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. ^

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. ^

Student Independent Projects Environmental Studies 2011: The Humber River Basin Human Values Project: Designing a Sampling Strategy for a Pilot Survey in the Corner Brook Area

Sustainability can be indicated by a number of factors. Populations need to be aged evenly, ensuring a healthy equilibrium. Job opportunities must be numerous and of wide varieties to balance incomes from different employment sectors. Regions must also sustain vital natural resources in the area which are directly related to a place being self-sustaining. These indicators prove to be true, especially in Newfoundland, where people have struggled to remain in the small traditional communities that they consider being there 'home.' The population of Corner Brook and the surrounding areas can be stratified according to the values people hold to their special place. Even though people in western Newfoundland hold strong ties to their home, some parts of the region even though people in western Newfoundland hold strong ties to their home, some parts of the region struggle with employment, low incomes, out-migration, and dependency on declining natural resources. The aim of this paper is to present the process of designing a sample strategy for a human values pilot survey conducted in the city of Corner Brook. It will present a theoretical background over the period 2002-2006 to be used for sampling strategy.

The Benefits of Sampling Sports During Childhood

Sampling may promote prolonged engagement in sport by limiting physical injuries (Fraser-Thomas et al., 2005). Overtraining injuries are a concern for young athletes who specialize in one sport and engage in high volumes of deliberate practice (Hollander, Meyers, & Leunes, 1995; Law, Côté, & Ericsson, 2007). For instance, young gymnasts who practice for over 16 hours a week have been shown to have higher incidences of back injuries (Goldstein, Berger, Windier, & Jackson, 1991). A sampling approach in child-controlled play (e.g. deliberate play) rather than highly adult-controlled practice (e.g. deliberate practice) has been proposed as a strategy to limit overuse and other sport-related injuries (Micheli, Glassman, & Klein, 2000). In summary, sampling may protect against sport attrition by limiting sport related injuries and allowing children to have early experiences in sport that are enjoyable. Psychosocial Benefits of Sampling Only a small percentage of children who participate in school sports ever become elite athletes. Therefore, the psychosocial outcomes of sport participation are particularly important to consider. Recent studies with youth between the ages of 11 to 17 have found that those who are involved in a variety of extracurricular activities (e.g. sports, volunteer, arts) score more favourably on outcome measures such as Grade Point Average (GPA; Fredricks & Eccles, 2006a) and positive peer relationships (Fredricks & Eccles, 2006b) than youth who participate in fewer activities. These patterns are thought to exist due to each extracurricular activity bringing its own distinct pattern of socialization experiences that reinforce certain behaviours and/or teach various skills (Fredricks & Eccles, 2006b; Rose-Krasnor, Bussen, Willoughby, & Chambers, 2006). This contention is corroborated by studies of children and youths' experiences in extracurricular activities indicating that youth have unique experiences in each activity that contribute to their development (Hansen, Larson, & Dworkin, 2003; Larson, Hansen, & Moneta, 2006). This has led Wilkes and Côté (2007) to propose that children who sample different activities (through their own choice or by virtue of parental direction), have a greater chance of developing the following five developmental outcomes compared to children who specialize in one activity: 1) life skills, 2) prosocial behaviour, 3) healthy identity, 4) diverse peer groups and 5) social capital.

Leveraging Stratification in Twitter Sampling

With Tweet volumes reaching 500 million a day, sampling is inevitable for any application using Twitter data. Realizing this, data providers such as Twitter, Gnip and Boardreader license sampled data streams priced in accordance with the sample size. Big Data applications working with sampled data would be interested in working with a large enough sample that is representative of the universal dataset. Previous work focusing on the representativeness issue has considered ensuring the global occurrence rates of key terms, be reliably estimated from the sample. Present technology allows sample size estimation in accordance with probabilistic bounds on occurrence rates for the case of uniform random sampling. In this paper, we consider the problem of further improving sample size estimates by leveraging stratification in Twitter data. We analyze our estimates through an extensive study using simulations and real-world data, establishing the superiority of our method over uniform random sampling. Our work provides the technical know-how for data providers to expand their portfolio to include stratified sampled datasets, whereas applications are benefited by being able to monitor more topics/events at the same data and computing cost.

