Method development for the analysis of smokeless powders and organic gunshot residue by ultra performance liquid chromatography with tandem mass spectrometry

The goal of this project was to develop a rapid separation and detection method for analyzing organic compounds in smokeless powders and then test its applicability on gunshot residue (GSR) samples. In this project, a total of 20 common smokeless powder additives and their decomposition products were separated by ultra performance liquid chromatography (UPLC) and confirmed by tandem mass spectrometry (MS/MS) using multiple reaction monitoring mode (MRM). Some of the targeted compounds included diphenylamines, centralites, nitrotoluenes, nitroglycerin, and various phthalates. The compounds were ionized in the MS source using simultaneous positive and negative electrospray ionization (ESI) with negative atmospheric pressure chemical ionization (APCI) in order to detect all compounds in a single analysis. The developed UPLC/MS/MS method was applied to commercially available smokeless powders and gunshot residue samples recovered from the hands of shooters, spent cartridges, and smokeless powder retrieved from unfired cartridges. Distinct compositions were identified for smokeless powders from different manufacturers and from separate manufacturing lots. The procedure also produced specific chemical profiles when tested on gunshot residues from different manufacturers. Overall, this thesis represents the development of a rapid and reproducible procedure capable of simultaneously detecting the widest possible range of components present in organic gunshot residue.^

Downhole logging of the AND-2A borehole, Victoria Land Basin, McMurdo Sound, Antarctica

Under the framework of the ANDRILL Southern McMurdo Sound (SMS) Project successful downhole experiments were conducted in the 1138.54 metre (m)-deep AND-2A borehole. Wireline logs successfully recorded were: magnetic susceptibility, spectral gamma ray, sonic velocity, borehole televiewer, neutron porosity, density, calliper, geochemistry, temperature and dipmeter. A resistivity tool and its backup both failed to operate, thus resistivity data were not collected. Due to hole conditions, logs were collected in several passes from the total depth at ~1138 metres below sea floor (mbsf) to ~230 mbsf, except for some intervals that were either inaccessible due to bridging or were shielded by the drill string. Furthermore, a Vertical Seismic Profile (VSP) was created from ~1000 mbsf up to the sea floor. The first hydraulic fracturing stress measurements in Antarctica were conducted in the interval 1000-1138 mbsf. This extensive data set will allow the SMS Science Team to reach some of the ambitious objectives of the SMS Project. Valuable contributions can be expected for the following topics: cyclicity and climate change, heat flux and fluid flow, seismic stratigraphy in the Victoria Land Basin, and structure and state of the modern crustal stress field.

(Table II, page 668-669) Distribution of elements between minerals soluble in 1M Hydroxylamine hydrochloride (Reducible); in 1m HCL (Acid-soluble) and in the insoluble residue of manganese nodules

Attempts to classify pelagic sediments have been based either on appearance and composition, or on the ultimate origin of the components. In particular it appears feasible to distinguish minerals which crystallized in sea-water from those which formed in magmas, in hydrothermal solution, or by weathering under acidic conditions. It is the case of iron and manganese oxide mineral aggregates which constitute one of the major types of rock encountered on the ocean floor; according to Menard (unpublished) about 10% of the pelagic area of the Pacific is covered by such nodules. The nodules consist of intimately intergrown crystallites of different minerals among those identified, besides detrital minerals and organic matter, are opal, goethite, rutile, anatase, barite, nontronite, and at least three manganese oxide minerals of major importance. Arrhenius and Korkisch (1959) have attempted to separate from each other the different minerals constituting the nodules, in order to establish the details of their structure and the localization of the heavy metal ions. The results demonstrate (Table II) that copper and nickel are concentrated in the manganese oxide phases concentrated in the reducible fraction. Cobalt, part of the nickel and most of the chromium are distributed between these and the acid-soluble group of the non-manganese minerals, dominated by goethite and disordered FeOOH.

