A new internal quality control chart based on biological variation

The instruments and analytical methods currently used in clinical laboratories today have better precision and stability than those used in the past. With the development of chemical and immunological methods and instrumentation technology, test precision has increased. However, the application of the Westgard multirule procedure to control sera in the Levey-Jennings chart may not be useful or cost-effective. We devised a new test-specific decision limit for accepting or rejecting runs based on the data of within-subject biological variation and prepared a control chart. We then applied these new limits and control chart to a group of tests performed in our laboratory. With the exception of the tests for albumin, total protein, and calcium, for which desirable performance standards could not be attained with the current technology and methodology, the application of these control limits was cost-effective and convenient. It is estimated that the value of healthy within-subject biological variations is constant, irrespective of the methodology, the area in which the study has been performed, and the number of subjects included in the study. We believe that control limits based on biological variation are reliable and cost-effective, and may be useful in modern and accredited laboratories.     

Use of uncertainty estimates as reported by participants in proficiency testing for the evaluation of their results: pros and cons

The aim of this paper is to study the measurement uncertainties reported in proficiency tests (PTs) using examples from PTs in the environmental sector and to compare the obtained measurement uncertainty estimates using different approaches. In addition, the paper focusses on the differences between the z-score and the zeta score. Since the year 2000, the Finnish Environment Institute has asked participants to report analytical methods as well as measurement uncertainties in connection with PT results. The measurement uncertainties of the assigned value have also been evaluated. On the basis of the results, the measurement uncertainties reported by the participants varied greatly. Participants often reported underestimated measurement uncertainties, but overestimated uncertainties were also reported. At the moment, it seems as if performance assessment should be based on the z-score because of a number of significant over- and underestimated measurement uncertainties. The zeta score should be used for information and educational purposes mainly.     

Quality assurance of X-ray spectrometry for chemical analysis

Three different techniques, energy dispersive X-ray fluorescence, total reflection X-ray fluorescence and particle induced X-ray emission were used to initiate an evaluation program on quality assurance (QA) procedures applied to X-ray spectrometry for chemical analysis. The use of standard methodologies to assure the statistical control of measurement data is the main objective of this work. Certified Reference Materials were used and up to 15 certified elements were analyzed to carry out the QA procedures. For the internal quality control, z-scores were calculated and control charts were produced. The plotted elemental data illustrate statistically controlled methodologies for the majority of the determinations. Even the cases where the control charts exhibit values out of control limits, the z-scores are below 3 in absolute value, indicating satisfactory results. Concerning external quality control the statistical methods applied showed that the results obtained for the three techniques are comparable, although some significant differences occur, mainly due to sample preparation. Therefore, the techniques are traceable to certified reference materials and the data gathered so far, enable to initiate a database for QA procedures.     

Quality of electron probe X-ray microanalysis determinations obtained from laboratory reference materials of the coppery alloys and basaltic glasses

Nine coppery alloys and five basaltic glasses have been quantitatively evaluated as the reference materials to employ in electron probe X-ray microanalysis. The optimum conditions for measurements were selected considering the dependence of intensity and detection limit on the conditions of the X-ray radiation excitation and analytical signal recording. The homogeneity of basaltic glasses and coppery alloys has been examined. The dependence of electron probe X-ray microanalysis accuracy on the homogeneity of reference materials was studied in the reference materials of coppery alloys.Six data sets comprising the average concentrations, standard deviations, relative standard deviations, confidence interval and the z-score of data quality were calculated for 50 control samples: 10 alloys, 14 glasses, 2 metals, 24 minerals and oxides. The average compositions of every control sample were derived in 8–16 analyses. The measured values were corrected for matrix effects applying the original program. These series of concentrations have been compared with each other and with the certified/recommended values using 2-pair selective Student's t-test.The results gained from both laboratory reference materials and certified glass reference materials show comparable accuracy. The quality of all available results complies with the “applied geochemistry” category of performance (2nd category). The laboratory reference materials give comparable accuracy to certified reference materials and can be used for calibrating microprobe techniques, as well as data quality control. The application of laboratory reference materials in microanalysis of silicate minerals and coppery alloys allows reliable analytical data to be acquired. The applications in mineralogy and metallurgy can be extended successfully to the targets when certified reference materials are not available.     