Characteristics of aerosols over the Indian region and their variability associated with atmospheric conditions

The aerosols in the atmosphere play major role in the radiation balance of the Earthatmosphere system. Direct and indirect impact of aerosols on the weather and climate still remains as a topic to be investigated in detail. The effect of aerosols on the radiation budget and thereby circulation pattern is important and requires further study. A detailed analysis of the aerosol properties, their variability and meteorological processes that affect the aerosol properties and distribution over the Indian region is performed in the thesis. The doctoral thesis entitled “Characteristics of aerosols over the Indian region and their variability associated with atmospheric conditions” contains 7 chapters. This thesis presents results on the analysis on the distribution (spatial and temporal) and characteristics of the aerosols over the Indian region and adjoining seas. Regional and stationwise data were analysed and methods such as modeling and statistical analysis are implemented to understand the aerosol properties, classification and transportation. Chapter-1 presents a brief introduction on the aerosols, their measurement techniques, impact of aerosols on the atmospheric radiation budget, climatic and geographic features of the study area and the literature review on the previous studies. It provides a basic understanding in the field of study and objective of the thesis. Definition of the aerosols, their sources/sinks and classification of the particles according to optical and microphysical properties are described. Different measurement techniques such as sampling and remote sensing methods are explained in detail. Physical parameters used to describe aerosol properties and effect of aerosols on the radiation distribution are also discussed. The chapter also explains the objectives of the thesis and description of climatic features of the study area.

An Integrated Framework To Improve The Concept Of Resource Specialisation.

Resource specialisation, although a fundamental component of ecological theory, is employed in disparate ways. Most definitions derive from simple counts of resource species. We build on recent advances in ecophylogenetics and null model analysis to propose a concept of specialisation that comprises affinities among resources as well as their co-occurrence with consumers. In the distance-based specialisation index (DSI), specialisation is measured as relatedness (phylogenetic or otherwise) of resources, scaled by the null expectation of random use of locally available resources. Thus, specialists use significantly clustered sets of resources, whereas generalists use over-dispersed resources. Intermediate species are classed as indiscriminate consumers. The effectiveness of this approach was assessed with differentially restricted null models, applied to a data set of 168 herbivorous insect species and their hosts. Incorporation of plant relatedness and relative abundance greatly improved specialisation measures compared to taxon counts or simpler null models, which overestimate the fraction of specialists, a problem compounded by insufficient sampling effort. This framework disambiguates the concept of specialisation with an explicit measure applicable to any mode of affinity among resource classes, and is also linked to ecological and evolutionary processes. This will enable a more rigorous deployment of ecological specialisation in empirical and theoretical studies.

Factors Associated With The Onset Of Hypertension In Women Of 50 Years Of Age Or More In A City In Southeastern Brazil.

To evaluate factors associated with hypertension in Brazilian women of 50 years of age or more. A cross-sectional population based study using self-reports. A total of 622 women were included. The association between sociodemographic, clinical and behavioral factors and the woman's age at the onset of hypertension was evaluated. Data were analyzed according to cumulative continuation rates without hypertension, using the life-table method and considering annual intervals. Next, a Cox multiple regression analysis model was adjusted to analyze the occurrence rates of hypertension according to various predictor variables. Significance level was pre-established at 5% (95% confidence level) and the sampling plan (primary sampling unit) was taken into consideration. Median age at onset of hypertension was 64.3 years. Cumulative continuation rate without hypertension at 90 years was 20%. Higher body mass index (BMI) at 20-30 years of age was associated with a higher cumulative occurrence rate of hypertension over time (coefficient=0.078; p<0.001). Being white was associated with a lower cumulative occurrence rate of hypertension over time (coefficient= -0.439; p=0.003), while smoking >15 cigarettes/day was associated with a higher rate over time (coefficient=0.485; p=0.004). The results of the present study highlight the importance of weight control in young adulthood and of avoiding smoking in preventing hypertension in women aged ≥50 years.