An Exploration of the challenges associated with software logging in large systems

Over the past few years, logging has evolved from from simple printf statements to more complex and widely used logging libraries. Today logging information is used to support various development activities such as fixing bugs, analyzing the results of load tests, monitoring performance and transferring knowledge. Recent research has examined how to improve logging practices by informing developers what to log and where to log. Furthermore, the strong dependence on logging has led to the development of logging libraries that have reduced the intricacies of logging, which has resulted in an abundance of log information. Two recent challenges have emerged as modern software systems start to treat logging as a core aspect of their software. In particular, 1) infrastructural challenges have emerged due to the plethora of logging libraries available today and 2) processing challenges have emerged due to the large number of log processing tools that ingest logs and produce useful information from them. In this thesis, we explore these two challenges. We first explore the infrastructural challenges that arise due to the plethora of logging libraries available today. As systems evolve, their logging infrastructure has to evolve (commonly this is done by migrating to new logging libraries). We explore logging library migrations within Apache Software Foundation (ASF) projects. We i find that close to 14% of the pro jects within the ASF migrate their logging libraries at least once. For processing challenges, we explore the different factors which can affect the likelihood of a logging statement changing in the future in four open source systems namely ActiveMQ, Camel, Cloudstack and Liferay. Such changes are likely to negatively impact the log processing tools that must be updated to accommodate such changes. We find that 20%-45% of the logging statements within the four systems are changed at least once. We construct random forest classifiers and Cox models to determine the likelihood of both just-introduced and long-lived logging statements changing in the future. We find that file ownership, developer experience, log density and SLOC are important factors in determining the stability of logging statements.

Insight into the mechanism of galactokinase: role of a critical glutamate residue and helix/coil transitions

Galactokinase, the enzyme which catalyses the first committed step in the Leloir pathway, has attracted interest due to its potential as a biocatalyst and as a possible drug target in the treatment of type I galactosemia. The mechanism of the enzyme is not fully elucidated. Molecular dynamics (MD) simulations of galactokinase with the active site residues Arg-37 and Asp-186 altered predicted that two regions (residues 174-179 and 231-240) had different dynamics as a consequence. Interestingly, the same two regions were also affected by alterations in Arg-105, Glu-174 and Arg- 228. These three residues were identified as important in catalysis in previous computational studies on human galactokinase. Alteration of Arg-105 to methionine resulted in a modest reduction in activity with little change in stability. When Arg-228 was changed to methionine, the enzyme’s interaction with both ATP and galactose was affected. This variant was significantly less stable than the wild-type protein. Changing Glu-174 to glutamine (but not to aspartate) resulted in no detectable activity and a less stable enzyme. Overall, these combined in silico and in vitro studies demonstrate the importance of a negative charge at position 174 and highlight the critical role of the dynamics in to key regions of the protein. We postulate that these regions may be critical for mediating the enzyme’s structure and function. 

Multi-residue analysis of 39 pesticides in surface waters of Ria de Aveiro

A multi-residue gas chromatography-mass spectrometry method was developed in order to evaluate the presence of 39 pesticides of different chemical families (organophosphorus, triazines, imidazole, organochlorine), as well as some of their transformation products, in surface water samples from Ria de Aveiro. Ria de Aveiro is an estuarine coastal lagoon, located in the northern west region of Portugal, which receives inputs from agriculture, urban and industrial activities. The analytical method was developed and validated according international guidelines and showed good linearity, with correlation coefficients higher than 0.9949 for all compounds, adequate precision and accuracy, and high sensitivity. Pesticides were chosen from the priority pollutants list of the Directive 2008/105/EC of the European Parliament and of the Council (on environmental quality standards in the field of water policy), or were selected due their common use in agricultural practices. Some of these 39 pesticides are, or are suspected to be, endocrine disruptor compounds (EDCs), being capable of altering the endocrine system of wildlife and humans, causing form malfunction and ultimately health problems. Even those pesticides which are not EDCs, are known to be awfully toxic and have a recognised impact in human health. The aquatic environment is particularly susceptible to pollution due to intentional and accidental release of chemicals to water [3]. Pesticide contamination of surface water is a national issue as it is often used as drinking water. This concern is especially important in rural agricultural areas where population uses small private water supplies, regularly without any laboratory surveillance. The study was performed in seven sampling points and the results showed a considerable concern pesticide contamination of all samples.

