Comparison of different excitation methods for X-ray spectral analysis: the case of synchrotron radiation

Different excitation means, protons, photons and electrons (PIXE, XRFA, and EPMA, respectively) have previously been compared with regard to the figures of merit, i.e. detection power, precision and accuracy. The aim in this article is to compare synchrotron radiation SR as another excitation method with the methods mentioned above. From this point of view the evaluation of (SR) was missing as an again independently optimized excitation method and was based as previously on practical problems of trace analysis, in this case on the determinations of traces in lead. The experiment has been performed with thick homogeneous samples of lead, the same samples already used in the former work, so that a direct comparison is possible. The calculation of the figures of merit is based on the measurements of the blank values and their relative standard deviation for the detection limit and on the random errors for the precision. Regarding the thick homogeneous target of lead XRFA still turns out to be the best method, whereas Synchrotron X-Ray Fluorescence SY-XRF compares favorably, at least for larger atomic numbers Z. Even PIXE is inferior to (SY-XRF) in the case of larger Z; when information on the lateral distribution of the elements is of interest, PIXE is indispensable.     

Direct spectrometry of solids in view of information characteristics

The development of atomic spectrometric methods in recent years is characterized by a remarkable orientation towards direct analysis of solids using various sample introduction techniques in connection with inductively coupled plasma excitation. The old-fashioned direct-current arc excitation with computer-controlled arc current vs. time programming has been studied as an alternative to the above mentioned methods. The influence of different electrode material, different sample preparation mode and working atmosphere on the main figures of merit (precision of the method, dynamic concentration range, determination limit, etc.) have been studied using an evaluation procedure based on the information theory. Received: 3 June 1998 / Revised: 15 July 1998 / Accepted: 18 July 1998     

A sequential injection cold-vapor atomic absorption method for the determination of total mercury

A sequential injection (SI) method for the determination of mercury via cold vapor atomic absorption spectrophotometry is presented. The method differs from flow injection (FI) cold vapor methods for the determination of mercury because of the simplicity of the system required for the method: one pump, one valve, a gas-liquid separator, and an atomic absorption spectrophotometer equipped with a quartz cell. Under optimal conditions, the method has the following figures of merit: a linear calibration range of 1.0 to 20 microg L(-1); a detection limit of 0.46 microg L(-1); and a precision of 0.90% RSD (8 microg L(-1)). The procedure allows for a sampling rate of one injection per 80 s (excluding sample pretreatment). Results from the determination of mercury in water and fish specimens are also presented. The figures of merit of the method are compared to two other SI methods for the determination of mercury.     

Comprehensive analytical figures of merit for fluorimetry of polynuclear aromatic hydrocarbons

The analytical figures of merit for fluorescence of sixty polynuclear aromatic hydrocarbons are presented. The limits of detection for most of the compounds are below 50 ng ml^-1 and the average relative standard deviation at 1 μg ml^-1 for each compound is 1.4%. The fluorescence excitation and emission peak wavelengths are listed. These results confirm the excellent detection limits and precision offered by this technique for quantification of polynuclear aromatic hydrocarbons.     

Electrochemical Detection of Steroid Hormones Using a Nickel‐Modified Glassy Carbon Electrode

This paper demonstrates the development of an analytical method for detecting steroid hormones by coupling HPLC to electrochemical detection, using a nickel‐modified glassy carbon electrode. The method was evaluated in terms of sensitivity, linear dynamic range, limit of detection, and response stability. The developed method exhibited good figures of merit for the steroid hormones studied with no evidence of electrode fouling. As an example, the limit of detection (S/N=3) for E3 was 0.10 µM and the response precision (n=5) was 0.6 %. The application of the method for the analysis of a real river water sample is demonstrated.     

