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Comprehensive forensic analyses of debris from the fatal explosion of a "cold fusion" electrochemical cell.

Selected components of explosion debris from the SRI International incident of January 2, 1992 were subjected to forensic analyses to elucidate potential causes of, or contributing factors to, the explosion. Interrogation of the debris encompassed nuclear, chemical, physical, and materials investigations. Nuclear studies for the determination of tritium and neutron-activation products in stainless steel and brass were conducted. No evidence for signature species indicative of orthodox nuclear events was detected. The inorganic and particulate analyses were likewise negative with respect to residues of unexpected chemical species. Such target compounds included conventional explosives, accelerants, propellants, or any exceptional industrial chemicals. Materials characterization identified the type of stainless steel used in the manufacture of the electrolytic cell as one relatively high in Mo concentration, probably type 316. Metallurgical analyses of the cell vessel wall and its detached base provided no evidence of corrosion or hydrogen embrittlement, leaving only ductile failure of the weld as contributing to the incident. The weld was found to have missed the center-line of the step joint, and the average penetration of the weld was measured to be 54%. The GC-MS analyses of trace organic components in the explosion debris provided a most interesting result. Although no evidence of organic explosives, oxidizers, or other unusual compounds was detected, the presence of an organic oil in the interior of the electrochemical cell was established. It is likely that the source of this oil was lubricating fluid from machining the metal cell components.(ABSTRACT TRUNCATED AT 250 WORDS)

Accidents, Occupational↗

Lens opacifications detected by slitlamp biomicroscopy are associated with exposure to organic nitrate explosives.

CONTEXT: Unusual cataracts (flecks) have been reported to occur at very low levels of trinitrotoluene exposure, but prevalence estimates vary widely. Cataracts have not been reported among workers in the United States exposed to organic nitrate explosives. OBJECTIVES: To determine the prevalence of unusual cataracts in a population of workers in the United States exposed to organic nitrate explosives, to determine whether associations exist with reported cataract risk factors, and to determine if other eye effects (eg, retinal hemorrhage) are associated with exposure. DESIGN: Cohort prevalence study. SETTING: A university-based ophthalmologic clinic. SUBJECTS: Sixty-one workers from an explosives plant comprised the exposed group. The comparison group consisted of 56 workers using chemicals other than organic nitrate explosives. OUTCOME MEASURES: The primary outcome measure was opacifications (flecks) of the crystalline lens, graded clinically on a scale of 0 to 4 +. Additional measures included visual acuity, applanation tonometry, and clinical evaluation using standard examination techniques. RESULTS: Sixty-three percent of the workers had anterior cortical lens opacifications in a pattern of peripheral flecks. Exposed subjects were 18 times more likely to exhibit changes than those not exposed, a statistically significant association (95% confidence interval [CI], 5.0-65.0; P<.001). A statistically significant association with the duration of exposure was also found. CONCLUSIONS: Asymptomatic, low-grade cataracts (flecks) were identified in 63% of the workers exposed to pentolite. No other eye effects were found to be associated with exposure. Cataracts were not associated with other known risk factors, but were associated with the duration of exposure. Biomicroscopy is widely available and useful for detecting changes in the asymptomatic stages.

Adult↗

In-line coupling capillary electrochromatography with amperometric detection for analysis of explosive compounds.

Amperometric detection at a bare gold electrode has been in-line coupled with capillary electrochromatography (CEC) for analysis of nitroaromatic and nitroamine explosives in contaminated soils and ground water. The CEC column packed with 3 microm C18 particles performed best using a mobile phase containing 70-80% methanol, 30 or 20% water, 5 mM sodium dodecyl sulfate (SDS) and 10mM 2-(N-morpholino)ethanesulfonic acid (MES). In contrast, the separation column packed with 1.5 km C18 particles exhibited the best separation when only 30% methanol was added to a mobile phase containing 70% water, 7 mM SDS, and 10 mM MES. The detection, based on electrochemical reduction of the explosives (-0.7 or -1 V vs. Ag/AgCl, depending upon the level of methanol in the mobile phase), was compatible with such mobile phases. The detection limits for 13 explosives ranged from 100 to 200 ppb, i.e., about twofold better than those obtained with electrokinetic chromatography (EKC)/amperometric detection. From an operational viewpoint, exhaustive column conditioning was a prerequisite and care should be taken to prevent bubble formation and current breakdown during the course of separation. The CEC column equipped with amperometric detection successfully measured explosives in ground water and extracts prepared from contaminated soils and the results obtained agreed well with those of the U.S. Environmental protection Agency (EPA) method.