Fault tolerance logging-based model for deterministic systems

Fault tolerance allows a system to remain operational to some degree when some of its components fail. One of the most common fault tolerance mechanisms consists on logging the system state periodically, and recovering the system to a consistent state in the event of a failure. This paper describes a general fault tolerance logging-based mechanism, which can be layered over deterministic systems. Our proposal describes how a logging mechanism can recover the underlying system to a consistent state, even if an action or set of actions were interrupted mid-way, due to a server crash. We also propose different methods of storing the logging information, and describe how to deploy a fault tolerant master-slave cluster for information replication. We adapt our model to a previously proposed framework, which provided common relational features, like transactions with atomic, consistent, isolated and durable properties, to NoSQL database management systems.

Motion compensation with minimal residue dispersion matching criteria

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Tecnoloigia, 2016.

Community satisfaction with indoor residue spraying for Malaria control in Karonga, Northern Malawi

Background The Malawi National Malaria Control Program conducted Indoor Residual Spraying (IRS) in 2010 and 2013 in selected hot districts along the valleys including Karonga, but no study has been done to measure community satisfaction levels in these areas. Aim To assess satisfaction levels of community with IRS in both rural and urban settings, in Karonga district. Methods A cross-sectional study was conducted in urban village of Mwahimba and rural village of Fundi. Qualitative and quantitative data was collected from households’ representatives through Focus Group Discussions (FGDs) using De Wets’s Schutte tool. Qualitative data was analysed using thematic analysis while numbers and percentages were generated using Microsoft excel. Results Overall level of satisfaction in Fundi was estimated at 69% while that of Mwahimba was at 60.9%. In Fundi village, 66.1 % (37) of the household representatives were satisfied while in Mwahimba village, 60.7 % (34) were satisfied with the IRS programme. Factors that led to satisfaction were minimal adverse effects of the chemical on people after spraying, killing of other insects, sprayer’ courtesy and good communication. Factors behind dissatisfaction include: short residual effect of the chemical used, over-dilution of the chemical and minimal community involvement. Conclusion Despite finding high satisfaction levels in rural village than in an urban village, overall all the villages reported low levels of satisfaction with IRS due to various factors some of which common to both villages. Karonga District Health Office needs to involve the community in the process of spraying by recruiting sprayers from the target area and also explaining the purpose of dilution and the dilution factor to community members.

Confronto tra le tecniche XRD e IHD per la misura di tensioni residue

Le rotture a fatica dei componenti sono dovute principalmente alle tensioni di trazione generate da carichi ciclici e variabili nel tempo. Le cricche causate da questo tipo di tensioni possono propagarsi e crescere fino a causare danni catastrofici nel componente. La fatica costituisce uno dei fattori principali di rottura delle strutture aeronautiche; in campo aeronautico sono quindi molto diffusi dei trattamenti superficiali che permettono di indurre tensioni di compressione che contrastano quelle di trazione, in modo tale da ritardare o prevenire le rotture dovute al fenomeno della fatica. Esistono diverse tecniche per raggiungere questo risultato e permettere di prolungare la vita a fatica di un componente metallico, la più nota è sicuramente il Laser Shock Peening (LSP). Nel corso degli ultimi anni la maggior parte delle ricerche condotte rispetto a questa tecnica sono state incentrate sugli effetti meccanici che questo trattamento ha sul materiale in modo da determinare la configurazione ottimale per ottenere una distribuzione delle tensioni il più efficace possibile ai fini della vita a fatica; sono state svolte diverse prove sperimentali per studiare il ruolo dei parametri del laser e ottimizzare la procedura del LSP. Tra le tecniche utilizzate per valutare gli effetti del LSP in termini di tensioni residue, spiccano, oltre ai metodi computazionali, l'X-ray Diffraction (XRD) e l'Incremental Hole Drilling (IHD). L'elaborato di tesi qui presentato ha come scopo il confronto tra i livelli di tensioni residue riscontrate all'interno di provini sottili in lega di alluminio, sottoposti a differenti trattamenti laser, attraverso i suddetti metodi XRD e IHD. I risultati, già noti, ottenuti con la tecnica l'XRD sono stati posti a verifica attraverso dei test svolti con l'IHD presso i laboratori MaSTeRLab della Scuola di Ingegneria dell'Università di Bologna.