A sequential injection cold-vapor atomic absorption method for the determination of total mercury

A sequential injection (SI) method for the determination of mercury via cold vapor atomic absorption spectrophotometry is presented. The method differs from flow injection (FI) cold vapor methods for the determination of mercury because of the simplicity of the system required for the method: one pump, one valve, a gas-liquid separator, and an atomic absorption spectrophotometer equipped with a quartz cell. Under optimal conditions, the method has the following figures of merit: a linear ¶calibration range of 1.0 to 20 μg L^–1; a detection limit of 0.46 μg L^–1; and a precision of 0.90% RSD (8 μg L^–1). The procedure allows for a sampling rate of one injection per 80 s (excluding sample pretreatment). Results from the determination of mercury in water and fish specimens are also presented. The figures of merit of the method are compared to two other SI methods for the determination of mercury.     

Fourier transform u.v.-visible molecular luminescence spectrometry: Fluorescence excitation spectra

The analytical utility of Fourier transform spectrometry in the u.v.-vis region was investigated. Molecular fluorescence excitation spectra were acquired for four polycyclic aromatic hydrocarbons frozen in Shpol'skii solvents. Analytical figures of merit were determined for coronene, including a limit of detection of 2 ppb and a precision better than 13% RSD. The major sources of noise in FT/u.v. molecular fluorescence spectrometry are discussed, and results are compared to those reported earlier from wavelength dispersive instruments.     

Precision and accuracy in standards analysis by PIXE

Four different approaches to PIXE data obtained in repeated measurements on thick standards have been evaluated in terms of precision and accuracy. Both were found to be the best when determinations relative to an external standard were normalized to a composition assumed to be 100% oxides.     

Evaluation of a pulsed flash-tube for inductively-coupled plasma atomic-fluorescence spectrometry

A pulsed continuum xenon flash-tube is used as an excitation source in ICP-AFS. The simultaneous excitation of many elements is attractive and avoids the one source per element as in conventional ICP-AFS. In this study, the pulsed continuum flash-tube is evaluated as an excitation source for multielement atomic fluorescence spectrometry in an ICP. Analytical figures of merit are given for the elements studied.     

Design and performance of a plasma-source mass spectrograph

A plasma-source, simultaneously detecting, Mattauch-Herzog mass spectrograph for multi-element analysis was developed. Simultaneous detection should improve throughput, precision, and sensitivity over those instruments that use quadrupole or sector mass spectrometers. The new instrument is compact (approximately 80 cm in length) and is designed to detect a complete atomic mass spectrum in two mass windows that straddle but avoid argon. The design and some figures of merit are presented. With a dc glow discharge source, a precision of 0. 5% determined from eight consecutive 10-s images was obtained for Cu isotope ratios in Naval Brass B. With the same sample, nickel and lead were detected at limits of 8 and 1 ppm. Measured Mg isotope ratios with an inductively coupled plasma source were within 4% of the expected values. The resolution at full width at half maximum is currently limited to approximately 60, in part because of poor peak shape. The origin of this peak shape has been determined to lie within the array detector and possibly results from its interaction with the fringing magnetic fields produced by the second sector.     

Microwave Assisted Extraction of Polycyclic Aromatic Hydrocarbons and their Determination by Gas Chromatography–Mass Spectrometry: Validation of the Method and Application to Marine Sediments

Microwave-assisted extraction of sixteen polycyclic aromatic hydrocarbons and their gas chromatographic mass spectrometric detection are presented herein. An efficient extraction was achieved in 15 minutes using 10 mL of 1:1 n-hexane-acetone while a clean-up step was developed studying the elution curves on solid phase extraction silica cartridges. The analytical method was optimized and validated using a certified reference marine sediment; satisfactory figures of merit were obtained with limits of detection in the range 0.001–0.004 µg/g, precision within 6%, and good linearity (regression coefficients generally higher than 0.998, in the concentration range 0.010–1.000 µg/mL). The developed method was successfully applied to the determination of polycyclic aromatic hydrocarbons in real marine sediments collected in two coastal areas of Italy exposed to different anthropic impact: three tourist sites of Liguria and the Venetian Lagoon. The total concentration of the analytes in the samples was in the range 1.027–3.827 µg/g and the use of common markers suggested their probable pyrolytic origin.     