The role of statistics in quality assurance

Summary The quality of data, which is to say its accuracy, must be known whenever it is to be used for purposes of decision. This is only possible as it is produced by a valid analytical system operating in a state of statistical control. A quality assurance program should be established, consisting of quality control of the analytical system and quality assessment of the data that are produced. Data quality objectives should be established for every measurement situation and the accuracy attained must be within these limits. Ideally, the attained accuracy should exceed the required accuracy by a factor of three, at a minimum. The estimation of attained accuracy is best made using reliable reference materials. When they are not available, spikes may be used with lesser confidence. No matter what estimation techniques are used, decisions must be made on the basis of statistical tests of significance. The evaluation of accuracy is a continuing operation and facilitated by the use of appropriate control charts. The paper discusses the above described concepts and summarizes the techniques most useful for evaluating the accuracy of analytical data.

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Die Rolle der Statistik in der Qualitätssicherung

     

Method validation procedures for environmental radiochemical measurements at AECS

The present paper describes the experience of the Atomic Energy Commission of Syria in relation to the application of Eurachem Guide on method validation for environmental radiochemical measurements. Methods validated include gamma and alpha spectrometry for natural and artificial radionuclides determination, and fluorometry determination for total uranium. Documents and records were first set to meet trackability and traceability requirements, where internal quality control mechanisms have been adopted. Methods stability was checked by means of Z-score control charts. Internal method validation parameters including method detection limits, repeatability limits, reproducibility limits, recovery coefficient and relative error were estimated. External method validation has been achieved by participating in international intercomparison exercises and proficiency tests organized by EML, IAEA and WU; some results of these activities are presented. Moreover, the application of both internal and external method validation gave the analysts in our laboratories more confidence in their skills, and it was of great assistance for our customers including regulatory authorities to evaluate the fitness of the method for their applications according to internationally agreed procedure. The steps followed here can be used for method validation in other laboratories with similar applications.     

Critical evaluation of laboratory performance from IAEA-452 (fish scallop) inter-comparison exercise results

The International Atomic Energy Agency Marine Environmental Laboratory (IAEA-MEL) conducted an intercomparison exercise for the “Trace elements and methyl mercury in fish scallop: IAEA-452” in 2009. The Neutron Activation Analysis (NAA) laboratory at PINSTECH, Pakistan took part in this exercise. Comparison with the IAEA results showed that of the 18 elements reported to the IAEA 7 had unacceptable z-scores while the data for two elements was questionable (2< |z-score| <3). Upon investigation it was discovered that the large number of elements having unacceptable z-scores was due to human error and the greater difficulty in analyzing biological samples which have low amounts of trace elements. Therefore selection of values corresponding to matrix matched reference materials (RMs), such as IAEA-436 and IAEA-407, and to non-interfering peaks the results obtained became comparable to the IAEA results with only the result for As having |z-score|> 3.     

Interpretation of interlaboratory comparison results to evaluate laboratory proficiency

Guidelines are given for the evaluation of proficiency test (PT) results in order to increase the effectivity of PT participation. For better understanding, some statistical background is given along with some examples to show the effects of the choices made by the PT provider. The calculation method of the assigned value and the selection of the standard deviation both affect the z-score that is used by the participating laboratory to judge the quality of its performance in the PT. Therefore, the participating laboratory is advised to use the PT results with care and, if necessary, to recalculate the z-scores. Finally, advice is given on how not to follow up bad PT results along with some valuable steps that could be part of an effective follow-up procedure.     

