Development of advanced capillary electrophoresis techniques with UV and mass spectrometry detection for forensic, pharmaceutical and environmental applications

Capillary electrophoresis (CE) is a modern analytical technique, which is electrokinetic separation generated by high voltage and taken place inside the small capillaries. In this dissertation, several advanced capillary electrophoresis methods are presented using different approaches of CE and UV and mass spectrometry are utilized as the detection methods. ^ Capillary electrochromatography (CEC), as one of the CE modes, is a recent developed technique which is a hybrid of capillary electrophoresis and high performance liquid chromatography (HPLC). Capillary electrochromatography exhibits advantages of both techniques. In Chapter 2, monolithic capillary column are fabricated using in situ photoinitiation polymerization method. The column was then applied for the separation of six antidepressant compounds. ^ Meanwhile, a simple chiral separation method is developed and presented in Chapter 3. Beta cycodextrin was utilized to achieve the goal of chiral separation. Not only twelve cathinone analytes were separated, but also isomers of several analytes were enantiomerically separated. To better understand the molecular information on the analytes, the TOF-MS system was coupled with the CE. A sheath liquid and a partial filling technique (PFT) were employed to reduce the contamination of MS ionization source. Accurate molecular information was obtained. ^ It is necessary to propose, develop, and optimize new techniques that are suitable for trace-level analysis of samples in forensic, pharmaceutical, and environmental applications. Capillary electrophoresis (CE) was selected for this task, as it requires lower amounts of samples, it simplifies sample preparation, and it has the flexibility to perform separations of neutral and charged molecules as well as enantiomers. ^ Overall, the study demonstrates the versatility of capillary electrophoresis methods in forensic, pharmaceutical, and environmental applications.^

The Effect of Sample and Sample Matrix on DNA Processing: Mechanisms for the Detection and Management of Inhibition in Forensic Samples

The presence of inhibitory substances in biological forensic samples has, and continues to affect the quality of the data generated following DNA typing processes. Although the chemistries used during the procedures have been enhanced to mitigate the effects of these deleterious compounds, some challenges remain. Inhibitors can be components of the samples, the substrate where samples were deposited or chemical(s) associated to the DNA purification step. Therefore, a thorough understanding of the extraction processes and their ability to handle the various types of inhibitory substances can help define the best analytical processing for any given sample. A series of experiments were conducted to establish the inhibition tolerance of quantification and amplification kits using common inhibitory substances in order to determine if current laboratory practices are optimal for identifying potential problems associated with inhibition. DART mass spectrometry was used to determine the amount of inhibitor carryover after sample purification, its correlation to the initial inhibitor input in the sample and the overall effect in the results. Finally, a novel alternative at gathering investigative leads from samples that would otherwise be ineffective for DNA typing due to the large amounts of inhibitory substances and/or environmental degradation was tested. This included generating data associated with microbial peak signatures to identify locations of clandestine human graves. Results demonstrate that the current methods for assessing inhibition are not necessarily accurate, as samples that appear inhibited in the quantification process can yield full DNA profiles, while those that do not indicate inhibition may suffer from lowered amplification efficiency or PCR artifacts. The extraction methods tested were able to remove >90% of the inhibitors from all samples with the exception of phenol, which was present in variable amounts whenever the organic extraction approach was utilized. Although the results attained suggested that most inhibitors produce minimal effect on downstream applications, analysts should practice caution when selecting the best extraction method for particular samples, as casework DNA samples are often present in small quantities and can contain an overwhelming amount of inhibitory substances.

