Assessment of the occurrence and potential risks of pharmaceuticals and their metabolites in fish and water using liquid chromatography mass spectrometry

A comprehensive method for the analysis of 11 target pharmaceuticals representing multiple therapeutic classes was developed for biological tissues (fish) and water. Water samples were extracted using solid phase extraction (SPE), while fish tissue homogenates were extracted using accelerated solvent extraction (ASE) followed by mixed-mode cation exchange SPE cleanup and analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS). Among the 11 target pharmaceuticals analyzed, trimethoprim, caffeine, sulfamethoxazole, diphenhydramine, diltiazem, carbamazepine, erythromycin and fluoxetine were consistently detected in reclaimed water. On the other hand, caffeine, diphenhydramine and carbamazepine were consistently detected in fish and surface water samples. In order to understand the uptake and depuration of pharmaceuticals as well as bioconcentration factors (BCFs) under the worst-case conditions, mosquito fish were exposed to reclaimed water under static-renewal for 7 days, followed by a 14-day depuration phase in clean water. Characterization of the exposure media revealed the presence of 26 pharmaceuticals while 5 pharmaceuticals including caffeine, diphenhydramine, diltiazem, carbamazepine, and ibuprofen were present in the organisms as early as 5 h from the start of the exposure. Liquid chromatography ultra-high resolution Orbitrap mass spectrometry was explored as a tool to identify and quantify phase II pharmaceutical metabolites in reclaimed water. The resulting data confirmed the presence of acetyl-sulfamethoxazole and sulfamethoxazole glucuronide in reclaimed water. To my knowledge, this is the first known report of sulfamethoxazole glucuronide surviving intact through wastewater treatment plants and occurring in environmental water samples. Finally, five bioaccumulative pharmaceuticals including caffeine, carbamazepine, diltiazem, diphenhydramine and ibuprofen detected in reclaimed water were investigated regarding the acute and chronic risks to aquatic organisms. The results indicated a low potential risk of carbamazepine even under the worst case exposure scenario. Given the dilution factors that affect environmental releases, the risk of exposure to carbamazepine will be even more reduced.

Design and construction of a portable force-reflecting manual controller for teleoperation systems

A man-machine system called teleoperator system has been developed to work in hazardous environments such as nuclear reactor plants. Force reflection is a type of force feedback in which forces experienced by the remote manipulator are fed back to the manual controller. In a force-reflecting teleoperation system, the operator uses the manual controller to direct the remote manipulator and receives visual information from a video image and/or graphical animation on the computer screen. This thesis presents the design of a portable Force-Reflecting Manual Controller (FRMC) for the teleoperation of tasks such as hazardous material handling, waste cleanup, and space-related operations. The work consists of the design and construction of a prototype 1-Degree-of-Freedom (DOF) FRMC, the development of the Graphical User Interface (GUI), and system integration. Two control strategies - PID and fuzzy logic controllers are developed and experimentally tested. The system response of each is analyzed and evaluated. In addition, the concept of a telesensation system is introduced, and a variety of design alternatives of a 3-DOF FRMC are proposed for future development.

Assessment of silicone polymer composites for the trace extraction of herbicides : a tool for environmental forensics

Passive samplers are not only a versatile tool to integrate environmental concentrations of pollutants, but also to avoid the use of live sentinel organisms for environmental monitoring. This study introduced the use of magnetic silicone polymer composites (Fe-PDMS) as passive sampling media to pre-concentrate a wide range of analytes from environmental settings. The composite samplers were assessed for their accumulation properties by performing lab experiments with two model herbicides (Atrazine and Irgarol 1051) and evaluated for their uptake properties from environmental settings (waters and sediments). The Fe-PDMS composites showed good accumulation of herbicides and pesticides from both freshwater and saltwater settings and the accumulation mechanism was positively correlated with the log Kow value of individual analytes. Results from the studies show that these composites could be easily used for a wide number of applications such as monitoring, cleanup, and/or bioaccumulation modeling, and as a non-intrusive and nondestructive monitoring tool for environmental forensic purposes.

Assessment of the Occurrence and Potential Risks of Pharmaceuticals and their Metabolites in Fish and Water Using Liquid Chromatography Mass Spectrometry

A comprehensive method for the analysis of 11 target pharmaceuticals representing multiple therapeutic classes was developed for biological tissues (fish) and water. Water samples were extracted using solid phase extraction (SPE), while fish tissue homogenates were extracted using accelerated solvent extraction (ASE) followed by mixed-mode cation exchange SPE cleanup and analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS). Among the 11 target pharmaceuticals analyzed, trimethoprim, caffeine, sulfamethoxazole, diphenhydramine, diltiazem, carbamazepine, erythromycin and fluoxetine were consistently detected in reclaimed water. On the other hand, caffeine, diphenhydramine and carbamazepine were consistently detected in fish and surface water samples. In order to understand the uptake and depuration of pharmaceuticals as well as bioconcentration factors (BCFs) under the worst-case conditions, mosquito fish were exposed to reclaimed water under static-renewal for 7 days, followed by a 14-day depuration phase in clean water. Characterization of the exposure media revealed the presence of 26 pharmaceuticals while 5 pharmaceuticals including caffeine, diphenhydramine, diltiazem, carbamazepine, and ibuprofen were present in the organisms as early as 5 h from the start of the exposure. Liquid chromatography ultra-high resolution Orbitrap mass spectrometry was explored as a tool to identify and quantify phase II pharmaceutical metabolites in reclaimed water. The resulting data confirmed the presence of acetyl-sulfamethoxazole and sulfamethoxazole glucuronide in reclaimed water. To my knowledge, this is the first known report of sulfamethoxazole glucuronide surviving intact through wastewater treatment plants and occurring in environmental water samples. Finally, five bioaccumulative pharmaceuticals including caffeine, carbamazepine, diltiazem, diphenhydramine and ibuprofen detected in reclaimed water were investigated regarding the acute and chronic risks to aquatic organisms. The results indicated a low potential risk of carbamazepine even under the worst case exposure scenario. Given the dilution factors that affect environmental releases, the risk of exposure to carbamazepine will be even more reduced.

Structural Health Monitoring Inside Concrete and Grout Using the Wireless Identification and Sensing Platform (WISP)

This research investigates the implementation of battery-less RFID sensing platforms inside lossy media, such as, concrete and grout. Both concrete and novel grouts can be used for nuclear plant decommissioning as part of the U.S. Department of Energy’s (DOE’s) cleanup projects. Our research examines the following: (1) material characterization, (2) analytical modeling of transmission and propagation losses inside lossy media, (3) maximum operational range of RFID wireless sensors embedded inside concrete and grout, and (4) best positioning of antennas for achieving longer communication range between RFID antennas and wireless sensors. Our research uses the battery-less Wireless Identification and Sensing Platform (WISP) which can be used to monitor temperature, and humidity inside complex materials. By using a commercial Agilent open-ended coaxial probe (HP8570B), the measurements of the dielectric permittivity of concrete and grout are performed. Subsequently, the measured complex permittivity is used to formulate analytical Debye models. Also, the transmission and propagation losses of a uniform plane wave inside grout are calculated. Our results show that wireless sensors will perform better in concrete than grout. In addition, the maximum axial and radial ranges for WISP are experimentally determined. Our work illustrates the feasibility of battery-less wireless sensors that are embedded inside concrete and grout. Also, our work provides information that can be used to optimize the power management, sampling rate, and antenna design of such sensors.