Analysis of N-nitrosames in water using micellar electrokinetic chromatography (MEKC) and development of online and offline methods of extraction and enrichment of neutral polar analytes

Evaluation of the quality of the environment is essential for human wellness as pollutants in trace amounts can cause serious health problem. Nitrosamines are a group of compounds that are considered potential carcinogens and can be found in drinking water (as disinfection byproducts), foods, beverages and cosmetics. To monitor the level of these compounds to minimize daily intakes, fast and reliable analytical techniques are required. As these compounds are relatively highly polar, extraction and enrichment from environmental samples (aqueous) are challenging. Also, the trend of analytical techniques toward the reduction of sample size and minimization of organic solvent use demands new methods of analysis. In light of fulfilling these requirements, a new method of online preconcentration tailored to an electrokinetic chromatography is introduced. In this method, electroosmotic flow (EOF) was suppressed to increase the interaction time between analyte and micellar phase, therefore the only force to mobilize the neutral analytes is the interaction of analyte with moving micelles. In absence of EOF, polarity of applied potential was switched (negative or positive) to force (anionic or cationic) micelles to move toward the detector. To avoid the excessive band broadening due to longer analysis time caused by slow moving micelles, auxiliary pressure was introduced to boost the micelle movement toward the detector using an in house designed and built apparatus. Applying the external auxiliary pressure significantly reduced the analysis times without compromising separation efficiency. Parameters, such as type of surfactants, composition of background electrolyte (BGE), type of capillary, matrix effect, organic modifiers, etc., were evaluated in optimization of the method. The enrichment factors for targeted analytes were impressive, particularly; cationic surfactants were shown to be suitable for analysis of nitrosamines due to their ability to act as hydrogen bond donors. Ammonium perfluorooctanoate (APFO) also showed remarkable results in term of peak shapes and number of theoretical plates. It was shown that the separation results were best when a high conductivity sample was paired with a BGE of lower conductivity. Using higher surfactant concentrations (up to 200 mM SDS) than usual (50 mM SDS) for micellar electrokinetic chromatography (MEKC) improved the sweeping. A new method for micro-extraction and enrichment of highly polar neutral analytes (N-Nitrosamines in particular) based on three-phase drop micro-extraction was introduced and its performance studied. In this method, a new device using some easy-to-find components was fabricated and its operation and application demonstrated. Compared to conventional extraction methods (liquid-liquid extraction), consumption of organic solvents and operation times were significantly lower.

Análisis y simulación de un rectificador trifásico controlado Active Front End (AFE)

Este artículo presenta un resultado de investigación financiado con recursos propios en el que se expone un modelo en espacio de estados de un rectificador trifásico controlado active front end. Utilizando este modelo se deriva una ley de control orientado al voltaje (VOC), enfocado en el comportamiento como carga resistiva, factor de potencia unitario, el cual es probado mediante simulación usando el Toolbox SimPowerSystem en Simulink de Matlab®.

Análise e proposição de estratégias de estimação e controle de velocidade para motores de indução trifásicos

This study presents a proposal of speed servomechanisms without the use of mechanical sensors (sensorless) using induction motors. A comparison is performed and propose techniques for pet rotor speed, analyzing performance in different conditions of speed and load. For the determination of control technique, initially, is performed an analysis of the technical literature of the main control and speed estimation used, with their characteristics and limitations. The proposed technique for servo sensorless speed induction motor uses indirect field-oriented control (IFOC), composed of four controllers of the proportional-integral type (PI): rotor flux controller, speed controller and current controllers in the direct and quadrature shaft. As the main focus of the work is in the speed control loop was implemented in Matlab the recursive least squares algorithm (RLS) for identification of mechanical parameters, such as moment of inertia and friction coefficient. Thus, the speed of outer loop controller gains can be self adjusted to compensate for any changes in the mechanical parameters. For speed estimation techniques are analyzed: MRAS by rotóricos fluxes MRAS by counter EMF, MRAS by instantaneous reactive power, slip, locked loop phase (PLL) and sliding mode. A proposition of estimation in sliding mode based on speed, which is performed a change in rotor flux observer structure is displayed. To evaluate the techniques are performed theoretical analyzes in Matlab simulation environment and experimental platform in electrical machinery drives. The DSP TMS320F28069 was used for experimental implementation of speed estimation techniques and check the performance of the same in a wide speed range, including load insertion. From this analysis is carried out to implement closed-loop control of sensorless speed IFOC structure. The results demonstrated the real possibility of replacing mechanical sensors for estimation techniques proposed and analyzed. Among these, the estimator based on PLL demonstrated the best performance in various conditions, while the technique based on sliding mode has good capacity estimation in steady state and robustness to parametric variations.

