The potential of solid phase microextraction (SPME) for the recovery of explosives followed by gas and liquid chromatographic analysis

The potential of solid phase microextraction (SPME) in the analysis of explosives is demonstrated. A sensitive, rapid, solventless and inexpensive method for the analysis of explosives and explosive odors from solid and liquid samples has been optimized using SPME followed by HPLC and GC/ECD. SPME involves the extraction of the organic components in debris samples into sorbent-coated silica fibers, which can be transferred directly to the injector of a gas chromatograph. SPME/HPLC requires a special desorption apparatus to elute the extracted analyte onto the column at high pressure. Results for use of GC/ECD is presented and compared to the results gathered by using HPLC analysis. The relative effects of controllable variables including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time have been optimized for various high explosives. ^

The Cuban military in Angola: The limits of internationalism

The Cuban military involvement in Angola has often been seen as a response to the wishes of the former Soviet Union. Yet, Castro intervened in Angola following his theory of internationalism. Internationalism, as conceived by Castro, sent Cubans on a voluntary basis to serve abroad, either in the military or in the civilian sector. This thesis will illustrate that from its inception, Castro sent military troops to Angola to divert domestic concerns and to boost Cuba's alliances throughout the world. Angola is different from other internationalist missions, because in Angola--for the first time--regular combat troops were used. Castro intervened in Angola to prevent a collapse of the Moviemento Popular de Libertacao de Angola (MPLA) government, and stayed on to ensure the viability of the MPLA. The primary sources are interviews conducted by the author, of participants in the Angolan civil war. The secondary sources consulted are works on Cuba, Southern Africa, Portuguese colonialism and Angola. ^

Improved sampling and detection of ignitable liquid residues and explosives by mass spectrometry and ion mobility spectrometry

Fire debris evidence is submitted to crime laboratories to determine if an ignitable liquid (IL) accelerant was used to commit arson. An ignitable liquid residue (ILR) may be difficult to analyze due to interferences, complex matrices, degradation, and low concentrations of analytes. Debris from an explosion and pre-detonated explosive compounds are not trivial to detect and identify due to sampling difficulties, complex matrices, and extremely low amounts (nanogram) of material present. The focus of this research is improving the sampling and detection of ILR and explosives through enhanced sensitivity, selectivity, and field portable instrumentation. Solid Phase MicroExtraction (SPME) enhanced the extraction of ILR by two orders of magnitude over conventional activated charcoal strip (ACS) extraction. Gas chromatography tandem mass spectrometry (GC/MS/MS) improved sensitivity of ILR by one order of magnitude and explosives by two orders of magnitude compared to gas chromatography mass spectrometry (GC/MS). Improvements in sensitivity were attributed to enhanced selectivity. An interface joining SPME to ion mobility spectrometry (IMS) has been constructed and evaluated to improve field detection of hidden explosives. The SPME-IMS interface improved the detection of volatile and semi-volatile explosive compounds and successfully adapted the IMS from a particle sampler into a vapor sampler. ^

Improving the scientific reliability of biological detection of explosives by Canis familiaris: Active odour signatures and their implications

The use of canines as a method of detection of explosives is well established worldwide and those applying this technology range from police forces and law enforcement to humanitarian agencies in the developing world. Despite the recent surge in publication of novel instrumental sensors for explosives detection, canines are still regarded by many to be the most effective real-time field method of explosives detection. However, unlike instrumental methods, currently it is difficult to determine detection levels, perform calibration of the canines' ability or produce scientifically valid quality control checks. Accordingly, amongst increasingly strict requirements regarding forensic evidence admission such as Frye and Daubert, there is a need for better scientific understanding of the process of canine detection. ^ When translated to the field of canine detection, just like any instrumental technique, peer reviewed publication of the reliability, success and error rates, is required for admissibility. Commonly training is focussed towards high explosives such as TNT and Composition 4, and the low explosives such as Black and Smokeless Powders are added often only for completeness. ^ Headspace analyses of explosive samples, performed by Solid Phase Microextraction (SPME) paired with Gas Chromatography - Mass Spectrometry (GC-MS), and Gas Chromatography - Electron Capture Detection (GC-ECD) was conducted, highlighting common odour chemicals. The odour chemicals detected were then presented to previously trained and certified explosives detection canines, and the activity/inactivity of the odour determined through field trials and experiments. ^ It was demonstrated that TNT and cast explosives share a common odour signature, and the same may be said for plasticized explosives such as Composition C-4 and Deta Sheet. Conversely, smokeless powders were demonstrated not to share common odours. An evaluation of the effectiveness of commercially available pseudo aids reported limited success. The implications of the explosive odour studies upon canine training then led to the development of novel inert training aids based upon the active odours determined. ^

