Chemical weapons are justly considered by the human society as the oldest type of weapons of mass destruction. Unfortunately the same human society has continued to apply and further develop the ancient principles of use of combat chemical substances. The current world, despite all the humanistic efforts to terminate the history of this type of weapons, continues to be physically threatened by their abuse. I must say that studies of the history of chemical weapons are very demanding and comprehensive. The whole process of historic development of these combat means is interconnected by multiple relations and circumstances and unfortunately has been the source of a lot of inconceivable human suffering. That is why I decided to take the courage and thread the path leading to a look back at the past, for I believe that such a retrospective not only reveals stories that are already buried in the distant past and are not needed any more, but also leads to understanding the present, learning a lesson from past mistakes and acquiring a humble approach to life. On the basis of studies of the many available resources I tried to submit in my diploma thesis a complex summary of current as well as historic knowledge of combat chemical substances, their research and testing on humans. While the issue of chemical weapons and wars as such is paid a lot of attention, the issue of chemical weapon testing on people has still been a marginal theme. The abovementioned facts inspired this thesis and I believe that my diploma theses might be beneficial for its readers. My greatest desire and aim was to present to the readers the historic path of application and the related research and testing of chemical weapons. I hope I have processed the theme to be better understandable to the reader, both professional and lay. I tried to proceed systematically and make my thesis interesting to enrich not only me but also its readers.

Comme l’a montré l’utilisation de sarin en Syrie en 2013, les agents chimiques de guerre restent une menace. L’exposition de populations est une situation d’urgence qui nécessite des moyens rapides et efficaces. La décontamination et le soin des personnes exposées restent une priorité. Les cheveux représentent une matrice couramment utilisée dans le domaine médico-légal. Dans ce travail, notre intérêt se porte sur la capacité du cheveu à capter et libérer des composés dans l’air, notamment l’ypérite, ainsi que sur l’efficacité de décontamination de cette matrice. Pour ce travail, nous avons utilisé deux composés aux propriétés physiques/chimiques proches de celles de l’ypérite : le salicylate de méthyle et le 2-chloroéthyl éthyl sulfure. Les deux similis ont été retenus par le cheveu avec une plus grande affinité pour le salicylate de méthyle. Nous avons observé une corrélation entre l’intensité d’exposition (influence de la dose et du temps) et la teneur en contaminants retrouvés sur les cheveux. Ces résultats montrent qu’il est possible d’utiliser le cheveu pour détecter une exposition individuelle. Après exposition, la teneur dans des cheveux laissés à désorber a été mesurée avec le salicylate de méthyle. Les résultats obtenus ont montré que les cheveux contaminés sont susceptibles de libérer les toxiques. Cela peut poser un problème sanitaire, qui implique donc que la décontamination des cheveux soit étudiée. Les protocoles de décontamination testés montrent une efficacité partielle (élimination de 40 à 80%). Ces résultats impliquent la nécessité d’optimiser les procédures actuelles ou de définir de nouveaux outils pour la décontamination du cheveu après exposition. / As shown by sarin use in Syria (2013), chemical warfare agents remain a threat. Chemical exposure of populations is an emergency situation, where quick and efficient means are mandatory. Decontamination and care of the victims are a priority. Scalp hair is routinely used as a biological matrix in forensic sciences. In this thesis work, interest focuses on hair capacity to trap and release compounds from atmosphere, especially sulphur mustard, as well as decontamination of this matrix. For this work, two molecules with similar physical/chemical properties to sulphur mustard were used: methyl salicylate and 2-chloroethyl ethyl sulphide. Both simulants were trapped by scalp hair, with higher affinity towards methyl salicylate. We observed a correlation between exposure intensity (influence from dose and time) and simulant content recovered from hair analysis. Results suggest that hair can be used to assess individual contamination. After exposure, evolution of methyl salicylate hair content has been measured. Results pointed out that contaminated hair can thereafter release the simulants. This can lead to health issue, highlighting the fact that hair decontamination must be investigated. Tested decontamination protocols showed a partial efficacy (40-80% removal). Those results evidenced the need to optimise current procedures or define new tools for hair decontamination after chemical exposure.

