Effect of sample matrix on the determination of total petroleum hydrocarbons (TPH) in soil by gas chromatography–flame ionization detection

Research papers in different fields of analytics indicate that the effect of matrix-induced chromatographic response enhancement (matrix effect) is a commonly encountered problem in gas chromatography applications. In this paper, an example of the effect of sample matrix on the quantitative determination of total petroleum hydrocarbons (TPH) by GC–FID in soil is presented. Two types of soil were selected for the evaluation. Extraction and analysis of the soil samples was in accordance with CEN prEN 14039. The relative systematic error resulting from the matrix effect was obtained for three different TPH concentrations by statistical comparison of the slopes of the matrix-matched calibration lines and a pure solvent calibration line. Too high TPH concentrations were obtained when conventional solvent calibration was used for quantitation. This demonstrates that matrix-matched calibration should be exploited in the determination of petroleum hydrocarbons in soil samples. However, there was also significant enhancement of the response due to an interfering matrix with decreasing analyte concentration. Enhancement seems to be especially evident in the quantification of TPH over the concentration range encountered in polluted environments. As a result, even when matrix-matched calibration is used for quantitation, it is still necessary to establish the range over which a linear response can be expected. Otherwise too high results for sample TPH concentrations will be obtained.     

Demethoxycarbonylation and oxidation of 13(S/R)-hydroxy-chlorophyll a to 13-demethoxycarbonyl-13-oxo-chlorophyll a and Mg-purpurin-18 phytyl ester

The conversion of 13²(S/R)-hydroxy-chlorophyll (Chl) a to 13²-demethoxycarbonyl-13²-oxo-Chl a in a yield of 40%, utilizing a simple pyrolysis technique, is described. About 10% of the phytyl ester of Mg-purpurin-18 was formed as a side product. The completely assigned ¹H and ¹³C NMR spectra are presented for 13²-demethoxycarbonyl-13²-oxo-Chl a and a likely mechanism for its formation is proposed. A slight extension of this mechanism also explains the formation of the Mg-purpurin-18 side product. The proposed mechanism has several features comparable with those previously suggested for the allomerization of 13²(R/S)-Chl a. Attempts to apply the same pyrolysis method to prepare 13²-demethoxycarbonyl-13²-oxo-Chl b from 13²(S/R)-hydroxy-Chl b were unsuccessful.     

Quantification of triacylglycerols in butterfat by gas chromatography-electron impact mass spectrometry using molar correction factors for [M-RCOO]+ ions

A quantitative electron impact GC-MS method using molar correction factors (MCFs) for [M-RCOO]+ ions has been developed for determination of molecular species of triacylglycerols (TAGs). MCFs were determined by linear calibration for 226 ions of 104 TAG species with good reproducibility: on the average, coefficient of determination was 0.975 +/- 0.043 and 0.963 +/- 0.115 for saturated and unsaturated TAGs, respectively. The MCFs of the sn-1(3) regioisomers of short-chain TAGs were lower than those of sn-2 isomers indicating ca. 2-3-fold higher cleavage of butyroyl and caproyl groups from the primary positions than from the secondary position. The method enabled quantification of 139 and 135 individual TAG species of butterfat (BF) and interesterified butterfat, respectively, including several regioisomers of short-chain TAGs. The most abundant molecular species of the even-numbered TAGs in BF were butyroylpalmitoyloleoylglycerol (5.05 mol%), butyroyldipalmitoylglycerol (4.75 mol%), and palmitoyldioleoylglycerol (3.32 mol%). The method provides an alternative for elucidation of nutritional and technological properties of relatively saturated TAG mixtures.     

