The name and the topic of this diploma thesis, Crash simulation vehicle carrying explosives, impacts and solutions, illustrates its main goal. That is, using the TerEx software program, to simulate a crash of vehicle transporting explosives, the impacts resulting from such an incident and, as a secondary goal, to propose solutions of such an incident for the Emergency Service units, with the connection to public safety. After resolving these tasks, it will be possible to answer the research question: What are the dangers of a crash of vehicle transporting explosives? In the beginning, the theoretical part of the thesis focuses on explosives as such. The history of their inventions, usage and development is outlined. In the next chapter, explosives are defined as substances capable of explosive transformation that can release a large amount of energy in a very short time upon a sudden external impulse. For the classification of explosives, it was necessary to characterize types of explosive transformations and general principles that lead to releasing energy. Very important are then the theoretical chapters of this thesis, where are described in detail the effects and phenomena of an explosion, which are necessary for the identification of imminent harmful effects and impacts on the environment in the case of their unwanted initiation. These phenomena include shock wave, thermal and fragmentational effect, recoil, routing, blocking and multiplication of the shock wave. Follows the part, where explosives are classified according to various aspects, from which the most important is the aspect of speed of explosive transformation, which cardinally affects the explosives' properties. This part is followed by a chapter that describes those characteristics. The second half of the theoretical part is concerned with transportation of hazardous materials, especially explosives. Packing and marking requirements, duties of transportation participants and training of the participants are specified there. One must not forget traffic requirements and other necessities connected with transportation, including the need for accompanying documents, transport staff, traffic unit, its construction and equipment and the course of transportation. The last section of the theoretical part of this thesis is dedicated to specific rules of explosives' transportation, which in the Czech Republic are set by the law. It includes mainly a duty to notify the Police Prezidium of the Czech Republic at least 24 hours prior to transportation of explosives and the duty for the vehicle used for transportation to be equipped with a tracking device. In this sense the explosives are the only group of hazardous materials, for which these stricter rules apply. In order to find an answer to the research question, it was necessary in the empirical part of the thesis to gather input data for the TerEx program, where the event was then simulated. These data were collected by an analysis of usage and occurrence of explosives in the area of the South Bohemian region. On the basis of this analysis, a highly brisant explosive NKG-500, which is commonly used for quarrying, special destructive works, underwater tasks and for priming of industrial explosives. It is a place, where the density and complexity of traffic has not yet been tackled accordingly. On the basis of output from thus performed simulation it was possible to assess that in such a densely populated area with the large number of residential and administrative buildings an accident of vehicle transporting explosives poses a considerable threat. In connection with the threats and impacts discovered in relation with such an incident, a unified course of action of the Emergency Service for their solution was designed, whereupon specific actions of its respective units were considered.

