Interlaboratory comparison study for the determination of halogenated hydrocarbons in water

Sixty laboratories of five different countries participated in a large-scale interlaboratory comparison test for the determination of halogenated hydrocarbons in water. Participants used their in-house method with 44 laboratories applying head space GC ECD analysis and 5 using liquid/liquid extraction. A set of two artificially produced samples was prepared; the halogenated hydrocarbons investigated were trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, trichloromethane, tetrachloromethane, 1,1-dichloroethylene, dichloromethane, dibromochloromethane, bromodichloromethane, 1,2-dichloroethane and tribromomethane. The procedure of sample preparation, storage and distribution was monitored by an extensive quality assurance system including homogeneity tests, stability tests, and trend analysis of the submitted data. The analytical results submitted by the participants exhibited RSD values of up to 35% and outlier rates of up to 19%. The percentage of false positive and false negative results was at the highest 12% for selected substances. Recovery rates varying from 86% to 106% proved the correctness of the analytical results submitted by the participants and showed that the procedure developed in this study for sample preparation and distribution is well suited for the performance of large-scale interlaboratory comparison tests of halogenated hydrocarbons in water. Received: 7 December 1998 / Revised: 23 March 1999 / Accepted: 24 March 1999     

Problems associated with interlaboratory comparisons of halogenated hydrocarbons in drinking water. The use of commercial control materials

Summary The study covers two interlaboratory comparisons on halogenated hydrocarbons in water. The results from the determination of trichloromethane in water at two concentration levels have been evaluated. A wide range of sample preparation procedures, instrument conditions and calibration materials were employed by the laboratories. Systematic errors were demonstrated when trichloromethane in samples with unknown concentrations were analyzed. Results of analyses from water samples prepared by the laboratories showed that the laboratories were apparently able to retrieve the quantities of added substance in samples with well known concentrations. Factors such as the use of commercial control materials, type of sample flasks, sample storage, sample preparation procedures and their influence on results are discussed.     

Evaluation of the long-term performance of water-analyzing laboratories

After 7 years of successful operation, the database of the proficiency testing (PT) scheme for water analysis organized by the Institute for Agrobiotechnology (IFA), Tulln contains nearly 4,000 data sets from over 300 interlaboratory comparison samples. About 70 analytical parameters (major ions, metals, trace ions, herbicides, volatile halogenated hydrocarbons, organochlorine pesticides and polycyclic aromatic hydrocarbons) were covered by the PT scheme. The data were evaluated using robust statistics in order to determine a set of coefficients of variation (CV) for each analytical parameter. Concentration and time dependence of the CV were checked. The CV were combined to obtain standard deviations for proficiency assessment (Z-score criteria). Furthermore, a viewer program was designed to facilitate monitoring of the analytical performance of participating laboratories.     

IAEA quality control studies on determining trace elements in bioindicators

Twenty laboratories from 17 countries around the world participated in two analytical quality control exercises, coded NAT-5 and NAT-6, on determining trace and minor elements in plant bioindicator samples. 1398 laboratory mean values for 51 elements were submitted for two lichen and two moss materials. The submitted measurement results were evaluated as interlaboratory comparison (IC) exercises and as proficiency tests (PT) following standard procedures developed by the International Atomic Energy Agency (IAEA). The evaluations confirmed good performance of the participating laboratories for many elements. Furthermore, the laboratories performance based on IC criteria improved from the first exercise to the second one. Subsequent NAT-5 evaluation revealed systematic differences between the analytical values obtained non-destructively or after the total sample dissolution and the measurements following nitric acid sample dissolution (without the use of hydrofluoric acid) for some elements. The most critical elements for this kind of discrepancies appeared to be Al, Ca, Cr, Fe, Na, Ni, and Pb. After changing analytical methodologies in the concerned laboratories, more consistent values for those elements were obtained in NAT-6. This revised version was published online in August 2006 with corrections to the Cover Date.     

