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.

Integrated Performance Assessment of Engineering Projects at the Interface of Emergent Properties and Uncertainty

Investigation of the performance of engineering project organizations is critical for understanding and eliminating inefficiencies in today’s dynamic global markets. The existing theoretical frameworks consider project organizations as monolithic systems and attribute the performance of project organizations to the characteristics of the constituents. However, project organizations consist of complex interdependent networks of agents, information, and resources whose interactions give rise to emergent properties that affect the overall performance of project organizations. Yet, our understanding of the emergent properties in project organizations and their impact on project performance is rather limited. This limitation is one of the major barriers towards creation of integrated theories of performance assessment in project organizations. The objective of this paper is to investigate the emergent properties that affect the ability of project organization to cope with uncertainty. Based on the theories of complex systems, we propose and test a novel framework in which the likelihood of performance variations in project organizations could be investigated based on the environment of uncertainty (i.e., static complexity, dynamic complexity, and external source of disruption) as well as the emergent properties (i.e., absorptive capacity, adaptive capacity, and restorative capacity) of project organizations. The existence and significance of different dimensions of the environment of uncertainty and emergent properties in the proposed framework are tested based on the analysis of the information collected from interviews with senior project managers in the construction industry. The outcomes of this study provide a novel theoretical lens for proactive bottom-up investigation of performance in project organizations at the interface of emergent properties and uncertainty

Advanced methodologies in dynamic traffic assignment modeling of managed lanes

Managed lane strategies are innovative road operation schemes for addressing congestion problems. These strategies operate a lane (lanes) adjacent to a freeway that provides congestion-free trips to eligible users, such as transit or toll-payers. To ensure the successful implementation of managed lanes, the demand on these lanes need to be accurately estimated. Among different approaches for predicting this demand, the four-step demand forecasting process is most common. Managed lane demand is usually estimated at the assignment step. Therefore, the key to reliably estimating the demand is the utilization of effective assignment modeling processes. ^ Managed lanes are particularly effective when the road is functioning at near-capacity. Therefore, capturing variations in demand and network attributes and performance is crucial for their modeling, monitoring and operation. As a result, traditional modeling approaches, such as those used in static traffic assignment of demand forecasting models, fail to correctly predict the managed lane demand and the associated system performance. The present study demonstrates the power of the more advanced modeling approach of dynamic traffic assignment (DTA), as well as the shortcomings of conventional approaches, when used to model managed lanes in congested environments. In addition, the study develops processes to support an effective utilization of DTA to model managed lane operations. ^ Static and dynamic traffic assignments consist of demand, network, and route choice model components that need to be calibrated. These components interact with each other, and an iterative method for calibrating them is needed. In this study, an effective standalone framework that combines static demand estimation and dynamic traffic assignment has been developed to replicate real-world traffic conditions. ^ With advances in traffic surveillance technologies collecting, archiving, and analyzing traffic data is becoming more accessible and affordable. The present study shows how data from multiple sources can be integrated, validated, and best used in different stages of modeling and calibration of managed lanes. Extensive and careful processing of demand, traffic, and toll data, as well as proper definition of performance measures, result in a calibrated and stable model, which closely replicates real-world congestion patterns, and can reasonably respond to perturbations in network and demand properties.^

Freeway Travel Time Estimation and Prediction Using Dynamic Neural Networks

Providing transportation system operators and travelers with accurate travel time information allows them to make more informed decisions, yielding benefits for individual travelers and for the entire transportation system. Most existing advanced traveler information systems (ATIS) and advanced traffic management systems (ATMS) use instantaneous travel time values estimated based on the current measurements, assuming that traffic conditions remain constant in the near future. For more effective applications, it has been proposed that ATIS and ATMS should use travel times predicted for short-term future conditions rather than instantaneous travel times measured or estimated for current conditions. This dissertation research investigates short-term freeway travel time prediction using Dynamic Neural Networks (DNN) based on traffic detector data collected by radar traffic detectors installed along a freeway corridor. DNN comprises a class of neural networks that are particularly suitable for predicting variables like travel time, but has not been adequately investigated for this purpose. Before this investigation, it was necessary to identifying methods for data imputation to account for missing data usually encountered when collecting data using traffic detectors. It was also necessary to identify a method to estimate the travel time on the freeway corridor based on data collected using point traffic detectors. A new travel time estimation method referred to as the Piecewise Constant Acceleration Based (PCAB) method was developed and compared with other methods reported in the literatures. The results show that one of the simple travel time estimation methods (the average speed method) can work as well as the PCAB method, and both of them out-perform other methods. This study also compared the travel time prediction performance of three different DNN topologies with different memory setups. The results show that one DNN topology (the time-delay neural networks) out-performs the other two DNN topologies for the investigated prediction problem. This topology also performs slightly better than the simple multilayer perceptron (MLP) neural network topology that has been used in a number of previous studies for travel time prediction.

