Evaluation of comprehensive two-dimensional gas chromatography coupled to rapid scanning quadrupole mass spectrometry for quantitative analysis

Comprehensive two-dimensional gas chromatography (GC x GC) is a powerful technique that provides excellent separation and identification of analytes in highly complex samples with considerable increase in GC peak capacities. However, since second dimension analyses are very fast, detectors with a rapid acquisition rate are required. Over the last years, quite a number of studies have discussed the potential and limitations of the combination GC x GC with a variety of quadrupole mass spectrometers. The present research focuses on the evaluation of qMS effectiveness at a 10,000-amu/s scan speed and 20-Hz scan frequency for the identification (full scan mode acquisition-TIC) and quantification (extracted ion chromatogram) of target pesticide residues in tomato samples. The following MS parameters have been evaluated: number of data points per peak, mass spectrum quality, peak skewing, and sensitivity. The validated proposed GC x GC/qMS method presented satisfactory results in terms of repeatability (coefficient of variation lower than 15%), accuracy (84-117%), and linearity (ranging from 25 to 500 ng/g), while significant enhancement in sensitivity was observed (a factor of around 10) under scan conditions. (C) 2012 Elsevier B.V. All rights reserved.

On-line microwave-based preconcentration device for inductively coupled plasma atomic emission spectrometry: Application to the elemental analysis of spirit samples

A microwave-based thermal nebulizer (MWTN) has been employed for the first time as on-line preconcentration device in inductively coupled plasma atomic emission spectrometry (ICP-AES). By the appropriate selection of the experimental conditions, the MWTN could be either operated as a conventional thermal nebulizer or as on-line analyte preconcentration and nebulization device. Thus, when operating at microwave power values above 100 W and highly concentrated alcohol solutions, the amount of energy per solvent mass liquid unit (EMR) is high enough to completely evaporate the solvent inside the system and, as a consequence, the analyte is deposited (and then preconcentrated) on the inner walls of the MWTN capillary. When reducing the EMR to the appropriate value (e.g., by reducing the microwave power at a constant sample uptake rate) the retained analyte is swept along by the liquid-gas stream and an analyte-enriched aerosol is generated and next introduced into the plasma cell. Emission signals obtained with the MWTN operating in preconcentration-nebulization mode improved when increasing preconcentration time and sample uptake rate as well as when decreasing the nozzle inner diameter. When running with pure ethanol solution at its optimum experimental conditions, the MWTN in preconcentration-nebulization mode afforded limits of detection up to one order of magnitude lowers than those obtained operating the MWTN exclusively as a nebulizer. To validate the method, the multi-element analysis (i.e. Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Pb and Zn) of different commercial spirit samples in ICP-AES has been performed. Analyte recoveries for all the elements studied ranged between 93% and 107% and the dynamic linear range covered up to 4 orders of magnitude (i.e. from 0.1 to 1000 μg L−1). In these analysis, both MWTN operating modes afforded similar results. Nevertheless, the preconcentration-nebulization mode permits to determine a higher number of analytes due to its higher detection capabilities.

IMPROVED SAMPLE INTRODUCTION SYSTEMS FOR INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROMETRY AND THEIR APPLICATION TO THE ANALYSIS OF SIMPLE AND COMPLEX MATRICES

The objective of this thesis is to explore new and improved methods for greater sample introduction efficiency and enhanced analytical performance with inductively coupled plasma optical emission spectrometry (ICP-OES). Three projects are discussed in which the capabilities and applications of ICP-OES are expanded: 1. In the first project, a conventional ultrasonic nebuliser was modified to replace the heater/condenser with an infrared heated pre-evaporation tube. In continuation from previous works with pre-evaporation, the current work investigated the effects of heating with infrared block and rope heaters on two different ICP-OES instruments. Comparisons were made between several methods and setups in which temperatures were varied. By monitoring changes to sensitivity, detection limit, precision, and robustness, and analyzing two certified reference materials, a method with improved sample introduction efficiency and comparable analytical performance to a previous method was established. 2. The second project involved improvements to a previous work in which a multimode sample introduction system (MSIS) was modified by inserting a pre-evaporation tube between the MSIS and torch. The new work focused on applying an infrared heated ceramic rope for pre-evaporation. This research was conducted in all three MSIS modes (nebulisation mode, hydride generation mode, and dual mode) and on two different ICP-OES instruments, and comparisons were made between conventional setups in terms of sensitivity, detection limit, precision, and robustness. By tracking both hydride-forming and non-hydride forming elements, the effects of heating in combination with hydride generation were probed. Finally, optimal methods were validated by analysis of two certified reference materials. 3. A final project was completed in collaboration with ZincNyx Energy Solutions. This project sought to develop a method for the overall analysis of a 12 M KOH zincate fuel, which is used in green energy backup systems. By employing various techniques including flow injection analysis and standard additions, a final procedure was formulated for the verification of K concentration, as well as the measurement of additives (Al, Fe, Mg, In, Si), corrosion products (such C from CO₃²¯), and Zn particles both in and filtered from solution. Furthermore, the effects of exposing the potassium zincate electrolyte fuel to air were assessed.

