Effect of multiple error sources on the calibration uncertainty.

The calibration uncertainty associated with the determination of metals at trace levels in a drinking water sample by ICP-MS was estimated when signals were affected by two error contributions, namely instrumental errors and operational condition errors. The calibration uncertainty was studied by using J concentration levels measured I times, as usual in experimental calibration procedures. The instrumental error was random in character whilst the operational error was assumed systematic at each concentration level but random among the J levels.

Theil-Sen nonparametric regression technique on univariate calibration, inverse regression and detection limits.

This paper reports the combined use of the nonparametric Theil-Sen (TS) regression technique and of the statistics of Lancaster-Quade (LQ) concerning the linear regression parameters to solve typical analytical problems, like method comparison, calculation of the uncertainty in the inverse regression, determination of the detection limit. The results of this new approach are compared to those obtained with appropriate reference methods, using simulated and real data sets. The nonparametric Theil-Sen regression technique appears a new robust tool for the problems considered because it is free from restrictive statistical constraints, avoids searching for the error nature on x and y, which may require long analysis times, and it is easy to use.

Overall calibration procedure via a statistically based matrix-comprehensive approach in the stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry analysis of pesticide residues in fruit-based soft drinks.

Stir bar sorptive extraction (SBSE)-thermal desorption (TD) procedure combined with gas chromatography mass spectrometry (GC-MS) and the statistical variance component model (VCM) is applied to the determination of semi-volatile compounds including organochlorine and organophosphorus pesticides in various synthetic and real fruit-based soft drink matrices. When the matrix effects are corrected using isotopically labelled or non labelled internal standard, but matrix/calibration run-induced deviations are still present in the measurements, the adoption of a variance component model (VCM) in the quantitative analysis of various matrices via an overall calibration curve is successful. The method produces an overall calibration straight line for any analyte accounting for the uncertainty due to all the sources of uncertainty, namely matrix-induced deviations, calibration runs performed at different times, measurement errors.

Effectiveness of isotopically labelled and non-isotopically labelled internal standards in the gas chromatography/mass spectrometry analysis of sulfur compounds in wines: use of a statistically based matrix comprehensive approach.

The effectiveness of isotopically and non-isotopically labelled internal standards in reducing matrix-induced effects is evaluated. The question is addressed in the quantitative analysis by gas chromatography/mass spectrometry (GC/MS) of dimethyl sulphide, chosen as a typical example of volatile sulphur compounds, in wine matrices. When matrix/run effects are not cancelled out the use of a variance component model (VCM) to handle the linear calibrations obtained by regression technique is successful.

Hyphenated gas chromatography-mass spectrometry analysis of 3-mercaptohexan-1-ol and 3-mercaptohexyl acetate in wine: Comparison with results of other sampling procedures via a robust regression.

This work describes a new purge and trap gas chromatography electron impact mass spectrometry (PT-GC-EIMS) method for quantifying 3-mercaptohexan-1-ol (3-MH) and 3-mercaptohexyl acetate (3-MHA), two molecules able to characterize some wines with their tropical scents. Firstly the experimental conditions of the purge and trap extraction (sample temperature, extraction time, trap temperature, flow rate) following a multivariate approach were optimized. Then the method through the construction of the calibration curves and the establishment of the detection limits was validated.

Gas chromatography-mass spectrometry determination of 3-mercaptohexan-1-ol and 3-mercaptohexyl acetate in wine: a comparison of headspace solid phase microextraction and solid phase extraction methods.

A gas chromatography-mass spectrometry method was established using headspace solid phase microextraction (HS-SPME) as the sampling procedure to analyse 3-mercaptohexan-1-ol (3-MH) and 3-mercaptohexyl acetate (3-MHA), two molecules with a tropical fruit aroma, in wine at trace level. This method offers important advantages, as it neither requires time-consuming sample preparation nor uses dangerous organic compounds, thus making control of wine aroma easier and suitable for routine analysis. As a comparison, a solid phase extraction (SPE) method, already described elsewhere for aroma analysis, was applied to quantify these analytes, extending this exhaustive enrichment to two important thiols.