In vitro studies of drug transformations: application to forensic toxicology

The forensic toxicologist faces challenges in the detection of drugs and poisons in biological samples due to transformations which occur both during life and after death. For example, changes can result from drug metabolism during life or from the use of formalin solution for post mortem embalming purposes. The former requires the identification of drug metabolites and the latter the identification of chemical reaction products in order to know which substances had been administered. The work described in this thesis was aimed at providing ways of tackling these challenges and was divided into two parts. Part 1 investigated the use of in vitro drug metabolism by human liver microsomes (HLM) to obtain information on drug metabolites and Part 2 investigated the chemical reactions of drugs and a carbamate pesticide with formalin solution and formalin-blood. The initial aim of part I was to develop an in vitro metabolism method using HLM, based on a literature review of previous studies of this type. MDMA was chosen as a model compound to develop the HLM method because its metabolism was known and standards of its metabolites were commercially available. In addition, a sensitive and selective method was developed for the identification and quantitation of hydrophilic phase I drug metabolites using LC/MS/MS with a conventional reverse-phase (C18) column. In order to obtain suitable retention factors for polar drug metabolites on this column, acetyl derivatives were evaluated for converting the metabolites to more lipophilic compounds and an optimal separation system was developed. Acetate derivatives were found to be stable in the HPLC mobile phase and to provide good chromatographic separation of the target analytes. In vitro metabolism of MDMA and, subsequently, of other drugs involved incubation of 4 µg drug substance in pH 7.4 buffer with an NADPH generating system (NGS) at 37oC for 90 min with addition of more NGS after 30 min. The reaction was stopped at 90 min by the addition of acetonitrile before extraction of the metabolites. Acetate derivatives of MDMA metabolites were identified by LC/MS/MS using multiple reaction monitoring (MRM). Three phase I metabolites (both major and minor metabolites) of MDMA were detected in HLM samples. 3,4-dihydroxy-methamphetamine and 4-hydroxy-3-methoxymethamphetamine were found to be major metabolites of MDMA whereas 3,4-methylenedioxyamphetamine was found to be a minor metabolite. Subsequently, ten MDMA positive urines were analysed to compare the metabolite patterns with those produced by HLM. An LC/MS method for MDMA and its metabolites in urine samples was developed and validated. The method demonstrated good linearity, accuracy and precision and insignificant matrix effects, with limits of quantitation of 0.025 µg/ml. Moreover, derivatives of MDMA and its metabolites were quantified in all 10 positive human urine samples. The urine metabolite pattern was found to be similar to that from HLM. The second aim of Part 1 was to use the HLM system to study the metabolism of some new psychoactive substances, whose misuse worldwide has necessitated the development of analytical methods for these drugs in biological specimens. Methylone and butylone were selected as representative cathinones and para-methoxyamphetamine (PMA) was chosen as a representative ring-substituted amphetamine, because of the involvement of these drugs in recent drug-related deaths, because of a relative lack of information on their metabolism, and because reference standards of their metabolites were not commercially available. An LC/MS/MS method for the analysis of methylone, butylone, PMA and their metabolites was developed. Three phase I metabolites of methylone and butylone were detected in HLM samples. Ketone reduction to β-OH metabolites and demethylenation to dihydroxy-metabolites were found to be major phase I metabolic pathways of butylone and methylone whereas N-demethylation to nor-methylone and nor-butylone were found to be minor pathways. Also, demethylation to para-hydroxyamphetamine was found to be a major phase I metabolic pathway of PMA whereas β-hydroxylation to β-OH-PMA was found to be a minor pathway. Formaldehyde is used for embalming, to reduce decomposition and preserve cadavers, especially in tropical countries such as Thailand. Drugs present in the body can be exposed to formaldehyde resulting in decreasing concentrations of the original compounds and production of new substances. The aim of part II of the study was to evaluate the in vitro reactions of formaldehyde with selected drug groups including amphetamines (amphetamine, methamphetamine and MDMA), benzodiazepines (alprazolam and diazepam), opiates (morphine, hydromorphone, codeine and hydrocodone) and with a carbamate insecticide (carbosulfan). The study would identify degradation products to serve as markers for the parent compounds when these were no longer detectable. Drugs standards were spiked in 10% formalin solution and 10% formalin blood. Water and whole blood without formalin were used for controls. Samples were analysed by LC/MS/MS at different times from the start, over periods of up to 30 days. Amphetamine, methamphetamine and MDMA were found to rapidly convert to methamphetamine, DMA and MDDMA respectively, in both formalin solution and formalin blood, confirming the Eschweiler-Clarke reaction between amine-containing compounds and formaldehyde. Alprazolam was found to be unstable whereas diazepam was found to be stable in both formalin solution and water. Both were found to hydrolyse in formalin solution and to give open-ring alprazolam and open-ring diazepam. Other alprazolam conversion products attached to paraformaldehyde were detected in both formalin solution and formalin blood. Morphine and codeine were found to be more stable than hydromorphone and hydrocodone in formalin solution. Conversion products of hydromorphone and hydrocodone attached to paraformaldehyde were tentatively identified in formalin solution. Moreover, hydrocodone and hydromorphone rapidly decreased within 24 h in formalin blood and could not be detected after 7 days. Carbosulfan was found to be unstable in formalin solution and was rapidly hydrolysed within 24 h, whereas in water it was stable up to 48 h. Carbofuran was the major degradation product, plus smaller amounts of other products, 3-ketocarbofuran and 3-hydrocarbofuran. By contrast, carbosulfan slowly hydrolysed in formalin-blood and was still detected after 15 days. It was concluded that HLM provide a useful tool for human drug metabolism studies when ethical considerations preclude their controlled administration to humans. The use of chemical derivatisation for hydrophilic compounds such as polar drug metabolites for analysis by LC/MS/MS with a conventional C18 column is effective and inexpensive, and suitable for routine use in the identification and quantitation of drugs and their metabolites. The detection of parent drugs and their metabolites or conversion and decomposition products is potentially very useful for the interpretation of cases in forensic toxicology, especially when the original compounds cannot be observed.