The deposition of Imam Muhammad al-Badr in September 1962 was the culmination of a Yemeni nationalist movement that began in the 1940s with numerous failed attempts to overthrow the traditional religious legal order. Prior to 1962, both the USSR and Egypt had been cultivating alliances with al-Badr in an effort to secure their strategic interests in South Arabia. In the days following the 1962 coup d'état, Abdullah Sallal and his cohort of Yemeni officers established a republic and concealed the fate of al-Badr who had survived an assault on his Sana'a palace and whose supporters had already begun organizing a tribal coalition against the republic. A desperate appeal by Yemeni republicans brought the first Egyptian troops to Yemen. Saudi Arabia, pressured by Egyptian troops, border tribal considerations and earlier treaties with the Yemeni Imamate, supported the Imam's royalist opposition. The battleground between Egyptian president Gamal Abdel Nasser and al-Badr was transformed into an arena for international conflict and diplomacy. The UN mission to Yemen, while portrayed as a symbol of failed and underfunded global peacekeeping at the time, was in fact instrumental in establishing the basis for a diplomatic resolution to the conflict. Bruce Condé, an American philatelist, brought global attention to the royalist-republican struggle to control the Yemeni postal system. The last remnants of the British Middle East Empire fought with Nasser to maintain a mutually declining level of influence in the region. Israeli intelligence and air force aided royalist forces and served witness to the Egyptian use of chemical weapons, a factor that would impact decision-making prior to the 1967 War. Despite concurrent Cold War tensions, Americans and Soviets appeared on the same side of the Yemeni conflict and acted mutually to confine Nasser to the borders of South Arabia. This internationalized conflict was a pivotal event in Middle East history as it oversaw the formation of a modern Yemeni state, the fall of Egyptian and British regional influence, another Arab-Israeli war, Saudi dominance of the Arabian Peninsula, and shifting power alliances in the Middle East.

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Chemical warfare agents are a toxic class of compounds that are incredibly harmful to human health. Methods of detoxification and decontamination currently exist, however they all suffer from problems that involve logistical transport or involve technologies that directly address liquid threats instead of vapors. One promising method of detoxification involves the oxidation of these compounds into less-harmful species. The relatively large chemical size and complexity of modern-day chemical warfare agents, however, precludes a straightforward analysis of the chemical transformations that take place on novel decontaminating materials. Additionally, a fundamental understanding of reaction mechanisms that occur on novel material surfaces is required before improved materials can be developed. To this end, the oxidation of three simpler, smaller organic molecules were studied over a variety of materials in order to build up a chemical understanding of the systems under study. The photoepoxidation of propene into propene oxide was observed to readily occur over an in-house developed dual titania-silica catalyst created by atomic layer deposition. The subsequent photoinduced degradation of produced propene oxide was observed to occur over the novel catalyst. Next, the oxidation of CO was studied over a Pt/TiO2 catalyst while in the presence of humidity. The addition of water was shown to enable an alternative, low energy pathway that closely followed the water gas shift, but ended upon the production of stable surface-bound formates. Gaseous oxygen was found to subsequently oxidize these surface formates into the full oxidation product, CO2. Next, the oxidation of methanol was studied over the same Pt/TiO2 catalyst. It was discovered that the water produced when methanol initially adsorbs to the catalyst surface is responsible for unlocking the oxidative capacity of the material. Finally, a custom packedbed reactor was designed and built that enabled unique experimental capabilities not yet available in commercial systems, and will be used in the future to directly test the oxidative capabilities of novel materials for chemical warfare agent destruction. / Doctor of Philosophy / The chemical interactions and reactions that occur between gases and surfaces are incredibly important for a multitude of technologies employed by governments, militaries, and citizens alike. The precise methods in which these gases interact with materials of interest determine whether said material can be used in a catalytic fashion. Much like how an automobile catalytic converter does not have to be replaced each time the vehicle is started; a catalyst is able to be used repeatedly without loss of function. Catalysts in general are unique in that they function to create or allow for chemical reactions to proceed through alternative, lower energy pathways that are more likely to occur under milder environmental conditions. In order to understand the chemical reactions that occur on a catalyst, a combination of specialized spectroscopic methods was used that allowed for tracking the precise chemical bonds that were formed or broken during reaction. A few different model chemical reactions are explored in this work, ranging from the conversion of carbon monoxide into CO2, and the oxidation of methanol, a small alcohol commonly found in fuel cells. The experimental techniques employed herein allowed for precise chemical mechanisms to be tracked, and the information gained will certainly be useful for the design of next-generation materials by future research.

