. In recent years, the use of these explosives in improvised explosive devices (IEDs) has increased. It is therefore important to develop methods which permit the identification of the nature of the original explosive from post-blast residues. Ascorbic acid-based propellants are low explosives which employ an ascorbic acid fuel source with a nitrate/perchlorate oxidizer. A method which utilized ion chromatography with indirect photometric detection was optimized for the analysis of intact propellants. Post-burn and post-blast residues if these propellants were analyzed. It was determined that the ascorbic acid fuel and nitrate oxidizer could be detected in intact propellants, as well as in the post-burn and post-blast residues. Degradation products of the nitrate and perchlorate oxidizers were also detected. With a quadrupole time-of-flight mass spectrometer (QToFMS), exact mass measurements are possible. When an HPLC instrument is coupled to a QToFMS, the combination of retention time with accurate mass measurements, mass spectral fragmentation information, and isotopic abundance patterns allows for the unequivocal identification of a target analyte. An optimized HPLC-ESI-QToFMS method was applied to the analysis of ascorbic acid-based propellants. Exact mass measurements were collected for the fuel and oxidizer anions, and their degradation products. Ascorbic acid was detected in the intact samples and half of the propellants subjected to open burning; the intact fuel molecule was not detected in any of the post-blast residue. Two methods were optimized for the analysis of trace levels of hydrogen peroxide: HPLC with fluorescence detection (HPLC-FD), and HPLC with electrochemical detection (HPLC-ED). Both techniques were extremely selective for hydrogen peroxide. Both methods were applied to the analysis of post-blast debris from improvised mixtures of concentrated hydrogen peroxide/fuel; hydrogen peroxide was detected on variety of substrates. Hydrogen peroxide was detected in the post-blast residues of the improvised explosives TATP and HMTD.

The Use of Hyphenated Spectrometric Techniques for the Environmental Forensic Assessment of Non-Traditional Pollutants and Degradates in the Greater Florida Everglades

A comprehensive investigation of sensitive ecosystems in South Florida with the main goal of determining the identity, spatial distribution, and sources of both organic biocides and trace elements in different environmental compartments is reported. This study presents the development and validation of a fractionation and isolation method of twelve polar acidic herbicides commonly applied in the vicinity of the study areas, including e.g. 2,4-D, MCPA, dichlorprop, mecroprop, picloram in surface water. Solid phase extraction (SPE) was used to isolate the analytes from abiotic matrices containing large amounts of dissolved organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-) in a Quadrupole Ion Trap mass spectrometer was used to perform the characterization of the herbicides of interest. The application of Laser Ablation-ICP-MS methodology in the analysis of soils and sediments is reported in this study. The analytical performance of the method was evaluated on certified standards and real soil and sediment samples. Residential soils were analyzed to evaluate feasibility of using the powerful technique as a routine and rapid method to monitor potential contaminated sites. Forty eight sediments were also collected from semi pristine areas in South Florida to conduct screening of baseline levels of bioavailable elements in support of risk evaluation. The LA-ICP-MS data were used to perform a statistical evaluation of the elemental composition as a tool for environmental forensics. A LA-ICP-MS protocol was also developed and optimized for the elemental analysis of a wide range of elements in polymeric filters containing atmospheric dust. A quantitative strategy based on internal and external standards allowed for a rapid determination of airborne trace elements in filters containing both contemporary African dust and local dust emissions. These distributions were used to qualitative and quantitative assess differences of composition and to establish provenance and fluxes to protected regional ecosystems such as coral reefs and national parks.

Elemental Analysis of Biological Matrices by Laser Ablation High Resolution Inductively Coupled Plasma Mass Spectrometry (LA-HR-ICP-MS) and High Resolution Inductively Coupled Plasma Mass Spectrometry (HR-ICP-MS)