The Use Of Medication And Associated Factors Among Adults Living In Campinas, São Paulo, Brazil: Differences Between Men And Women.

The objective of this study was to verify factors associated with the use of medication by adults, with emphasis on the differences between men and women. It was a population-based, cross-sectional study with cluster sampling conducted in two stages in Campinas in the state of São Paulo in 2008. Among the 2,413 individuals aged 20 or older, the prevalence of use of at least one drug in the three days before the research was 45.4% (95% CI: 41.3 - 49.4) in men and 64.6% (95% CI: 59.8 - 69.2) in women. For adult men over 40 years old who were not working, former smokers, with one or more chronic diseases, with two or more health problems and who sought health care or a health professional in the two weeks preceding the research showed higher prevalence of medication use. Among women, a higher prevalence of use was observed in females over 40, obese, former smokers, who reported a short sleep pattern, with one or more chronic diseases and two or more health problems, and who reported seeking a health care service or professional in the past 15 days. The findings showed some differences in the determinants of drug use in relation to gender, revealing the greater importance of health-related behavior among women.

A New Platinum Complex With Tryptophan: Synthesis, Structural Characterization, Dft Studies And Biological Assays In Vitro Over Human Tumorigenic Cells.

A new platinum(II) complex with the amino acid L-tryptophan (trp), named Pt-trp, was synthesized and characterized. Elemental, thermogravimetric and ESI-QTOF mass spectrometric analyses led to the composition [Pt(C11H11N2O2)2]⋅6H2O. Infrared spectroscopic data indicate the coordination of trp to Pt(II) through the oxygen of the carboxylate group and also through the nitrogen atom of the amino group. The (13)C CP/MAS NMR spectroscopic data confirm coordination through the oxygen atom of the carboxylate group, while the (15)N CP/MAS NMR data confirm coordination of the nitrogen of the NH2 group to the metal. Density functional theory (DFT) studies were applied to evaluate the cis and trans coordination modes of trp to platinum(II). The trans isomer was shown to be energetically more stable than the cis one. The Pt-trp complex was evaluated as a cytotoxic agent against SK-Mel 103 (human melanoma) and Panc-1 (human pancreatic carcinoma) cell lines. The complex was shown to be cytotoxic over the considered cells.

Surface and subsurface erosion of primary enamel by acid beverages over time

This study evaluated the influence of a cola-type soft drink and a soy-based orange juice on the surface and subsurface erosion of primary enamel, as a function of the exposure time. Seventy-five primary incisors were divided for microhardness test (n=45) or scanning electron microscopy (SEM) analysis (n=30). The specimens were randomly assigned to 3 groups: 1 - artificial saliva (control); 2 - cola-type soft drink; and 3 - soy-based orange juice. Immersion cycles in the beverages were undertaken under agitation for 5 min, 3 times a day, during 60 days. Surface microhardness was measured at 7, 15, 30, 45 and 60 days. After 60 days, specimens were bisected and subsurface microhardness was measured at 30, 60, 90, 120, 150 and 200 µm from the surface exposed. Data were analyzed by ANOVA and Tukey’s test (a=0.05). Groups 2 and 3 presented similar decrease of surface microhardness. Regarding subsurface microhardness, group 2 presented the lowest values. SEM images revealed that after 60 days the surfaces clearly exhibited structural loss, unlike those immersed in artificial saliva. It may be concluded that erosion of the surfaces exposed to the cola-type soft drink was more accentuated and directly proportional to the exposure time.

An Eulerian Immersed Boundary Method for flow simulations over stationary and moving rigid bodies

The fluid flow over bodies with complex geometry has been the subject of research of many scientists and widely explored experimentally and numerically. The present study proposes an Eulerian Immersed Boundary Method for flows simulations over stationary or moving rigid bodies. The proposed method allows the use of Cartesians Meshes. Here, two-dimensional simulations of fluid flow over stationary and oscillating circular cylinders were used for verification and validation. Four different cases were explored: the flow over a stationary cylinder, the flow over a cylinder oscillating in the flow direction, the flow over a cylinder oscillating in the normal flow direction, and a cylinder with angular oscillation. The time integration was carried out by a classical 4th order Runge-Kutta scheme, with a time step of the same order of distance between two consecutive points in x direction. High-order compact finite difference schemes were used to calculate spatial derivatives. The drag and lift coefficients, the lock-in phenomenon and vorticity contour plots were used for the verification and validation of the proposed method. The extension of the current method allowing the study of a body with different geometry and three-dimensional simulations is straightforward. The results obtained show a good agreement with both numerical and experimental results, encouraging the use of the proposed method.

