Performance of flowing sample neutron activation analysis technique for determination of multi-elemental content

In order to measure and obtain reliable data about elements via measuring of short-lived isotopes in liquid samples using neutron activation analysis, experiments have been carried out using a flowing sample neutron activation analysis method. During this work the performance and reliability for the proposed method have been tested using synthetic multi elements liquid samples. The radionuclide, associated elements and their concentration level have been measured using a counting system with a fixed dead-time. An HPGe spectrometry system was used to determine the most important γ-ray energies and intensities of these isotopes. The obtained results demonstrated the reliability and accuracy (bias <5 % and zeta score <2) of the tested method for determination the elemental content of liquid samples.     

Electrochemical detectors for flowing liquid systems

A review of the theory, applications, and advantages and disadvantages of the major types of electrochemical detectors in flowing systems is presented in this report.     

Optimisation of poly-beta-hydroxyalkanoate analysis using gas chromatography for enhanced biological phosphorus removal systems

Poly-beta-hydroxyalkanoate (PHA) is a polymer commonly used in carbon and energy storage for many different bacterial cells. Polyphosphate accumulating organisms (PAOs) and glycogen accumulating organisms (GAOs), store PHA anaerobically through metabolism of carbon substrates such as acetate and propionate. Although poly-beta-hydroxybutyrate (PHB) and poly-beta-hydroxyvalerate (PHV) are commonly quantified using a previously developed gas chromatography (GC) method, poly-beta-hydroxy-2-methylvalerate (PH2MV) is seldom quantified despite the fact that it has been shown to be a key PHA fraction produced when PAOs or GAOs metabolise propionate. This paper presents two GC-based methods modified for extraction and quantification of PHB, PHV and PH2MV from enhanced biological phosphorus removal (EBPR) systems. For the extraction of PHB and PHV from acetate fed PAO and GAO cultures, a 3% sulfuric acid concentration and a 2-20 h digestion time is recommended, while a 10% sulfuric acid solution digested for 20h is recommended for PHV and PH2MV analysis from propionate fed EBPR systems.     

14 MeV neutron activation analysis applied to a non-aqueous flowing system

The feasibility and advantages of fast neutron activation analysis in a non-aqueous flowing system, using economical irradiation techniques are outlined. The application of the method to the determination in solution of elements producing isotopes with half lives in the range 588—29.4 sec, the selection of the optimum flow rate to minimise interferences for each element, and their limits of detection are also given. A method for the prediction of the optimum flow rate, on a given system, for the determination of any element producing an isotope of known half life is also given.     

Optimisation and characterisation of silica-based reversed-phase liquid chromatographic systems for the analysis of basic pharmaceuticals

Reversed-phase liquid chromatography using silica-based columns is successfully applied in many separations. However, also some drawbacks exist, i.e. the analysis of basic compounds is often hampered by ionic interaction of the basic analytes with residual silanols present on the silica surface, which results in asymmetrical peaks and irreproducible retention. In this review, options to optimise the LC analysis of basic pharmaceutical compounds are discussed, i.e. eluent optimisation (pH, silanol blockers) and stationary phase optimisation (development of new columns with minimised ionic interactions). The applicability of empirical based, thermodynamically based and test methods based on a retention model to characterise silica-based reversed phase stationary phases, as well as the influence of the eluent composition on the LC analysis of basic substances is described. Finally, the applicability of chemometrical techniques in column classification is shown.     

Optimisation of total-reflection X-ray fluorescence for aerosol analysis

The capabilities of total-reflection X-ray fluorescence (TXRF) analysis were investigated to develop an efficient, simple, rapid and low cost analytical method for aerosols. The technique involves direct impaction of airborne particulate matter on the quartz sample-reflector discs for TXRF. Special attention was paid to bounce-off effects, and hence the aerosol size distributions for the impactor stages; influence of siliconizing the quartz discs on the adhesion of particles; choice of the internal standard; local distribution of the material deposited on the quartz disc; and alternative materials for aerosol collection. Moreover, the proposed method could be used in combination with a one-stage impactor for total aerosol mass collection and analysis.     

A new flow cell design for chemiluminiscence analysis

The present study proposes a new flow cell called a bundle cell for chemiluminescence analysis. The results obtained were compared with those achieved by manual and automated batch procedures and flow manifolds with different cells: an common quartz flow cell, a helix cell and the most used spiral cell. Figures of merit such as limit of detection, sensitivity, accuracy and precision for the Cr(III) determination were established with light emission produced by catalysed Cr(III) luminol oxidation by hydrogen peroxide in a basic aqueous solution. An improvement in sensitivity about 50% as compared with the spiral cell and even larger with respect to the other flow cells tested was observed. The limit of detection provided was lower than those obtained with the other flow cells. In reference to the batch mode, similar results were obtained with the bundle flow cell. Good results were obtained for several real water samples containing chromium at different concentrations.     