Stability analysis based on birfurcation theory of the DSTATCOM operating in current control mode

This paper presents the stability analysis for a distribution static compensator (DSTATCOM) that operates in current control mode based on bifurcation theory. Bifurcations delimit the operating zones of nonlinear circuits and, hence, the capability to compute these bifurcations is of important interest for practical design. A control design for the DSTATCOM is proposed. Along with this control, a suitable mathematical representation of the DSTATCOM is proposed to carry out the bifurcation analysis efficiently. The stability regions in the Thevenin equivalent plane are computed for different power factors at the point of common coupling. In addition, the stability regions in the control gain space, as well as the contour lines for different Floquet multipliers are computed. It is demonstrated through bifurcation analysis that the loss of stability in the DSTATCOM is due to the emergence of a Neimark bifurcation. The observations are verified through simulation studies.

Small signal stability analysis of a DFIG based wind power system with tuned damping controller under super/sub-synchronous mode of operation

This paper focuses on the super/sub-synchronous operation of the doubly fed induction generator (DFIG) system. The impact of a damping controller on the different modes of operation for the DFIG based wind generation system is investigated. The co-ordinated tuning of the damping controller to enhance the damping of the oscillatory modes using bacteria foraging (BF) technique is presented. The results from eigenvalue analysis are presented to elucidate the effectiveness of the tuned damping controller in the DFIG system. The robustness issue of the damping controller is also investigated

A coupled SPH/FEM analysis of portable water filled barriers

Portable water filled barriers (PWFB) are semi-rigid roadside barriers which have the potential to display good crash attenuation characteristics at low and moderate impact speeds. The traditional mesh based numerical methods alone fail to simulate this type of impact with precision, stability and efficiency. This paper proposes to develop an advanced simulation model based on the combination of Smoothed Particles Hydrodynamics (SPH), a meshless method, and finite element method (FEM) for fluid-structure analysis using the commercially available software package LS-Dyna. The interaction between SPH particles and FEA elements is studied in this paper. Two methods of element setup at the element boundary were investigated. The response of the impacted barrier and fluid inside were analysed and compared. The system response and lagging were observed and reported in this paper. It was demonstrated that coupled SPH/FEM can be used in full scale PWFB modelling application. This will aid the research in determining the best initial setup to couple FEA and SPH in road safety barrier for impact response and safety analysis in the future.

The kineikonic mode : a multimodal analysis of students’ claymation movies

Globalised communication in society today is characterised by multimodal forms of meaning making in the context of increased cultural and linguistic diversity. This research paper responds to these imperatives, applying Halliday's (1978, 1994) categories of systemic functional linguistics - representational or ideational, interactive or interpersonal, and compositional or textual meanings. Following the work of Kress (2000), van Leeuwen (Kress and van Leeuwen, 1996), and Jewitt (2006), multimodal semiotic analysis is applied to claymation movies that were collaboratively designed by Year 6 students. The significance of this analysis is the metalanguage for textual work in the kineikonic mode - moving images.

Fluid-structure interaction analysis of full scale vehicle-barrier impact using coupled SPH-FEA

Portable water-filled barriers (PWFB) are roadside structures used to separate moving traffic from work-zones. Numerical PWFB modelling is preferred in the design stages prior to actual testing. This paper aims to study the fluid-structure interaction of PWFB under vehicular impact using several methods. The strategy to treat water as non-structural mass was proposed and the errors were investigated. It was found that water can be treated with the FEA-NSM model for velocities higher than 80kmh-1. However, full SPH/FEA model is still the best treatment for water and necessary for lower impact velocities. The findings in this paper can be used as guidelines for modelling and designing PWFB.

