Evaluation and Improvement of Capillary Microextraction of Volatiles Coupled to Gas Chromatography-Mass Spectrometry for the Analysis of Ignitable Liquid Residues in Fire Debris

A key aspect of fire debris analysis is the ability to extract the remnants of an ignitable liquid from a matrix with a high degree of reliability and sensitivity. Although there are several robust, standardized methods, there is no single technique universally applicable to casework. In this work a novel extraction technique – Capillary Microextraction of Volatiles (CMV) – has been applied, for the first time, for ignitable liquid residue (ILR) extraction. A 20-minute dynamic sampling laboratory protocol from traditional 1 L paint cans was established and optimized based upon ASTM guidelines. The development of new adsorption phases for CMV use are also reported. A phenyl-modified sol-gel phase demonstrated up to 8-fold higher recoveries of BTEX compounds from headspace sampling compared to previously reported CMV phases and four additional differently functionalized phases were synthesized and evaluated. Preliminary comparisons of the CMV to activated charcoal strips (ACS) and to solid-phase microextraction (SPME) demonstrated equivalent or slightly higher extraction efficiency relative to SPME, and over two orders of magnitude greater extraction efficiency relative to ACS. The versatility of the CMV has also been extended to portable analytical instrumentation. The device was successfully coupled to a TRIDION-9 portable GC-MS when combined with a needle trap, and both were evaluated for their applicability to fire debris analysis. The CMV/NTD technique demonstrated extraction capabilities similar to the CMV alone; however, ILR analysis by the T9 was heavily impacted by the limited chromatographic resolution resulting in complicated data interpretation. The CMV was similarly coupled to a Griffin G510 for dual evaluation. Also presented for the first time is a field ILR headspace sampling protocol involving the use of a paper drinking cup. A five-minute sampling/extraction protocol was sufficient to recover six key gasoline analytes from a 0.01 µL spike of gasoline with typical mass recoveries of 4 – 24 ng. An overall 21-minute analytical method was developed using the CMV/Cup protocol capable of detecting several ILR-associated compounds at up to 10x greater sensitivity than traditional extraction techniques. This body of work demonstrates the overall versatility of the CMV as applied to the entire field of fire debris analysis

Utilizing Headspace Solid-Phase Microextraction for the Characterization of Volatile Organic Compounds Released from Contraband and its Implications for Detector Dog Training

Improving the accuracy and reliability of odor detection dogs is of utmost importance particularly for legal reasons. Field testing in conjunction with headspace analysis of volatile organic compounds (VOCs) has in recent times allowed for these improvements, by providing scientifically based recommendations for optimum training protocols. The current project leveraged on these established capabilities to enhance three areas of odor detection: illicit drugs, explosives and mass storage devices. With hemp being legalized under the 2018 Farm Bill, legal questions have been raised regarding a dog’s ability to ignore hemp if trained to detect marijuana, as both are types of Cannabis. Results concluded that most dogs do alert to hemp; however, they can be successfully trained over time to discriminate between hemp and marijuana. Headspace analysis showed marked similarities between sets of both products with minor differences. These differences can be further investigated to determine if characteristic marijuana VOCs exist that can be included in canine training regimens. Other tests showed that dogs imprinted on current marijuana odor mimics can falsely respond to hemp as the VOC components of these mimics are not specific to marijuana. These mimics should therefore be avoided for further training purposes. Dogs have been trained to detect and locate explosives such as triacetone triperoxide (TATP) that cannot be detected by most instrumental detectors. Headspace analysis showed TATP consisting primarily of the TATP molecule with relatively smaller amounts of the precursor acetone. Field tests determined that dogs imprinted on TATP may also falsely respond solely to the precursors acetone or hydrogen peroxide and as a result, additional training to ignore these VOCs should be considered. Detection of mass storage device (MSDs) is a relatively new field with little understanding of optimum training methods for dogs. Headspace analysis of various MSDs showed that they do have characteristic VOCs that can allow for successful odor detection with specificity. Additionally, the validity of 1-hydroxyclohexylphenyl ketone and triphenylphosphine oxide (TPPO) as training compounds were also investigated. 1-hydroxyclohexylphenyl ketone was detected in MSDs but also in other electronic controls while TPPO was not detected in MSD components