Initial bacterial attachment in slow flowing systems: effects of cell and substrate surface properties

Bacterial biofilm can have significant effects on the behaviors and/or performance of natural and man-made systems. Understanding the factors governing initial bacterial attachment is critical to biofilm management. In this study, the initial attachment of three bacteria, Pseudomonas aeruginosa, Escherichia coli and Pseudomonas putida, on two substrates, glass and octadecyltrichlorosilane (OTS) modified glass, was examined in flow chambers. The flow chambers were designed and operated to mimic slow moving water bodies and minimize the gravitational settlement of cells. The hydrophobicity of bacterial surface was evaluated by partitioning of cells to the water-hexadecane interface and the liquid contact angles on cell layers collected on filter papers. On the more hydrophilic glass surface, the attachment trend was found to be E. coli>P. putida>P. aeruginosa, while the opposite trend was observed on the hydrophobic, OTS modified surface. The attachment trend on glass could be explained by the magnitude of the negative interaction energy at secondary minima, as predicted by the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory. The much higher attachments of P. aeruginosa and P. putida on the OTS-modified substrate, on the other hand, suggested that these cells could overcome the energy barrier between the primary and secondary minima of interaction energy to become attached to the primary minimum. The extent of primary-minimum attachment appeared to correlate with the scale of the energy barrier, with higher attachments in the bacteria-substrate combinations of lower energy barriers. The study generated important insights into the effects of cell and substrate surface properties on initial bacterial attachment.     

A review of chemical gradient systems for cell analysis

Microfluidic spatial and temporal gradient generators have played an important role in many biological assays such as in the analysis of wound healing, inflammation, and cancer metastasis. Chemical gradient systems can also be applied to other fields such as drug design, chemical synthesis, chemotaxis, etc. Microfluidic systems are particularly amenable to gradient formation, as the length scales used in chips enable fluid processes that cannot be conducted in bulk scale. In this review we discuss new microfluidic devices for gradient generation and applications of those systems in cell analysis.     

Optimisation of plasma techniques for trace analysis of refractory metals

Besides atomic absorption spectrometry, the plasma techniques can be seen as state-of-the-art instrumentation in an industrial laboratory for the analysis of trace elements today. For the analysis of refractory metals, e.g. Mo and W, the determination limits which can be reached by ICP-AES techniques are mainly restricted by the spectral background of the matrix. Advantages and disadvantages of sequential and simultaneous detection as well as different methods of evaluation, such as Kaiman filtering and multiple component spectral fitting, are discussed. The results are compared with trace matrix separation techniques and on-line coupling of ion chromatography with ICP-AES and ICP-MS. Furthermore, the limitations of all techniques with respect to their applicability for routine analysis, especially the complexity of sample preparation, degree of automation, time consumption and cost are shown. With respect to the detection capability, TMS with ICP-MS end determination is the most powerful technique, but for routine analysis simultaneous multielement determination from the matrix is favourable.     

Optimisation of irradiation and decay times in nuclear activation analyses

A mathematical model has been developed to describe the behaviour of the statistical error in the determination of gamma-ray peak areas in instrumental activation analysis as a function of the irradiation and decay times. This model has been used to investigate the best values of these parameters for the determination of a particular peak in a complex spectrum. It has also been used to investigate the effect of the maximum count rate on the best precision obtainable.     

A thin-layer contactless conductivity cell for detection in flowing liquids

The design is described of a thin-layer contactless conductivity detector suitable for liquid chromatography and flow-injection analysis. Its principal analytical parameters have been determined using a potassium chloride solution: the linear dynamic range extends from 7.5 × 10⁻⁶ to 1.5 × 10⁻² S m⁻¹, corresponding to the KCl concentration range from 0.5 to 1000 μM, the limit of detection equals 3.5 × 10⁻⁶ S m⁻¹ (0.2 μM KCl), the detection repeatability, expressed in terms of the relative standard deviation, amounts to 1.13% and the detection volume is 0.6 μL. The detector was applied to detection of ionic compounds, benzoic, lactic and octanesulfonic acids, and sodium capronate, after their separation by liquid chromatography in a Biospher PSI 100C 18 columns using a 60% aqueous acetonitrile mobile phase. The frequency characteristics of the detector are reasonably theoretically described on the basis of a simple model which is commonly used in the field of contactless impedance detectors.     

The anodic behaviour of zinc in flowing electrolyte systems

The current-time behaviour has been calculated for successive two dimensional nucleation under potentiostatic conditions. Using numerical integration the contributions due to the first 50 layers have been found and the steady state behaviour has been estimated.     