Os fungos do gênero Pleurotus são basidiomicetos que se destacam na degradação de substâncias recalcitrantes do ambiente, como por exemplo, os compostos nitroaromáticos, que são poluentes prioritários constituintes do efluente Água Vermelha (AV), uma água residuária gerada em uma das etapas de fabricação do explosivo comercial e militar 2,4,6-trinitrotolueno (TNT). O objetivo deste trabalho foi estudar a capacidade dos fungos Pleurotus ostreatus POS 560 e Pleurotus floridae PSP 1 de degradar os compostos nitroaromáticos presentes na AV. O potencial impactante deste efluente foi avaliado com base em antecedentes bibliográficos relevantes e através de ensaios de caracterização física, química e ecotoxicológica. Para avaliar aspectos relacionados com a ecotoxicologia dos efluentes, bioensaios foram realizados utilizando-se Daphnia magna e apresentaram o Fator de Toxicidade (FT) 16 para o efluente AV na concentração de 1% e FT 4 para o efluente AV 0,5% em 24 horas do ensaio demonstrando a toxicidade e a importância do seu tratamento. Os estudos de tratabilidade fúngica foram baseados na condução de um procedimento com planejamento fatorial de experimentos realizado em meio sólido, onde o crescimento foi medido em função da variação de: espécie do fungo, pH, concentração do efluente e concentração de glicose. Dentre os fatores mais favoráveis estatisticamente, destacaram-se a concentração de efluente (0,5%), a espécie de fungo P. floridae, o pH 6,0 e concentração de 10 g/L de glicose. Estas condições foram consideradas como base experimental para o tratamento fúngico do efluente AV da indústria de explosivos por 15 dias em meio líquido com frascos agitados. Os resultados obtidos indicaram que o P. floridae nas condições de estudo foi capaz de reduzir os parâmetros de DQO, DBO e Fenóis em 55, 51 e 25% respectivamente. Obteve-se também redução da toxicidade em relação ao bioensaio realizado com D. Magna, onde o FTD baixou para 4 em 48 horas. Adicionalmente, P. floridae foi capaz de converter e degradar totalmente ambos os compostos nitroaromáticos identificados (2,4 e 2,6-dinitrotolueno) em tempos da ordem de 2 e 8 dias. O conjunto de resultados obtidos indicam e sugerem que P. floridae possui potencialidade para a remediação de efluentes contendo espécies químicas de relevância ambiental como os compostos nitroaromáticos. / The fungi of the genus Pleurotus are basidiomycetes that stand out in the degradation of recalcitrant environmental substances. For example, nitroaromatic compounds, which are priority pollutants constituents of the effluent Red Water (RW), a wastewater generated in one of the manufacturing steps of commercial and military used explosive 2,4,6-trinitrotoluene (TNT). The objective of this work was to study the ability of fungi Pleurotus ostreatus and Pleurotus floridae POS 560 PSP 1 to degrade nitroaromatic compounds of the RW. The potential impact of this effluent was evaluated based on a relevant bibliographical history and through physical, chemical and ecotoxicological testing assessment. To evaluate aspects related to effluent ecotoxicology, bioassays were conducted using Daphnia magna, showing a toxicity factor (TF) 16 in a 1% RW concentration and FT 4 in a 0.5% RW concentration during a 24 hour testing, proving its toxicity and the importance of its treatment. The fungal treatability studies were based on the conduct of a procedure with factorial planning of experiments performed on solid medium, where growth was measured considering the variation of fungal species, pH, effluent concentration and glucose concentration. Among the most favorable factors, stood out the 0.5% effluent concentration, P. floridae fungus species, pH 6.0, and 10 g/L glucose concentration. These conditions were considered as the experimental basis for the fungal treatment of RW explosives industry effluent for 15 days in liquid medium in shaker flasks. The results indicated that P. floridae was able to reduce the parameters of COD, BOD and phenols at 55, 51 and 25% respectively. It was also obtained less toxicity compared to the bioassay using D. magna, where TF decreased to 4 in 48 hours. Additionally, P. floridae was able to fully convert and degrade both nitroaromatic compounds identified (2,4 and 2,6 dinitrotoluene) between 2 and 8 days interval. The results indicate and suggest that P. floridae have potential for the remediation of wastewater containing chemical species with environmental relevance as nitroaromatic compounds.