Azocines↗

Biological remediation of explosives and related nitroaromatic compounds.

Nitroaromatics form an important group of recalcitrant xenobiotics. Only few aromatic compounds, bearing one nitro group as a substituent of the aromatic ring, are produced as secondary metabolites by microorganisms. The majority of nitroaromatic compounds in the biosphere are industrial chemicals such as explosives, dyes, polyurethane foams, herbicides, insecticides and solvents. These compounds are generally recalcitrant to biological treatment and remain in the biosphere, where they constitute a source of pollution due to both toxic and mutagenic effects on humans, fish, algae and microorganisms. However, relatively few microorganisms have been described as being able to use nitroaromatic compounds as nitrogen and/or carbon and energy source. The best-known nitroaromatic compound is the explosive TNT (2,4,6-trinitrotoluene). This article reviews the bioremediation strategies for TNT-contaminated soil and water. It comes to the following conclusion: The optimal remediation strategy for nitroaromatic compounds depends on many site-specific factors. Composting and the use of reactor systems lend themselves to treating soils contaminated with high levels of explosives (e.g. at former ammunition production facilities, where areas with a high contamination level are common). Compared to composting systems, bioreactors have the major advantage of a short treatment time, but the disadvantage of being more labour intensive and more expensive. Studies indicate that biological treatment systems, which are based on the activity of the fungus Phanerochaete chrysosporium or on Pseudomonas sp. ST53, might be used as effective methods for the remediation of highly contaminated soil and water. Phytoremediation, although not widely used now, has the potential to become an important strategy for the remediation of soil and water contaminated with explosives. It is best suited where contaminant levels are low (e.g. at military sites where pollution is rather diffuse) and where larger contaminated surfaces or volumes have to be treated. In addition, phytoremediation can be used as a polishing method after other remediation treatments, such as composting or bioslurry, have taken place. This in-situ treatment method has the advantage of lower treatment costs, but has the disadvantage of a considerable longer treatment time. In order to improve the cost-efficiency, phytoremediation of nitroaromatics (and other organic xenobiotics) could be combined with bio-energy production. This requires, however, detailed knowledge on the fate of the contaminants in the plants as well as the development of efficient treatment methods for the contaminated biomass that minimise the spreading of the contaminants into the environment during post harvest treatment.

Basidiomycota↗

Laboratory and field experiments used to identify Canis lupus var. familiaris active odor signature chemicals from drugs, explosives, and humans.

This paper describes the use of headspace solid-phase microextraction (SPME) combined with gas chromatography to identify the signature odors that law enforcement-certified detector dogs alert to when searching for drugs, explosives, and humans. Background information is provided on the many types of detector dog available and specific samples highlighted in this paper are the drugs cocaine and 3,4-methylenedioxy- N-methylamphetamine (MDMA or Ecstasy), the explosives TNT and C4, and human remains. Studies include the analysis and identification of the headspace "fingerprint" of a variety of samples, followed by completion of double-blind dog trials of the individual components in an attempt to isolate and understand the target compounds that dogs alert to. SPME-GC/MS has been demonstrated to have a unique capability for the extraction of volatiles from the headspace of forensic specimens including drugs and explosives and shows great potential to aid in the investigation and understanding of the complicated process of canine odor detection. Major variables evaluated for the headspace SPME included fiber chemistry and a variety of sampling times ranging from several hours to several seconds and the resultant effect on ratios of isolated volatile components. For the drug odor studies, the CW/DVB and PDMS SPME fibers proved to be the optimal fiber types. For explosives, the results demonstrated that the best fibers in field and laboratory applications were PDMS and CW/DVB, respectively. Gas chromatography with electron capture detector (GC/ECD) and mass spectrometry (GC/MS) was better for analysis of nitromethane and TNT odors, and C-4 odors, respectively. Field studies with detector dogs have demonstrated possible candidates for new pseudo scents as well as the potential use of controlled permeation devices as non-hazardous training aids providing consistent permeation of target odors.

Animals↗

Vitreoretinal surgery of the posterior segment for explosive trauma in terrorist warfare.