Multielement trace determination in SiC powders: assessment of interlaboratory comparisons aimed at the validation and standardization of analytical procedures with direct solid sampling based on ETV ICP OES and DC arc OES

The members of the committee NMP 264 “Chemical analysis of non-oxidic raw and basic materials” of the German Standards Institute (DIN) have organized two interlaboratory comparisons for multielement determination of trace elements in silicon carbide (SiC) powders via direct solid sampling methods. One of the interlaboratory comparisons was based on the application of inductively coupled plasma optical emission spectrometry with electrothermal vaporization (ETV ICP OES), and the other on the application of optical emission spectrometry with direct current arc (DC arc OES). The interlaboratory comparisons were organized and performed in the framework of the development of two standards related to “the determination of mass fractions of metallic impurities in powders and grain sizes of ceramic raw and basic materials” by both methods. SiC powders were used as typical examples of this category of material. The aim of the interlaboratory comparisons was to determine the repeatability and reproducibility of both analytical methods to be standardized. This was an important contribution to the practical applicability of both draft standards. Eight laboratories participated in the interlaboratory comparison with ETV ICP OES and nine in the interlaboratory comparison with DC arc OES. Ten analytes were investigated by ETV ICP OES and eleven by DC arc OES. Six different SiC powders were used for the calibration. The mass fractions of their relevant trace elements were determined after wet chemical digestion. All participants followed the analytical requirements described in the draft standards. In the calculation process, three of the calibration materials were used successively as analytical samples. This was managed in the following manner: the material that had just been used as the analytical sample was excluded from the calibration, so the five other materials were used to establish the calibration plot. The results from the interlaboratory comparisons were summarized and used to determine the repeatability and the reproducibility (expressed as standard deviations) of both methods. The calculation was carried out according to the related standard. The results are specified and discussed in this paper, as are the optimized analytical conditions determined and used by the authors of this paper. For both methods, the repeatability relative standard deviations were <25%, usually ~10%, and the reproducibility relative standard deviations were <35%, usually ~15%. These results were regarded as satifactory for both methods intended for rapid analysis of materials for which decomposition is difficult and time-consuming. Also described are some results from an interlaboratory comparison used to certify one of the materials that had been previously used for validation in both interlaboratory comparisons. Thirty laboratories (from eight countries) participated in this interlaboratory comparison for certification. As examples, accepted results are shown from laboratories that used ETV ICP OES or DC arc OES and had performed calibrations by using solutions or oxides, respectively. The certified mass fractions of the certified reference materials were also compared with the mass fractions determined in the interlaboratory comparisons performed within the framework of method standardization. Good agreement was found for most of the analytes.     

Quality control in extended measurement campaigns: selection of contract laboratories by proficiency testing exemplified for the trace analysis of anilines in groundwater

An interlaboratory comparison for the determination of aniline, nine methylated anilines and chlorinated anilines in contaminated groundwater (each compound between 1 µg L^?1 and 750 µg L^?1) was conducted as proficiency test for the selection of contract laboratories for a groundwater monitoring campaign. For the 13 participants, two different test sample series were prepared from a stabilized real case groundwater. Series A was the groundwater as sampled in the field and series B was prepared from series A by spiking with selected anilines. Homogeneity and stability investigations revealed that contaminated groundwater provides a viable basis for the preparation of ring test samples for the determination of anilines. Analytical procedures were limited to the standardized liquid–liquid extraction or solid-phase extraction in combination with gas chromatography/mass spectrometry (DIN 38407-16:1999). The robust consensus values were evaluated according to the standardized protocol of DIN 38402-45:2013. Robust reproducibility standard deviations ranged largely between 20?% and 60?% depending on the analyte. The proficiency assessment of individual participants combined the qualitative aspect of correct peak identification with the quantitative determination of individual concentrations within set limits in a unified approach. It could be shown that the accreditation status of laboratory and the existence of a standardized analytical procedure do not substitute a problem-related proficiency assessment of potential contractors.     

Determination of hydrocarbons in water – interlaboratory method validation before routine monitoring

The clarification of hydrocarbon input into the Baltic sea via rivers is one of the priority issues of the 4th Pollution Load Compilation (PLC-4) within the framework of international Baltic Sea marine monitoring. An interlaboratory comparison was conducted to check the applicability of a new method for the determination of hydrocarbons by solvent extraction and gas chromatography. Surrogate oil solutions with known hydrocarbon content were distributed among the participants for preparation of water samples of different hydrocarbon concentration. In using these concentrations as assigned values and by setting target values for precision, the proficiency of participating laboratories could be tested as a qualifying step before involvement in PLC-4 routine monitoring. The results of the exercise indicate that hydrocarbons in water samples can be monitored as a mandatory test item within the framework of PLC-4. Received: 31 October 2000 Accepted: 3 January 2001     

Analysis of interlaboratory performance in the determination of total selenium in water

This study explored the performance of experienced laboratories in the analysis for total selenium in water by a variety of analytical methods. The goal of the study was to examine intra- and interlaboratory variability. Replicates (n = 7) of 7 sample types that included a reference material of known Se concentration, natural waters, and treated wastewaters were submitted to 7 laboratories with prequalified Se analytical experience. Results of the study indicated wide ranges in minimum and maximum results, distinct differences in laboratory precision, and routine reporting of numerical results below statistical limits of quantitation. Hydride generation as a sample introduction technique demonstrated superior performance. In general, the study supports a caution advisory about using low-level Se data, especially results lower than about 10 micrograms Se/L, without quantitating the statistical uncertainty of the data. Because this study used data from samples that were submitted in bulk to participating laboratories prequalified for Se analytical expertise and experience, it can be considered a best-case demonstration of performance.     