Foundational Forensic Techniques for Cellular and Ad Hoc Multi-hop Networks

The Internet has become an integral part of our nation's critical socio-economic infrastructure. With its heightened use and growing complexity however, organizations are at greater risk of cyber crimes. To aid in the investigation of crimes committed on or via the Internet, a network forensics analysis tool pulls together needed digital evidence. It provides a platform for performing deep network analysis by capturing, recording and analyzing network events to find out the source of a security attack or other information security incidents. Existing network forensics work has been mostly focused on the Internet and fixed networks. But the exponential growth and use of wireless technologies, coupled with their unprecedented characteristics, necessitates the development of new network forensic analysis tools. This dissertation fostered the emergence of a new research field in cellular and ad-hoc network forensics. It was one of the first works to identify this problem and offer fundamental techniques and tools that laid the groundwork for future research. In particular, it introduced novel methods to record network incidents and report logged incidents. For recording incidents, location is considered essential to documenting network incidents. However, in network topology spaces, location cannot be measured due to absence of a 'distance metric'. Therefore, a novel solution was proposed to label locations of nodes within network topology spaces, and then to authenticate the identity of nodes in ad hoc environments. For reporting logged incidents, a novel technique based on Distributed Hash Tables (DHT) was adopted. Although the direct use of DHTs for reporting logged incidents would result in an uncontrollably recursive traffic, a new mechanism was introduced that overcome this recursive process. These logging and reporting techniques aided forensics over cellular and ad-hoc networks, which in turn increased their ability to track and trace attacks to their source. These techniques were a starting point for further research and development that would result in equipping future ad hoc networks with forensic components to complement existing security mechanisms.

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.

Validation of an Analytical Method for the Identification of SmartWater CSI Forensic Marking Technology

SmartWater is a chemical taggant used as a crime deterrent. The chemical taggant is a colorless liquid that fluoresces yellow under ultra-violet (UV) light and contains distinctive, identifiable and traceable elemental composition. For instance, upon a break and entry scenario, the burglar is sprayed with a solution that has an elemental signature custom-made to a specific location. The residues of this taggant persist on skin and other objects and can be easily recovered for further analysis. The product has been effectively used in Europe as a crime deterrent and has been recently introduced in South Florida. In 2014, Fourt Lauderdale Police Department reported the use of SmartWater products with a reduction in burglaries of 14% [1]. The International Forensic Research Institute (IFRI) at FIU validated the scientific foundation of the methods of recovery and analysis of these chemical tagging systems using LA-ICP-MS. Analytical figures of merit of the method such as precision, accuracy, limits of detection, linearity and selectivity are reported in this study. Moreover, blind samples were analyzed by LA-ICP-MS to compare the chemical signatures to the company’s database and evaluate error rates and the accuracy of the method. This study demonstrated that LA-ICP-MS could be used to effectively detect these traceable taggants to assist law enforcement agencies in the United States with cases involving transfer of these forensic coding systems.

The Development of Forensic Social Work in Spain

The focus of this article is to explain the state of research work with regard to the specialty of forensic social work in Spain. The study was carried out as part of the activities developed by Research Team 940102 ‘Observatory for Social Intervention in Organizations’ from the University Complutense of Madrid and funded by this university.

Samoyedic Diary : Early Years of Visual Anthropology in the Soviet Arctic

Peer reviewed

Analysis of White Latex Paints using Laser Induced Breakdown Spectroscopy for Forensic Applications

The analysis of white latex paint is a problem for forensic laboratories because of difficulty in differentiation between samples. Current methods provide limited information that is not suitable for discrimination. Elemental analysis of white latex paints has resulted in 99% discriminating power when using LA-ICP-MS; however, mass spectrometers can be prohibitively expensive and require a skilled operator. A quick, inexpensive, effective method is needed for the differentiation of white latex paints. In this study, LIBS is used to analyze 24 white latex paint samples. LIBS is fast, easy to operate, and has a low cost. Results show that 98.1% of variation can be accounted for via principle component analysis, while Tukey pairwise comparisons differentiated 95.6% with potassium as the elemental ratio, showing that the discrimination capabilities of LIBS are comparable to those of LA-ICP-MS. Due to the many advantages of LIBS, this instrument should be considered a necessity for forensic laboratories.

Development of Advanced Capillary Electrophoresis Techniques with UV and Mass Spectrometry Detection for Forensic, Pharmaceutical and Environmental Applications