A new approach in assessing microbiological results in water analysis proficiency testing

Due to the relatively large spread in the results of microbiological proficiency tests, the z-scores are often not able to detect zero or low results as being ‘bad’ results. This paper describes an adapted z-score based on the average or the standard deviation of the 50% ‘highest’ results. The combination of the adapted z-scores of four samples enables a better judgement of the performance of each laboratory. Papers published in this section do not necessarily reflect the opinion of the Editors, the Editorial Board or the Publisher.     

The influence of a quality system according to ISO/IEC 17025 on the performance of Brazilian laboratories in proficiency testing in the environmental area

This paper presents a performance analysis of laboratories in proficiency testing (PT) with the main objective of evaluating whether having accreditation to ISO/IEC 17025 or not having an implemented quality system has an influence on the performance of these laboratories. This research was conducted with data from an accredited PT scheme of physical–chemical water analyses. Nine metals were considered in the analysis, with a total of 896 results. The performance indicator was z-score. The proposed analysis was conducted through statistical methods of analysis of variance, Dunnett’s test, Chi-square and cross-tabulation. It was verified that there is a significant difference between the performance of accredited laboratories, recognised laboratories, and laboratories that do not have an implemented quality system. It was established that an accredited or recognised quality system has a positive influence on the laboratory performance, resulting in a lower z-score (in module) and in a larger percentage of satisfactory results.     

Integration of metrological principles and performance evaluation in a proficiency testing scheme in support of the Council Directive 98/83/EC

Proficiency testing as a means of external quality assessment plays the role of independent evidence of laboratories’ performance. To enable laboratories to fulfil the requirements stated in legislation, methodology for evaluation of laboratories’ performance in proficiency testing schemes should incorporate principles of measurement results which are fit for intended use and incorporate evaluation of laboratories’ performances based on independent reference value. A proficiency testing scheme was designed to support Drinking Water Directive (98/83/EC) specifically. The methodology for performance evaluation, which takes into account a “fitness for purpose”-based standard deviation for proficiency assessment, is proposed and discussed in terms of requirements of the Drinking Water Directive. A ζ′-score, modified by application of target uncertainty was developed in a way that fulfils requirements defined in the legislation. As an illustration, results are reported for nitrate concentration in water. The approach presented can also be applied to other fields of measurements.     

An interlaboratory study as useful tool for proficiency testing of chemical oxygen demand measurements using solid substrates and liquid samples with high suspended solid content

In 2008, the first Proficiency Testing Scheme of Chemical Oxygen Demand (1^stCOD-PT^ADG) was conducted to assess the results obtained for different research groups whose field work is mainly anaerobic digestion. This study was performed using four samples, two solid samples as raw materials and two solid samples to prepare high concentration suspended solid solutions. Invitations were sent to a large number of laboratories, mainly to anaerobic digestion research groups. Finally, thirty labs from sixteen countries agreed to participate, but for different reasons four participants could not send any data. In total, twenty-six results were reported to the COD-PT coordinator.This study showed the importance of continuous participation in proficiency testing (PT) schemes in order to compare the results obtained. Taking into account the lack of a general standard method and high quality certified reference materials (CRMs), the traceability of COD determination is not currently easy to check. In addition, the spread of participants’ results obtained was high and pointed to the advisability of using consensus values due to their unreliability. Therefore, the theoretical oxygen demand (ThOD) values were considered as assigned values for all the samples analysed. On the other hand, in this PT the established standard deviation (ESD) has been determined by the Horwitz modified function.Participants of this 1^stCOD-PT^ADG were asked to give a short report on the analytical method used. Although all the participants used potassium dichromate as their oxidant reagent, their experimental procedures were very different. With the purpose of comparing the results obtained, the different experimental conditions used were classified into five methods, corresponding to two main categories, open and closed reflux. The performance of laboratories was expressed by the z-score, whose value is considered satisfactory when z-score ≤±2. The overall analytical data evaluation showed that 64% of z-scores obtained were outside the accepted limits.     

