How to achieve international comparability for chemical measurements

It is the central aim of the current activities of metrology in chemistry to build confidence in the reliability of chemical measurement results so that they are accepted without costly duplication being necessary. An important prerequisite for such confidence is comparability based on traceability to recognised common references, ideally the SI units. Since metrology is organised within a national framework according to the national laws and regulations, a two-step procedure is to be followed to achieve international comparability for chemical measurements which is increasingly required as a result of the globalization of trade and economy: (1) establishment of national traceability structures for chemical measurements and (2) mutual recognition of the national traceability structures on the basis of equivalence criteria. The first step is at present being taken in many countries. Examples are presented for Germany. The second step has been initiated by the Mutual Recognition Arrangement (MRA) of the Meter Convention for national measurement standards and measurements and calibrations provided by national metrology institutes, which is based on international comparison measurements (key comparisons) carried out on the national standards level. Chemical analysis is included in this process through the Consultative Committee for Amount of Substance (CCQM).     

International comparability of chemical measurement results

The international system of units (SI) is an internationally recognized system based on standards of long-term stability; by the use traceable measurements it provides an international infrastructure for realizing comparable measurements. The work of the Consultative Committee for Amount of Substance (CCQM) and the implementation of the Mutual Recognition Arrangement (MRA) are facilitating an international programme for metrology in chemistry to extend this infrastructure to the field of chemical measurements. The major points of this programme, which include the execution of international comparisons and the construction of a key comparison and calibration database at the BIPM, are described.     

How to achieve rapid separations in counter-current chromatography

A new generation of high performance coil planet centrifuges is now making it possible to realize the enormous potential of liquid-liquid partition chromatography for the rapid and predictable scale up of separation processes. This paper uses a separation of flavonoids to demonstrate how rapid fractionations can be obtained at high flow rates with limited loss of resolution and with significant increase in throughput. Furthermore, it is shown that chromatograms at various flows can be modeled so that optimum conditions can be rapidly assessed.     

Proficiency testing scheme for the harmonization and comparability of analytical measurements

According to the experience of the successful implementation of proficiency tests (PT) by using the certified reference value as the assigned value, a new scheme of evaluation is presented by suggesting the use of the uncertainty associated with the certified value. The technical performance of laboratories is evaluated by the parameter quadratic mean error (QME), which is the square root of the sum of the square of the bias and that of the standard deviation of the laboratory. This parameter is considered as the estimate of the measurement uncertainty of the laboratory and is compared to the uncertainty (U) associated with the certified value provided by an NMI. Considering that the calibration and measurement capability, known as the CMC, is recognized among NMIs, the ratio QME/U enables us to compare the PT relative to the CMC of an NMI, and, consequently, to any other comparison results based on the CMC of signatories of the mutual recognition arrangement (MRA) of the International Committee of Weights and Measure (CIPM). Presented at BERM-11, October 2007, Tsukuba, Japan.     

How to achieve higher repeatability and reproducibility in capillary electrophoresis.

The influence of experimental parameters on precision of migration times and accuracy of integration has been studied. The repeatability of migration times strongly depends on the proper selection of the rinse steps between each run of a CE system. The rinse steps have to be optimized additionally with each separation system. This is especially important for systems providing an anodic electroosmotic flow. The errors introduced by the integration software were studied by transferring the same data sets to different commercial available integration softwares. A strategy for the transfer of raw data files between several softwares is described. By using systems with identical peak areas or with identical peak heights it could be shown that the newly introduced softwares can cope better with the leading or tailing peaks. The RSD of quantitation strongly depends on the signal-to-noise ratio. At S/N ratios larger than 35 no differences between the various softwares studied could be observed. At lower S/N ratios the newly released softwares are to be preferred.     

A national traceability system for chemical measurements

Current developments in Germany for establishing a traceability system for chemical measurements are reported. The focus is on a dissemination mechanism which employs chemical calibration laboratories accredited within the framework of the German Calibration Service (DKD) and acting as "multipliers" between the national standards level and the user level by providing the user with calibration means which are traceable to the SI via national standards. At the national standards level, a network of high-level chemistry institutes coordinated by the national metrology institute, PTB, provides the primary references for chemical measurements.The use of the metrological dissemination system provided by the DKD also for chemical measurements is a logical extension of a traceability mechanism, successful for more than two decades in general metrology, to metrology in chemistry. In detail, traceability structures in clinical chemistry, electrochemistry, elemental analysis and gas analysis are described. This system has become an important part of the efforts made in Germany to support chemical laboratories in meeting the traceability requirements of the market and of legal regulations.     