An amplitude quotient based method to analyze changes in the shape of the glottal pulse in the regulation of vocal intensity

This study presents an approach to visualizing intensity regulation in speech. The method expresses a voice sample in a two-dimensional space using amplitude-domain values extracted from the glottal flow estimated by inverse filtering. The two-dimensional presentation is obtained by expressing a time-domain measure of the glottal pulse, the amplitude quotient (AQ), as a function of the negative peak amplitude of the flow derivative (d(peak)). The regulation of vocal intensity was analyzed with the proposed method from voices varying from extremely soft to very loud with a SPL range of approximately 55 dB. When vocal intensity was increased, the speech samples first showed a rapidly decreasing trend as expressed on the proposed AQ-d(peak) graph. When intensity was further raised, the location of the samples converged toward a horizontal line, the asymptote of a hypothetical hyperbola. This behavior of the AQ-d(peak) graph indicates that the intensity regulation strategy changes from laryngeal to respiratory mechanisms and the method chosen makes it possible to quantify how control mechanisms underlying the regulation of vocal intensity change gradually between the two means. The proposed presentation constitutes an easy-to-implement method to visualize the function of voice production in intensity regulation because the only information needed is the glottal flow wave form estimated by inverse filtering the acoustic speech pressure signal.     

Multidimensional investment problem

In this paper we demonstrate that the Riesz representation of excessive functions is a useful and enlightening tool to study optimal stopping problems. After a short general discussion of the Riesz representation we concretize to geometric Brownian motions. After this, a classical investment problem, also known as exchange-of-baskets-problem, is studied. It is seen that the boundary of the stopping region in this problem can be characterized as a unique solution of an integral equation arising immediately from the Riesz representation of the value function. The two-dimensional case is studied in more detail and a numerical algorithm is presented.     

New Heteroaromatic Complexing Agents and Luminescence of Their Europium(III) and Terbium(III) Chelates

Twelve heteroaromatic complexing agents 9a–I were synthesized with the purpose to develop suitable labels for time-resolved luminescence-based bioaffinity assays. The relative luminescence yields, excitation maxima, and emission decay constants of their europium(III) and terbium(III) chelates were determined. According to these results, 2,2′,2″,2?-[(2,2′-bipyridine-6,6′-diyl)bis(methylenenitrilo)]tetrakis (acetic acid) ( 9e ) and 2,2′,2″,2?-[(2,2′:6′,2″-terpyridine-6,6″-diyl)bis(methylenenitrilo)] tetrakis(acetic acid) ( 91 ) are the most promising agents.     

Determination of xanthates as Cu(II) complexes by high-performance liquid chromatography – Inductively coupled plasma tandem mass spectrometry

The present study provides a novel, selective analysis method for the determination of low xanthate concentrations. The rising concern over the environmental effects of xanthates demands the development of analysis methods which this study answers. Complex formation in aqueous solution between xanthates and an excess of Co(II), Ni(II), Pb(II), Cd(II), Cu(II), and Zn(II) ions was utilized to selectively determine xanthates by high-performance liquid chromatography–inductively coupled plasma tandem mass spectrometry for the first time. The complexes that were formed were extracted to ethyl acetate using liquid–liquid extraction and separated by high-performance liquid chromatography technique before the quantitative determination of metal ions and sulfur in the xanthate complexes. Good separation and high measurement sensitivity were achieved using Cu(II) as the complex metal ion. The analysis method was optimized for the determination of sodium isopropyl xanthate and sodium isobutyl xanthate with detection limits of 24.7 and 13.3 μg/L, respectively. With a linear calibration range of 0.1–15 mg/L and a total analysis time of 4–5 min, the present method is a fast and sensitive option for selective xanthate determination.     

On Occupation Times of One-Dimensional Diffusions

Journal of Theoretical Probability - In this paper, we study the moment generating function and the moments of occupation time functionals of one-dimensional diffusions. Assuming, specifically,...     

Effect of synthesis method variables on particle size in the preparation of homogeneous doped nano ZnO material

Homogeneous doped ZnO nanoparticles were synthesised by the Pechini method. A statistical experimental design was used to study the effects of the synthesis method variables on the particle size. The variables were the molar ratios of the reagents and the calcination temperature. The results indicated that the calcination temperature was the only factor that had a significant effect on the particle size. The particle size of ZnO varied between 16 and 76 nm with calcination temperatures of 400–800 °C. The homogeneity was studied by the ICP-MS technique, and the powders were found to be highly homogeneous.