Anti-HIV quality assurance programs in Australia and the southeast Asian and Western Pacific regions

Anti-HIV testing is the most regulated area of laboratory medicine in Australia. These regulations have placed the National Sero-logy Reference Laboratory, Australia (NRL) in a unique position to implement a comprehensive quality assurance (QA) program for HIV testing. The elements of our QA program include pre-market evaluation of assays, external quality assessment schemes (EQAS), quality control, specificity monitoring, consultations, and training workshops. The results of the NRL EQAS for Australian laboratories were compared with those of a program developed by the NRL for reference laboratories in the Southeast Asian and Western Pacific (SEAWP) regions. For laboratories authorized to use tests for HIV in Australia, participation in the entire QA program is mandatory, whereas the SEAWP EQAS program is voluntary. While the overall percentage of discrepant results for these programs are similar, the percentage of false negatives, variation in laboratory results, and choice of assay differ. These differences have decreased with time with improvements in assays and laboratory testing practices. The educational component of both EQAS, which comprises workshops, laboratory questionnaires, consultancies, and newsletters, has had a critical impact on the testing practices of laboratories. Received: 30 October 2000 Accepted: 9 December 2000     

Multi‐constituent determination and fingerprint analysis of Scutellaria indica L. using ultra high performance liquid chromatography coupled with quadrupole time‐of‐flight mass spectrometry

An ultra‐performance liquid chromatography coupled with quadrupole time‐of‐flight mass spectrometry method integrating multi‐constituent determination and fingerprint analysis has been established for quality assessment and control of Scutellaria indica L. The optimized method possesses the advantages of speediness, efficiency, and allows multi‐constituents determination and fingerprint analysis in one chromatographic run within 11 min. 36 compounds were detected, and 23 of them were unequivocally identified or tentatively assigned. The established fingerprint method was applied to the analysis of ten S. indica samples from different geographic locations. The quality assessment was achieved by using principal component analysis. The proposed method is useful and reliable for the characterization of multi‐constituents in a complex chemical system and the overall quality assessment of S. indica.     

Comparison of different approaches to the statistical evaluation of proficiency tests

The objective of this study was to compare different z-score calculation for the results from proficiency testing programmes. The comparison was carried out on the data from proficiency tests for four different matrices and for all analytes included in the proficiency testing programmes organised by UKZUZ institute from the year 2005 to 2007. It represented 99 samples (three periods per year and eleven samples distributed in each period); the number of determined analytes was 108 in each period. The total number of investigated data sets was 953. Three different approaches to z-score calculation were compared. The results gave reasonably comparable evaluation in most cases but sometimes UKZUZ method proved to be rather strict. The procedure using the robust average and robust standard deviation calculated according to Algorithm A described in ISO 13528 was found to be the most suitable for matrices and level of measurands in UKZUZ proficiency tests.     

Laboratory assessment by combined z score values in proficiency tests: experience gained through the European Union proficiency tests for pesticide residues in fruits and vegetables

The obligation for accredited laboratories to participate in proficiency tests under ISO 17025, performing multiresidue methods (MRMs) for pesticide residues, involves the reporting of a large number of individual z scores making the evaluation of the overall performance of the laboratories difficult. It entails, time and again, the need for ways to summarise the laboratory’s overall assessment into a unique combined index. In addition, the need for ways to continually evaluate the performance of the laboratory over the years is equally acknowledged. For these reasons, following 14 years of the European Union Reference Laboratory for Pesticide Residues in Fruits and Vegetables (EUPT-FV), useful formulas have been designed to globally evaluate the assessment of the participating laboratories. The aim is to achieve a formula which is easy to understand, which can be applied and which fits the purposes of long-term evaluation detecting positive and negative trends. Moreover, consideration is needed for a fair compensation of bad results in MRM, taking into account the large number of compounds that are covered. It is therefore important to be aware of the difficulties in getting satisfactory values from a wide range of compounds. This work presents an evaluation of the main well-established combined z score formulas together with those new ones developed here which have been applied to the European proficiency test results (EUPTs) over the years. Previous formulas such as the rescaled sum of z score (RSZ), the sum squared of z score (SSZ) and the relative laboratory performance (RLP) are compared with the newer ones: the sum of weighted z scores (SWZ) and the sum of squared z scores (SZ2). By means of formula comparisons, conclusions on the advantages, drawbacks and the most fit-for-purpose approach are achieved.     

