Evaluating uncertainty in routine analysis

In this article, we critically describe the different approaches proposed so far for calculating uncertainty in chemical measurements: (1) the ISO approach, adapted for the analytical field by EURACHEM (commonly known as `bottom-up'), and (2) the Analytical Methods Committee approach (commonly known as `top-down'), based on interlaboratory information. We also propose a new procedure, which is totally consistent with the ISO approach in the sense that all the sources of error are identified, quantified and combined, but which is conceptually more similar to the `top-down' approach because of its holistic character. This new procedure estimates uncertainty from the information generated during the process of assessing accuracy.     

Improving accuracy in routine instrumental activation analysis

An INAA procedure for routine analysis of rock samples is described. Samples are irradiated using a rotating sample holder. Measurement of the induced gamma activity is performed using an automatic gamma spectrometer and the elemental concentrations are calculated by a computer. The analytical error is discussed and the precision and accuracy evaluated experimentally. An average error of ±3–5% without considering counting statistics is obtained. Results for 19 elements in 8 international standard rocks are reported. A short discussion of the cost of the analysis is included.     

Reactor-detector calibration for routine instrumental neutron activation analysis of geological materials

A reactor-detector combination has been calibrated for routine determination of trace elements by instrumental neutron activation analysis using the semi-absolute method with flux corrections. The reproducibility of the calibration constants is studied using the standard rock AGV-1 for the activities¹⁴⁰La,¹⁴¹Ce,¹⁵³Sm,¹⁶⁰Tb,¹⁵²Eu,¹⁷⁵Yb,¹⁷⁷Lu,¹³¹Ba,⁶⁰Co,⁵¹Cr,¹³⁴Cs,¹⁸¹Hf,²³³Pa,⁴⁶Sc, and¹⁸²Ta. The results show that a calibration reproducibility with a relative precision of better than 5% can be achieved in many of the cases without any special precautions. To study the applicability of the calibration constants, concentrations of the corresponding elements have been determined in standard rocks, G-2, W-1 and GSP-1 and are compared with the recommended values.     

A model for the evaluation of uncertainty in routine multi-element analysis

A model for calculating uncertainty in routine multi-element analysis is described. The model is constructed according to the principles of GUM/EURACHEM. Control chart results are combined with other existing data and results from the actual measurement into a concentration-dependent estimate of combined standard uncertainty. Since possible sources of bias are included in the calculation, overall bias as estimated from the data is used only as a control to identify needs for modification of the model and/or the analytical procedure. For each individual sample, uncertainty can be calculated automatically based on two pre-calculated parameters together with measured concentration and instrumental standard deviation. As an example, the model is demonstrated for inductively coupled plasma-mass spectrometry (ICP-MS) analysis of sewage sludge including laboratory sub-sampling, sample preparation, and instrumental determination.     

Multi-element standard for routine instrumental activation analysis of trace elements in rocks and tectites

The use of high-resolution Ge(Li) detectors in non-destructive instrumental neutron activation analysis (INAA) of mineral materials makes possible the simultaneous determination of a number of trace elements. In routine applications of INAA the use of a multi-element standard (MES) has proved to have advantages over a set of standards for each determined element. An MES has been prepared containing 8 trace elements mixed in a suitable proportion and giving, after neutron activation, long-lived γ-emitters, the γ-ray lines of which regularly occur in the γ-ray spectra of silicate mineral materials. This method has been used in the determination of Sc, Cr, Co, Rb. Cs, Eu, Hf and Th in samples of standard rocks and moldavites.     

The application of a252Cf neutron multiplier for routine instrumental neutron activation analysis

The successful application of instrumental neutron activation analysis for routine determinations depends on the ability to produce accurate and precise analytical results in a relatively short time. An important factor in obtaining the desired speed has been the availability of a low-cost, moderate-flux neutron source for on-site use. The²⁵²Cf neutron multiplier (CFX), designed and constructed by Intelcom Rad Tech Corporation of San Diego, California, is a subcritical assembly capable of continuous, stable operation and has provided us with the ability to determine more than 35 elements as major and minor components. The CFX produces a thermal neutron flux of ∼2×10³ n/cm²-sec by a 100-fold multiplication of the neutrons emitted from a 1 mg²⁵²Cf source. Of particular importance in its application at Kodak has been the determination of the halogens Cl, Br, and I, both singly and simultaneously, in various matrices including photographic materials.     

Cross validation and uncertainty estimates in independent component analysis

A data analysis tool, known as independent component analysis (ICA), is the main focus of this paper. The theory of ICA is briefly reviewed, and the underlying statistical assumptions and a practical algorithm are described. This paper introduces cross validation/jack-knifing and significance tests to ICA. Jack-knifing is applied to estimate uncertainties for the ICA loadings, which also serve as a basis for significance tests. These tests are shown to improve ICA performance, indicating how many components are mixed in the observed data, and also which parts of the extracted sources that contain significant information. We address the issue of stability for the ICA model through uncertainty plots. The ICA performance is compared to principal component analysis (PCA) for two selected applications, a simulated experiment and a real world application.     