A hybrid heuristic for the multi-plant capacitated lot sizing problem with setup carry-over

This paper addresses the capacitated lot sizing problem (CLSP) with a single stage composed of multiple plants, items and periods with setup carry-over among the periods. The CLSP is well studied and many heuristics have been proposed to solve it. Nevertheless, few researches explored the multi-plant capacitated lot sizing problem (MPCLSP), which means that few solution methods were proposed to solve it. Furthermore, to our knowledge, no study of the MPCLSP with setup carry-over was found in the literature. This paper presents a mathematical model and a GRASP (Greedy Randomized Adaptive Search Procedure) with path relinking to the MPCLSP with setup carry-over. This solution method is an extension and adaptation of a previously adopted methodology without the setup carry-over. Computational tests showed that the improvement of the setup carry-over is significant in terms of the solution value with a low increase in computational time.

Temporal variation of the phytoplankton community at short sampling intervals in the Mundaú reservoir, Northeastern Brazil

The aim of this study was to determine how abiotic factors drive the phytoplankton community in a water supply reservoir within short sampling intervals. Samples were collected at the subsurface (0.1 m) and bottom of limnetic (8 m) and littoral (2 m) zones in both the dry and rainy seasons. The following abiotic variables were analyzed: water temperature, dissolved oxygen, electrical conductivity, total dissolved solids, turbidity, pH, total nitrogen, nitrite, nitrate, total phosphorus, total dissolved phosphorus and orthophosphate. Phytoplankton biomass was determined from biovolume values. The role abiotic variables play in the dynamics of phytoplankton species was determined by means of Canonical Correspondence Analysis. Algae biomass ranged from 1.17×10(4) to 9.21×10(4) µg.L-1; cyanobacteria had biomass values ranging from 1.07×10(4) to 8.21×10(4) µg.L-1. High availability of phosphorous, nitrogen limitation, alkaline pH and thermal stability all favored cyanobacteria blooms, particularly during the dry season. Temperature, pH, total phosphorous and turbidity were key factors in characterizing the phytoplankton community between sampling times and stations. Of the species studied, Cylindrospermopsis raciborskii populations were dominant in the phytoplankton in both the dry and rainy seasons. We conclude that the phytoplankton was strongly influenced by abiotic variables, particularly in relation to seasonal distribution patterns.

A prática de exercícios físicos em pacientes com transtornos alimentares

CONTEXTO: Diferentes estudos discutem a relação da prática excessiva de exercícios físicos com transtornos alimentares como estratégia para perda de peso. OBJETIVO: Revisar a literatura sobre a prática de exercícios físicos em pacientes com transtornos alimentares, discutindo definições, critérios diagnósticos e propostas terapêuticas. MÉTODOS: Levantamento bibliográfico foi realizado por meio de MedLine, LiLacs e Cochrane Library, com os termos "transtornos alimentares", "anorexia", "bulimia", "exercício físico excessivo", "atividade física", "exercício obrigatório", "exercício compulsivo" e "exercício excessivo". RESULTADOS: Dos 80 artigos encontrados, foram selecionados 12 que incluíam a investigação de um padrão de atividade física considerado excessivo em indivíduos acima dos 18 anos e uso de algum instrumento de avaliação para essa finalidade. A prática de exercícios físicos em pacientes com transtornos do comportamento alimentar é revisada. CONCLUSÃO: Não há consenso sobre critérios diagnósticos e instrumentos para considerar o exercício físico como inadequado ou excessivo e seu uso como recurso para perder peso. Por outro lado, a prática de exercícios físicos durante o tratamento de pacientes com transtornos alimentares pode ser benéfica desde que orientada e supervisionada.