Identification of the Active Odors From Illicit Substances for the Development of Optimal Canine Training Aids

The exploitation of illicit substances, such as drugs and explosives, is on the rise. Special attention must therefore be considered to reduce the transportation and storage of these illicit substances by improving the capability of detection, even when hidden from view. Although analytical methods of detection for both drugs and explosives have improved over time, biological detectors, such as canines, are still commonly used. In comparison to humans, these canines have a larger number of olfactory receptors and a greater olfactory epithelium surface area, providing them with a more enhanced olfaction than that of humans. The premise for the detection of illicit drugs and explosives is based on the premise that these substances though hidden, will emit volatile organic compounds (VOCs). These VOCs are not often the parent drug or explosive, they are essentially a chemical associated with the source and provide a reliable indication of the illicit substance. Previous successful research has been conducted on the identification of the active odors present in the headspace of cocaine, methamphetamine, and MDMA but instead for marijuana and heroin there have been minimum success. Thus, in the present research a method using headspace solid-phase microextraction coupled to gas chromatography-mass spectrometry (HS-SPME-GC-MS) was optimized to identify the VOCs makeup of heroin and marijuana to further identify the active odor compound(s) responsible for the alert response of biological detectors (canines). A mixture of acetic acid and acetylsalicylic acid was identified as target odor mimic for heroin by certified detector canines, while a mixture of limonene and caryophyllene was recognized as odor mimic for marijuana by conducting ORTs. The training aids developed successfully mimic the scent of the actual illicit substance and can be used to improve the capabilities of both drug and explosive detection canines. Additionally, as growing threat of improvised explosives has created a worldwide concern and emphasized the requirement of a greater spectra of canine training aids that covers the complete range of explosives available, a new approach for the creation of training aids for IEDs have been evaluated. The use of a dynamic collection system have proved to be an option to develop fast and reliable canine training aids for IEDs

First dice your dill – new methods and techniques in sample handling

This book is dedicated to celebrate the 60th birthday of Professor Rainer Huopalahti. Professor Rainer “Repe” Huopalahti has had, and in fact is still enjoying a distinguished career in the analysis of food and food related flavor compounds. One will find it hard to make any progress in this particular field without a valid and innovative sample handling technique and this is a field in which Professor Huopalahti has made great contributions. The title and the front cover of this book honors Professor Huopahti’s early steps in science. His PhD thesis which was published on 1985 is entitled “Composition and content of aroma compounds in the dill herb, Anethum graveolens L., affected by different factors”. At that time, the thesis introduced new technology being applied to sample handling and analysis of flavoring compounds of dill. Sample handling is an essential task that in just about every analysis. If one is working with minor compounds in a sample or trying to detect trace levels of the analytes, one of the aims of sample handling may be to increase the sensitivity of the analytical method. On the other hand, if one is working with a challenging matrix such as the kind found in biological samples, one of the aims is to increase the selectivity. However, quite often the aim is to increase both the selectivity and the sensitivity. This book provides good and representative examples about the necessity of valid sample handling and the role of the sample handling in the analytical method. The contributors of the book are leading Finnish scientists on the field of organic instrumental analytical chemistry. Some of them are also Repe’ s personal friends and former students from the University of Turku, Department of Biochemistry and Food Chemistry. Importantly, the authors all know Repe in one way or another and are well aware of his achievements on the field of analytical chemistry. The editorial team had a great time during the planning phase and during the “hard work editorial phase” of the book. For example, we came up with many ideas on how to publish the book. After many long discussions, we decided to have a limited edition as an “old school hard cover book” – and to acknowledge more modern ways of disseminating knowledge by publishing an internet version of the book on the webpages of the University of Turku. Downloading the book from the webpage for personal use is free of charge. We believe and hope that the book will be read with great interest by scientists working in the fascinating field of organic instrumental analytical chemistry. We decided to publish our book in English for two main reasons. First, we believe that in the near future, more and more teaching in Finnish Universities will be delivered in English. To facilitate this process and encourage students to develop good language skills, it was decided to be published the book in English. Secondly, we believe that the book will also interest scientists outside Finland – particularly in the other member states of the European Union. The editorial team thanks all the authors for their willingness to contribute to this book – and to adhere to the very strict schedule. We also want to thank the various individuals and enterprises who financially supported the book project. Without that support, it would not have been possible to publish the hardcover book.Siirretty Doriast