La divination par les sorts dans le monde oriental méditerranéen du IIe au VIe siècle après J.-C. : étude comparative des sortes Homericae, sortes Astrampsychi et tables d'astragalomancie en Asie mineure

Cette thèse se propose de comparer exhaustivement trois systèmes de divination par voie de tirage au sort qui ont été contemporains dans l’antiquité tardive. À l’aide d’une analyse rigoureuse des thèmes évoqués, des stratégies rhétoriques employées, du vocabulaire présent et des probabilités d’obtention des réponses offertes, plusieurs points communs ressortent. Les énoncés positifs et négatifs se veulent, dans tous les cas, équilibrés et ils optent souvent pour des variantes temporelles afin de tempérer les prédictions. Lorsqu’ils ne s’appliquent pas à des questions spécifiques, ils misent sur l’imaginaire des consultations littéraires qui allie proverbes et éléments épiques, sans toutefois déroger des thèmes communs liés aux préoccupations quotidiennes des consultants. La rhapsodomancie s’inscrit dans cette mouvance et prouve à quel point l’épopée est une source propice à l’élaboration de systèmes oraculaires, sans jamais que le contexte narratif et littéraire des vers sélectionnés n’entre en jeu.

Voltage and current spectra for matrix power converters

Matrix power converters are used for transforming one alternating-current power supply to another, with different peak voltage and frequency. There are three input lines, with sinusoidally varying voltages which are 120◦ out of phase one from another, and the output is to be delivered as a similar three-phase supply. The matrix converter switches rapidly, to connect each output line in sequence to each of the input lines in an attempt to synthesize the prescribed output voltages. The switching is carried out at high frequency and it is of practical importance to know the frequency spectra of the output voltages and of the input and output currents. We determine in this paper these spectra using a new method, which has significant advantages over the prior default method (a multiple Fourier series technique), leading to a considerably more direct calculation. In particular, the determination of the input current spectrum is feasible here, whereas it would be a significantly more daunting procedure using the prior method instead.