This dissertation argues that the origins of civil defense are to be found in pre-World War II Britain and that a driving force of this early civil defense scheme was fear of poison gas. Later iterations of civil defense, such as the Cold War system in America, built on already existing regimes that had proven their worth during WWII. This dissertation demonstrates not only that WWII civil defense served as a blueprint for later civil defense schemes, but also that poison gas anxiety served as a particular tool for the implementation and success of civil defense. The dissertation is organized thematically, exploring the role of civilians and volunteers in the civil defense scheme, as well as demonstrating the vital importance of physical manifestations of civil defense, such as gas masks and air raid shelters, in ensuring the success of the scheme. By the start of World War II, many civilians had already been training in civil defense procedures for several years, learning how to put out fires, recognize bombs, warn against gas, decontaminate buildings, rescue survivors, and perform first aid. The British government had come to the conclusion, long before the threat became realized, that the civilian population was a likely target for air attacks and that measures were required to protect them. World War I (WWI) saw the first aerial attacks targeted specifically at civilians, suggesting a future where such attacks would occur more frequently and deliberately. Poison gas, used in WWI, seemed a particularly horrifying threat that presented significant problems. Civil defense was born out of this need to protect the civil population from attack by bombs or poison gas. For the next five years of war civil defense worked to maintain British morale and to protect civilian lives. This was the first real scheme of civil defense, instituted by the British government specifically for the protection of its civilian population.

In 1981 the apartheid military initiated a chemical and biological warfare (CBW) programme (code-named Project Coast). The programme, terminated in 1993, was aimed at developing novel irritating and incapacitating agents for internal and external use, covert assassination weapons for use against apartheid opponents, and defensive equipment for use by South African Defence Force (SADF) troops in Angola. The CBW programme was driven by a single individual, Dr Wouter Basson, who reported to a military management committee (the Co-ordinating Management Committee) which comprised a select group of high ranking officers. Practical and financial oversight of the programme was weak which allowed both for the abuse of programme funds and for senior military officers to deny knowledge of aspects of the programme. The biological component of Project Coast was conducted in violation of the commitments of the South African government to the Biological and Toxins Weapons Convention (BTWC). While the state’s commitment to the BTWC was one of the factors considered when initiating the programme, it was not a sufficient constraint to prevent the development of the biological weapons programme, but rather influenced its structure such that the programme could avoid national and international detection. Despite efforts to conceal the military front companies where the chemical and biological warfare (CBW) research and development was undertaken, evidence presented in this thesis shows that the United States had sufficient information about the programme to have been aware of its existence. Yet, it was only in 1993, on the eve of the democratic election in South Africa, that any attempt was made by the US administration to pressure the government to terminate the programme. This thesis considers the factors which influenced the decision to develop Project Coast; the structure and nature of the programme; the motivations of scientists to become involved in the programme and remain involved; the use of chemical and biological agents against opponents of the state, and the factors which influenced the termination of the programme on the eve of the first democratic elections in 1994. It also considers the nature and exent of international support, both tacit and overt, for the programme and argues that the failure of Western nations to call for the termination of the programme before the early 1990s was a function of political expediency and indicates a significant weakness in the ability of international agreements to constrain the development of such programmes.

This thesis is dedicated to the topic of the nerve agents with special emphasis on antidotal treatment utilizing application of the auto-injectors. Two methods were used ? literature research and quantitative research. Since this topic covers plenty of information as regards chemical warfare agents and in particular nerve agents these issues were addressed in the theoretical part of the thesis. In the chapter on current status based on literature resources a summary of evolution of the auto-injector is presented; from firsts notes until the situation today. Practical part of the thesis is concentrated on University of Southern Bohemia in ČeskéBudějovice, Faculty of Health and Social Studies students' knowledge in the area of nerve agents. The results of the research were acquired by the method of quantitative research ? questionnaires with 18 questions. With respect to each of the questions a selection of the 2 to 7 answers was offered to the students, whereas in every case only 1 answer was correct. The results were analyzed both with reference to each of the questions and with reference to each of the students. By this method it has been discovered that the respondents have a good knowledge in the area of nerve agents. Furthermore, the practical part of the thesis included an experiment concerning speed with which the respondents were able to apply antidotum with a training auto-injector by themselves with no prior instructions in comparison to how quickly they were able to do the same after being instructed. By this method were tested the quality of the instructions provided to the auto-injectors and its ergonomic qualities (intuitiveness of its application). Recorded times were statistically analyzed and the results, although materially different, were assessed as satisfactory.