Fluid-structure interaction analysis by coupled FE-SPH model based on a novel searching algorithm

Fluid–Structure Interaction (FSI) problem is significant in science and engineering, which leads to challenges for computational mechanics. The coupled model of Finite Element and Smoothed Particle Hydrodynamics (FE-SPH) is a robust technique for simulation of FSI problems. However, two important steps of neighbor searching and contact searching in the coupled FE-SPH model are extremely time-consuming. Point-In-Box (PIB) searching algorithm has been developed by Swegle to improve the efficiency of searching. However, it has a shortcoming that efficiency of searching can be significantly affected by the distribution of points (nodes in FEM and particles in SPH). In this paper, in order to improve the efficiency of searching, a novel Striped-PIB (S-PIB) searching algorithm is proposed to overcome the shortcoming of PIB algorithm that caused by points distribution, and the two time-consuming steps of neighbor searching and contact searching are integrated into one searching step. The accuracy and efficiency of the newly developed searching algorithm is studied on by efficiency test and FSI problems. It has been found that the newly developed model can significantly improve the computational efficiency and it is believed to be a powerful tool for the FSI analysis.

Confirmatory factor analysis of the baby eating behaviour questionnaire and associations with infant weight, gender and feeding mode in an Australian sample

The aim of this study was to evaluate the factor structure of the Baby Eating Behaviour Questionnaire (BEBQ) in an Australian community sample of mother-infant dyads. A secondary aim was to explore the relationship between the BEBQ subscales and infant gender, weight and current feeding mode. Confirmatory factor analysis (CFA) utilising structural equation modelling examined the hypothesised 4-factor model of the BEBQ. Only mothers (N=467) who completed all items on the BEBQ (infant age: M=17 weeks, SD=3 weeks) were included in the analysis. The original 4-factor model did not provide an acceptable fit to the data due to poor performance of the Satiety responsiveness factor. Removal of this factor (3 items) resulted in a well-fitting 3-factor model. Cronbach’s α was acceptable for the Enjoyment of food (α=0.73), Food responsiveness (α=0.78) and Slowness in eating (α=0.68) subscales but low for the Satiety responsiveness (α=0.56) subscale. Enjoyment of food was associated with higher infant weight whereas Slowness in eating and Satiety responsiveness were both associated with lower infant weight. Differences on all four subscales as a function of feeding mode were observed. This study is the first to use CFA to evaluate the hypothesised factor structure of the BEBQ. Findings support further development work on the Satiety responsiveness subscale in particular, but confirm the utility of the Enjoyment of food, Food responsiveness and Slowness in eating subscales.

Dynamics of mode transitions in inductively-coupled plasmas

The dynamics of transitions between the electrostatic and electromagnetic discharge modes of the low-frequency (460 kHz) inductively coupled plasma (LF ICP) reactor is studied. A series of images of plasma glows in Ar and N2 gases taken in the process of continuous variation of the input power confirms the discharge bistability and hysteresis. The operation regimes and parameters making the LF ICP reactor attractive for materials synthesis and processing applications are discussed.

Power transfer and mode transitions in low-frequency inductively coupled plasmas

Operation and mode jumps in low-frequency (500 kHz) radio-frequency inductively coupled plasmas are investigated. The discharge is driven by a flat inductive coil which can excite the electrostatic (E) and electromagnetic (H) discharge modes. The power transfer efficiency and mode transition behavior are studied. It is found that the power reflection coefficient as a function of the input power is minimal in the vicinity of the mode transitions and exhibits hysteresis, which is also observed when the operating gas pressure is varied.

Discharge mode transitions in low-frequency inductively coupled plasmas with internal oscillating current sheets

Transitions between the two discharge modes in a low-frequency (∼460 kHz) inductively coupled plasma sustained by an internal oscillating radio frequency (rf) current sheet are studied. The unidirectional rf current sheet is generated by an internal antenna comprising two orthogonal sets of synphased rf currents driven in alternately reconnected copper litz wires. It is shown that in the low-to-intermediate pressure range the plasma source can be operated in the electrostatic (E) and electromagnetic (H) discharge modes. The brightness of the E -mode argon plasma glow is found remarkably higher than in inductively coupled plasmas with external flat spiral "pancake" coils. The cyclic variations of the input rf power result in pronounced hysteretic variations of the optical emission intensity and main circuit parameters of the plasma source. Under certain conditions, it appears possible to achieve a spontaneous E→H transition ("self-transition"). The observed phenomenon can be attributed to the thermal drift of the plasma parameters due to the overheating of the working gas. The discharge destabilizing factors due to the gas heating and step-wise ionization are also discussed. © 2005 American Vacuum Society.