Nonlinear development of matrix-converter instabilities

Matrix converters convert a three-phase alternating-current power supply to a power supply of a different peak voltage and frequency, and are an emerging technology in a wide variety of applications. However, they are susceptible to an instability, whose behaviour is examined herein. The desired “steady-state” mode of operation of the matrix converter becomes unstable in a Hopf bifurcation as the output/input voltage transfer ratio, q, is increased through some threshold value, qc. Through weakly nonlinear analysis and direct numerical simulation of an averaged model, we show that this bifurcation is subcritical for typical parameter values, leading to hysteresis in the transition to the oscillatory state: there may thus be undesirable large-amplitude oscillations in the output voltages even when q is below the linear stability threshold value qc.

Soil management system effects on N availability and tree productivity in chestnut planatations under Mediterranean conditions

Soil tillage with chisel ploughing is the conventional soil management system in chestnut stands for fruit production in Northern Portugal. A study was developed to assess the effects of three soil management systems on in situ soil N mineralization dynamics, tree nutrition status and fruit productivity, in a 50-yr old chestnut stand. The treatments were: conventional tillage with a chisel ploughing twice a year (CT), no-tillage with rainfed improved pasture with leguminous and grasses plants (NIP), and no-tillage with spontaneous herbaceous vegetation - natural pasture (NP). The CT treatment showed a strong increase of the soil N mineral concentration following soil disturbance by tillage, but the cumulative net N mineralized along the year was significantly lower (51.8 kg ha-1) than in the NIP (85.1 kg ha-1) treatment. The NP treatment (65.9 kg ha-1) did not cause a reduction in the soil N mineralization when compared to the CT treatment. The mineralization rate (g mineralized N kg-1 total N) in 2004 was about 26, 30 and 38 in the treatments CT, NP and NIP, respectively. Treatments showed different soil N dynamics, the proportion of mineralized NO3--N being lower in the NP (10-48%) than in CT and NIP treatments (53-74%). Our study indicates that no-tillage systems improve the tree nutrition status and enhance productivity

La multifuncionalidad de los SIALES en zonas rurales de países en desarrollo. El caso de la agroindustria panelera Colombiana.

La multifuncionalidad (MF) de la agricultura tradicionalmente ha sido abordada desde la perspectiva de países desarrollados y muy pocas veces se ha analizado en el contexto de países en desarrollo. El presente estudio, mediante un trabajo de campo que consulta a varios actores sociales, identifica la presencia de múltiples funciones sociales, económicas y ambientales relevantes que van mas allá de la función productiva en el caso de la agroindustria de la panela (Azúcar no centrifugado) en Colombia y establece características diferenciales en la relevancia y ámbito de estas funciones en tres sistemas agroalimentarios locales (SIAL) de la panela. Finalmente, a partir de estos hallazgos plantea nuevos retos de investigación para la mediación de la MF y para el diseño de políticas basadas en la MF que permitan activar y fortalecer los SIAL de países en desarrollo.   ABSTRACT The multifunctionality (MF) of the agriculture traditionally has been approached from the perspective of developed countries and very few times it has been analyzed in the context of countries in development. The present study, by means of a field work that consults several social actor, identifies the presence of multiple social, economic and environmental functions that they go beyond the productive function in the case of the agroindustry of the panela (not centrifuged sugar) in Colombia and it establishes differential characteristics  in the relevance and environment of these function in three local agrifood systems (LAS) of the panela. Finally, starting from these discoveries it outlines new research challenges to measure the MF and for the design of policies based on the MF that allow to activate and strengthen LAS of undeveloped countries.

An application of an extended effort-reward imbalance model to police absenteeism behaviour

Purpose – Frequent absences from work can be highly disruptive, whilst also potentially indicating problematic working conditions that can lead to increased withdrawal behaviour. The purpose of this paper is to test the predictive capability of an expanded effort-reward imbalance model on employee absenteeism within the context of policing.

Design/methodology/approach – Three separate reward systems are identified by the effort-reward imbalance model. In this study, the authors assessed these individual components for their contribution to officer withdrawal behaviour in the form of absenteeism frequency. Data were gathered from a sample of operational officers (n=553) within a large Australian police agency.