Os fungos do gênero Pleurotus são basidiomicetos que se destacam na degradação de substâncias recalcitrantes do ambiente, como por exemplo, os compostos nitroaromáticos, que são poluentes prioritários constituintes do efluente Água Vermelha (AV), uma água residuária gerada em uma das etapas de fabricação do explosivo comercial e militar 2,4,6-trinitrotolueno (TNT). O objetivo deste trabalho foi estudar a capacidade dos fungos Pleurotus ostreatus POS 560 e Pleurotus floridae PSP 1 de degradar os compostos nitroaromáticos presentes na AV. O potencial impactante deste efluente foi avaliado com base em antecedentes bibliográficos relevantes e através de ensaios de caracterização física, química e ecotoxicológica. Para avaliar aspectos relacionados com a ecotoxicologia dos efluentes, bioensaios foram realizados utilizando-se Daphnia magna e apresentaram o Fator de Toxicidade (FT) 16 para o efluente AV na concentração de 1% e FT 4 para o efluente AV 0,5% em 24 horas do ensaio demonstrando a toxicidade e a importância do seu tratamento. Os estudos de tratabilidade fúngica foram baseados na condução de um procedimento com planejamento fatorial de experimentos realizado em meio sólido, onde o crescimento foi medido em função da variação de: espécie do fungo, pH, concentração do efluente e concentração de glicose. Dentre os fatores mais favoráveis estatisticamente, destacaram-se a concentração de efluente (0,5%), a espécie de fungo P. floridae, o pH 6,0 e concentração de 10 g/L de glicose. Estas condições foram consideradas como base experimental para o tratamento fúngico do efluente AV da indústria de explosivos por 15 dias em meio líquido com frascos agitados. Os resultados obtidos indicaram que o P. floridae nas condições de estudo foi capaz de reduzir os parâmetros de DQO, DBO e Fenóis em 55, 51 e 25% respectivamente. Obteve-se também redução da toxicidade em relação ao bioensaio realizado com D. Magna, onde o FTD baixou para 4 em 48 horas. Adicionalmente, P. floridae foi capaz de converter e degradar totalmente ambos os compostos nitroaromáticos identificados (2,4 e 2,6-dinitrotolueno) em tempos da ordem de 2 e 8 dias. O conjunto de resultados obtidos indicam e sugerem que P. floridae possui potencialidade para a remediação de efluentes contendo espécies químicas de relevância ambiental como os compostos nitroaromáticos. / The fungi of the genus Pleurotus are basidiomycetes that stand out in the degradation of recalcitrant environmental substances. For example, nitroaromatic compounds, which are priority pollutants constituents of the effluent Red Water (RW), a wastewater generated in one of the manufacturing steps of commercial and military used explosive 2,4,6-trinitrotoluene (TNT). The objective of this work was to study the ability of fungi Pleurotus ostreatus and Pleurotus floridae POS 560 PSP 1 to degrade nitroaromatic compounds of the RW. The potential impact of this effluent was evaluated based on a relevant bibliographical history and through physical, chemical and ecotoxicological testing assessment. To evaluate aspects related to effluent ecotoxicology, bioassays were conducted using Daphnia magna, showing a toxicity factor (TF) 16 in a 1% RW concentration and FT 4 in a 0.5% RW concentration during a 24 hour testing, proving its toxicity and the importance of its treatment. The fungal treatability studies were based on the conduct of a procedure with factorial planning of experiments performed on solid medium, where growth was measured considering the variation of fungal species, pH, effluent concentration and glucose concentration. Among the most favorable factors, stood out the 0.5% effluent concentration, P. floridae fungus species, pH 6.0, and 10 g/L glucose concentration. These conditions were considered as the experimental basis for the fungal treatment of RW explosives industry effluent for 15 days in liquid medium in shaker flasks. The results indicated that P. floridae was able to reduce the parameters of COD, BOD and phenols at 55, 51 and 25% respectively. It was also obtained less toxicity compared to the bioassay using D. magna, where TF decreased to 4 in 48 hours. Additionally, P. floridae was able to fully convert and degrade both nitroaromatic compounds identified (2,4 and 2,6 dinitrotoluene) between 2 and 8 days interval. The results indicate and suggest that P. floridae have potential for the remediation of wastewater containing chemical species with environmental relevance as nitroaromatic compounds.