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Organisationseinheit der BAM
Eingeladener Vortrag
- nein (96)
Analysis of natural gas by gas chromatography Reduction of correlated uncertainties by normalisation
(2004)
The results of gas chromatographic analysis of natural gas mixtures reveal strong correlations (Pearson correlation coefficient of >0.96) between the uncertainty of each component and variations in the ambient pressure. Although correction for ambient pressure variations can reduce this variability, normalisation of the results of each analysis using the assumption that the sum of all component amount fractions is unity provides significantly greater reductions in the uncertainty of each measured component. We show that the uncertainty in normalised components can be estimated approximately using the correlation coefficient as a measure of the correlation present in the measurements, or exactly using a full calculation of the variance/covariance (V/C) structure of the data.
Zusammenfassung
If the value of a derived measurement standard is assigned by comparison with a reference standard of the same quantity, the uncertainty is increased by the additional uncertainty on the difference measurement. This basic fact has lead to the general belief that the uncertainty of derived standards is always larger than that of the reference standards. However, if the value of a derived standard is assigned by comparison with several independent reference standards using an appropriate average, the increase of uncertainty due to the uncertainty on difference measurement may be counterbalanced by the the well-known decrease of uncertainty through averaging. The gain of accuracy made possible by this mechanism is restricted to second-generation standards. Further gain through iteration is prevented by correlation between standards derived from the same set of reference standards. As a consequence, the concept of metrological hierarchy levels, relating to traceability chains, becomes questionable for traceability networks.
Uncertainty propagation via preparation, calibration and comparison steps in traceability networks
(1999)
With measurement uncertainty estimation accounting for all relevant uncertainty contributions, the results of measurements using the same procedure on different objects or samples may no longer be considered as being independent, and correlations have to be taken into account. For this purpose, a simple approximation for the estimation of covariances is derived and applied to the estimation of uncertainty for some basic combinations of two measurement results. This covariance estimate is also applied to the estimation of uncertainty for the mean value of the results of replicate measurements on the same object or sample.
A first international 26Al interlaboratory comparison was initiated and evaluation of the results of the eight participating accelerator mass spectrometry (AMS) laboratories on four synthetic samples shows no difference in the sense of simple statistical significance. However, certain interlaboratory bias is observed with more detailed statistical analyses. Some laboratories seem to underestimate the uncertainties of their measurements, and others may overestimate measurement reproducibility.
KALIBRIERUNSICHERHEIT?
(2004)
After finishing Part I of the first international 26Al interlaboratory comparison with accelerator mass spectrometry (AMS) laboratories [S. Merchel, W. Bremser, Nucl. Instr. and Meth. B 223224 (2004) 393], the evaluation of Part II with radionuclide counting laboratories took place. The evaluation of the results of the seven participating laboratories on four meteorite samples shows a good overall agreement between laboratories, i.e. it does not reveal any statistically significant differences if results are compared sample-by-sample. However, certain interlaboratory bias is observed with a more detailed statistical analysis including some multivariate approaches.
Deoxynivalenol (DON), nivalenol (NIV) and zearalenone (ZEN) are toxic secondary metabolites produced by several species of Fusarium fungi. These mycotoxins are often found together in a large variety of cereal-based foods, which are regulated by maximum content levels of DON and ZEN. To date, suitable certified reference materials (CRM) intended for quality control purposes are lacking for these Fusarium mycotoxins. In order to overcome this lack, the first CRM for the determination of DON, NIV and ZEN in naturally contaminated wheat flour (ERM®-BC600) was developed in the framework of a European Reference Materials (ERM®) project. This article describes and discusses the whole process of ERM®-BC600 development, including material preparation, homogeneity and stability studies, and an interlaboratory comparison study for certification. A total of 21 selected expert laboratories from different European countries with documented expertise in the field of mycotoxin analysis took part in the certification study using various gas and liquid chromatographic methods. The certified values and their corresponding expanded uncertainties (k=2) were assigned in full compliance with the requirements of ISO Guide 35 and are as follows: 102±11 µgkg-1 for DON, 1000±130 µgkg-1 for NIV and 90±8 µgkg-1 for ZEN.
Temperature is one factor that influences the performance of immunoassays. Most commonly all incubation steps of the immunoassay are performed at ambient temperature. To systematically study the influence of temperature deviations on assay parameters like signal variation coefficients, limit of detection and measurement range, direct competitive enzyme immunoassays for the determination of two anthropogenic markers, caffeine and carbamazepine, were run at different temperatures above and below room temperature during individual assay steps. The temperature during the competition step had the greatest impact on the assay sensitivity yielding changes in test midpoints by a factor of 10 to 15. For carbamazepine, the test midpoints varied from 36 ng L-1, 108 ng L-1 to 378 ng L-1 employing 4 °C, 21 °C, or 37 °C as incubation temperature, respectively. The edge effect can be minimized resulting in a good plate homogeneity with small variation coefficients, when the assay is performed at ambient temperature.