Performance of concrete incorporating amorphous silica residue and biomass fly ash

L'industrie du ciment est l'une des principales sources d'émission de dioxyde de carbone. L'industrie mondiale du ciment contribue à environ 7% des émissions de gaz à effet de serre dans l'atmosphère. Afin d'aborder les effets environnementaux associés à la fabrication de ciment exploitant en permanence les ressources naturelles, il est nécessaire de développer des liants alternatifs pour fabriquer du béton durable. Ainsi, de nombreux sous-produits industriels ont été utilisés pour remplacer partiellement le ciment dans le béton afin de générer plus d'économie et de durabilité. La performance d'un additif de ciment est dans la cinétique d'hydratation et de la synergie entre les additions et de ciment Portland. Dans ce projet, deux sous-produits industriels sont étudiés comme des matériaux cimentaires alternatifs: le résidu de silice amorphe (RSA) et les cendres des boues de désencrage. Le RSA est un sous-produit de la production de magnésium provenant de l'Alliance Magnésium des villes d'Asbestos et Thedford Mines, et les cendres des boues de désencrage est un sous-produit de la combustion des boues de désencrage, l'écorce et les résidus de bois dans le système à lit fluidisé de l'usine de Brompton située près de Sherbrooke, Québec, Canada. Récemment, les cendres des boues de désencrage ont été utilisées comme des matériaux cimentaires alternatifs. L'utilisation de ces cendres comme matériau cimentaire dans la fabrication du béton conduit à réduire la qualité des bétons. Ces problèmes sont causés par des produits d'hydratation perturbateurs des cendres volantes de la biomasse quand ces cendres sont partiellement mélangées avec du ciment dans la fabrication du béton. Le processus de pré-mouillage de la cendre de boue de désencrage avant la fabrication du béton réduit les produits d'hydratation perturbateurs et par conséquent les propriétés mécaniques du béton sont améliorées. Les approches pour étudier la cendre de boue de désencrage dans ce projet sont : 1) caractérisation de cette cendre volante régulière et pré-humidifiée, 2) l'étude de la performance du mortier et du béton incorporant cette cendre volante régulière et pré-humidifiée. Le RSA est un nouveau sous-produit industriel. La haute teneur en silice amorphe en RSA est un excellent potentiel en tant que matériau cimentaire dans le béton. Dans ce projet, l'évaluation des RSA comme matériaux cimentaires alternatifs compose trois étapes. Tout d'abord, la caractérisation par la détermination des propriétés minéralogiques, physiques et chimiques des RSA, ensuite, l'optimisation du taux de remplacement du ciment par le RSA dans le mortier, et enfin l'évaluation du RSA en remplacement partiel du ciment dans différents types de béton dans le système binaire et ternaire. Cette étude a révélé que le béton de haute performance (BHP) incorporant le RSA a montré des propriétés mécaniques et la durabilité, similaire du contrôle. Le RSA a amélioré les propriétés des mécaniques et la durabilité du béton ordinaire (BO). Le béton autoplaçant (BAP) incorporant le RSA est stable, homogène et a montré de bonnes propriétés mécaniques et la durabilité. Le RSA avait une bonne synergie en combinaison de liant ternaire avec d'autres matériaux cimentaires supplémentaires. Cette étude a montré que le RSA peut être utilisé comme nouveaux matériaux cimentaires dans le béton.

Regeneration in felling gaps after logging in Acre state, Western Amazon.

Regeneration of tree species in felling gaps were studied during the first two years following harvesting in a tropical forest in Acre state, Brazil. Felling gaps averaged 340 m2 in size, while canopy openings averaged 17%. Seedling mortality in adjacent undisturbed forest was 4.6% yr', and 59.6% yr·1 and 100% yr' in the crown and trunk zones respectively, two years after logging. Recruitment of new seedlings inthe undisturbed forest understorey averaged 462 plants ha' yr', two years after gap creation. Inthe crown zones of the gaps, recruitment of seedlings averaged 1350 ha' yr', and in the trunk zones 1392 ha' yr'. The entire seedling community in trunk zones after logging was composed of new recruits. lhere was a tendency for seedling growth rates to increase from the natural forest (0,21cm yr-1) to the crown zone (0.40cm yr'), Before gap creation, species richness and diversity and seedling density were quite similar. After gap creation a sharp decrease could be verified in the gap.zones, however the differences between gap and undisturbed forest decreased rapidly in the second year after gap creation. lhe regeneration of commercial species was not affected by gap creation apart from the increase in growth rates.