Investigation of the functionality of different burner types used for the Wickbold decomposition method

The functionality of different burner types used for the Wickbold decomposition method was investigated to understand the low recovery rate problem. The elements chlorine and sulphur were the subject of recovery experiments. The influence of the amount of sample transported into the oxyhydrogen flame on the efficiency of combustion is presented. The difference between the manner of transportation into the flame, direct nebulisation of liquids or previous evaporation are investigated. A new nebuliser for introducing liquids into the oxyhydrogen flame with an evaporation step was developed to reduce decomposition problems. Received: 6 November 1996 / Revised: 16 December 1996 / Accepted: 3 January 1997     

The Wickbold combustion method for the determination of mercury under statistical aspects

The combination of the Wickbold combustion apparatus with a mercury/hydride atomic absorption spectrometer for the routine determination of mercury is investigated. A flow injection system is used to introduce the solution from the decomposition into the spectrometer. The data obtained are treated by several statistical tests which have been recommended for quality control purposes. Simplicity of the statistical treatment is emphasized. The mercury content of certified reference materials is determined using the Wickbold combustion unit, and the resulting data are analyzed statistically.     

Pression De Vapeur Et Decomposition Thermique De La Monomethylhydrazine

Monomethylhydrazine (MMH) (CH₃)NHNH₂ is currently used as fuel for spacecraft engine combustion chambers. The Aestus engine of the upper stage of Ariane 5 is fed with MMH under pressure of 16 bars. The propellant, initially at room temperature, is about 393 K when introduced into the combustion chamber, due to heating up through the regenerative circuit. As MMH is unstable above 373 K, it has been necessary to check its decomposition rate and vapor pressure under such conditions. The vapor pressure of this propellant has been measured in a pressure vessel and the thermal decomposition rate was determined with the same device up to 500 K. This revised version was published online in August 2006 with corrections to the Cover Date.     

Closed vessel microwave-assisted wet digestion with simultaneous control of pressure and temperature in all vessels

A novel system for microwave-assisted wet digestion in closed vessels is described. Six pressure vessels made of quartz or Hostaflon^? TFM are placed in a special rotor in a microwave oven. During sample decomposition the pressure and temperature are measured in each vessel, and the data are transferred from the rotor by means of infrared light to the control unit. This means that no pneumatic or electronic connections to the vessels need to be established, providing very easy handling. The temperature history of each vessel is recorded; so the progress of each sample digestion may be reconstructed later on. Thus the requirements for quality control in sample digestion are available for the first time. For sample digestion at 75 bar and up to 280° C, quartz vessels with 50 mL volume are used. Depending on the matrix, the maximum sample loading capacity is 1.2 g. TFM-vessels with 100 mL volume work at 30 bar up to 240° C. The performance of the digestion system was tested with twelve standard reference materials. The results closely matched the certified values. Received: 18 September 1997 / Revised: 3 November 1997 / Accepted: 6 November 1997     

Novel dissolution procedure using a mixture of manganese dioxide and hydrochloric acid for the matrix-independent determination of gold

 A mixture of manganese dioxide and hydrochloric acid has been used for the accurate and precise determination of gold in various gold-bearing matrices. Results of intermethod comparison studies, F-test on variances, Mann-Whitney U-test, Spearman rank correlation and regression analyses are presented. The recommended method can be applied to a quality control programme and for the evaluation of reference materials. Various standard reference materials (SRM) of diverse matrices have been examined to check the validity of the method and the results were found to be in very good agreement with the certified data. Sample decomposition is straight forward [1–10 g sample (roasted at 600–700 °C)+5 g of MnO₂+30 mL of 2 mol/L HCl]. Gold is coprecipitated with potassium tellurite using tin (II) chloride solution. The precipitate is extracted into toluene and finally stripped back into aqua-regia solution for final nebulization into an air-acetylene flame for atomic absorption spectrophotometry. The method is very simple and easily adaptable, and more convenient than conventional methods involving aqua regia or a hydrobromic acid-bromine water mixture. Received: 23 October 1995/Revised: 18 March 1996/Accepted: 23 March 1996     

Validation of an analytical method to determine trace metal impurities in fluoride compounds by flame atomic absorption spectroscopy

 The development of an analytical method for the determination of some heavy metals (Fe, Cu, Co, Zn and Ni) in fluoride compounds [Cu(BF₄)₂, Sn(BF₄)₂, Pb(BF₄)₂ and HBF₄] by flame atomic absorption spectroscopy is described. This method is to be used as a routine analytical method in an industrial quality control laboratory. To this end the "performance characteristics" of an instrumental analytical method such as matrix effects, sensitivity, linearity, detection and quantitation limits, precision and accuracy were evaluated for every system under study. The results of these investigations showed that non-spectral interferences (due to the presence of large concentrations of major metals such as Cu, Sn and Pb) were observed. Nevertheless it was possible to define a matrix concentration interval where matrix effects were not statistically significant, and therefore a direct calibration approach could be used as the calibration tool whenever the major metal concentration was not higher than 40×10^–3 kg l^–1. A guide to the developement of an analytical method for trace metal determination is provided. General tools for quality control have been used in order to show how an analytical method can be tested daily and evaluated in a convenient manner. Received: 29 January 1997 Accepted: 11 March 1997     