BACKGROUND: To describe surgical management and establish anatomic and visual results of patients with explosive ocular trauma in terrorist attacks treated with extreme vitreoretinal surgery. METHODS: Retrospective study of clinical records (6-month follow-up) of patients with visual acuity (VA) of light perception or better with posterior segment injuries [vitreous hemorrhage, retinal detachment (RD), intra-ocular foreign bodies (IOFB), perforating trauma (PT)] from explosive weapons who underwent vitreoretinal surgery. We reviewed the demographic characteristics, type of weapon, time between injury and surgery, VA at arrival and 6 months after surgery, and type of trauma according to the International Trauma Classification. RESULTS: Fifty-seven out of 236 patients with ocular injuries from explosive weapons were included in the study; all of them were military men, average age 22 years (range 16-53 years). The average time between the blast and primary closing was 1 day, and 10 days between primary closing and vitreoretinal surgery. Open traumas by laceration accounted for 96% of cases and 4% were closed traumas; 76% of the eyes had IOFB, of which 18% involved PT; 5% had endophthalmitis. Contusion was the diagnosis for 100% of the closed traumas. Of the open traumas, 40% were localized at zone I, 44% at zone II, and 16% at zone III. Upon arrival, 98% of patients had VA 20/800-LP and 2% had >20/40. The patients with closed trauma had the injuries at zone III and presented VA 20/800-LP. All patients underwent posterior vitrectomy, scleral buckling, endotaponade and when required, lensectomy (82%), IOFB removal (72%), and/or retinectomy (25%). Postoperative VA improved in 43% of the patients, stabilized in 41% and evolved to NLP in 15% of the cases. Initial expressions of ocular trauma such as RD, PT and endophthalmitis suggest bad prognosis. CONCLUSIONS: We presented a series of patients with severe ocular trauma of the posterior segment from explosive weapons. These patients were treated according to our surgical protocol with extreme vitreoretinal surgery within the first 2 weeks after the blast; with our procedure we obtained stabilization or improvement of the VA for 84% of the cases.

Adolescent↗

Use of reversed-phase high-performance liquid chromatography-diode array detection for complete separation of 2,4,6-trinitrotoluene metabolites and EPA Method 8330 explosives: influence of temperature and an ion-pair reagent.

Explosives such as 2,4,6-trinitrotoluene (TNT), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) are widely distributed environmental contaminants. Complete chromatographic separation is necessary in order to accurately determine and quantify explosives and their degradation products in environmental samples and in (bio)transformation studies. The present study describes a RP-HPLC method with diode array detection using a LC-8 guard column, a Supelcosil LC-8 chromatographic column, and a gradient elution system. This gradient method is capable of baseline separating the most commonly observed explosives and TNT transformation metabolites including 2,4,6-triaminotoluene (TAT) in a single run. The TNT metabolites separated were 2-hydroxylamino-4,6-dinitrotoluene, 4-hydroxylamino-2,6-dinitrotoluene, 2,4-dihydroxylamino-6-nitrotoluene, 4,4',6,6'-tetranitro-2,2'-azoxytoluene, 2,2',6,6'-tetranitro-4,4'-azoxytoluene, 4,4',6,6'-tetranitro-2,2'-azotoluene, 2,2',6,6'-tetranitro-4,4'-azotoluene, 2-amino-4,6-dinitrotoluene, 4-amino-2, 6-dinitrotoluene, 2,6-diamino-4-nitrotoluene, 2,4-diamino-6-nitrotoluene, and TAT. The same gradient method at a different column temperature can also be used to baseline separate the explosives targeted in the Environmental Protection Agency (EPA) Method 8330 with approximately 22% reduction in total run time and 48% decrease in solvent consumption compared to previously published methods. Good separation was also obtained when all TNT metabolites and EPA Method 8330 compounds (a total of 23 compounds) were analyzed together; only 2,6-DANT and HMX co-eluted in this case. The influence of temperature (35-55 degrees C) and the use of an ion-pair reagent on the chromatographic resolution and retention were investigated. Temperature was identified as the key parameter for optimal baseline separation. Increased temperature resulted in shorter retention times and better peak resolution especially for the aminoaromatics investigated. The use of an ion-pair reagent (octanesulfonic acid) generally resulted in longer retention times for compounds containing amine functional groups, more baseline noise, and decreased peak resolution.

Chromatography, High Pressure Liquid↗

Simple determination of performance of explosives without using any experimental data.