Improving Storage Performance Through Layout Optimizations

Disk drives are the bottleneck in the processing of large amounts of data used in almost all common applications. File systems attempt to reduce this by storing data sequentially on the disk drives, thereby reducing the access latencies. Although this strategy is useful when data is retrieved sequentially, the access patterns in real world workloads is not necessarily sequential and this mismatch results in storage I/O performance degradation. This thesis demonstrates that one way to improve the storage performance is to reorganize data on disk drives in the same way in which it is mostly accessed. We identify two classes of accesses: static, where access patterns do not change over the lifetime of the data and dynamic, where access patterns frequently change over short durations of time, and propose, implement and evaluate layout strategies for each of these. Our strategies are implemented in a way that they can be seamlessly integrated or removed from the system as desired. We evaluate our layout strategies for static policies using tree-structured XML data where accesses to the storage device are mostly of two kinds - parent-tochild or child-to-sibling. Our results show that for a specific class of deep-focused queries, the existing file system layout policy performs better by 5-54X. For the non-deep-focused queries, our native layout mechanism shows an improvement of 3-127X. To improve performance of the dynamic access patterns, we implement a self-optimizing storage system that performs rearranges popular block accesses on a dedicated partition based on the observed workload characteristics. Our evaluation shows an improvement of over 80% in the disk busy times over a range of workloads. These results show that applying the knowledge of data access patterns for allocation decisions can substantially improve the I/O performance.

Physical dynamic simulation of shipboard power system components in a distributed computational environment

Shipboard power systems have different characteristics than the utility power systems. In the Shipboard power system it is crucial that the systems and equipment work at their peak performance levels. One of the most demanding aspects for simulations of the Shipboard Power Systems is to connect the device under test to a real-time simulated dynamic equivalent and in an environment with actual hardware in the Loop (HIL). The real time simulations can be achieved by using multi-distributed modeling concept, in which the global system model is distributed over several processors through a communication link. The advantage of this approach is that it permits the gradual change from pure simulation to actual application. In order to perform system studies in such an environment physical phase variable models of different components of the shipboard power system were developed using operational parameters obtained from finite element (FE) analysis. These models were developed for two types of studies low and high frequency studies. Low frequency studies are used to examine the shipboard power systems behavior under load switching, and faults. High-frequency studies were used to predict abnormal conditions due to overvoltage, and components harmonic behavior. Different experiments were conducted to validate the developed models. The Simulation and experiment results show excellent agreement. The shipboard power systems components behavior under internal faults was investigated using FE analysis. This developed technique is very curial in the Shipboard power systems faults detection due to the lack of comprehensive fault test databases. A wavelet based methodology for feature extraction of the shipboard power systems current signals was developed for harmonic and fault diagnosis studies. This modeling methodology can be utilized to evaluate and predicate the NPS components future behavior in the design stage which will reduce the development cycles, cut overall cost, prevent failures, and test each subsystem exhaustively before integrating it into the system.

Advanced Methodologies in Dynamic Traffic Assignment Modeling of Managed Lanes

Managed lane strategies are innovative road operation schemes for addressing congestion problems. These strategies operate a lane (lanes) adjacent to a freeway that provides congestion-free trips to eligible users, such as transit or toll-payers. To ensure the successful implementation of managed lanes, the demand on these lanes need to be accurately estimated. Among different approaches for predicting this demand, the four-step demand forecasting process is most common. Managed lane demand is usually estimated at the assignment step. Therefore, the key to reliably estimating the demand is the utilization of effective assignment modeling processes. Managed lanes are particularly effective when the road is functioning at near-capacity. Therefore, capturing variations in demand and network attributes and performance is crucial for their modeling, monitoring and operation. As a result, traditional modeling approaches, such as those used in static traffic assignment of demand forecasting models, fail to correctly predict the managed lane demand and the associated system performance. The present study demonstrates the power of the more advanced modeling approach of dynamic traffic assignment (DTA), as well as the shortcomings of conventional approaches, when used to model managed lanes in congested environments. In addition, the study develops processes to support an effective utilization of DTA to model managed lane operations. Static and dynamic traffic assignments consist of demand, network, and route choice model components that need to be calibrated. These components interact with each other, and an iterative method for calibrating them is needed. In this study, an effective standalone framework that combines static demand estimation and dynamic traffic assignment has been developed to replicate real-world traffic conditions. With advances in traffic surveillance technologies collecting, archiving, and analyzing traffic data is becoming more accessible and affordable. The present study shows how data from multiple sources can be integrated, validated, and best used in different stages of modeling and calibration of managed lanes. Extensive and careful processing of demand, traffic, and toll data, as well as proper definition of performance measures, result in a calibrated and stable model, which closely replicates real-world congestion patterns, and can reasonably respond to perturbations in network and demand properties.

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.