Procedure for quality control of chemiluminogenic labels

A method is presented to monitor the chemical, chemiluminogenic and immunochemical properties of steroid N-(4-aminobutyl)-N-ethylsoluminol (ABEI) labels. The label preparation was applied to an isocratic reversed-phase HPLC system (with on-line ultraviolet detection) and fractionated into seventy 12-s fractions. In the fractions, the immunochemicla response was determined by radioimmunoassay and the chemiluminescence was determined in a luminometer or with photplate detection. From the results of the three detection techniques, conclusions can be drawn about the quality and purity of the label. The presence and identity of immunochemically or chemiluminogenically reactive decomposition products cn also be monitored. As an example, a preparation of 17β-testoterone-3-carboxymethyloxime/aminobutylethylisoluminol is analyzed. Possibilities for quality control, stability control and preparative purification are discussed.     

Digestion of biological materials using the microwave-assisted sample combustion technique

In this study a procedure for sample digestion based on sample combustion assisted by microwave radiation is proposed. Combustion is started by microwave radiation in the presence of oxygen under pressure using ammonium nitrate as aid for ignition. The system was adapted in a microwave oven with quartz closed vessels. A quartz piece is used simultaneously as a sample holder and as protection to the cap of quartz vessel from the flame generated in the combustion process. Sample was pressed into a pellet and placed on a disc paper in the holder and 50 μl of 50% m/v ammonium nitrate solution was added. The influence of the absorption solution (diluted and concentrated nitric acid or water) on the recoveries for Cu and Zn was evaluated. About 3 s of microwave irradiation was necessary to start the combustion. The combustion process was evaluated in relation to the influence of sample mass on the ignition time, combustion time and maximum operation pressure. Bovine liver, milk powder and oyster tissue certified reference materials were used to evaluate the accuracy of the procedure for determination of copper and zinc. Good agreement for zinc (96% to 103%) was obtained from bovine liver certified reference material when microwave combustion and microwave combustion followed by reflux were used to sample decomposition, even if water was used for absorption of analyte. For copper, the combustion followed by reflux of 5 min allows an agreement from 96% to 100%. Similar results were obtained for oyster tissue samples. However, for milk powder good agreement close to 100% was obtained only if 4 mol l^− 1 HNO₃ was used with a reflux step. Results from the proposed procedure were also compared to those from conventionally used procedures for biological samples decomposition, such as wet digestion in open vessels and microwave-assisted digestion in closed vessels. The advantages of this procedure include the complete sample decomposition in less time than other procedures and the acid consumption was always lower than 2%. Another advantage is the low residual carbon content, less of 1.4% without reflux and less than 0.3% with the reflux step and the possibility of use of diluted acid as absorbing solution. Moreover, the new holder allows an effective protection of the vessel cap to burnt high masses.     

Pterostilbene: A Highly Reliable Quality-Control Marker for the Ayurvedic Antidiabetic Plant `Bijasar'

Summary In the Indian Ayurvedic system of medicine the heart wood of Bijasar (Lat: Pterocarpus marsupium; Fam: Leguminaceae) has been extensively used to treat diabetes mellitus. Detailed chemical and HPTLC analysis has been performed to identify a reliable marker for quality control of Pterocarpus marsupium and to check commercial samples for authenticity and purity. The two anti-diabetic principles viz. pterostilbene (1) and marsupsin (2) were isolated by extensive chromatographic screening of its ethyl acetate extract. HPTLC studies of these two compounds revealed that levels of pterostilbene are several times more than that of marsupsin both in plant samples and in commercial formulations. The HPTLC method gave reproducible results and response was linearly dependent on amount analysed in the range 200–500 ng. Pterostilbene can therefore be regarded as a reliable marker for evaluation of the quality of Pterocarpus marsupium.     

Lanthanum nitrate decomposition by both temperature programmed heating and citrate gel combustion

Thermal decomposition of lanthanum nitrate to lanthanum oxide was carried out by both temperature programmed heating (TPH) and citrate-gel combustion. The temperature programmed heating was carried out under flow of oxidizing (air), neutral (nitrogen) and reducing (25 vol.% hydrogen+argone mixture) gases, and the processes were controlled by simultaneous thermogravimetry and differential thermal analysis. It was shown that hydrogen atmosphere helps to reduce temperatures of all decomposition steps. The results of TPH were utilized to check the nature of residues in the products of lanthanum nitrate-to-oxide conversion performed via citrate-gel combustion technique.     

