Novel analytical methodologies for the monitoring of traditional and non-traditional pollutants in different environmental compartments of South Florida

Routine monitoring of environmental pollution demands simplicity and speed without sacrificing sensitivity or accuracy. The development and application of sensitive, fast and easy to implement analytical methodologies for detecting emerging and traditional water and airborne contaminants in South Florida is presented. A novel method was developed for quantification of the herbicide glyphosate based on lyophilization followed by derivatization and simultaneous detection by fluorescence and mass spectrometry. Samples were analyzed from water canals that will hydrate estuarine wetlands of Biscayne National Park, detecting inputs of glyphosate from both aquatic usage and agricultural runoff from farms. A second study describes a set of fast, automated LC-MS/MS protocols for the analysis of dioctyl sulfosuccinate (DOSS) and 2-butoxyethanol, two components of Corexit®. Around 1.8 million gallons of those dispersant formulations were used in the response efforts for the Gulf of Mexico oil spill in 2010. The methods presented here allow the trace-level detection of these compounds in seawater, crude oil and commercial dispersants formulations. In addition, two methodologies were developed for the analysis of well-known pollutants, namely Polycyclic Aromatic Hydrocarbons (PAHs) and airborne particulate matter (APM). PAHs are ubiquitous environmental contaminants and some are potent carcinogens. Traditional GC-MS analysis is labor-intensive and consumes large amounts of toxic solvents. My study provides an alternative automated SPE-LC-APPI-MS/MS analysis with minimal sample preparation and a lower solvent consumption. The system can inject, extract, clean, separate and detect 28 PAHs and 15 families of alkylated PAHs in 28 minutes. The methodology was tested with environmental samples from Miami. Airborne Particulate Matter is a mixture of particles of chemical and biological origin. Assessment of its elemental composition is critical for the protection of sensitive ecosystems and public health. The APM collected from Port Everglades between 2005 and 2010 was analyzed by ICP-MS after acid digestion of filters. The most abundant elements were Fe and Al, followed by Cu, V and Zn. Enrichment factors show that hazardous elements (Cd, Pb, As, Co, Ni and Cr) are introduced by anthropogenic activities. Data suggest that the major sources of APM were an electricity plant, road dust, industrial emissions and marine vessels.

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.

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.^

Novel Analytical Methodologies for the Monitoring of Traditional and Non-traditional Pollutants in different Environmental Compartments of South Florida

Routine monitoring of environmental pollution demands simplicity and speed without sacrificing sensitivity or accuracy. The development and application of sensitive, fast and easy to implement analytical methodologies for detecting emerging and traditional water and airborne contaminants in South Florida is presented. A novel method was developed for quantification of the herbicide glyphosate based on lyophilization followed by derivatization and simultaneous detection by fluorescence and mass spectrometry. Samples were analyzed from water canals that will hydrate estuarine wetlands of Biscayne National Park, detecting inputs of glyphosate from both aquatic usage and agricultural runoff from farms. A second study describes a set of fast, automated LC-MS/MS protocols for the analysis of dioctyl sulfosuccinate (DOSS) and 2-butoxyethanol, two components of Corexit®. Around 1.8 million gallons of those dispersant formulations were used in the response efforts for the Gulf of Mexico oil spill in 2010. The methods presented here allow the trace-level detection of these compounds in seawater, crude oil and commercial dispersants formulations. In addition, two methodologies were developed for the analysis of well-known pollutants, namely Polycyclic Aromatic Hydrocarbons (PAHs) and airborne particulate matter (APM). PAHs are ubiquitous environmental contaminants and some are potent carcinogens. Traditional GC-MS analysis is labor-intensive and consumes large amounts of toxic solvents. My study provides an alternative automated SPE-LC-APPI-MS/MS analysis with minimal sample preparation and a lower solvent consumption. The system can inject, extract, clean, separate and detect 28 PAHs and 15 families of alkylated PAHs in 28 minutes. The methodology was tested with environmental samples from Miami. Airborne Particulate Matter is a mixture of particles of chemical and biological origin. Assessment of its elemental composition is critical for the protection of sensitive ecosystems and public health. The APM collected from Port Everglades between 2005 and 2010 was analyzed by ICP-MS after acid digestion of filters. The most abundant elements were Fe and Al, followed by Cu, V and Zn. Enrichment factors show that hazardous elements (Cd, Pb, As, Co, Ni and Cr) are introduced by anthropogenic activities. Data suggest that the major sources of APM were an electricity plant, road dust, industrial emissions and marine vessels.