pH and electrolytic conductivity as parameters to characterize bioethanol

To guarantee the quality of bioethanol and avoid damage to the fuel system in a car, the determination of acidity, water content, as well as chloride, sulfate, alkali metal and alkaline earth metal content are important. Electrochemical quantities like pH and electrolytic conductivity are frequently used in biofuel analysis as sum parameters mainly to indicate the risk of corrosion. Many standards and measurement methods used today in the analysis of biofuel are adopted from specifications and test methods originally developed for fossil-based fuels and commercial alcohol. This results from the rapid expansion of the biofuel production. There are efforts to solve remaining metrological and regulatory issues on a regional and international basis on a short term. In the following an overview on the fundamentals for the measurement of pH in bioethanol blends is given. It will be discussed if the electrolytic conductivity of the bioethanol could be a reliable measure of corrosion causing ionic contaminations in biofuel. State of the art, limitations and future tasks for metrology will be discussed.     

Visualisation of proficiency test exercise results in Kiri plots

A novel graphical method (‘Kiri plots’) for the presentation of proficiency test exercise results is presented. The Kiri plot visualises the evaluation of the proficiency test results based on three statistical tests (the z score, the zeta score and the relative uncertainty outlier test) by defining six zones including a central “in agreement” zone.     

Evaluation of laboratory performance using proficiency test exercise results

The IAEA conducted the IAEA-CU-2006-06 Proficiency Test (PT) on “The determination of major, minor and trace elements in ancient Chinese ceramic” in 2006. The results of this PT showed that of the 21 analytes reported by our laboratory 9 failed the precision criteria. Therefore the results reported by our laboratory along with the results of other laboratories which carried out analysis using neutron activation analysis (NAA) were studied. It was found that the major factor contributing towards data falling in the “Warning” category, failing the precision criteria was the high uncertainties cited in the certificates of the reference materials (RMs) used for quantification of data. In this regard, it is recommended that synthetic standards should be prepared and used on a routine basis especially for the measurement of the elements K, Eu, Lu, Ta, Tb and Yb.     

Reliability of proficiency test results for metals and phthalates in plastics

In a recent article it was concluded that the Horwitz curve could not be used for evaluation of results from analysis of plastics. This conclusion was based on 15 different proficiency tests of which 11 were organized by the Institute for Interlaboratory Studies. The authors suggest that part of the poor interlaboratory reproducibility can be explained by the inhomogeneity of consumer plastic products. Also, the lack of standard methods has been mentioned as problematic. The value of the iis data sets used by the authors is discussed in this paper. More recent data are also investigated to determine whether the situation with regard to analysis of plastics is as bad as suggested by Ritter and Meyer.     

Performance of commercial soil laboratories in a proficiency test program in Brazil

A soil proficiency test (PT) was administered to 50 participant laboratories in which two sets of samples, consisting of 20 yearly PT samples and 5 ‘blind’ samples in clients’ names were analyzed for pH, organic matter, total acidity, extractable calcium, magnesium, potassium and phosphorus by the laboratories. Our objective was to determine whether laboratories take extra care to analyze clients’ samples as they do with regular PT samples. The analytical data were evaluated essentially by the procedure described in the international harmonized protocol for proficiency testing of analytical chemistry laboratories. Performance of participant laboratories was assessed by z-scores and summary z-scores statistics involving sum of squared z-scores interpreted as chi-square ( c_n² ) \left( {\chi_{n}^{2} } \right) distribution for zero-centered z-scores with unit variance. From 8 750 determinations, outliers and stragglers accounted for less than 2% of the entire data. Over 93% of the data were satisfactory, whereas between 2 and 4% were either unsatisfactory or questionable in both the PT and ‘blind’ tests. On the basis of sum of squared z-scores interpreted from c_n² \chi_{n}^{2} distribution table, between 30 and 40% of the laboratories had more than 90% probability of having their measurement data within the robust mean and standard deviation for each soil parameter, while another 30–42% of the laboratories had less than 50% probability of having measurement data within the robust mean and standard deviation. Overall, 21 laboratories (42%) were ranked in Class A either in the PT or ‘blind’ tests out of which 12 of them (57%) retained this ranking in both tests. Fourteen laboratories (28%) were ranked in Class C in either the PT or ‘blind’ tests with only 5 of them (36%) consistently ranking in this class in both tests.     