Quality assurance in analytical measurement

 The peculiarities of analytical measurement require to check characteristics of the error (its components) of the obtained analysis results to assure the quality of the measurements. This article deals with the various quality assurance procedures and algorithms which are used to check the quality indices, i.e. the accuracy, reproducibility, certainty and repeatability of analytical measurements: These procedures include: laboratory rapid control; Intra-laboratory statistical control (statistical selection control by alternative attribute, statistical selection control by quantity method of periodic check of the analysis procedure for conformity to the specified requirements) and external control (inter-laboratory control checks, inter-laboratory comparison tests, and intra-laboratory control algorithms carried out by the appropriate supervisory body.) in the separately taken laboratory. The respective algorithms, control plans and control requirements, specified according to the different control aims and assurance tasks, enable the quality and certianty of analytical information obtained in laboratories in Russia to be assured. Received: 9 November 1998 / Accepted: 24 November 1998     

Recent Development of Technology in Scale-up of Plasma Reactors for Environmental and Energy Applications

To date, numerous studies have investigated the aftertreatment of exhaust gases from fossil-fueled combustors and combustion engines by plasmas as an environmental plasma application. Owing to the high power requirements of environmental plasma, it is difficult to use the plasma alone for aftertreatment; hence, a hybrid process that combines plasma processing with other techniques is required to reduce the overall power consumption. In developing countries, low-cost plasma hybrid processing has attracted considerable attention as an alternative to the selective catalytic reduction NO_x decomposition (De-NO_x) method and wet lime–gypsum SO_x decomposition method. Moreover, reduced catalytic activity can be enhanced by the plasma because of the decreased exhaust gas temperature, owing to the increased combustion efficiency. This paper reviews studies on successful air pollutant decomposition processes using the plasma chemical process with scale-up reactors. First, experimental techniques and block diagrams of various environmental plasma systems are presented. Subsequently, real-world systems of scale-up plasma reactors are described in detail. Several experimental results suggest that the hybrid treatment of particulate matter and dry De-NO_x is very promising from the viewpoint of energy consumption and material recycling. CO₂ treatment is a very important direction for future work in environmental plasma.

     

Modification of the integral isoconversional method to account for variation in the activation energy

Integral isoconversional methods may give rise to noticeable systematic error in the activation energy when the latter strongly varies with the extent of conversion. This error is eliminated by using an integration technique that properly accounts for the variation in the activation energy. The technique is implemented as a modification of the earlier proposed advanced isoconversional method [Vyazovkin, S. J Comput Chem 1997, 18, 393]. The applications of the modified method are illustrated by simulations as well as by processing of data on the thermal decomposition of calcium oxalate monohydrate and ammonium nitrate. © 2000 John Wiley & Sons, Inc. J Comput Chem 22: 178–183, 2001     

Key requirements for introducing quality assurance in measurement laboratories

 The implementation of a quality assurance system is fraught with difficulties. However, these difficulties may be overcome if the laboratory uses suitable means to facilitate the process. It is necessary to mobilise the intelligence and energy of all members of the laboratory. In order to command adherence, the project must be shared, and this necessitates a major effort by all concerned. Communication is a major factor in obtaining the support of all parties. Six important steps must be distinguished: – Defining quality policy – Creating awareness, information, training – Creating a quality structure – Establishing a deadline for obtaining accreditation – Progressive implementation – Experimentation and validation. Even if the task of obtaining and maintaining accreditation remains difficult, it clearly promotes a minimum level of organisation and stepwise progress in quality assurance. The laboratory must keep improving its quality system, using European Standard EN 45001 as an effective management model. Received: 9 April 1997 · Accepted: 11 September 1997     

Robustness testing of control charts employed by analytical laboratories

 The robustness of Shewhart control charts for subgroup means and subgroup ranges was tested by using the Monte Carlo method using training data sets comprising various numbers of points, with two repetitions in each subgroup (as in routine laboratory practice). The following control chart designs were tested: conventional based on the arithmetic mean and standard deviation, robust based on the median and/or the trimmed mean and Winsorized standard deviation, and a two-step design. The methods were applied to the system in the state of statistical control (outliers excluded) and to the system without statistical control (outliers included). Satisfactory results for both cases were only obtained when using the two-stage control charts. The conventional charts led to underestimation of the effect of outliers in the system without statistical control, whereas the robust control charts led to overestimation of the effect of outliers (false alarm) in the system under statistical control. The tests also gave evidence that the training set should include 20 points as a minimum. Received: 13 January 1997 Accepted: 12 February 1997     

A novel rapid method for preparation of sample solution for chemical characterisation of titanium minerals by atomic spectrometry