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-07-20T13:16:55Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) dissertação final - andrevhity - cd - bdtd.pdf: 7048267 bytes, checksum: 0a2bd5941283791f51f6e1671f68b201 (MD5) / Made available in DSpace on 2016-07-20T13:16:55Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) dissertação final - andrevhity - cd - bdtd.pdf: 7048267 bytes, checksum: 0a2bd5941283791f51f6e1671f68b201 (MD5) Previous issue date: 2015-12-09 / CAPEs / As operações unitárias em pedreiras tais como: desmonte, perfuração e britagem são imprescindíveis, e são etapas que exige controle na produção e que demandam quantidade razoável de elementos essenciais para a produção e que desgastam rapidamente, por essa razão estes procedimentos necessitam de análise e acompanhamento contínuo. Uma maneira de otimizar a produção em pedreiras e garantir com isso melhor controle na produção é realizando uma análise estrutural mais detalhada do maciço rochoso e determinando previamente as suas descontinuidades, seu estágio de deformação e o seu comportamento mediante a aplicação de explosivos. Um modelo matemático pode ser aplicado para simular a fragmentação do desmonte de rochas e posteriormente adequar a granulometria proveniente da mina (ROM – Run of Mine) obtendo uma melhoria no desempenho do desmonte e otimizando a britagem com o aumento da eficiência/produtividade. O modelo consiste nas equações propostas de Kuznetsov (1973), Cunningham (1983), Lilly (1986) e Tidman e Rosin-Rammler (1933), e são utilizadas para maior interação entre explosivo e rocha. / The unit operations in quarries such as blasting, drilling and crushing are essential, and are steps that require control in production and demand reasonable amount of essential elements for the production and wear out quickly, therefore these procedures require analysis and monitoring continuous. One way to optimize the production in quarries and thereby ensure better control of production, making it a more detailed structural analysis of the rock mass and previously determining the discontinuities, its deformation stage and its behavior upon the application of explosives. A mathematical model can be applied to simulate the rock blasting fragmentation and then tailor the grain size from the mine (ROM - Run of Mine) obtaining an improvement in the performance of dismantling and optimizing crushing with increasing efficiency and productivity. The model consists of the equations proposed Kuznetsov (1973), Cunningham (1983), Lilly (1986) and Rosin - Rammler and Tidman (1933), and are used for higher interaction between explosive and rock.

The Master´s thesis concerns with the choice of sources of risks and their evaluation with storage of explosives. It is divided into four parts. The first two parts are research ones and they deal with accesses to the choice of sources of risks with storage of explosives and statutory requirements for explosives, their storage, manipulation and transport and then with the buildings, which the explosives are stored in. In the next part the accesses to selection and evaluation of sources of risks in real storage units are chosen and compared. In the final part there is the chosen methodology used in case studies.

In recent years, there has been a dramatic increase in the use of improvised explosive devices (IEDs) due to ease of synthesis and improved controls placed on commercial/military explosives. Commonly used materials for IED preparations include fertilizers and industrial chemicals containing oxidizers such as ClO3-, ClO4-, and NO3-, as well as other less stable compounds, such as peroxides. Due to these materials having a wide range of volatility, polarity, and composition, detection can be challenging, increasing the amount of time before any analytical information on the identity of the explosive can be determined. Therefore, this research project developed two analytical methods to aid in the rapid detection of multiple explosive compounds. The use of microfluidic paper-based analytical devices (µPADs) allows for the development of inexpensive paper devices utilizing colorimetric reactions, which can perform five or more simultaneous analyses in approximately five minutes. Two devices were developed: one for the detection of inorganic explosives including ClO3-, ClO4-, NH4+, NO3-, and NO2-, and the second device detects high/organic explosives including RDX, TNT, urea nitrate, and peroxides. Limits of detection ranged from 0.4 µg – 20 µg of explosive residue with an analysis time of less than five minutes. Development of a confirmatory method utilizing infusion electrochemical detection-electrospray ionization-time-of-flight mass spectrometry (EC-ESI-TOF MS) and 18-crown-6 ethers to produce guest/host complexes with inorganic ions has also been completed. Utilizing this method the inorganic ions present in many IEDs can be successfully detected as ion pairs, while still allowing for the detection of other high explosives1. Placing an electrochemical detector before the mass spectrometer permits the detection of hydrogen peroxide, an analyte normally difficult to detect through mass spectrometry. Limits of detection ranged from 0.06 ppm - 2 ppm with an analysis time of less than two minutes. The development of these presumptive and confirmatory analytical methods permits the detection of a wide range of components present in IEDs. These methods decrease the amount of time required to relay information on the type of explosives present by simplifying the analysis process in the field and in a laboratory.