A new approach for proficiency test exercise data evaluation

In this paper, a new data evaluation method for proficiency test exercises consisting of a combination of a z-test, a zeta test and an uncertainty outlier test is presented. This new method is compared with eight other evaluation methods (both measurement uncertainty using and measurement uncertainty ignoring) in common use and/or recommended by ISO 13528. The data set used to test the evaluation methods is real data and consists of the ⁹⁵Nb results of the National Physical Laboratory Environmental Radioactivity Proficiency Test Exercise 2007. The evaluation of 14 out of 32 results were affected by the choice of method.     

The relationship between accreditation status and performance in a proficiency test

In the FAPAS proficiency testing scheme, participants are asked to state whether the analytical method used was accredited or not accredited. It is thus possible to compare the stated accreditation status with performance in the scheme. For this purpose, fifty qualifying examples of analyte-test material combination were selected at random from the reports from the year 2006. The accredited/non-accredited subsets of results from each example were subjected to a statistical analysis to determine whether any significant differences between the distributions of results could be detected. Outliers were removed from the datasets before the main statistical tests and considered separately. The inlying data were subjected to non-parametric tests for differences in central tendency and dispersion. A few significant examples were found, but could be reasonably attributed to chance. Among the inliers there were no grounds to reject the overall null hypothesis, that is, that accreditation has no effect on performance. However, the proportion of outliers was about twice as high among the non-accredited group.     

ISTA quality assurance programme – The proficiency test rating system

Ohne Zusammenfassung     

Comparison of different statistical methods for evaluation of proficiency test data

In analytical chemistry, proficiency testing usually consists in tests that laboratories conduct under routine conditions and report the result to the PT provider who then converts the result to a score which helps the participant to assess the accuracy of the result. The aim of this work is to show PT providers, accreditations bodies, and participating laboratories that different scoring results can be achieved depending on the evaluation system selected. The influence of different evaluation techniques on the results of an interlaboratory comparison for determination of gold in precious metals alloys was investigated. Results from 19 participating laboratories were evaluated by means of the three procedures: (1) classical statistical approach—outliers detection; (2) robust methods—(2A) robust procedure and (2B) ISO 13528; and (3) fitness for purpose. Evaluation of the same PT data revealed very interesting issues depending on the different scoring systems that were used and the robustness of the statistical methods used for detecting outliers. As a general rule, laboratories with scoring Z > 2 offered clearly poorer performance in robust approaches than classical ones. In order to support this first evidence, we evaluated a second data set with results from 24 laboratories (mercury from soil samples) by means of the four mentioned approaches. Selection and comparison of different scoring systems must be done very carefully, because sometimes they are not the best approach for studying the data population or the more appropriate one for evaluating the distribution of the data. Finally it should be taken into account that sometimes the robust scoring systems are not always suitable for evaluating the results of some PT schemes.     

A trial proficiency test of eight NAA laboratories in Asia using stream sediments

Eight neutron activation analysis research groups from seven countries have participated in a trial proficiency test under the auspices of the Forum for Nuclear Cooperation in Asia. Three stream sediment reference materials were used in the test. A high degree of proficiency was found in the quantification of Co and Sc and more than 20 elements were well quantified by the majority of laboratories. The results support the use of neutron activation analysis, as practised by the participants, for geochemical mapping. The data produced in this study may provide an opportunity to improve the characterisation of the three reference materials.     

New certified reference materials and proficiency test for environmental radioactivity measurements

A reliable determination of natural and anthropogenic radionuclides in environmental samples is necessary to comply with the radiation protection and environmental regulations. This paper presents the results of the characterisation of massic activities of natural and anthropogenic radionuclides in soil and water matrices produced as test items to conduct the proficiency test ERAD-PT-2013. The proficiency test ERAD-PT-2013 was designed to investigate analytical performance in analysing both natural and anthropogenic radionuclides, to assist laboratories to identify analytical problems, and to improve the quality of measurement results. The proficiency test items, their spectral interferences and the activity concentration levels of the analytes were designed in a way to enable identification of potential analytical problems. Methodologies, data evaluation approach and evaluation of proficiency test results for each radionuclide are described and discussed.     

Intercalibrated radionuclide activities in spiked water samples of the IAEA worldwide open proficiency test

Proficiency testing is one of methods for regularly assessing the accuracy of the analytical data produced by laboratories for particular measurements. In 2008 and 2010, we participated in the IAEA 2008 and 2010 worldwide open proficiency tests on the determination of natural radionuclides in water spiked with ²²⁶Ra, ²³⁴U and ²³⁸U for activity analysis and with ⁹⁰Sr and ²³⁰Th for gross alpha/beta analysis. Feedback statistics from the IAEA final report showed that the radioactivities of all of the samples fell within an acceptable range according to the IAEA. For ²²⁶Ra analysis, our result showed that ²²⁹Th–²²⁵Ra is suitable as a chemical tracer, although there are doubts that different co-precipitation efficient between parent ²²⁹Th and its daughter nuclide ²²⁵Ra in published literature. The impact factors of the analysis results, such as the lower limit of detection, standard substances, the background and efficiency for daily determination, are discussed in detail.     