Les menaces constantes de terrorisme nécessitent le développement d'instruments permettant de détecter efficacement des agents chimiques de guerre. L'objectif de ce travail était la réalisation d'un spectromètre de masse devant effectuer des analyses de type : LC/ESI-MS et GC/EI-MS, sur des échantillons sous tous les états : solide, liquide, gazeux et qui soit rapide. Une première partie de ce travail a consisté à étudier le fonctionnement du spectromètre de masse LTQ Velos, puis de faire une étude des modes d'injection axiale et radiale des ions par simulation à l'aide du logiciel SIMION. L'étude de l'injection radiale, nous a démontré la faisabilité de ce mode d'injection dans un piège linéaire. Ainsi, lors d'applications spécifiques dans lesquelles l'axe central doit être libéré, le mode d'activation par IRMPD peut être envisagé. Une deuxième partie de ce travail a consisté à modifier la source CI du module ETD en source EI. Trois sources EI (la Thermo, la NERMAG et la source trappe) ont été étudiées afin de déterminer celle qui serait la plus efficace et offrirait un bon compromis en terme de coût et de temps de développement. La source Thermo a été retenue et a ensuite été implémentée dans le module ETD du LTQ Velos qui a été couplé à un GC rapide pour effectuer des tests préliminaires de faisabilité de ce couplage. Ainsi, ces tests ont permis de caractériser le GC/EI-LTQ Velos comme étant capable d'effectuer des analyses en GC/MS rapide (de l'ordre de ? 5 min). Ce GC/MS rapide a ensuite été intégré dans le démonstrateur ainsi que le collecteur aérien chimique et le détecteur TIC et POC. Des essais préliminaires concluants ont été réalisés sur ce démonstrateur. / Constant threats of terrorism require the development of tools to effectively detect chemical warfare agents. The aim of this work was to develop a mass spectrometer capable of performing rapid LC/ESI-MS and GC/EI-MS analyses on samples from all states: solid, liquid and gaseous. The first part of this work was to study the principle of operation of the linear ion trap LTQ Velos, then to study axial and radial ion injection in the linear ion trap by means of computer simulation using SIMION. The feasibility of performing radial ion injection has been demonstrated, thus in specific applications in which the central axis needs to be released, the IRMPD activation mode may be considered. A second part of this work was to adapt the existing ETD module to accommodate EI. Three EI sources (the Thermo, the NERMAG and the trap source) were studied to determine which one would be the most effective and offer a good compromise in terms of cost and development time. The Thermo source has been selected and modified to conduct EI within the ETD module of the LTQ Velos which was interfaced to a fast GC (Heracles II). Preliminary tests characterized the dual pressure ion trap as a mass analyzer for performing rapid GC/MS analyses. The results showed that the GC-LIT with its high scanning speed was able to provide sufficient scans across chromatographic peaks when working in both the conventional and the fast GC modes, and further offered good EI spectral information. This GC/MS was then implemented into the demonstrator as well as the air sampler and the TIC/POC detector. Conclusive preliminary tests have been made on this demonstrator.

Les agents chimiques de guerre et leurs dérivés pesticides sont des molécules toxiques qui provoquent une incapacité temporaire ou des dommages permanents allant jusqu’à la mort de l’individu. Une des voies majeures de la contamination est la pénétration cutanée. La protection de la peau semble donc importante pour prévenir de ces dangers. Cette thèse concerne l’élaboration de nouveaux topiques protecteurs cutanés contenant des polymères HASE fluorés greffés avec des nanoparticules de silice, cérine ou titane. Dans un premier temps les actifs ont été synthétisés en grosse quantité et leurs propriétés de mouillabilité améliorées. Les tests toxicologiques ont montré que les actifs n’étaient pas irritants pour la peau et non toxiques pour l’environnement. La formulation de ces polymères a permis le développement de deux nouvelles crèmes barrières contre la pénétration du paraoxon dont l’efficacité est dépendante de la présence des nanoparticules. Le greffage des nanoparticules à un polymère HASE fluoré et leur formulation a donc permis le développement de nouveaux topiques efficaces. L’évaluation de l’efficacité a été réalisée sur membranes artificielles et confirmée sur explants de peaux humaines. Enfin, le peu de disponibilité des explants de peaux humaines a motivé le développement d’un modèle d’efficacité utilisant des épidermes humains reconstruits. / Chemical warfare agents and pesticides are toxic molecules causing temporary incapacitation or permanent harms leading to the death of people. One of the major routes of contamination is the percutaneous penetration. Skin protection is important to prevent these dangers. The aim of this thesis is to develop new active topical skin protectants based on nanoparticular networks containing fluorinated HASE polymers grafting with silica, cerium or titanium nanoparticles. First, polymers were synthesized in larger quantity and their wettability properties improved. Toxicological studies have showed that these compounds are non-irritant and non-toxic for the environment. The formulation of these polymers has led to the elaboration of two new barrier creams against paraoxon penetration whose efficiency is dependent on the presence of nanoparticles. Therefore, the grafting of nanoparticles to fluorinated HASE polymer and their formulation have enabled the development of new active topical skin protectant. Efficiency evaluation was done using artificial membranes and was confirmed on ex vivo human skin. The limited availability of human skin explants has motivated the development of a new efficiency model using reconstructed human epidermis.