The genotoxicity of energetic compounds (i.e., explosives) that are known to be present in contaminated soils at military training sites has not been extensively investigated. Thus, the Salmonella mutagenicity and Muta(TM)Mouse assays were employed as in vitro assays to examine the mutagenic activity of twelve explosive compounds, as well as three soil samples from Canadian Forces Base Petawawa. Salmonella analyses employed strains TA98 (frameshift mutations) and TA100 (base-pair substitution mutations), as well as the metabolically-enhanced YG1041 (TA98 background) and YG1042 (TA100 background), with and without exogenous metabolic activation (S9). For Salmonella analyses, the results indicate that ten of the explosive compounds were mutagenic, and consistently elicited direct-acting, base-pair substitution activity. All three soil samples were also observed to be mutagenic, eliciting direct-acting, frameshift activity. Mutagenic potencies were significantly higher on the metabolically-enhanced strains for all compounds and soil samples. For Muta(TM)Mouse analyses on FE1 cells, the results indicate that the majority of explosive compounds did not exhibit mutagenic activity. All three soil samples elicited significant positive responses (PET 1 and PET 3 without S9, and PET 2 with S9), and although there is some evidence of a concentration-related trend, the responses were weak. Correspondence of the mutagenic activity observed with the two assay systems, for both the explosive compounds and soil samples, was negligible. The differential response is likely due to differences in metabolic capacity between the two assay systems. Furthermore, it is likely that there are unidentified compounds present in these soil samples that are, at least in part, responsible for the observed mutagenic activity. Additional testing of other explosive compounds, as well as soil samples from other military training sites, using a variety of in vitro and in vivo assays, is warranted in order to reliably estimate mutagenic hazard and subsequently assess risk to human health.

TNT (2,4,6-trinitrotoluene) is a persistent contaminant at many military installations and poses a threat to aquatic ecosystems. Data from environmental fate and toxicity studies with TNT revealed that sediment toxicity test procedures required modification to accurately assess sediment TNT toxicity. Key modifications included aging TNT-spiked sediments 8-14 d, basing lethal dose on measured sediment concentrations of the molar sum of TNT and its main nitroaromatic (NA) transformation products (SNA), basing sublethal dose on average sediment SNA concentrations obtained from integration of sediment SNA transformation models, avoiding overlying water exchanges, and minimizing toxicity test durations. Solid phase microextraction fibers (SPMEs) were investigated as a biomimetic chemical measure of toxicity and bioavailability. Both organism and SPME concentrations provided measures of lethal dose independent of exposure scenario (TNT-spiked sediment or TNT-spiked water) for Tubifex tubifex. Among all benthic organisms tested (Chironomus tentans, Ceriodaphnia dubia, T. tubifex) and matrixes, median lethal dose (LC50) estimates based on SPME and organism concentrations ranged from 12.6 to 55.3 mmol SNA/ml polyacrylate and 83.4 to 172.3 nmol SNA/g tissue, ww, respectively. For Tubifex, LC50s (95% CI) based on SNA concentrations in sediment and SPMEs were 223 (209-238) nmol SNA/g, dw and 27.8 (26.0-29.8) mmol SNA/ml, respectively. Reproductive effects occurred at slightly lower exposures. Median effective dose (EC50) estimates (95% CI) for Tubifex cocoon production, based on sediment and SPME concentrations, were 118 (114-122) nmol SNA/g, dw and 21.8 (21.2-22.4) mmol SNA/ml, respectively. Bioconcentration experiments with Tubifex revealed that compound hydrophobicity predicted the toxicokinetics and bioconcentration of these compounds from water, however, there was a large discrepancy between the toxicokinetics of absorbed versus metabolically-generated aminodinitrotoluenes. A large portion of bioconcentrated, radiolabeled TNT transformation products could not be identified. In addition to their ability to provide matrix-independent measures of dose, SPME concentrations were more accurate indicators of bioavailable NAs than were sediment concentrations.