A statistical overview on univariate calibration, inverse regression, and detection limits: Application to gas chromatography/mass spectrometry technique.

The paper summarizes critically the current approaches for the calculation of the limits of detection and quantification. In the context of the description of the method based on the calibration line, the arguments concerning the underlying experimental design, the choice of the appropriate model in the univariate regression, the effects of the dispersion characteristics of the data are deeply discussed. The effects of the scedasticity of the experimental data are taken into account in the obtainment of the calibration curve and in its utilization.

Headspace solid phase micro extraction GC-ECD determination of volatile organic chlorinated hydrocarbons in soils.

Soil samples were suspended in a suitable aqueous solvent and a solid phase microextraction (SPME) fibre was used to sample the headspace (HS) for five volatile chlorinated compounds (VOX). Their determination was made by GC-ECD technique in the splitless mode. Preliminary studies on the effects of methanol and of the sand/clay ratio on the fibre extraction were made.

Electrochemical determination of pharmaceuticals in spiked water samples.

The electrochemical behaviour of acidic and neutral pharmaceutical active compounds (PhACs) was studied by cyclic voltammetry and pulse voltammetric techniques on mercury, carbon nanotube paste, carbon paste and gold electrodes. The best results, in terms of sensitivity, linearity range and detection limits, were obtained by differential pulse voltammetry (DPV) for ofloxacin (LOD 5.2 microM), differential pulse polarography (DPP) for clofibric acid (LOD 4.

Electrocatalytic oxidation of NADH at single-wall carbon-nanotube-paste electrodes: kinetic considerations for use of a redox mediator in solution and dissolved in the paste.

Cyclic voltammetry has been successfully used to study the oxidation of nicotinamide adenine dinucleotide (NADH) at single-wall carbon-nanotube-paste (CNTP) electrodes modified with p-methylaminophenolsulfate (p-MAP) and 3,4-dihydroxybenzaldehyde (3,4-DHB). Diffusion-like behaviour was observed for p-MAP-modified electrodes, and a diffusion coefficient of 2.4x10(-6) cm2 s(-1) was calculated for p-MAP in the paste.

A comparison between the use of a redox mediator in solution and of surface modified electrodes in the electrocatalytic oxidation of nicotinamide adenine dinucleotide.

Cyclic voltammetry was successfully applied to study the oxidation of nicotinamide adenine dinucleotide (NADH) both in homogeneous and heterogeneous phase. The first case was realized with a solution containing p-methylamino-phenolsulphate (MAP) as redox mediator and the diaphorase (DI) from Clostridium kluveri as enzyme while the second one by using both a glassy carbon (GC) and a carbon nanotube paste (CNTP) electrode modified with electrodeposited films derived from 3,4-dihydroxybenzaldehyde (3,4-DHB). Such systems were successively coupled with glucose dehydrogenase (GDH) reaction to realize the redox chain present in glucose biosensors.

Non-linear and non-constant variance calibration curves in analysis of volatile organic compounds for testing of water by the purge-and-trap method coupled with gas chromatography/mass spectrometry.

Currently used operating conditions for analysing volatile organic compounds (VOCs) by purge-and-trap gas chromatography/mass spectrometry (GC/MS) produced non-linear calibration curves with non-uniform variance. Second-order polynomial models therefore had to be used in weighted regression analysis of measurements of replicates spiked at various concentrations. A transparent procedure based on a reported method of very low computational complexity allowed calculation of the parameters of second-order models, confidence bands of regression lines, prediction bands, and confidence intervals of discriminated analyte concentrations.

The use of cyclic voltammetric measurements for the determination of kinetic constants in enzyme-based electrocatalysis. The case of the redox mediated dihydronicotinamide adenine dinucleotide oxidation catalyzed by flavoproteins.

On the basis of simulated voltammetric curves used as testing data, practical methods to extract the bimolecular rate constant for a mediated enzymatic catalysis with an excess of the substrate are examined. The evaluation criteria are the simplicity of treatment and the agreement between the expected and the obtained values of the rate constants. The results obtained indicate that the different approaches examined are equivalent.