Auswertung eines Ringversuches im Spurenbereich

Summary The evaluation of an interlaboratory comparison in trace analysis has to take account of the log-normal distribution of the results. This distribution leads to the geometric mean as a measure for the content of the investigated sample, and to a relative error for the confidence interval for the reproducibility and the repeatibility. The log-normal distribution allows to pool together the relative standard deviations from the different components of the sample. In this way the confidence interval gets narrower and the criteria for reproducibility and repeatibility can be improved, even when there was an insufficient number of laboratories taking part in the interlaboratory comparison.     

Organization and evaluation of interlaboratory comparison studies among southern african water analysis laboratories

Interlaboratory comparison studies provide a useful "external" supplement to the various "internal" quality-control procedures which must be employed in the water-analysis laboratory in order to maintain a high degree of reliability in the production of analytical results. Such studies have been made regularly for many years by various overseas organizations, and were introduced in South Africa in 1976. Since that time 16 studies have been made, involving more than 40 laboratories. In this paper the various factors involved in the successful organization of interlaboratory comparison studies are discussed, and details are given of the sample-preparation, analysis-instruction and result-reporting procedures used in the southern African studies. Techniques used for the statistical evaluation of the analytical results submitted are described and discussed, for example, methods for the rejection of outliers, measures of accuracy and precision, determination of total error, tests of significance, Greenberg's assessment technique, Madden's ranking technique and Youden's graphical technique. A brief review is given of the studies made to date, along with specific findings and recommendations arising from them. The need for a recognized updated set of standard methods for use by water and wastewater analysis laboratories in southern Africa is highlighted.     

The determination of organochlorine compounds and petroleum hydrocarbons in a seaweed sample: results of a world-wide intercomparison exercise

A seaweed sample (Fucus sp.) was prepared, homogenised and distributed to laboratories worldwide as the IAEA-140 intercomparison material for the analysis of organochlorine compounds and petroleum hydrocarbons. A total of 80 laboratories from 51 countries reported results for this sample. The data sets reported by laboratories were evaluated statistically and the mean concentration values could be computed with 95% confidence limits for a large number of analytes. The accuracy of the analytical performance of each laboratory has been introduced by using Z-scores. The spread of results reported generally indicates that the accurate determination of many persistent organic pollutants, such as hexachlorobenzene, lindane, Aroclors or fluoranthene, is still difficult for many laboratories. The final results of this intercomparison exercise enable individual participants to assess their performance and, where necessary, to introduce appropriate modifications in their analytical procedures. Furthermore, as a series of statistical criteria was fulfilled for a number of compounds, the sample IAEA-140 can now be used as a reference material for quality control in the determination of chlorinated compounds and petroleum hydrocarbons in environmental samples.     

Macrozoobenthos interlaboratory comparison on taxonomical identification and counting of marine invertebrates in artificial sediment samples including testing various statistical methods of data evaluation

A macrozoobenthos interlaboratory comparison was carried out by 16 laboratories to check the taxonomical expertise and the precision of sorting and counting. Participating laboratories had to determine and count in an artificial sediment sample 22 selected macrozoobenthos species taken from the western Baltic Sea. Two methods for the analysis of data were applied: assessment of qualitative and quantitative successful hits and the maximum-likelihood method.The results of counting were mostly precise (one lab without mistake). Four laboratories had a rate of false determination of 10%, eight laboratories between 10 and 20% and four laboratories of more than 20%.The species Arctica islandica, Retusa obtusa, Fabricia stellaris, Polydora quadrilobata, Pholoe assimilis, Microdeutopus gryllotalpa, and Corophium crassicorne caused some problems at the species determination step.The comparison of the different methods of statistical data analysis shows that the maximum-likelihood method is more sensitive than the method of successful hits.Presented at the Eurachem PT Workshop September 2005, Portorož, Slovenia.     

