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.^

Uso da cinza do bagaço da cana-de-açúcar como matéria-prima na substituição dos fundentes para aplicações em porcelanato

The present study aims to evaluate the potential use of bagasse ash from sugar cane (CBC) as a flux, replacing phyllite and/or feldspar in standard industrial mass production of enameled porcelain, verifying the possibility of the CBC contribute to the overall reduction of the coefficient of thermal expansion of the ceramic mass. To this end, as a result of the research, we characterized the raw material components of the standard mass (clay, phyllite, kaolin, feldspar, quartz and talc) and the residue of BCC, by testing by XRF, XRD, AG, DTA and ATG. Specimens (CDP) were manufactured in the dimensions of 100 mm x 50 mm x 8 mm in uniaxial matrix under compaction pressure of 33 MPa, assembled in batches of 3 units subsequently sintered at temperatures of 1150°C to 1210°C by varying the Rating Scale at 10°C, heating and cooling ramp of 50°C/min and 25°C/min, with levels of 1 min, 3 min, 5 min, 8 min, 10 min, 15 min, 30 min and 60 min. analyzing the results of the physical properties of water absorption (WA), linear firing shrinkage (LFS), dilatometric analysis (DTA), flexural strain (SFT) and SEM of the sintered bodies in order to verify the adequacy of CDP to ISO 13006, ISO 10545, NBR 13816 standards; NBR 13817 and NBR 13818. The study showed that the formulations that best suit the requirements of the standards are:. G4 - which was applied in 10% of replacing the CBC phyllite, sintering temperature 1210 ° C for 10 min and porch, and F3 - with application of 7.5% of CBC to replace the feldspar in the sintering temperatures of 1190°C, 1200°C and 1210°C for 10 min and porch. These formulations showed better performance regarding the formation of primary and secondary mullite, with considerable reduction of cracks and pores, meeting the prerequisites of standards for glazed porcelain. The results shows that the use of the CBC as a flux in the preparation of porcelain mass meets standard parameters for the manufacture of the product, and thereby can reduce environmental impact and the cost of production. Therefore, it is recommended to use this residue in the ceramics industry, due to its industrial, commercial and collaborative viability for sustainability.

Measurements of stress-optic coefficient and Young's modulus in PMMA fibers drawn under different conditions

We have systematically measured the differential stress-optic coefficient, ΔC, and Young's modulus, E, in a number of PMMA fibers drawn with different stress, ranging from 2 up to 27 MPa. Effect of temperature annealing on those parameters was also investigated. ΔC was determined in transverse illumination by measuring the dependence of birefringence on additional axial stress applied to the fiber. Our results show that ΔC in PMMA fibers has a negative sign and ranges from -4.5 to -1.5×10-12 Pa -1 depending on the drawing stress. Increase of the drawing stress results in greater initial fiber birefringence and lower ΔC. The dependence of ΔC and initial birefringence upon drawing stress is nonlinear and gradually saturates for higher drawing stress. Moreover, we find that ΔC is linearly proportional to initial fiber birefringence and that annealing the fiber has no impact on the slope of this dependence. On the other hand, no clear dependence was observed between the fiber drawing stress and the Young's modulus of the fibers as measured using microscopic digital image correlation with the fibers tensioned using an Instron tension tester. © 2010 SPIE.

(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.

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. 

Analysis of heat transfer coefficient in silica nanofluids with water as base fluid under transitional flow

The effect of Reynolds number variation in a vertical double pipe counterflow heat exchanger due to the changes in viscosity can cause the change in flow regime, for instance, when heats up and cools down, it can convert from turbulent to laminar or inversely, that can have significant effect on heat transfer coefficient and pressure drop. Mainly, the range of transition phase has been studied in this study with the investigation of silica nanofluid dispersed in water in three different concentrations. The results have been compared with distilled water sample and showed a remarkable raise in heat transfer coefficient while pressure drop has been increased respectively, as well. Although pumping power has to go up at the same time and it is a drawback, heat transfer efficiency grows for diluted samples. On the other hand, for the most concentrated sample, effect of pressure drop dominates which leads to decline in the overall efficiency.

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.

Controller system design using the coefficient diagram method

Coefficient diagram method is a controller design technique for linear time-invariant systems. This design procedure occurs into two different domains: an algebraic and a graphical. The former is closely paired to a conventional pole placement method and the latter consists on a diagram whose reading from the plotted curves leads to insights regarding closed-loop control system time response, stability and robustness. The controller structure has two degrees of freedom and the design process leads to both low overshoot closed-loop time response and good robustness performance regarding mismatches between the real system and the design model. This article presents an overview on this design method. In order to make more transparent the presented theoretical concepts, examples in Matlab®code are provided. The included code illustrates both the algebraic and the graphical nature of the coefficient diagram design method. © 2016, King Fahd University of Petroleum & Minerals.