Acitivities of ISO/REMCO
(2011)
The reliability in measurement results obtained during environmental monitoring is crucial for the assessment and further planning of remediation efforts on the respective contaminated sites by the responsible authorities. A case study concerned with groundwater contaminated with perchloroethylene, trichloroethylene and 1,1,2-trichlorotrifluoroethane including their degradation products which involves private contract laboratories and an independent provider of quality assurance (QA) is presented. The experience gained with biannual monitoring campaigns over 14 years indicates that the selection of contractors on basis of accreditation status and successful performance in interlaboratory comparisons are not sufficient. Rather the auditing of the contractors by the QA provider prior to each campaign and the crosschecking of selected monitoring samples by the QA provider led to a lasting improvement of reliability in the contractors' measurement results. A mean deviation of 20% from the reference value determined by the QA provider for the crosschecked samples was reached.
Mycotoxins are important non-anthropogenic food and feed contaminants, which can be present on almost every agricultural commodity. Effective consumer protection therefore essentially depends on food surveillance by reliable quantitative analysis enabled by appropriate quality control. Certified (matrix) reference materials (CRMs) are versatile tools to support Quality assurance. However, in the case of ochratoxin A (OTA), a hepato- and nephrotoxic mycotoxin, which is regulated in various foods, there is a lack of suitable CRMs. This lack has now been overcome by the development of two European Reference Materials (ERM®) for the Determination of OTA in roasted coffee (ERM®-BD475) and red wine (ERM®-BD476). This article discusses the material preparation process as well as the results of homogeneity and stability testing. Furthermore, the results of the inhouse certification studies carried out at BAM Federal Institute for Materials Research and Testing are presented and discussed. Interlaboratory comparison studies involving selected expert laboratories with documented Expertise in the field of mycotoxin analysis were conducted to confirm the certified values determined by BAM. The certified ochratoxin A values and their corresponding expanded uncertainties (k = 2) were assigned in full compliance with the requirements of ISO Guide 35 and are as follows:
(6.0 ± 0.6) µg kg-1 for roasted coffee, ERM®-BD475, and (0.52 ± 0.11) µg L-1 for red wine, ERM®-BD476.
The 2010 CCQM-K79 'Comparison of value-assigned CRMs and PT materials: Ethanol in aqueous media' is the second key comparison directly testing the chemical measurement services provided to customers by National Metrology Institutes (NMIs) and Designated Institutes (DIs). CCQM-K79 compared the assigned ethanol values of proficiency test (PT) and certified reference materials (CRMs) using measurements made on these materials under repeatability conditions. Nine NMIs submitted 27 CRM or value-assigned PT materials for evaluation. These materials represent many of the higher-order reference materials then available for this commercially and forensically important measurand.
The assigned ethanol mass fraction in the materials ranged from 0.1 mg/kg to 334 mg/kg. All materials were stored and prepared according the specifications provided by each NMI. Samples were processed and analyzed under repeatability conditions by one analytical team using a gas chromatography with flame ionization detection (GC-FID) method of demonstrated trueness and precision.
Given the number of materials and the time required for each analysis, the majority of the measurements were made in two measurement campaigns ('runs'). Due to a shipping delay from one NMI, an unanticipated third campaign was required. In all three campaigns, replicate analyses (three injections of one preparation separated in time) were made for one randomly selected unit of each of the 27 materials. Nine of the 27 materials were gravimetrically diluted before measurement to provide solutions with ethanol mass fraction in the established linear range of the GC-FID method. The repeatability measurement value for each analyzed solution was estimated as the mean of all replicate values. The within- and between-campaign variance components were estimated using one-way ANOVA. Markov Chain Monte Carlo Bayesian analysis was used to estimate 95% level-of-confidence coverage intervals for the mean values.
Uncertainty-weighted generalized distance regression was used to establish the key comparison reference function (KCRF) relating the assigned values to the repeatability measurements. On the basis of leave-one-out cross-validation, all of the assigned values for all 27 materials were deemed equivalent at the 95% level of confidence. These materials were used to define the KCRF.
Parametric bootstrap Monte Carlo was used to estimate 95% level-of-confidence coverage intervals for the degrees of equivalence of materials, d ± U95(d), and of the participating NMIs, D ± U95(D). Because of the very wide range of ethanol mass fraction in the materials, these degrees of equivalence are expressed in percent relative form: %d ± U95(%d) and %D ± U95(%D). The median of the absolute values of the %D for the participating NMIs is less than 0.05% with a median U95(%D) of less than 1%. These results demonstrate that the participating NMIs have the ability to correctly value-assign CRMs and proficiency test materials for ethanol in aqueous media and similar measurands.