A simple procedure is introduced by which detonation pressure of CaHbNcOd explosives can be predicted from a, b, c, d and calculated gas phase heat of formation of explosives at any loading density without using any assumed detonation products and experimental data. It is shown here that the loading density, simply calculated heat of formation by additivity rule and atomic composition can be integrated into an empirical formula for predicting the detonation pressure of proposed explosives. Calculated detonation pressures by the introduced method for both pure and explosive formulations show good agreement with respect to measured detonation pressure over a wide range of loading density. The deviations are within about experimental errors.

Explosions↗

A simple approach for determining detonation velocity of high explosive at any loading density.

A simple empirical relationship is introduced between detonation velocity at any loading density and chemical composition of high explosive as well as its gas phase heat of formation, which is calculated by group additivity rules. The present work may be applied to any explosive that contains the elements of carbon, hydrogen, nitrogen and oxygen with no difficulties. The new correlation can easily be applied for determining detonation velocity of explosives with loading densities less than 1g/cm3 as well as greater than 1g/cm3. Calculated detonation velocities by this procedure for both pure and explosive formulations show good agreement with respect to measured detonation velocity over a wide range of loading density.

Carbon↗

Determination of performance of non-ideal aluminized explosives.

Non-ideal explosives can have Chapman-Jouguet (C-J) detonation pressure significantly different from those expected from existing thermodynamic computer codes, which usually allows finding the parameters of ideal detonation of individual high explosives with good accuracy. A simple method is introduced by which detonation pressure of non-ideal aluminized explosives with general formula C(a)H(b)N(c)O(d)Al(e) can be predicted only from a, b, c, d and e at any loading density without using any assumed detonation products and experimental data. Calculated detonation pressures show good agreement with experimental values with respect to computed results obtained by complicated computer code. It is shown here how loading density and atomic composition can be integrated into an empirical formula for predicting detonation pressure of proposed aluminized explosives.

Explosions↗

Trauma from tire and rim explosions: A retrospective analysis.

PURPOSE: The purpose of this study is to review injuries occurring as a result of tire and rim explosions treated at a level I trauma center. MATERIALS AND METHODS: The retrospective audit evaluated the university hospital trauma database based on ICD-9 code to isolate patients sustaining tire and rim explosion injuries. A total of 12 complete patient records were derived from this search to allow determination of injuries and outcome assessments. RESULTS: Injury patterns from tire and rim explosions were categorized in terms of anatomic region, treatment and hospitalization, disposition, and outcome assessment. Maxillofacial injuries were further subdivided into specific injuries involving a total of 7 patients from this case series. CONCLUSIONS: Significant blast injuries can result from tire and rim explosions, which can often involve the maxillofacial region due to proximity to the source. Reductions in injuries have been seen since the implementation of physical safety measures by the Occupational Safety and Health Administration and the National Highway Transportation Safety Board.

Accidents, Occupational↗

An exploratory approach to modeling explosive compound persistence and flux using dissolution kinetics.

Recent advances in the description of aqueous dissolution rates for explosive compounds enhance the ability to describe these compounds as a contaminant source term and to model the behavior of these compounds in a field environment. The objective of this study is to make predictions concerning the persistence of 2,4,6-trinitrotoluene (TNT) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in solid form both as individual explosive compounds and components of octol, and the resultant concentrations of explosives in water as a result of dissolution using three exploratory modeling approaches. The selection of dissolution model and rate greatly affect not only the predicted persistence of explosive compound sources but also their resulting concentrations in solution. This study identifies the wide range in possible predictions using existing information and these modeling approaches to highlight the need for further research to ensure that risk assessment, remediation and predicted fate and transport are appropriately presented and interpreted.

Azocines↗

Airblast TNT equivalence for a range of commercial blasting explosives.

Results are reported from a programme of work undertaken by the UK Health and Safety Executive to investigate the airblast produced by commercial sector explosives having velocities of detonation (VoD) in the range 2000-8200 m s(-1). The data produced will be useful in evaluating the blast hazards of such explosives in industrial circumstances and also as a means of assessing post-accident damage. All of the solid explosive materials studied produced blast waves which ramped up into shock-wave form close to the point of initiation. The dependence of peak overpressure and positive phase impulse on scaled distance is presented and compared to that of TNT. The TNT equivalence (TNT(e)) technique is shown to be applicable to solid phase explosives with a wide range of VoD, although the precise values of TNT(e) vary with distance.

Air Movements↗

Flixborough revisited - an explosion simulation approach.