The need for elemental analysis of biological matrices such as bone, teeth, and plant matter for sourcing purposes has emerged within the forensic and geochemical laboratories. Trace elemental analyses for the comparison of aterials such as glass by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS has been shown to offer a high degree of discrimination between different manufacturing sources. Unit resolution ICP-MS instruments may suffer from some polyatomic interferences including 40Ar16O+, 40Ar16O1H+, and 40Ca16O+ that affect iron measurement at trace levels. Iron is an important element in the analysis of glass and also of interest for the analysis of several biological matrices. A comparison of the nalytical performance of two different ICP-MS systems for iron analysis in glass for determining the method detection limits (MDLs), accuracy, and precision of the measurement is presented. Acid digestion and laser ablation methods are also compared. Iron polyatomic interferences were reduced or resolved by using dynamic reaction cell and high resolution ICP-MS. MDLs as low as 0.03 ìg g-1 and 0.14 ìg g-1 for laser ablation and solution based analyses respectively were achieved. The use of helium as a carrier gas demonstrated improvement in the detection limits of both iron isotopes (56Fe and 57Fe) in medium resolution for the HR-ICP-MS and with a dynamic reaction cell (DRC) coupled to a quadrupole ICP-MS system. The development and application of robust analytical methods for the quantification of trace elements in biological matrices has lead to a better understanding of the potential utility of these measurements in forensic chemical analyses. Standard reference materials (SRMs) were used in the development of an analytical method using HR-ICP-MS and LA-HR-ICP-MS that was subsequently applied on the analysis of real samples. Bone, teeth and ashed marijuana samples were analyzed with the developed method. Elemental analysis of bone samples from 12 different individuals provided discrimination between individuals, when femur and humerus bones were considered separately. Discrimination of 14 teeth samples based on elemental composition was achieved with the exception of one case where samples from the same individual were not associated with each other. The discrimination of 49 different ashed plant (cannabis)samples was achieved using the developed method.

Design Optimization of Modern Machine-drive Systems for Maximum Fault Tolerant and Optimal Operation

Modern electric machine drives, particularly three phase permanent magnet machine drive systems represent an indispensable part of high power density products. Such products include; hybrid electric vehicles, large propulsion systems, and automation products. Reliability and cost of these products are directly related to the reliability and cost of these systems. The compatibility of the electric machine and its drive system for optimal cost and operation has been a large challenge in industrial applications. The main objective of this dissertation is to find a design and control scheme for the best compromise between the reliability and optimality of the electric machine-drive system. The effort presented here is motivated by the need to find new techniques to connect the design and control of electric machines and drive systems. A highly accurate and computationally efficient modeling process was developed to monitor the magnetic, thermal, and electrical aspects of the electric machine in its operational environments. The modeling process was also utilized in the design process in form finite element based optimization process. It was also used in hardware in the loop finite element based optimization process. The modeling process was later employed in the design of a very accurate and highly efficient physics-based customized observers that are required for the fault diagnosis as well the sensorless rotor position estimation. Two test setups with different ratings and topologies were numerically and experimentally tested to verify the effectiveness of the proposed techniques. The modeling process was also employed in the real-time demagnetization control of the machine. Various real-time scenarios were successfully verified. It was shown that this process gives the potential to optimally redefine the assumptions in sizing the permanent magnets of the machine and DC bus voltage of the drive for the worst operating conditions. The mathematical development and stability criteria of the physics-based modeling of the machine, design optimization, and the physics-based fault diagnosis and the physics-based sensorless technique are described in detail. To investigate the performance of the developed design test-bed, software and hardware setups were constructed first. Several topologies of the permanent magnet machine were optimized inside the optimization test-bed. To investigate the performance of the developed sensorless control, a test-bed including a 0.25 (kW) surface mounted permanent magnet synchronous machine example was created. The verification of the proposed technique in a range from medium to very low speed, effectively show the intelligent design capability of the proposed system. Additionally, to investigate the performance of the developed fault diagnosis system, a test-bed including a 0.8 (kW) surface mounted permanent magnet synchronous machine example with trapezoidal back electromotive force was created. The results verify the use of the proposed technique under dynamic eccentricity, DC bus voltage variations, and harmonic loading condition make the system an ideal case for propulsion systems.

Laser cooling and trapping of argon metastable atomic beam

The high velocity of free atoms associated with the thermal motion, together with the velocity distribution of atoms has imposed the ultimate limitation on the precision of ultrahigh resolution spectroscopy. A sample consisting of low velocity atoms would provide a substantial improvement in spectroscopy resolution. To overcome the problem of thermal motion, atomic physicists have pursued two goals; first, the reduction of the thermal motion (cooling); and second, the confinement of the atoms by means of electromagnetic fields (trapping). Cooling carried sufficiently far, eliminates the motional problems, whereas trapping allows for long observation times. In this work the laser cooling and trapping of an argon atomic beam will be discussed. The experiments involve a time-of-flight spectroscopy on metastable argon atoms. Laser deceleration or cooling of atoms is achieved by counter propagating a photon against an atomic beam of metastable atoms. The solution to the Doppler shift problem is achieved using spatially varying magnetic field along the beam path to Zeeman shift the atomic resonance frequency so as to keep the atoms in resonance with a fixed frequency cooling laser. For trapping experiments a Magnetooptical trap (MOT) will be used. The MOT is formed by three pairs of counter-propagating laser beams with mutual opposite circular polarization and a frequency tuned slightly below the center of the atomic resonance and superimposed on a magnetic quadrupole field.