EAL interlaboratory comparison Wa1 – Testing of potable water

 The accreditation of laboratories has emphasized the use of interlaboratory comparisons as a tool to monitor the comparability and accuracy of results laboratories produce. An interlaboratory comparison for water laboratories was organized among European Cooperation for Accreditation (EA) member countries; 30 laboratories, 7 of which were not accredited, from 14 European countries participated in this intercomparison. All the laboratories were chosen by the appropriate national accreditation bodies, with the instruction to select as participants those laboratories which act as national reference laboratories in this field. About 90% of the data collected was considered satisfactory after statistical treatment. Non-accredited laboratories performed as well as accredited laboratories. The laboratories were asked to take corrective action and report the corrections to the accreditation bodies. A great variation in the reported uncertainties of the results was observed. There seems to be a need to organize EA interlaboratory comparisons for national reference laboratories analysing water. It is obvious that even reference laboratories need training in how to estimate the uncertainty of results. Received: 22 July 1998 · Accepted: 21 September 1998     

Interlaboratory study of the bioluminescence inhibition tests for rapid wastewater toxicity assessment

Several toxicity procedures are currently being used for the wastewater toxicity assessment. We have undertaken an interlaboratory comparison of the use of different bioluminescence inhibition toxicity tests based on Vibrio fischeri, in order to evaluate their reproducibility for the rapid wastewater toxicity assessment. Twenty-two laboratories took part in this study organized by the Institut Català de Tecnologia (ICT) and the Consejo Superior de Investigaciones Cientificas (CSIC). During the exercise, six series of six samples were analyzed along 5 months. Every batch of samples was composed by three real samples and three standard solutions. The real samples were: an untreated effluent of a paper industry, a sample from a first settlement of a wastewater treatment plant (WWTP) and the final effluent of the WWTP. The goals of the interlaboratory study were to evaluate the repeatability (r) and reproducibility (R) when different laboratories conduct the test, the influence of different matrix samples, the variability between different tests based on the same principle: the bioluminescence inhibition of V. fischeri, but involving different commercial devices and to determine the rate at which participating laboratories successfully completed tests initiated. The maximum number of outlier values was corresponding to a non-treated effluent from a paper industry. This also was the most complex and toxic sample analyzed. An increase on the non-convergent values obtained for the participants was observed at higher matrix complexity and at lower toxicity level. In comparison with other editions of this interlaboratory study the matrixes of real samples analyzed were more complex, nevertheless the final variability coefficient for the exercise was nearby to the average value for the past editions. Due to the high complexity of some samples involved in this intercalibration the stability of real samples were also followed during the test. On the other hand, no relation was found between final results and the different devices, as show the cluster analysis.     

The BIOREMA project—Part 2: International interlaboratory comparison for biodiesel test methods

The results of an interlaboratory comparison, using various measurement methods to carry out biodiesel testing, are presented and the findings are discussed. The interlaboratory comparison was organised within the framework of an EU-funded project called BIOREMA. A general overview of the project and results of an interlaboratory comparison on bioethanol are published as Part 1 and 2 of this series of papers. In the study presented here, reference values, provided by national metrology institutes and expert laboratories, were used for evaluating the results. Consensus values, derived from the results of all participants, were used to assess any bias between the results from the national metrology institutes and testing laboratories. The emphasis in this interlaboratory comparison was not the performance rating of the individual laboratories, but recognising and interpreting differences caused by the measurement methods applied. For most biodiesel parameters, a good agreement of measurement results was found among different methods, and between the consensus and reference values. The study material was a rapeseed oil fatty acid methyl ester, for which it was demonstrated that it is feasible to prepare and characterise reference materials for biodiesel with well-established reference values for many parameters.     

Interlaboratory comparison to evaluate a standardized calibration procedure for the headspace analysis of aromatic solvents in blood

The determination of volatile organic compounds in blood by headspace gas chromatography is one of the central and long-established analytical techniques in occupational medical biomonitoring. Nevertheless, the relatively low success rate in intercomparison programs shows that the headspace technique is insufficiently standardized. A critical stage of the analytical procedure seems to be the preparation of calibration standards in biological matrices. As part of an extensive interlaboratory comparison by the Analyses of Hazardous Substances in Biological Materials working group of the DFG Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area, three typical procedures were compared with one another using typical aromatic solvents as an example. The best correlations between the participating laboratories and the best results for the analyses of samples from interlaboratory comparisons were obtained when highly concentrated stock solutions of the aromatic compounds in ethanol were first diluted with physiological saline and then used for spiking horse blood in headspace vials. This procedure can be easily standardized and is therefore recommended by the Analyses of Hazardous Substances in Biological Materials working group for the preparation of headspace calibration standards for aromatic compounds.Dr. Regine Heinrich-Ramm, our highly valued colleague, died in 2002From the Analyses of Hazardous Substances in Biological Materials working group of the Analytical Chemistry Group (Chair: J. Angerer, Erlangen) of the DFG Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area (Chair: H. Greim, Weihenstephan)     