A literature study of explosion estimation reports from the Flixborough accident was performed and commented. The results from this survey were compared to the results obtained from explosion simulations. The simulations were done with a computer model of the Flixborough plant using the EXSIM software simulation tool. The comparison showed that explosion magnitude estimates in the literature based on visual inspection are much lower than the simulated results, while the estimates based on calculations to a large degree conform with the simulations. The simulations also showed that the exact location of the ignition source does not seem to be significant for the magnitude of the explosion.

Accidents, Occupational↗

Theoretical and experimental investigation into the explosive boiling potential of thermally stratified liquid-liquid systems.

The occurrence of a rapid phase transition, or so-called explosive boiling, when a cold volatile liquid comes into contact with a hot liquid or hot surface is a potential hazard in industry. This study was focused on the explosive boiling potential of thermally stratified liquid-liquid systems that result from a runaway reaction. The experimental runs were performed on both a non-reacting and a reacting system. The experimental results showed that under the analysed conditions, the cold phase was superheated but did not evaporate explosively, as the limits of superheat of the phase were not achieved. The response of the cold phase appeared to be completely controlled by the interface temperature between the hot and the cold phase. In general, based on the order of magnitude of temperature differences that result from a runaway reaction in a multi-phasic system and the fact that the system is pressurised by its own vapour pressure, the occurrence of explosive boiling under runaway conditions appears unlikely for these type of systems.

Accidents↗

Passive explosion suppression by blast-induced atomisation from water containers.

The experimental findings of a combined wind tunnel and field-scale explosion study of blast-induced water release and its effect on blast suppression are reported. The release of water, and its subsequent atomisation, from containers both with open and partly enclosed surfaces, was first studied in a wind tunnel. An array of water containers were then placed at differing positions from the ignition point, together with flame acceleration obstacle arrays at fixed positions, inside a 5.1 m long by 0.3 m(2) cross-section explosion duct. The droplet size and the minimum flame speed necessary for the container array to suppress the explosion were found to depend upon the number of containers in the array and on their shape and size. One particular container array extinguished the flame when placed at any position beyond 1.7 m from the ignition point. When extinction was observed the internal over-pressure was substantially reduced and the external over-pressure completely eliminated. This study suggests a new approach toward passive explosion suppression.

Explosions↗

Thermal hazard assessment of AN and AN-based explosives.

Ammonium nitrate (AN) is an essential ingredient in most fertilizers. It is also widely used in the commercial explosives industry. In this latter application, it is mostly mixed with fuel oil to form the most popular commercial explosive: ANFO. In both the fertilizer and the explosive industry, aqueous AN solutions (ANS) of various concentrations are processed. These solutions also form the basis of ammonium nitrate emulsion explosives (also called ammonium nitrate emulsions or ANE), which are produced either in bulk or in packaged form. For all these AN-based products, quantities of the order of 20,000kg are being manufactured, transported, stored, and processed at elevated temperatures and/or elevated pressures. Correspondingly, major accidents involving overheating of large quantities of these products have happened in several of these operations. In comparison, convenient laboratory quantities to investigate thermal decomposition properties are generally less than 1kg. As a result, in order to provide information applicable to real-life situations, any laboratory study must use techniques that minimize heat losses from the samples to their environment. In the present study, two laboratory-scale calorimeters providing an adiabatic environment were used: an accelerating rate calorimeter (ARC) and an adiabatic Dewar calorimeter (ADC). Experiments were performed on pure AN, ANFO, various ANS systems, and typical bulk and packaged ANE systems. The effects of sample mass, atmosphere, and formulation on the resulting onset temperatures were studied. A comparison of the results from the two techniques is provided and a proposed method to extrapolate these results to large-scale inventories is examined.

Atmosphere↗

Explosives detection using prompt-gamma neutron activation and neural networks.

This work describes a study of the application of a neural network to determine the presence of explosives using the neutron capture prompt gamma-ray spectra of the substances as patterns which were simulated via Monte Carlo N-particle transport code, version 4B. After the training of the neural networks, it was possible to determine the presence of the C-4 explosive, even when they were occluded by several materials. The neural network was a powerful tool, able to recognize prompt gamma-ray explosive patterns in spite of the presence of occluding materials. Besides that, the network was able to generalize, identify the presence of explosive in cases in which it had not been trained. In that way, it was revealed as a potential tool for in situ inspection systems.

Explosions↗