Optimisation of a microfluidic analysis chamber for the placement of microelectrodes

The behaviour of droplets entering a microfluidic chamber designed to house microelectrode detectors for real time analysis of clinical microdialysate is described. We have designed an analysis chamber to collect the droplets produced by multiphase flows of oil and artificial cerebral spinal fluid. The coalescence chamber creates a constant aqueous environment ideal for the placement of microelectrodes avoiding the contamination of the microelectrode surface by oil. A stream of alternating light and dark coloured droplets were filmed as they passed through the chamber using a high speed camera. Image analysis of these videos shows the colour change evolution at each point along the chamber length. The flow in the chamber was simulated using the general solution for Poiseuille flow in a rectangular chamber. It is shown that on the centre line the velocity profile is very close to parabolic, and an expression is presented for the ratio between this centre line velocity and the mean flow velocity as a function of channel aspect ratio. If this aspect ratio of width/height is 2, the ratio of flow velocities closely matches that of Poiseuille flow in a circular tube, with implications for connections between microfluidic channels and connection tubing. The droplets are well mixed as the surface tension at the interface with the oil dominates the viscous forces. However once the droplet coalesces with the solution held in the chamber, the no-slip condition at the walls allows Poiseuille flow to take over. The meniscus at the back of the droplet continues to mix the droplet and acts as a piston until the meniscus stops moving. We have found that the no-slip conditions at the walls of the chamber, create a banding effect which records the history of previous drops. The optimal position for sensors is to be placed at the plane of droplet coalescence ideally at the centre of the channel, where there is an abrupt concentration change leading to a response time ?16 ms, the compressed frame rate of the video. Further away from this point the response time and sensitivity decrease due to convective dispersion.     

Optimisation of epsomite transformation into periclase using experimental design methodology

In this work, the experimental design methodology is applied to optimise MgO production from magnesium sulphate salt. This is a two‐step process through an intermediate product (Brucite: Mg(OH)₂). For the first step, a fractional factorial design and a centred composite one are used in order to establish appropriate experimental conditions for Mg(OH)₂ obtention. The most favourable conditions for the second step to obtain MgO were determined using only a fractional factorial design. The decomposition of the optimal precipitated Mg(OH)₂ was analysed by DTA/TGA and the crystallisation process was observed by XRD. The morphological properties of the MgO agglomerates were examined by SEM. Copyright © 2010 John Wiley & Sons, Ltd.     

Meaningful activation energies for complex systems

It is known that the application of an inappropriate kinetic method to the thermal analysis of complex systems can lead to misleading results. To avoid this problem, the new parameter instantaneous mean activation energy is introduced and the Ozawa-Flynn-Wall method is assessed as a means of obtaining it. It is concluded that good results can generally be obtained by this method, provided that the various reactions occurring in the complex system are of the same type. The pyrolysis of coal is considered as a possible application of the method.

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Zusammenfassung Es ist bekannt, da\ die Anwendung einer ungeeigneten kinetischen Methode bei der thermischen Analyse komplexer Systeme zu falschen Ergebnissen führen kann. Um dieses Problem zu vermeiden, wird der neue Parameter momentane mittlere Aktivierungsenergie eingeführt. Die Ozawa-Flynn-Wall-Methode wird als zur Bestimmung dieses Parameters geeignet angesehen. Es wird der Schlu\ gezogen, da\ mit dieser Methode im allgemeinen gute Ergebnisse zu erhalten sein sollten, vorausgesetzt, da\ die in komplexen Systemen verlaufenden verschiedenen Reaktionen vom gleichen Typ sind. Die Pyrolyse von Kohle wird als mögliche Anwendung dieser Methode angesehen.

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The author wishes to thank the British Gas Corporation for permission to publish this work.     

Optimisation of headspace solid-phase microextraction for analysis of aromatic compounds in vinegar

Headspace solid-phase microextraction has been applied to the analysis of aroma compounds in vinegar. Silica fibre coated with Carboxen-polydimethylsiloxane was found to be more efficient at extracting these compounds than other fibres such as those coated with polydimethylsiloxane, Carbowax-divinylbenzene, and polydimethylsiloxane-divinylbenzene, but its repeatability was low. Different parameters such as extraction time, temperature of the sample during the extraction, ionic strength, and sample volume were optimised using a two-level factorial design expanded further to a central composite design. This chemometric tool is very appropriate in screening experiments where the aim is to investigate several possibly influential and/or interacting factors. The extraction efficiency is inversely affected by the acetic acid content-an increase in the acetic acid concentration decreases the extraction efficiency. No interference is observed with the increase in content of polyphenols.     

Optimisation of focused-microwave assisted digestion procedure for Kjeldahl nitrogen determination in bean samples by factorial design and Doehlert design

In the present paper a focused-microwave Kjeldahl digestion procedure without metal catalyst for nitrogen determination in bean samples was developed. Temperature at which the decomposition plateau occurs, mass of potassium sulphate and either volume of sulphuric acid or hydrogen peroxide were optimised. Results of the two-level full factorial design (2⁴) based on an analysis of variance demonstrated that only the decomposition plateau temperature and the sulphuric acid volume were statistically significant. Optimal conditions for the digestion of bean samples were obtained by using Doehlert design. The modified digestion procedure of 0.25 g of bean samples has been performed in 27 min at optimised conditions. The accuracy of the developed procedure by the analysis of the two certified reference materials, peach leaves (NIST 1547) and apple leaves (NIST 1515). The t-test applied to the results revealed that they are in agreement (p > 0.05) with the certified values. The precision, expressed as relative standard deviation (R.S.D.) was of 0.96% for four successive Kjeldahl nitrogen determinations. In addition, interlaboratory exercises were performed with several bean samples in reference Brazilian food control laboratory.