First proficiency test for the determination of NORM in contaminated soil from the oil field

The Atomic Energy Commission of Syria (AECS), in cooperation with the Arabic Atomic Energy Agency (AAEA), has initiated the first proficiency test exercise for the determination of naturally occurring radioactive materials (NORM) in contaminated soil from the oil field. The soil sample was collected from one of the most highly radioactively contaminated lagoons with production water in the Syrian oil fields, which was then prepared, characterised and certified according to a standard procedure. Samples were dispatched to laboratories from eight Arab countries; Kuwait, Egypt, Yemen, Tunisia, Jordan, the Kingdom of Saudi Arabia, Libya and Syria. The results were evaluated using three statistical criteria; z-score, the U _test score and the relative bias. These statistical methods were used to evaluate the performance of each laboratory, in addition to the overall evaluation for each radionuclide. This evaluation has indicated that 57% and 86% of the results passed the criteria set for precision and accuracy applied for this test in relation to ²²⁶Ra and ²²⁸Ra, respectively. These two radionuclides are considered to be the most important radionuclides in the oil industry.     

A CRL–IRMM joint proficiency test for trace elements in fish tissue

The Community Reference Laboratory (CRL) for residues and contaminants in food of animal origin at the Istituto Superiore di Sanità (ISS) plans and undertakes on a regular basis Proficiency Tests Schemes (PTSs) focused on the residues under its responsibility, as prescribed by the Council Directive 96/23/EC of April 29, 1996. In consideration of the benefits ensuing from a constant monitoring of the daily activities of the National Reference Laboratories (NRLs) for residues in the Member States, the ISS–CRL frequently prepares test materials to promote comparability of data and support harmonisation of routine analytical procedures. When target values for the analytes are set, the PTSs also provide objective assessment and improvement of the analytical trueness in the daily work.In this context, an interlaboratory comparison for trace elements in tuna fish matrix was organised in cooperation with the Institute for Reference Materials and Measurements (IRMM), Joint Research Centre, European Commission. Freeze-dried tuna fish samples were sent out to the NRLs for chemical elements in the Member States. Participants were requested to carry out at least three independent measurements of the elements As, Cd, Cr, Cu, Fe, Hg, Pb and Zn. The assessment of the proficiency was based on the z-score approach and a relative bias better than or equal to 10% of the target value was deemed to be an acceptable performance for this kind of measurements. On this basis, more than 50% of the laboratories returned accurate results for As, Cu, Fe, Hg and Zn, whereas the analysis of Cd, Cr and Pb appeared to be more problematic.     

Development of pH sensor based on aromatic polyurethane matrix

The synthesized aromatic polyurethane (APU)-based all-solid-state (ASS) pH sensor was developed with the same APU-based reference site in an ASS multi sensing electrode. The best analytical performance (the linear range of pH 3.0–11.5, slopes of 57 mV pH⁻¹) was obtained with the membrane composition of 33:66:1 (wt.%) of APU/plasticizer (NPOE)/ionophore (N,N-dioctadecylmethylamine) with the addition of lipophilic additive (KTpClPB, 5 mol.%). This ASSE exhibits more advantages of increasing stability, reducing membrane resistance and reducing anion interference.     

Expression of results with uncertainty for the determination of pesticides in melon--experience in a proficiency test.

The expression of results with an uncertainty through the "bottom-up" approach, involving the estimation and combination of all the sources of uncertainty, represents a challenge when the analytical method includes mass transfer steps (MTS). These steps (e.g. extraction, evaporation, digestion, etc.) with inherently different from 100% recoveries lack models capable of describing their precision and efficiency. Recently, a new methodology was published aimed at the estimation of the performance of these critical steps. Comparison of the experimental dispersion from the replicated analysis of spiked samples with the combination of the uncertainty associated with gravimetric, volumetric and instrumental quantification steps (described by well established models) allows the estimation of the MTS uncertainty. Evaluation of the behaviour of the MTS within the analytical range supports the use of developed estimations over a wide concentration range. This methodology was applied, with success, to the determination of pesticide residues in melon in one particular proficiency test organised by the Food Analysis Performance Assessment Scheme (FAPAS) between November 2000 and February 2001.