Assessing the detectability of antioxidants in two‐dimensional high‐performance liquid chromatography

This paper explores the analytical figures of merit of two‐dimensional high‐performance liquid chromatography for the separation of antioxidant standards. The cumulative two‐dimensional high‐performance liquid chromatography peak area was calculated for 11 antioxidants by two different methods—the areas reported by the control software and by fitting the data with a Gaussian model; these methods were evaluated for precision and sensitivity. Both methods demonstrated excellent precision in regards to retention time in the second dimension (%RSD below 1.16%) and cumulative second dimension peak area (%RSD below 3.73% from the instrument software and 5.87% for the Gaussian method). Combining areas reported by the high‐performance liquid chromatographic control software displayed superior limits of detection, in the order of 1 × 10^?6 M, almost an order of magnitude lower than the Gaussian method for some analytes. The introduction of the countergradient eliminated the strong solvent mismatch between dimensions, leading to a much improved peak shape and better detection limits for quantification.     

XRF induced by PIXE: Comparison with PIXE

Two different modes of sample excitation have been used for elemental analysis of thin standard reference materials and of chemical standards with known composition. PIXE /2.5 MeV protons/ and XRF induced by PIXE, will be called XRF-PIXE /2.5 MeV protons on Mo primary target/. The same samples were alternatively exposed to protons and X-ray beams. The sensitivities under standard running conditions are determined for both an XRF-PIXE and a PIXE analysis system. It is shown that the sensitivity of the PIXE spectrometer depends strongly on the sample matrix, whereas the XRF-PIXE sensitivity is rather constant with respect to different kinds of samples. In addition, the advantages of one mode of excitation on the other are discussed. It is shown that XRF-PIXE can be a useful complement to PIXE analysis.     

Comparison of analytical figures of merit of an active nitrogen afterglow and a flame ionization detector for gas chromatography

A comparison of the analytical figures of merit of an atmospheric pressure, active nitrogen afterglow and a conventional flame ionization detector revealed that the latter had slightly superior powers of detection and a considerably higher range of linear response. The selectivity of the afterglow detector was far superior because of its specific response to carbon-containing compounds and its potential, as previously demonstrated, of being a metal-specific, multielement detector as well.     

Figures of merit for an ICP-echelle spectrometer system

Figures of merit of an ICP-echelle Spectrometer System are presented for 55 elements. The analytical importance of each figure of merit is discussed. The analytical results obtained with the ICP-echelle system compare well with previously published figures for ICP studies.     

Sequential injection spectrophotometric determination of ritodrine hydrochloride using 4-aminoantipyrine

A sequential injection spectrophotometric determination of ritodrine hydrochloride is described. The method is based on the condensation of aminoantipyrine with phenols in the presence of an alkaline oxidizing agent to yield a pink coloured product the absorbance of which is monitored at 503 nm. Different sequential injection analysis (SIA) parameters including reagent concentrations have been optimised and used to obtain the analytical figures of merit. A linear concentration range of 3.1-123.5 μmol L⁻¹ and a detection limit (as 3σ-value) of 1.0 μmol L⁻¹ were obtained. The precision was 2.4 and 2.3% relative standard deviation (R.S.D.) at 6.2 and 15.4 μmol L⁻¹, respectively. This method is superior over previously reported ones in terms of linear range, short analysis time, high sample throughput, excellent reagent economy and minimum waste generation.     

Current Figures of Merit in ICP-AES with a Special Emphasis on Limits of Detection

Since its introduction, ICP atomic emission spectrometry has increasingly attracted the interest of analysts and is widely used for routine elemental analysis. Some improvements in the analytical characteristics have recently appeared. These analytical characteristics can be described by using figures of merit that will reflect the quality of the analytical results,i.e. repeatability (precision) and accuracy, and of the instrument,i.e. number of elements that can be determined,selectivity (i.e. resolution),long-term stability, robustness (i.e. susceptibility to matrix effects), and limits of detection.