The Master´s thesis concerns with the choice of sources of risks and their evaluation with storage of explosives. It is divided into four parts. The first two parts are research ones and they deal with accesses to the choice of sources of risks with storage of explosives and statutory requirements for explosives, their storage, manipulation and transport and then with the buildings, which the explosives are stored in. In the next part the accesses to selection and evaluation of sources of risks in real storage units are chosen and compared. In the final part there is the chosen methodology used in case studies.

<div>Polymer bonded explosives (PBXs) consist of energetic material (EM) crystals embedded inside a polymeric binder. These are highly heterogeneous structures designed to explode under controlled conditions. However, accidental ignition of PBXs leading to deflagration, or even detonation, may take place due to non-shock stimulus such as low velocity impacts and vibration. Thus, assessing the safety of PBXs under non-shock stimulus is very important.</div><div><br></div><div>The ignition in PBXs depends on several microstructural features which include mechanical properties of EM particles and polymeric binder, as well as the adhesive properties of interface between EM particles and binder. It is also sensitive to initial defects in EM particles including cracks or voids. EM particle size distribution, distance between particles and their relative location are also shown to be affecting the ignition behavior of PBXs. This study focuses on PBX composition consisting of HMX as EM and Sylgard or HTPB as polymeric binder. Among several mechanisms of hot-spot formation, this study focuses on frictional heating at cracks or debonded surfaces.</div><div><br></div><div>Finite element simulations are performed on a domain containing a single EM particle embedded inside polymer binder under compressive and tensile loading at 10 m/s. The effect of the binder properties and the particle surface properties, on damage evolution and corresponding temperature rise due to frictional heat generation, is investigated. Two binders, Sylgard and HTPB, while two surface qualities for HMX particle, low and high, are compared. The adhesion strength of the particle-polymer interface is varied and damage evolution is qualitatively compared with experimental results to estimate interfacial energy release rate for HMX-Sylgard and HMX-HTPB interfaces. Simulations of two HMX particles inside Sylgard binder, subjected to vibration loading, are performed to analyze the effect of particle-particle distance and relative location of particles on the damage evolution and frictional heating in the particles.</div><div><br></div><div>The results of impact simulations show that the low surface quality HMX particle inside HTPB is likely to propagate cracks as compared to high surface quality particle. The HMX particle inside Sylgard shows crack propagation irrespective of particle surface quality. The impact simulations with the lower stiffness binder do not show a significant increase in temperature after impact. A polymer with higher stiffness induces more particle damage under impact contributing to a larger temperature rise. Furthermore, high quality surface and higher adhesion strength induces larger stresses and increase the temperature rise. The vibration simulations show that a small particle is less likely to damage when it is shielded by a large particle irrespective of its distance, within 40-200$\mu$m, from the large particle. However, the small particle is likely to damage when it is in parallel to the large particle with respect to loading. The temperature rise in the small particle is higher than the larger particle only in case of parallel configuration. The adhesion between the particles and the polymer has a direct effect on the formation of hot-spots due to friction and through local increase of compressive stresses that may cause a surge in heat generation.</div><div><br></div><div>The energetic materials often show anisotropy in elastic and crystalline properties. Fracture in HMX along the preferred cleavage plane is considered. Anisotropy in the elastic constants is also incorporated in the fracture model. The dependence of pressure on temperature is considered using Mie-Gruneisen equation of state which is shown to be important for damage evolution in HMX at impact velocity of 100 m/s.</div>