Participation in IAEA proficiency test exercise on major,minor and trace elements in ancient Chinese ceramic (IAEA-CU-2006-06) using low power research reactor

A proficiency test (PT) exercise was offered by the International Atomic Energy Agency (IAEA) for major, minor and trace elements in Chinese ceramic reference material (IAEA-CU-2006-06). Neutron activation analysis (NAA) laboratory at PINSTECH, Pakistan participated in the exercise and submitted the results for 28 elements. The aim of participation was to develop a suitable methodology for accurate measurement of as many elements as possible in ceramic material using a low power reactor (PARR-2) as this would help future investigation in a project on the authenticity of art objects, for provenance, conservation and management of ancient cultural heritage of the country. After receiving the final report of the PT exercise, a critical review of our data and final scoring of each element is made to check the suitability of our methodology and reliability of the acquired data. Most of the reported results passed different statistical evaluation criterion such as relative bias, z-score and u-scores and ratio of our results and IAEA target values. One element (Yb) falls in the unacceptable range of relative bias and z-scores. Hf and Tb showed slightly high z-scores within the questionable range. Ho, Mo and Sn were determined during this study but their results were not submitted to the IAEA. The confidence of accuracy observed for most of the elements in ceramic material has made it mandatory to report their results as information values.     

Computer generation of matching polynimials of chemical graphs and lattices

A computer program in Pascal is developed for computing the matching polynomials of graphs and lattices. This program is based on the recursive relation for matching polynomials outlined by Hosoya [Bull. Chem. Soc. Jpn., 44 , 2332 (1971)], Gutman and Hosoya [Theor. Chim. Acta, 48 , 279 (1978)], and others. The graph whose matching polynomial is of interest is reduced recursively until the graph reduces to several trees. The characteristic polynomial of a tree is the same as the matching polynomial. The characteristic polynomials of resulting trees are computed using the computer program based on Frame's method developed by Balasubramanian [Theor. Chim. Acta, 65 , 49 (1984)]; J. Comput. Chem., 5 , 387 (1984). The resulting polynomials are then assembled to compute the matching polynomial of the initial graph. The program is especially useful in generating the matching polynomials of graphs containing a large number of vertices. The matching polynomials thus generated are potentially useful in several applications such as lattice statistics (dimer covering problem), aromaticity, valence bond methods (enumeration of perfect matchings) in the calculation of grand canonical partition functions, in the computation of thermodynamic properties of saturated hydrocarbons, and in chemical documentation.     

A proficiency test scheme for the quality control of black tea and development of quality control material for internal quality control

A proficiency test (PT) was organized for quality control analysis of black tea. Test materials for the analyses of total content of powder tea, moisture, total ash, acid-insoluble ash, water-soluble ash, alkalinity of water-soluble ash, water extract, crude fiber and caffeine were sent to the participant laboratories (n:43) in 2009. The assigned value, standard deviation of the parameters and z-scores of the participant laboratories were calculated using the data reported by the participants. The percentage of the reported results for analytes was found to be ranged from 67.5 to 100%. Acceptable z-scores were achieved by 80.5–97.5% of the participant laboratories. More than 15% of unacceptable results were obtained for acid-insoluble ash and caffeine analyses. The quality control material for quality control analysis of black tea was developed from the remaining material.