On the use of parent—Daughter relations in routine instrumental neutron activation analysis

Measurements on daughter radionuclides of parent-daughter relations can be used in routine instrumental neutron activation analysis if appropriate corrections for differences in irradiation, decay and counting time are applied. These corrections and their precision are discussed.     

Estimation of uncertainty in routine pH measurement

A procedure for estimation of measurement uncertainty of routine pH measurement (pH meter with two-point calibration, with or without automatic temperature compensation, combination glass electrode) based on the ISO method is presented. It is based on a mathematical model of pH measurement that involves nine input parameters. Altogether 14 components of uncertainty are identified and quantified. No single uncertainty estimate can be ascribed to a pH measurement procedure: the uncertainty of pH strongly depends on changes in experimental details and on the pH value itself. The uncertainty is the lowest near the isopotential point and in the center of the calibration line and can increase by a factor of 2 (depending on the details of the measurement procedure) when moving from around pH 7 to around pH 2 or 11. Therefore it is necessary to estimate the uncertainty separately for each measurement. For routine pH measurement the uncertainty cannot be significantly reduced by using more accurate standard solutions than ±0.02 pH units – the uncertainty improvement is small. A major problem in estimating the uncertainty of pH is the residual junction potential, which is almost impossible to take rigorously into account in the framework of a routine pH measurement.¹ Received: 11 August 2001 Accepted: 22 February 2002     

Contribution to the use of data processing to establish instrumental multi-element activation analysis as a routine method

A computer program has been worked out for the following requirements: (1) The program is to render a listing of the elements detected, together with their respective concentrations, not just an evaluation of the gamma-spectrum (peak energies and areas). (2) There should be no necessity to intermediate decisions, i.e. execution of the program should be possible by auxiliary personnel. (3) Gamma-ray spectra recorded under widely different conditions should be amenable to evaluation. This implies a large range of variation of the number of channels per peak. (4) In order to have the most extensive capability of executing multi-element analyses instrumentally, it must be possible to evaluate complex spectra with many superpositions. The program involves the fitting of Gaussians. It is shown that this evaluation method gives more precise peak area determinations than the summation method and also yields reasonable results in the case of strong superposition.     

Low uncertainty determination of manganese and vanadium in environmental and biological reference materials by instrumental neutron activation analysis

The elements Mn and V were determined by INAA in about 5 mg and 100 mg aliquots of NIST SRM 1648 to elucidate discrepancies between our previous results for the 0.5 mg to 15 mg aliquots and the NIST certified and/or information values. Simultaneously, other NIST SRMs 1633a, 2704, and BCR CRMs 038, 101 and 143 were also analyzed. Special attention was given to evaluating and minimizing uncertainties of all steps of analysis. Our results compared very well with the respective certified and/or information values (if available) of all SRMs and CRMs studied, except for NIST SRM 1648. For this SRM we have found significantly lower results than the NIST values which suggests that the NIST values are positively biased by about 10%. A new value for V in BCR CRM 143 was also obtained.     

Electrolytic preconcentration in instrumental analysis

The use of electrolytic deposition as a separation and preconcentration step in trace metal analysis is reviewed. Both the principles and applications of the technique are dealt with in some detail. Electrolytic preconcentration can be combined with a variety of instrumental techniques. Special attention is given to stripping voltammetry, potentiometric stripping analysis, different combinations with atomic-absorption spectrometry, and the use of flow-through porous electrodes. It is pointed out that the electrolytic preconcentration technique deserves more extensive use as well as fundamental investigation.     

Teabags: Computer programs for instrumental neutron activation analysis

Described is a series of INAA data reduction programs collectively known as TEABAGS (Trace Element Analysis By Automated Gamma-ray Spectrometry). The programs are written in FORTRAN and run on a Nuclear Data ND-6620 computer system, but should be adaptable to any medium-sized minicomputer. They are designed to monitor the status of all spectra obtained from samples and comparison standards irradiated together and to do all pending calculations without operator intervention. Major emphasis is placed on finding all peaks in the spectrum, properly identifying all nuclides present and all contributors to each peak, determining accurate estimates of the background continua under peaks, and producing realistic uncertainties on peak areas and final abundances.     

An isotope catalogue for instrumental activation analysis,I

Journal of Radioanalytical and Nuclear Chemistry -     

Versatile automatic stopped-flow system for routine analysis

A versatile, automatic stopped-flow system featuring a mixing module and real-time data collection and treatment is presented. The mixing module is compatible with a number of spectrophotometers and spectrofluorimeters. The fast reaction between iron(III) and thiocyanate is used to evaluate the performance of the system and to develop a routine procedure for the determination of iron in wines, with a reaction time of 3 s. The calibration is linear over the range 1–30 μg ml^?1, with a r.s.d. of 0.9% (n = 11) for 10 μg Fe ml^?1 and a high sample throughput (120 h^?1) is achieved.