The development of optimized high performance liquid chromatography systems for the analysis of improvised explosives

Existing instrumental techniques must be adaptable to the analysis of novel explosives if science is to keep up with the practices of terrorists and criminals. The focus of this work has been the development of analytical techniques for the analysis of two types of novel explosives: ascorbic acid-based propellants, and improvised mixtures of concentrated hydrogen peroxide/fuel. In recent years, the use of these explosives in improvised explosive devices (IEDs) has increased. It is therefore important to develop methods which permit the identification of the nature of the original explosive from post-blast residues. Ascorbic acid-based propellants are low explosives which employ an ascorbic acid fuel source with a nitrate/perchlorate oxidizer. A method which utilized ion chromatography with indirect photometric detection was optimized for the analysis of intact propellants. Post-burn and post-blast residues if these propellants were analyzed. It was determined that the ascorbic acid fuel and nitrate oxidizer could be detected in intact propellants, as well as in the post-burn and post-blast residues. Degradation products of the nitrate and perchlorate oxidizers were also detected. With a quadrupole time-of-flight mass spectrometer (QToFMS), exact mass measurements are possible. When an HPLC instrument is coupled to a QToFMS, the combination of retention time with accurate mass measurements, mass spectral fragmentation information, and isotopic abundance patterns allows for the unequivocal identification of a target analyte. An optimized HPLC-ESI-QToFMS method was applied to the analysis of ascorbic acid-based propellants. Exact mass measurements were collected for the fuel and oxidizer anions, and their degradation products. Ascorbic acid was detected in the intact samples and half of the propellants subjected to open burning; the intact fuel molecule was not detected in any of the post-blast residue. Two methods were optimized for the analysis of trace levels of hydrogen peroxide: HPLC with fluorescence detection (HPLC-FD), and HPLC with electrochemical detection (HPLC-ED). Both techniques were extremely selective for hydrogen peroxide. Both methods were applied to the analysis of post-blast debris from improvised mixtures of concentrated hydrogen peroxide/fuel; hydrogen peroxide was detected on variety of substrates. Hydrogen peroxide was detected in the post-blast residues of the improvised explosives TATP and HMTD.

The construction and optimization of an ion mobility spectrometer for the analysis of explosives and drugs

Today, over 15,000 Ion Mobility Spectrometry (IMS) analyzers are employed at worldwide security checkpoints to detect explosives and illicit drugs. Current portal IMS instruments and other electronic nose technologies detect explosives and drugs by analyzing samples containing the headspace air and loose particles residing on a surface. Canines can outperform these systems at sampling and detecting the low vapor pressure explosives and drugs, such as RDX, PETN, cocaine, and MDMA, because these biological detectors target the volatile signature compounds available in the headspace rather than the non-volatile parent compounds of explosives and drugs.^ In this dissertation research volatile signature compounds available in the headspace over explosive and drug samples were detected using SPME as a headspace sampling tool coupled to an IMS analyzer. A Genetic Algorithm (GA) technique was developed to optimize the operating conditions of a commercial IMS (GE Itemizer 2), leading to the successful detection of plastic explosives (Detasheet, Semtex H, and C-4) and illicit drugs (cocaine, MDMA, and marijuana). Short sampling times (between 10 sec to 5 min) were adequate to extract and preconcentrate sufficient analytes (> 20 ng) representing the volatile signatures in the headspace of a 15 mL glass vial or a quart-sized can containing ≤ 1 g of the bulk explosive or drug.^ Furthermore, a research grade IMS with flexibility for changing operating conditions and physical configurations was designed and fabricated to accommodate future research into different analytes or physical configurations. The design and construction of the FIU-IMS were facilitated by computer modeling and simulation of ion’s behavior within an IMS. The simulation method developed uses SIMION/SDS and was evaluated with experimental data collected using a commercial IMS (PCP Phemto Chem 110). The FIU-IMS instrument has comparable performance to the GE Itemizer 2 (average resolving power of 14, resolution of 3 between two drugs and two explosives, and LODs range from 0.7 to 9 ng). ^ The results from this dissertation further advance the concept of targeting volatile components to presumptively detect the presence of concealed bulk explosives and drugs by SPME-IMS, and the new FIU-IMS provides a flexible platform for future IMS research projects.^