Much has been published over the last years on finding the best (consensus) reference value (RV) for a given set of laboratory data attained in inter- or key comparisons (the latter with a specific view to the CIPM MRA). However, the discussion is ongoing. Except cases where real reference values are available from other sources, the quality of the (consensus value is of major importance in proficiency testing, method Validation, or reference material certification.
A distribution-free, self-consistent RV estimation approach has been developed which is based on the single criterion of participant's compatibility, at the cost of adjusted uncertainties. The final result is a fully compatible data set with minimum Overall variance, and adjusted uncertainties for those values reported which had to be made compatible with the (key comparison) reference value.
Any outlier discussion becomes obsolete, including considerations concerning different degrees of robustness of the various location and .dispersion estimators available. The penalty for "badly" performing laboratories is a large attributed uncertainty which forces them to either improve the measurement or adjust (i.e. reduce) their performance Claims. The evaluation algorithm is described. An example from a CCQM comparison is given, and consequences for the performance Claims of the participants discussed.
Inhouse-Seminar und -Workshop "Umsetzung des Konzeptes der Messunsicherheit im analytischen Labor"
(2005)
What's new in ISO REMCO?
(2007)
In many areas of material sciences, hydrogen analysis is of particular importance. For example, hydrogen is most abundant as impurity in thin film materials depending on the deposition process and has great influence on the chemical, physical and electrical properties of many materials. Existing bulk reference materials (RMs) are not suited for surface sensitive analytical methods like elastic recoil detection analysis (ERDA) or nuclear reaction analysis (NRA). To overcome this serious lack of (certified) thin-layer reference materials for the determination of hydrogen in the near-surface region (12 µm depth), we produced stable, homogeneous amorphous silicon layers on Si-wafers (aSi:HSi) by means of chemical vapour deposition (CVD), while about 10% of hydrogen was incorporated in the Si-layer. Homogeneity and stability were proved by NRA whereas traceability of reference values has been assured by an international interlaboratory comparison.
Endevours of ISO REMCO
(2008)
ISO Guide 35 deals with RM stability issues and scrutinizes the evaluation of stability testing results under the assumption that either there is no trend at all (a rather rare situation), or any observed deterministic change is insignificant and thus can be neglected. However, market demands for reliable reference materials are obviously not limited to stable or at least seemingly stable materials. In many analytical applications, analytes and measurands under consideration are known, or at least suspected, to be unstable on time scales that may vary widely from measurand to measurand. The Federal Institute for Materials Research and Testing (BAM) has developed (and successfully uses) an integrated approach in its certification practice. The approach is based on an initial stability study and subsequent post-certification monitoring. Data evaluation is model-based and takes advantage of all information collected in the stability testing scheme(s). It thus allows one to deal with any kind of instability observed, to assess limiting time intervals at any stress condition in the range tested, to estimate a final expiry date for materials with detected instabilities or the maximum admissible re-testing interval for seemingly stable materials, and to assess maximum admissible stress loads during delivery of the material to the customer. The article describes (and exemplifies) typical study layout, the model selection, and the integrated data assessment.
The 'uncertainty matrix', i.e. the variance/covariance matrix associated with a set of values obtained by measurement of multiple measurands, is discussed as the multivariate analogue of the standard uncertainty (or rather the variance) of a value obtained for a single measurand. The main topics are the characterization and comparison of uncertainty matrices with respect to the level of uncertainty of derived quantities and the level of correlation effects on the uncertainty of derived quantities. Examples include a comprehensive application study on the normalization of natural gas composition data. Supplementary technical material such as basic properties of uncertainty matrices and mathematical proofs are included in an appendix.
The performance of twelve laboratories with previously established proficiency in the determination of the mineral oil content in a fresh water sediment is described. The summation parameter total petrol hydrocarbon (TPH) is defined according to ISO 16703:2004 with regard to the sample preparation to be applied, the flame ionisation detection (FID) and the boiling range of C10C40 to be integrated. Comprehensive tests of homogeneity and stability have been carried out on the candidate material using appropriate models. The outcome of the study served as the basis for the certification of the candidate reference material as ERM-CC015a. The certified mass fraction is 1,820±130mgkg-1 and traceability was established by using an appropriate calibration standard certified for the mass fraction of C10C40. The interlaboratory scatter of measurement results in this exercise can largely be explained by the variability of the individual calibrations based on this common calibration standard.