The potential of solid phase microextraction (SPME) for the recovery of explosives followed by gas and liquid chromatographic analysis

The potential of solid phase microextraction (SPME) in the analysis of explosives is demonstrated. A sensitive, rapid, solventless and inexpensive method for the analysis of explosives and explosive odors from solid and liquid samples has been optimized using SPME followed by HPLC and GC/ECD. SPME involves the extraction of the organic components in debris samples into sorbent-coated silica fibers, which can be transferred directly to the injector of a gas chromatograph. SPME/HPLC requires a special desorption apparatus to elute the extracted analyte onto the column at high pressure. Results for use of GC/ECD is presented and compared to the results gathered by using HPLC analysis. The relative effects of controllable variables including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time have been optimized for various high explosives. ^

The potential of solid phase microextraction (spme) for the recovery of explosives followed by gas and liquid chromatographic analysis

The potential of solid phase microextraction (SPME) in the analysis of explosives is demonstrated. A sensitive, rapid, solventless and inexpensive method for the analysis of explosives and explosive odors from solid and liquid samples has been optimized using SPME followed by HPLC and GC/ECD. SPME involves the extraction of the organic components in debris samples into sorbent-coated silica fibers, which can be transferred directly to the injector of a gas chromatograph. SPME/HPLC requires a special desorption apparatus to elute the extracted analyte onto the column at high pressure. Re suits for use of GC[ECD is presented and compared to the results gathered by using HPLC analysis. The relative effects of controllable variables including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time have been optimized for various high explosives.

The utilization of chiral ion mobility spectrometry for the detection of enantiomeric mixtures and thermally labile compounds

This dissertation utilized electrospray ion mobility mass spectrometry (ESI-IMS-MS) to develop methods necessary for the separation of chiral compounds of forensic interest. The compounds separated included ephedrines and pseudoephedrines, that occur as impurities in confiscated amphetamine type substances (ATS) in an effort to determine the origin of these substances. The ESI-IMS-MS technique proved to be faster and more cost effective than traditional chromatographic methods currently used to conduct chiral separations such as gas and liquid chromatography. Both mass spectrometric and computational analysis revealed the separation mechanism of these chiral interactions allowing for further development to separate other chiral compounds by IMS. Successful separation of chiral compounds was achieved utilizing a variety of modifiers injected into the IMS drift tube. It was found that the modifiers themselves did not need to be chiral in nature and that achiral modifiers were sufficient in performing the required separations. The ESI-IMS-MS technique was also used to detect thermally labile compounds which are commonly found in explosive substances. The methods developed provided mass spectrometric identification of the type of ionic species being detected from explosive analytes as well as the appropriate solvent that enhances detection of these analytes in either the negative or positive ion mode. An application of the developed technique was applied to the analysis of a variety of low explosive smokeless powder samples. It was found that the developed ESI-IMS-MS technique not only detected the components of the smokeless powders, but also provided data that allowed the classification of the analyzed smokeless powders by manufacturer or make. ^

The Role of Agriculture and Food Consumption in Tropical Conservation

A growing human population, shifting human dietary habits, and climate change are negatively affecting global ecosystems on a massive scale. Expanding agricultural areas to feed a growing population drives extensive habitat loss, and climate change compounds stresses on both food security and ecosystems. Understanding the negative effects of human diet and climate change on agricultural and natural ecosystems provides a context within which potential technological and behavioral solutions can be proposed to help maximize conservation. The purpose of this research was to (1) examine the potential effects of climate change on the suitability of areas for commercial banana plantations in Latin America in the 2050s and how shifts in growing areas could affect protected areas; (2) test the ability of small unmanned aerial vehicles (UAVs) to map productivity of banana plantations as a potential tool for increasing yields and decreasing future plantation expansions; (3) project the effects on biodiversity of increasing rates of animal product consumption in developing megadiverse countries; and (4) estimate the capacity of global pasture biomass production and Fischer-Tropsch hydrocarbon synthesis (IGCC-FT) processing to meet electricity, gasoline and diesel needs. The results indicate that (1) the overall extent of areas suitable for conventional banana cultivation is predicted to decrease by 19% by 2050 because of a hotter and drier climate, but all current banana exporting countries are predicted to maintain some suitable areas with no effects on protected areas; (2) Spatial patterns of NDVI and ENDVI were significantly positively correlated with several metrics of fruit yield and quality, indicating that UAV systems can be used in banana plantations to map spatial patterns of fruit yield; (3) Livestock production is the single largest driver of habitat loss, and both livestock and feedstock production are increasing in developing biodiverse tropical countries. Reducing global animal product consumption should therefore be at the forefront of strategies aimed at reducing biodiversity loss; (4) Removing livestock from global pasture lands and instead utilizing the biomass production could produce enough energy to meet 100% of the electricity, gasoline, and diesel needs of over 40 countries with extensive grassland ecosystems, primarily in tropical developing countries.

Emergence and Fate of Siloxanes in Waste Streams: Release Mechanisms, Partitioning and Persistence in Three Environmental Compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.

The role of agriculture and food consumption in tropical conservation

A growing human population, shifting human dietary habits, and climate change are negatively affecting global ecosystems on a massive scale. Expanding agricultural areas to feed a growing population drives extensive habitat loss, and climate change compounds stresses on both food security and ecosystems. Understanding the negative effects of human diet and climate change on agricultural and natural ecosystems provides a context within which potential technological and behavioral solutions can be proposed to help maximize conservation. The purpose of this research was to (1) examine the potential effects of climate change on the suitability of areas for commercial banana plantations in Latin America in the 2050s and how shifts in growing areas could affect protected areas; (2) test the ability of small unmanned aerial vehicles (UAVs) to map productivity of banana plantations as a potential tool for increasing yields and decreasing future plantation expansions; (3) project the effects on biodiversity of increasing rates of animal product consumption in developing megadiverse countries; and (4) estimate the capacity of global pasture biomass production and Fischer-Tropsch hydrocarbon synthesis (IGCC-FT) processing to meet electricity, gasoline and diesel needs. The results indicate that (1) the overall extent of areas suitable for conventional banana cultivation is predicted to decrease by 19% by 2050 because of a hotter and drier climate, but all current banana exporting countries are predicted to maintain some suitable areas with no effects on protected areas; (2) Spatial patterns of NDVI and ENDVI were significantly positively correlated with several metrics of fruit yield and quality, indicating that UAV systems can be used in banana plantations to map spatial patterns of fruit yield; (3) Livestock production is the single largest driver of habitat loss, and both livestock and feedstock production are increasing in developing biodiverse tropical countries. Reducing global animal product consumption should therefore be at the forefront of strategies aimed at reducing biodiversity loss; (4) Removing livestock from global pasture lands and instead utilizing the biomass production could produce enough energy to meet 100% of the electricity, gasoline, and diesel needs of over 40 countries with extensive grassland ecosystems, primarily in tropical developing countries.^

Emergence and fate of siloxanes in waste streams: Release mechanisms, partitioning and persistence in three environmental compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. ^ The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. ^ Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.^