Findings – Findings indicate that there was a strong influence of social rewards such as social support and recognition in the workplace on officer absenteeism rates. Low workload was associated with a higher frequency of absenteeism suggesting a potential underloading effect. There were a number of significant interactions providing support for the effort-reward imbalance mechanism and the separation of the reward construct. Security rewards were particularly influential and significantly moderated the relationship between effort and absenteeism.

Research limitations/implications – Differential effects of occupational rewards were identified in the study, indicating that there are significant opportunities for expansion of the effort-reward imbalance model along with opportunities for HRM practitioners in terms of employee recognition and remuneration programmes. This research was focused on a specific sample of operational officers, therefore should be expanded to include multiple occupational groups.

Originality/value – This paper considers and expanded model of worker strain and contributes a longitudinal assessment of the association between perceived effort and reward systems and worker absenteeism.

A review of the game-centred approaches to teaching and coaching literature since 2006

Background: In 2006, Oslin and Mitchell published a review of the game-centred approaches (GCAs) to teaching and coaching literature highlighting a number of core concepts thought to provide justification for the use of GCAs including (a) its potential to enhance participant motivation, (b) potential for tactical transfer, and (c) development of decision-making skills and effective decision-makers. Oslin and Mitchell also suggested recommendations for future GCA research.Purpose: The purpose of this paper was threefold: (a) to present a review of Anglophone research into GCAs building on the previous review of Oslin and Mitchell published in 2006; (b) to identify new trends in research since 2006; and (c) to investigate the extent to which the initial suggestions and future research directions suggested by Oslin and Mitchell have been addressed.Data collection: GCA literature since 2006 was searched systematically using a three-phase approach. Phase 1 included initial searches of the EBSCO database using terms associated with GCAs and their acronyms (e.g. TGfU (teaching games for understanding), GS (Game Sense), etc.). Phase 2 expanded the search adopting more generic terms from keywords located in the recent literature (e.g. teaching games, tactical development, game performance, etc.). Multiple searches through the EBSCO database were conducted, whereby key terms were cross-referenced until a saturation point was reached. Phase 3 involved removing those publications that were not empirical, peer reviewed, intervention studies or published in English.Findings: Forty-four studies on GCA implementation were identified and the methodological and substantive nature of these studies was examined. The review noted two positive trends: (a) the expansion of research which included the growth of research on GCAs in Europe and Southeast Asia and (b) an increased amount of research in the affective domain. The review found, however, that a number of key challenges remain within GCA research, which include (a) the need for improved articulation of GCA verification procedures; (b) further assessment of tactical awareness development; (c) extended inquiry about GCAs in coaching contexts; (d) more research into ‘newer’ GCAs (i.e. PP (play practice), IGCM (invasion game competence model) and TDLM (tactical decision learning model)); (e) use of longitudinal research designs; (f) inadequate length of GCA induction and training for teachers and coaches, and (g) examination of GCAs in terms of fitness and special populations.Conclusions: GCA pedagogies are of significant importance as they have the potential to promote change within current adult-centric cultures of youth sport and encourage engagement in physical activity over the life course. To meet these needs, it is recommended that GCA research undergo continued expansion with the use of research designs and data collection techniques that aid the examination of different philosophical understandings of GCAs (e.g. ethnographic, phenomenological and psycho-phenomenological). These are paramount to the exploration of ‘who the individual is’ and ‘how the learner is motivated to continue to participate’ and further permit the in-depth, contextual and ecological analysis of GCA interventions that Oslin and Mitchell recommended in their previous review.