Purity determination as needed for the realisation of primary standards for elemental determination: status of international comparability

Within the National Metrology Institutes (NMIs) and designated laboratories, an interlaboratory comparison, CCQM-P107, was conducted to verify the degree of international comparability concerning the results of purity analysis. The mass fractions of Ag, Bi, Cd, Cr, Ni, Tl at the lower mg/kg-level in a high purity zinc material were determined, but the real measurand in metrological sense was the sum of the six mass fractions. Homogeneity was investigated by glow discharge mass spectrometry, reference values were obtained using isotope dilution mass spectrometry. Six NMIs participated, contributing eight independent data sets. The agreement amongst the results of the participants, their median and the agreement with the reference values were usually excellent and in almost all cases below the target uncertainty of 30% relative. In this manner, the accuracy of results and the comparability between the participants was demonstrated to be established.     

Test for non-linearity concerning linear calibrated chemical measurements

Linear calibrated chemical measurements are based on the assumption of linearity. Due to influences of matrices at real samples the condition of linearity can be violated. Therefore, a profound examination has to attach much importance on the linearity of calibration. However, different procedures have been applied for this purpose in literature. In order to examine linear calibration for non-linearity, a recently presented procedure is compared with conventional techniques. The associated statistical models and estimations are represented. The applicability of the different procedures is demonstrated in some practical examples, the determination of arsenic in surface water samples taken from different sites in abandoned mining areas in central Germany. Recommendations for using the indicators and tests of non-linearity are given.     

Design and model of calibration for chemical measurements

The international standard ISO 11843 specifies basic methods to design experiments for estimation of critical values referring to the capability of detection. The detection capability depends on the experimental design, the calibration model used, and the errors of the measurement process. This study reports how the specification of the calibration points within the calibration range can be used as a-priori information for evaluation of calibration uncertainty without any consideration of the response variables of the calibration. As result of investigation of the experimental designs, calibration points within the calibration range can be omitted without significant changes of calibration uncertainty. The approach is demonstrated at a practical example, the determination of arsenic in surface water samples taken from a river in Germany.     

Principles to guide international standard tests for liquid chemical germicides: a proposal.

This review discusses issues involved in developing standard tests for liquid chemical germicides and suggests some guiding principles to be considered for future development of harmonized international standard methods for testing disinfectants and sterilants. A published test method to measure sporicidal activity is used as an example of the implementation of these principles.     

Validation steps for traceability of linear calibrated chemical measurements

Based on the new draft of the EURACHEM/CITAC Guide Traceability in Chemical Measurement, this publication describes how traceability can be achieved for chemical measurements using a linear calibration function. Traceability can be accomplished without larger expenditure, if the measurement is calibrated on the basis of appropriate reference standards and the linear regression employed is selected and validated statistically in a suitable form. The determination of nickel in aqua regia eluates of sediment samples, employed for an ICP-OES measurement, is used as a practical illustration of this approach.     

如何浏览Internet上的化学信息资源

作为一个普通的化学工作者如何浏览Internet的上化学信息资源呢?笔者通过学习和实践,总结了几种方法。     

How to add chemical abstracts service registry numbers and structures to databases via chemical names comparison

For the conversion of nonstructural chemical databases to structure databases, a series of algorithms to find the closest match between existing names to names in a reference database are described. On the basis of the best match, new fields such as the Chemical Abstracts Service Registry Number (CASRN) or structures were added to the database.     

Target measurement uncertainties for results of chemical measurements in Slovenia

Target measurement uncertainties (TMUs), which should be achieved in chemical measurements, are proposed. Such TMUs are intended to set goals for measurement laboratories and could provide independent and objective criteria for laboratory assessors verifying the measurement capability of laboratories. A TMU is specified relative to a stated metrological reference for the measurand concerned. TMUs are common and objective, but are external criteria for both the measurement laboratories and their assessors. They are decided on the basis of the intended use of the measurement result, not evaluated as is the case for measurement uncertainty. The concept of TMU is illustrated by means of desirable applications in food measurements in Slovenia.P. De Bièvre is an Independent Consultant on Metrology in ChemistryPresented at the session Metrology in Chemistry of the XVII IMEKO World Congress, 26 June 2003, Dubrovnik-Cavtat, Croatia