Improved sampling, pre-concentration, and detection of hidden explosives and illicit drugs by a novel solid phase microextraction geometry coupled to ion mobility spectrometry

The 9/11 Act mandates the inspection of 100% of cargo shipments entering the U.S. by 2012 and 100% inspection of air cargo by March 2010. So far, only 5% of inbound shipping containers are inspected thoroughly while air cargo inspections have fared better at 50%. Government officials have admitted that these milestones cannot be met since the appropriate technology does not exist. This research presents a novel planar solid phase microextraction (PSPME) device with enhanced surface area and capacity for collection of the volatile chemical signatures in air that are emitted from illicit compounds for direct introduction into ion mobility spectrometers (IMS) for detection. These IMS detectors are widely used to detect particles of illicit substances and do not have to be adapted specifically to this technology. For static extractions, PDMS and sol-gel PDMS PSPME devices provide significant increases in sensitivity over conventional fiber SPME. Results show a 50–400 times increase in mass detected of piperonal and a 2–4 times increase for TNT. In a blind study of 6 cases suspected to contain varying amounts of MDMA, PSPME-IMS correctly detected 5 positive cases with no false positives or negatives. One of these cases had minimal amounts of MDMA resulting in a false negative response for fiber SPME-IMS. A La (dihed) phase chemistry has shown an increase in the extraction efficiency of TNT and 2,4-DNT and enhanced retention over time. An alternative PSPME device was also developed for the rapid (seconds) dynamic sampling and preconcentration of large volumes of air for direct thermal desorption into an IMS. This device affords high extraction efficiencies due to strong retention properties under ambient conditions resulting in ppt detection limits when 3.5 L of air are sampled over the course of 10 seconds. Dynamic PSPME was used to sample the headspace over the following: MDMA tablets (12–40 ng detected of piperonal), high explosives (Pentolite) (0.6 ng detected of TNT), and several smokeless powders (26–35 ng of 2,4-DNT and 11–74 ng DPA detected). PSPME-IMS technology is flexible to end-user needs, is low-cost, rapid, sensitive, easy to use, easy to implement, and effective. ^

The Use of the Military for Law Enforcement Activities in Central America

Faced with the violence, criminality and insecurity now threatening peace and democratic governance in Central America, the region’s governments have decided to use the Armed Forces to carry out actions in response to criminal actions, looking to improve their performance. Although public demand for including the Armed Forces in these functions takes place within a legally legitimate framework, it is motivated by tangible circumstances such as increased levels of violence, delinquency and crime. Despite being coupled with the perception of institutional weakness within the security and judicial system (particularly police) and the recognition of prestige, efficiency, discipline and severity in fulfilling the Armed Forces’ missions, these arguments are insufficient to legitimize the use of the military as a police force. Within this context, this paper reflects on the implications or consequences of the use of the Armed Forces in duties traditionally assigned to the police in the Central American region with the goal of contributing to the debate on this topic taking place in the Americas. To achieve this end, first we will focus on understanding the actual context in which a decision is made to involve the Armed Forces in security duties in the region. Second, we will examine the effects and implications of this decision on the Armed Forces’ relations within their respective societies. Third and finally, considering this is already a reality in the region, this paper will provide recommendations. The main findings of this research, resulting from the application of an analyticaldescriptive and historically based study, are organized in three dimensions: the political dimension, by implication referring to the relationship between the ultimate political authority and the Armed Forces; the social dimension, by implication the opinion of citizens; and other implications not only affecting the structural and cultural organization of armies and police but also the complementary operational framework within a context of comprehensive response by the State. As a main conclusion, it poses there is an environment conducive to the use of the Armed Forces in citizen’s security, in view of the impact of threats provoked by criminal structures of a military nature currently operating in Central America. However, this participation creates an inevitable social and political impact if implemented in isolation or given a political leading role and/or operational autonomy. This participation poses risks to the institutions of the Armed Forces and the police as well. Finally, this paper identifies an urgent need for the Armed Forces’ role to be more clearly defined with regard to security matters, limiting it to threats that impact States’ governability and existence. Nonetheless, Central American States should seek a COMPREHENSIVE response to current crime and violence, using all necessary institutions to confront these challenges, but with defined roles and responsibilities for each and dynamic coordination to complement their actions.