A comparison between mobile and stationary gas chromatography–mass spectrometry devices for analysis of complex volatile profiles (advance online)

On-site analysis of volatile organic compounds (VOCs) with miniaturized gas chromatography–mass spectrometry (GC–MS)systems is a very rapidly developing field of application. While, on the one hand, major technological advances are improv-ing the availability of these systems on the market, on the other hand, systematic studies to assess the performance of suchinstruments are still lacking. To fill this gap, we compared three portable GC–MS devices to a state-of-the-art benchtop(stationary) system for analysis of a standard mixture of 18 VOCs. We systematically compared analytical parameters suchas the sensitivity and similarity of the signal response pattern and the quality of the obtained mass spectra. We found that theinvestigated mobile instruments (i) showed different response profiles with a generally lower number of identified analytes.Also, (ii) mass spectral reproducibility (% relative standard deviation (RSD) of the relative abundance of selective fragments)was generally worse in the mobile devices (mean RSD for all targeted fragments~9.7% vs. ~3.5% in the stationary system).Furthermore, mobile devices (iii) showed a poorer mass spectral similarity to commercial reference library spectra (>20%deviation of fragment ion relative intensity vs. ~10% in the stationary GC–MS), suggesting a less reliable identification ofanalytes by library search. Indeed, (iv) the performance was better with higher-mass and/or more abundant fragments, whichshould be considered to improve the results of library searches for substance identification. Finally, (v) the estimation ofthe signal-to-noise ratio (S/N) in mobile instruments as a measure of sensitivity revealed a significantly lower performancecompared to the benchtop lab equipment (with a ratio among medians of~8 times lower). Overall, our study reveals not only apoor signal-to-noise ratio and poor reproducibility of the data obtained from mobile instruments, but also unfavorable resultswith respect to a reliable identification of substances when they are applied for complex mixtures of volatiles

The Identification of Volatile Organic Compounds from Synthetic Cathinone Derivatives for the Development of Odor Mimic Training Aids

Methylone, Ethylone, Methylenedioxypyrovalerone (MDPV), and α-Pyrrolidinopentiophenone (α-PVP) collectively referred to as bath salts are a new trend of illicit substances known as synthetic cathinones. Designed by chemically modifying the core structure of the compound cathinone, synthetic cathinones became prevalent within the United States around the mid-2000s. As a cheap and less controlled alternative to methylenedioxymethamphetamine (MDMA, ecstasy), it has become heavily abused, prompting emergency scheduling by federal regulators. Although regulations have been placed to halt incoming traffic of these drugs, lack of ground efforts still leave a large percentage of bath salts available. This study is two-fold, as it seeks to develop an extraction method for the development of Volatile Organic Compound profiles associated with various synthetic cathinones; and also determine the odorant used for canine recognition. The initial goal of this dissertation was to develop an extraction method to characterize various cathinone derivatives. The present study concluded that by employing a Polydimethylsiloxane Divinylbenzene (PDMS/DVB) coated fiber along with complimentary soft ionization techniques, the volatile components and all parent drugs could be identified within sixteen synthetic cathinone cases. The second goal of the dissertation was to assess and enhance the detection capabilities of narcotic detection teams. Canine field detection is routinely used to stop the increasing distribution influx of drugs into the United States that go undetected by standard procedures currently employed. Although currently canines can detect a multitude of drugs including heroin, cocaine, MDMA, and methamphetamine; this study revealed that more than ten canine teams (throughout south Florida) were not able to detect the presence of synthetic cathinones with current training material. While concerns have grown concerning the safety and reliability of canines being trained on various illicit substances, this research aimed to develop a safe, efficient, controlled alternative to training any canine for detection in the form of a Controlled Mimic Permeation System (COMPS). Field examination concluded that 3,4-methylenedioxypriophenone was the odorant responsible for the canine recognition of the cathinone derivative odor. Therefore a mimic training aid was developed and deployed within the field to enhance the detection capabilities of various canine teams