Interlaboratory comparison for the determination of five residual organochlorine pesticides in ginseng root samples by gas chromatography

An interlaboratory comparison study for the determination of 5 residual organochlorine pesticides (hexachlorobenzene and 4 hexachlorocyclohexane isomers) in ginseng root was performed. This program [Asia Pacific Laboratory Accreditation Cooperation (APLAC) T049] was the first of its kind for an herbal matrix and involved the participation of 70 laboratories from 26 countries worldwide. Consensus mean values were computed statistically from the reported results, which were eventually used to assess the performance of individual laboratories in terms of the z-scores. The distribution of analytical data was found to be widespread, with standard deviation ranging from 43.9 to 55.9%, and the result patterns obtained were similar to those residue pesticide programs using other matrixes. Although the estimation of measurement uncertainty is a crucial requirement for all quantitative tests for laboratories that meet the requirements of International Organization for Standardization/International Electrotechnical Commisssion (ISO/IEC) 17025, some laboratories in this program had difficulties and showed unfamiliarity with respect to that quality criterion. It was recommended that laboratories review and rectify the situation promptly so that they would have a better understanding of measurement uncertainty or the test service provided.     

Measurement of PAHs in environmental matrices: results from an interlaboratory comparison on the different steps of the measurement procedure

Proficiency testing (PT) is becoming a feature of laboratory accreditation and the PT results are used to assess the technical competence of the participating laboratories. ISPRA (former APAT) plays an important role in supporting the Italian laboratories belonging to the network of the Regional Environmental Agencies to improve the quality of their analytical measurements. As a consequence, ISPRA organized an interlaboratory comparison to assess the performance of the laboratories on PAH measurement procedure. The interlaboratory comparison was drawn separating the different steps of the measurement (from the extraction to the instrumental measurement). Two matrix reference materials: (1) a polluted soil and (2) an extract reference material of the same polluted soil and a “blind” PAH mixture standard stock solution were distributed to 59 Italian laboratories. The results of interlaboratory comparison showed a significant dispersion of the PAH measurements that masks the effects of the different extraction and cleanup procedures used, but it is consistent with the results of other European interlaboratory comparisons.     

Interlaboratory study of the Charm ROSA Safe Level Aflatoxin M1 Quantitative lateral flow test for raw bovine milk

An interlaboratory study of 21 public health, state agriculture, and industry laboratories in the United States tested raw commingled bovine milk containing aflatoxin M1 using the Charm Rapid One Step Assay (ROSA) Safe Level Aflatoxin M1 Quantitative lateral flow method. Blind coded sample pairs were fortified with 0, 300, 350, 400, 450, 500, and 550 parts per trillion (ppt) aflatoxin M1. A ROSA reader quantitatively interpreted test strips with ppt readings. Readings < or = 400 ppt were interpreted as negative, and readings >400 ppt were interpreted as positive. Initial positive samples were subsequently assayed 2 additional times. If both retest results were >400 ppt, the sample was called positive/ actionable relative to U.S. and Codex levels, 500 ppt. The concentration of 400 ppt was chosen for the positive/negative interpretation to provide 90% sensitivity with 95% confidence at the 500 ppt legislative level. The combined false negative rate was <5% (4 of 83) for samples at 500 and 550 ppt. The false violatives at 0, 300, 350, 400, and 450 ppt (n = 42 at each level) were 0, 0, 21, 14, and 93%, respectively. The 90% positive concentration with 95% confidence was 503 ppt by probit analysis. The average intralaboratory repeatability was 11% and average interlaboratory reproducibility was 13% for the fortified sample pairs. High-performance liquid chromatography analysis of the study samples by 5 laboratories showed 38% false negatives with the 500 and 550 ppt samples, and a 0% false-violative rate with samples less than the 500 ppt action level.     

Evaluation of analytical interlaboratory comparisons and certification of reference materials

A procedure for the evaluation of results of interlaboratory comparisons of trace multi-component determinations is presented. The distribution of interlaboratory comparison data may differ significantly from the normal distribution and, therefore, various types of median and modal values approximate their central values better than the mean. The simple median and its confidence interval, calculated on the basis of a nonparametric distribution after the rejection of outlying results, is shown to be the optimal indicator of the central values. The total procedure consists of three parts: statistical evaluation of the data, classification of the results according to a special set of analytical criteria, and graphic presentation of the data. The application of the results of such comparisons for certification of analytical reference materials is discussed.