Capabilities of Police and Military Forces in Central America -- A Comparative Analysis of Guatemala, El Salvador, Honduras an d Nicaragua

A difficult transition to a new paradigm of Democratic Security and the subsequent process of military restructuring during the nineties led El Salvador, Honduras, Guatemala and Nicaragua to re-consider their old structures and functions of their armed forces and police agencies. This study compares the institutions in the four countries mentioned above to assess their current condition and response capacity in view of the contemporary security challenges in Central America. This report reveals that the original intention of limiting armies to defend and protect borders has been threatened by the increasing participation of armies in public security. While the strength of armies has been consolidated in terms of numbers, air and naval forces have failed to become strengthened or sufficiently developed to effectively combat organized crime and drug trafficking and are barely able to conduct air and sea operations. Honduras has been the only country that has maintained a proportional distribution of its armed forces. However, security has been in the hands of a Judicial Police, supervised by the Public Ministry. The Honduran Judicial Police has been limited to exercising preventive police duties, prohibited from carrying out criminal investigations. Nicaragua, meanwhile, possesses a successful police force, socially recognized for maintaining satisfactory levels of security surpassing the Guatemalan and El Salvadoran police, which have not achieved similar results despite of having set up a civilian police force separate from the military. El Salvador meanwhile, has excelled in promoting a Police Academy and career professional education, even while not having military attachés in other countries. Regarding budgetary issues, the four countries allocate almost twice the amount of funding on their security budgets in comparison to what is allocated to their defense budgets. However, spending in both areas is low when taking into account each country's GDP as well as their high crime rates. Regional security challenges must be accompanied by a professionalization of the regional armies focused on protecting and defending borders. Therefore, strong institutional frameworks to support the fight against crime and drug trafficking are required. It will require the strengthening of customs, greater control of illicit arms trafficking, investment in education initiatives, creating employment opportunities and facilitating significant improvements in the judicial system, as well as its accessibility to the average citizen.

The Transitioning Economic Dynamics of the Military in Communist Regimes: A Comparison of Cuba, China and Vietnam [Student's Paper Series]

Several factors can increase or decrease military-economic involvement in communist regimes. This anomalous form of military behavior, labeled as the Military Business Complex (MBC), emerged in various communist regimes in the 1980s. However, in early 2000s, the communist governments of China and Vietnam began to decrease the number of military-managed industries, while similar industries increased in Cuba. This paper explains why military industries in Cuba have increased over the last two decades, while they decreased in the Chinese and Vietnamese examples. This question is answered by comparatively testing two hypotheses: the Communist Party and the Bureaucratic-Authoritarian (BA) Hypotheses. The Communist Party hypotheses helps explain how the historical and current structures of Party oversight of the military have been lacking in strength and reliability in Cuba, while they traditionally have been more robust in China and Vietnam. The BA hypotheses helps explain how, due to the lack of a strong civilian institutional oversight, the Cuban military has grown into a bureaucratic entity with many political officers holding autonomous positions of power, an outcome that is not prevalent in the Chinese and Vietnamese examples. Thus, with the establishment of a bureaucratic military government and with the absence of a strong party oversight, the Cuban military has been able to protect its economic endeavors while the Chinese and Vietnamese MBC regimes have contracted.