A new rapid decomposition and dissolution method with a mixture of sodium di-hydrogen orthophosphate and di-sodium hydrogen orthophosphate as a novel flux is described. The minerals are fused with (1:1) mixture of the above salts (flux) and the melt is dissolved in distilled water. The solution is diluted to desired volume depending on the instrumental technique used for determination. ICP-OES is used for the determination of Al, Ca, Mg, Cr, V, Si, Fe and Ti without interference from titanium, iron and sodium phosphate (introduced as flux). All the elements except Si and V are also determined by AAS. The use of nitrous oxide–acetylene flame eliminates the depression due to titanium in the measurement of Mg, Mn, Cr and Fe in air–acetylene flame. Synthetic mixture conforming to ilmenite and rutile composition are analyzed by ICP-OES and AAS to check the validity of the method. The results are in good agreement. The proposed method has been applied to natural samples and the results are evaluated against the established decomposition method using potassium bisulphate. Both ICP-OES and AAS yielded comparable results. The R.S.D. of the proposed method in case of ICP-OES varies from 0.5 to 2%, whereas for AAS it varies from 1.5 to 3% for different elements (n = 5). The novelty of the proposed sample decomposition lies in its simplicity, ease and speed of fusion with minimal skills besides being eco-friendly unlike the reported tedious complicated decomposition procedures involving variety of fluxes and lot of hazardous chemicals.     

Application of the Combustion Method in a Closed Flask to the Lead Determination in Atmospheric Aerosols

Abstract

The destruction of the filter for metal determination in atmospheric aerosols is an important step in the analysis. Nowadays the decomposition of this kind of sample has not been completely solved, so it is interesting to study new methods for filter sample attack. In the present work the application of the combustion method in a closed flask for mixed cellulose esters filter decomposition for lead determination is proposed. For this purpose optimum operating conditions as stopper flask design, sample size, flask volume, shaking time and volume and concentration of absorbing solution are established, and accuracy and precision of the proposed method using AAS for the measurements is given. The results obtained by the closed flask combustion are compared with those found by wet attack with HNO₃. The method proposed is rapid, has low reagent contamination and no loss of lead by volatilization or by amalgamation occurs. This method shows an accuracy and a precision in good agreement with the standard method.     

煤系高岭岩中固定碳燃烧动力学特性

煤系高岭岩中可燃矿物与不可燃矿物的共生组合增加了可燃矿物燃烧的复杂性,研究这类"燃料"的燃烧特性对充分利用煤矸石资源有积极的意义。参照FCC催化剂结焦燃烧机理,基于一系列假设,建立了煤系高岭岩中固定碳燃烧反应模型—未反应收缩核模型。采用空气气氛下等温热重法研究了煤系高岭土中固定碳的燃烧反应。研究表明,低于700℃,反应的控制步骤是煤系高岭岩中固定碳燃烧界面化学反应。通过对非均一颗粒体系的未反应核收缩模型计算分析,获得煤系高岭岩中固定碳燃烧反应动力学参数,活化能(E)为100.12kJ/mol,频率因子(A)为2.27×106s-1。     

Monte Carlo generated spectra for QA/QC of automated NAA routine

A quality check for an automated system of analyzing large sets of neutron activated samples has been developed. Activated samples are counted with an HPGe detector, in conjunction with an automated sample changer and spectral analysis tools, controlled by the Canberra GENIE 2K and REXX software. After each sample is acquired and analyzed, a Microsoft Visual Basic program imports the results into a template Microsoft Excel file where the final concentrations, uncertainties, and detection limits are determined. Standard reference materials are included in each set of 40 samples as a standard quality assurance/quality control (QA/QC) test. A select group of sample spectra are also visually reviewed to check the peak fitting routines. A reference spectrum was generated in MCNP 4c2 using an F8, pulse-height, tally with a detector model of the actual detector used in counting. The detector model matches the detector resolution, energy calibration, and counting geometry. The generated spectrum also contained a radioisotope matrix that was similar to what was expected in the samples. This spectrum can then be put through the automated system and analyzed along with the other samples. The automated results are then compared to expected results for QA/QC assurance.     

Determination of iodine in diverse botanical and dietary matrices by pre-irradiation combustion followed by neutron activation analysis

Summary The method chosen for determination of iodine in this investigation is an extension of an existing analytical technique to food samples which was developed for environmental samples. The method is based on pre-irradiation combustion of the sample to liberate iodine, trapping the iodine on charcoal, and quantitating the element by neutron activation analysis (NAA). Existing botanical and dietary reference materials were used to check the validity of the method. Several mixed diet samples with high fat content from the U.S. Total Diet Study and composites of cereals with both low and high iodine content were analyzed. This method of pre-irradiation combustion followed by NAA has been shown to be a viable technique for the determination of iodine in dietary samples. However, with a detection limit of about 50 ng of iodine, large amounts of sample (>1 g) are typically required for each determination.