Using a delphi process to extend a rural mental health workforce recruitment initiative

Purpose – The Gippsland Mental Health Vacation School program has been shown to positively change student participants’ interest and attitudes to living and working in a rural area. A range of factors are impacting on the future viability of the initiative including: limitations on the number of student participants, the reusability of content, staffing, time pressures, a dwindling funding base, and a drop-off in interest in living and working in a rural setting. The paper aims to discuss these issues. Design/methodology/approach – A three-phase Delphi Study was employed to engage with expert knowledge of the program’s key stakeholder groups (student participants and service provider staff) in order to inform the initial steps of shifting the program toward a blended model, distributed across space and time. Findings – The results suggest that: first, the current mode of delivery, a week-long intensive face-to-face format, should be transitioned to a more sustainable blended learning approach that includes both on-line content and an in situ component; and second, trailing the use of social media as a mechanism to maintain student interest in rural mental health work following the vacation school. Originality/value – This study highlights how the transition to a sustainable approach to the delivery of a novel rural mental health workforce recruitment strategy was informed through a three-phase Delphi Study that involved the key stakeholders (groups of student participants and service provider staff). The study has important implications for addressing the shortage of mental health practitioners in rural areas. It will and be of interest to educators, administrators, researchers and bureaucrats.

Nitrogen removal and sustainability of vertical flow constructed wetlands for small scale wastewater treatment

The challenge for wastewater professionals is to design and operate treatment processes that support human well being and are environmentally sensitive throughout the life-cycle. This research focuses on one technology for small-scale wastewater treatment: the vertical flow constructed wetland (VFCW), which is herein investigated for the capacity to remove ammonium and nitrate nitrogen from wastewater. Hydraulic regime and presence/absence of vegetation are the basis for a three-phase bench scale experiment to determine oxygen transfer and nitrogen fate in VFCWs. Results show that 90% NH4+-N removal is achieved in aerobic downflow columns, 60% NO3--N removal occurs in anaerobic upflow columns, and 60% removal of total nitrogen can be achieved in downflow-upflow in-series. The experimental results are studied further using a variably saturated flow and reactive transport model, which allows a mechanistic explanation of the fate and transport of oxygen and nitrogen. The model clarifies the mechanisms of oxygen transport and nitrogen consumption, and clarifies the need for readily biodegradable COD for denitrification. A VFCW is then compared to a horizontal flow constructed wetland (HFCW) for life cycle environmental impacts. High areal emissions of greenhouse gases from VFCWs compared to HFCWs are the driver for the study. The assessment shows that because a VFCW is only 25% of the volume of an HFCW designed for the same treatment quality, the VFCW has only 25-30% of HFCW impacts over 12 impact categories and 3 damage categories. Results show that impacts could be reduced by design improvements. Design recommendations are downflow wetlands for nitrification, upflow wetlands for denitrification, series wetlands for total nitrogen removal, hydraulic load of 142 L/m2d, 30 cm downflow wetland depth, 1.0 m upflow wetland depth, recycle, vegetation and medium-grained sand. These improvements will optimize nitrogen removal, minimize gaseous emissions, and reduce wetland material requirements, thus reducing environmental impact without sacrificing wastewater treatment quality.

Perceptions of Character Education in a Seventh-Day Adventist School

Character education has been viewed by many educators as having significant historical, academic, and social value. Many stakeholders in education argue for character development as a curricular experience. While understanding the degree to which character education is of worth to stakeholders of institutions is important, understanding students, teachers, and administrators perspectives from their lived experiences is likewise significant. The purpose of this phenomenological study was to gain a deeper understanding of character education within a Biblical framework environment by examining the lived experiences of students, administrators, and teachers of a Seventh-day Adventist School. Phenomenology describes individuals’ daily experiences of phenomena, the manner in which these experiences are structured, and focuses analysis on the perspectives of the persons having the experience (Moustakas, 1994). ). This inquiry was undertaken to answer the question: What are the perceptions of students, teachers, and an administrator toward character education in a Seventh-day Adventist school setting? Ten participants (seven students and three adults) formed the homogeneous purposive sample, and the major data collection tool was semi-structured interviews (Patton, 1990; Seidman, 2006). Three 90-minute open-ended interviews were conducted with each of the participants. Data analysis included a three-phase process of description, reduction and interpretation. The findings from this study revealed that participants perceived that their involvement in the school’s character education program decreased the tendency to violence, improved their conduct and ethical sensibility, enhanced their ability to engage in decision-making concerning social relationships and their impact on others, brought to their attention the emerging global awareness of moral deficiency, and fostered incremental progress from practice and recognition of vices to their acquisition of virtues. The findings, therefore, provide a model for teaching character education from a Seventh-day Adventist perspective. The model is also relevant for non-Seventh day Adventists who aspire to teach character education as a means to improving social and moral conditions in schools.