Innovating from the War Economy: Formal, Informal, and Illicit Economic Activities of the Military in Colombia

Over the last decade, the Colombian military has successfully rolled back insurgent groups, cleared and secured conflict zones, and enabled the extraction of oil and other key commodity exports. As a result, official policies of both the Uribe and Santos governments have promoted the armed forces to participate to an unprecedented extent in economic activities intended to consolidate the gains of the 2000s. These include formal involvement in the economy, streamlined in a consortium of military enterprises and social foundations that are intended to put the Colombian defense sector “on the map” nationally and internationally, and informal involvement expanded mainly through new civic action development projects intended to consolidate the security gains of the 2000s. However, failure to roll back paramilitary groups other than through the voluntary amnesty program of 2005 has facilitated the persistence of illicit collusion by military forces with reconstituted “neoparamilitary” drug trafficking groups. It is therefore crucially important to enhance oversight mechanisms and create substantial penalties for collusion with illegal armed groups. This is particularly important if Colombia intends to continue its new practice of exporting its security model to other countries in the region. The Santos government has initiated several promising reforms to enhance state capacity, institutional transparence, and accountability of public officials to the rule of law, which are crucial to locking in security gains and revitalizing democratic politics. Efforts to diminish opportunities for illicit association between the armed forces and criminal groups should complement that agenda, including the following: Champion breaking existing ties between the military and paramilitary successor groups through creative policies involving a mixture of punishments and rewards directed at the military; Investigation and extradition proceedings of drug traffickers, probe all possible ties, including as a matter of course the possibility of Colombian military collaboration. Doing so rigorously may have an important effect deterring military collusion with criminal groups. Establish and enforce zero-tolerance policies at all military ranks regarding collusion with criminal groups; Reward military units that are effective and also avoid corruption and criminal ties by providing them with enhanced resources and recognition; Rely on the military for civic action and development assistance as minimally as possible in order to build long-term civilian public sector capacity and to reduce opportunities for routine exposure of military forces to criminal groups circulating in local populations.

Making and Evaluating Strategy: Learning from the Military

Use of military analogy is rampant and considered an acceptable part of business vernacular. However, analogies only illustrate, and bad analogies make bad strategy. There are important lessons to be learned from military strategy, though. This article identifies "the ten principles of strategy" that corporate strategists could utilize in testing their strategic theories, concepts, and plans.

The development of calibrants through characterization of volatile organic compounds from peroxide based explosives and a non-target chemical calibration compound

Detection canines represent the fastest and most versatile means of illicit material detection. This research endeavor in its most simplistic form is the improvement of detection canines through training, training aids, and calibration. This study focuses on developing a universal calibration compound for which all detection canines, regardless of detection substance, can be tested daily to ensure that they are working with acceptable parameters. Surrogate continuation aids (SCAs) were developed for peroxide based explosives along with the validation of the SCAs already developed within the International Forensic Research Institute (IFRI) prototype surrogate explosives kit. Storage parameters of the SCAs were evaluated to give recommendations to the detection canine community on the best possible training aid storage solution that minimizes the likelihood of contamination. Two commonly used and accepted detection canine imprinting methods were also evaluated for the speed in which the canine is trained and their reliability. As a result of the completion of this study, SCAs have been developed for explosive detection canine use covering: peroxide based explosives, TNT based explosives, nitroglycerin based explosives, tagged explosives, plasticized explosives, and smokeless powders. Through the use of these surrogate continuation aids a more uniform and reliable system of training can be implemented in the field than is currently used today. By examining the storage parameters of the SCAs, an ideal storage system has been developed using three levels of containment for the reduction of possible contamination. The developed calibration compound will ease the growing concerns over the legality and reliability of detection canine use by detailing the daily working parameters of the canine, allowing for Daubert rules of evidence admissibility to be applied. Through canine field testing, it has been shown that the IFRI SCAs outperform other commercially available training aids on the market. Additionally, of the imprinting methods tested, no difference was found in the speed in which the canines are trained or their reliability to detect illicit materials. Therefore, if the recommendations discovered in this study are followed, the detection canine community will greatly benefit through the use of scientifically validated training techniques and training aids.