Capillary electrophoresis (CE) is a modern analytical technique, which is electrokinetic separation generated by high voltage and taken place inside the small capillaries. In this dissertation, several advanced capillary electrophoresis methods are presented using different approaches of CE and UV and mass spectrometry are utilized as the detection methods. Capillary electrochromatography (CEC), as one of the CE modes, is a recent developed technique which is a hybrid of capillary electrophoresis and high performance liquid chromatography (HPLC). Capillary electrochromatography exhibits advantages of both techniques. In Chapter 2, monolithic capillary column are fabricated using in situ photoinitiation polymerization method. The column was then applied for the separation of six antidepressant compounds. Meanwhile, a simple chiral separation method is developed and presented in Chapter 3. Beta cycodextrin was utilized to achieve the goal of chiral separation. Not only twelve cathinone analytes were separated, but also isomers of several analytes were enantiomerically separated. To better understand the molecular information on the analytes, the TOF-MS system was coupled with the CE. A sheath liquid and a partial filling technique (PFT) were employed to reduce the contamination of MS ionization source. Accurate molecular information was obtained. It is necessary to propose, develop, and optimize new techniques that are suitable for trace-level analysis of samples in forensic, pharmaceutical, and environmental applications. Capillary electrophoresis (CE) was selected for this task, as it requires lower amounts of samples, it simplifies sample preparation, and it has the flexibility to perform separations of neutral and charged molecules as well as enantiomers. Overall, the study demonstrates the versatility of capillary electrophoresis methods in forensic, pharmaceutical, and environmental applications.

Digital anthropology and educational eGames: learning through behavioural patterns in digital, game-based contexts

The selected publications are focused on the relations between users, eGames and the educational context, and how they interact together, so that both learning and user performance are improved through feedback provision. A key part of this analysis is the identification of behavioural, anthropological patterns, so that users can be clustered based on their actions, and the steps taken in the system (e.g. social network, online community, or virtual campus). In doing so, we can analyse large data sets of information made by a broad user sample,which will provide more accurate statistical reports and readings. Furthermore, this research is focused on how users can be clustered based on individual and group behaviour, so that a personalized support through feedback is provided, and the personal learning process is improved as well as the group interaction. We take inputs from every person and from the group they belong to, cluster the contributions, find behavioural patterns and provide personalized feedback to the individual and the group, based on personal and group findings. And we do all this in the context of educational games integrated in learning communities and learning management systems. To carry out this research we design a set of research questions along the 10-year published work presented in this thesis. We ask if the users can be clustered together based on the inputs provided by them and their groups; if and how these data are useful to improve the learner performance and the group interaction; if and how feedback becomes a useful tool for such pedagogical goal; if and how eGames become a powerful context to deploy the pedagogical methodology and the various research methods and activities that make use of that feedback to encourage learning and interaction; if and how a game design and a learning design must be defined and implemented to achieve these objectives, and to facilitate the productive authoring and integration of eGames in pedagogical contexts and frameworks. We conclude that educational games are a resourceful tool to provide a user experience towards a better personalized learning performance and an enhance group interaction along the way. To do so, eGames, while integrated in an educational context, must follow a specific set of user and technical requirements, so that the playful context supports the pedagogical model underneath. We also conclude that, while playing, users can be clustered based on their personal behaviour and interaction with others, thanks to the pattern identification. Based on this information, a set of recommendations are provided Digital Anthropology and educational eGames 6 /216 to the user and the group in the form of personalized feedback, timely managed for an optimum impact on learning performance and group interaction level. In this research, Digital Anthropology is introduced as a concept at a late stage to provide a backbone across various academic fields including: Social Science, Cognitive Science, Behavioural Science, Educational games and, of course, Technology-enhance learning. Although just recently described as an evolution of traditional anthropology, this approach to digital behaviour and social structure facilitates the understanding amongst fields and a comprehensive view towards a combined approach. This research takes forward the already existing work and published research onusers and eGames for learning, and turns the focus onto the next step — the clustering of users based on their behaviour and offering proper, personalized feedback to the user based on that clustering, rather than just on isolated inputs from every user. Indeed, this pattern recognition in the described context of eGames in educational contexts, and towards the presented aim of personalized counselling to the user and the group through feedback, is something that has not been accomplished before.

Parading through the Peace Process:Anthropology, Governance and Crisis in Northern Ireland

Because the authors both did work on the North Ireland parades, they became integrally involved as fieldworking anthropologists in the monitoring of these events, and in the creation of policy for their management. They detail how they worked with individuals and groups at every level, from protestors on the street up to the Secretary of State for the region. Later funded to examine legal and policing approaches to protests in other countries, especially South Africa, they show how they used this comparative knowledge to urge the implementation of measures which appear to have led to a diminution of violence in the parades. Finally, they assess their own contribution to the peace process in terms of contingency, timing, luck, flexibility, and industry.