Consensus values for NIST biological and environmental Standard Reference Materials

The National Institute of Standards and Technology (NIST, formerly the National Bureau of Standards or NBS) has produced numerous Standard Reference Materials (SRM) for use in biological and environmental analytical chemistry. The value listed on the “NIST Certificate of Analysis” is the present best estimate of the “true” concentration of that element and is not expected to deviate from that concentration by more than the stated uncertainty. However, NIST does not certify the elemental concentration of every constituent and the number of elements reported in the NIST programs tends to be limited. Numerous analysts have published concentration data on these reference materials. Major journals in analytical chemistry, books, proceedings and “technical reports” have been surveyed to collect these available literature values. A standard statistical approach has been employed to evaluate the compiled data. Our methodology has been developed in a series of previous papers. Some subjective criteria are first used to reject aberrant data. Following these eliminations, an initial arithmetic mean and standard deviation (S.D.) are computed from remaining data for each element. All data now outside two S.D. from the initial mean are dropped and a second mean and S.D. recalculated. These final means and associated S.D. are reported as “consensus values” in our tables. Received: 25 April 1997 / Revised: 24 July 1977 / Accepted: 25 July 1997     

Evaluation of relative comparator and <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>-NAA for characterization of Aboriginal Australian ochre

Ochre is a significant material in Aboriginal Australian cultural expression from ceremonial uses to its application on many types of artifacts. However, ochre is a complex material, with associated surrounding minerals potentially challenging the overall analysis. In recent literature several studies have attempted to characterize ochre by a variety of techniques to understand procurement and trade. However, ochre is difficult to differentiate on major elemental or mineralogical composition and requires a detailed analysis of its geochemical “fingerprint”. Neutron activation analysis (NAA) provides the high sensitivity (sub-ppm), precision and accuracy in multi-elemental analysis required for ochre. The elements of interest for ochre generally include rare earth elements (REEs) and certain transition metal elements as well as arsenic and antimony. Data from relative comparator NAA (MURR, University of Missouri, USA) is compared with data from k ₀-NAA OPAL (ANSTO, Lucas Heights, Australia). A discussion of the two methods will be examined for their utility in “fingerprinting” the provenance of ochre. The continuing importance of NAA to archaeometry will also be discussed.     

Concentration profiles of trace elements in small silica components by INAA and controlled sequential dissolution

The promotion of radioanalysis as an elegant, predominantly instrumental, analytical method is a major achievement of Vincent P. Guinn. As an example the sequential analysis for trace elements in the mm-range of small “pure” silica components from the electronic industry of various, often irregular, shapes is presented here. The idea reaches back to our discussions in the early seventies. This revised version was published online in July 2006 with corrections to the Cover Date.     

Non-selective chemical sensors in analytical chemistry: from “electronic nose” to “electronic tongue”

Development, recent historical background and analytical applications of promising sensor instruments based on sensor arrays with data processing by pattern recognition methods have been described. Attention is paid to the “electronic tongue” based on an array of original non-specific (non-selective) potentiometric chemical sensors. Application results for integral qualitative analysis of beverages and for quantitative analysis of biological liquids and solutions, containing heavy metals are reported. Discriminating abilities and precision obtained allow to consider “electronic tongue” as a perspective analytical tool. Received: 17 July 1997 / Revised: 19 February 1998 / Accepted: 24 February 1998     

Warning: false sense of certainty from the illusion of accuracy and precision in measurements

The illusion of accuracy and precision in testing is often associated with overconfident safety checks before catastrophes: National Aeronautics and Space Administration (NASA) “no safety-of-flight issues,” Deepwater Horizon site in Gulf Mexico reported as “industry model for safety” a year before its explosion, and Fukushima nuclear plant safety test found “satisfactory” at seismic magnitude viewed highest possible. In health care, testing overuse and misuse play significant roles in overconfidence and mistakes. Gaps between systems are most susceptible to errors, such as in miscommunications between the laboratory and the clinic. A safety culture is characterized by ability to communicate, anticipation of misunderstanding and resilient learning from failures. The discussion will show how messages from the laboratory may reduce the false sense of certainty from a test result; how results of tests are meaningless without pre-test estimates; how multiplicity of routine tests increases chances of false positivity; and how reporting measurement limitations can educate all users, including laboratory technicians, clinicians and patients, about the importance of quality assurance and about the pervasive nature of uncertainty beyond analytical performance. In conclusion, an illusion of accuracy and precision in testing evokes among clinicians a false sense of certainty leading to overuse and misuse of tests. Messages from the laboratory may reduce overconfidence from test results and lead to safer use of testing.     

Reference materials characterized for impurities in uranium matrices: An overview and re-evaluation of the NBL CRM 124 series

The characterized concentrations of 24 impurity elements in New Brunswick Laboratory (NBL) Certified Reference Material (CRM) 124 were reevaluated. A provisional certificate of analysis was issued in September 1983 based upon the “as prepared” values (gravimetric mixing). The provisional certificate does not state uncertainties for the characterized values, or estimate the degree of homogeneity. Since release of the provisional certificate of analysis various laboratories have reported analytical results for CRM 124. Based upon the reported data a re-evaluation of the characterized values with an estimate of their uncertainties was performed in this work. An assessment of the degree of homogeneity was included. The overall difference between the re-evaluated values for the 24 impurity elements and the “as prepared” values from the provisional certificate of analysis is negligible compared to the uncertainties. Therefore, NBL will establish the “as prepared” values as the certified values and use the derived uncertainties from this work for the uncertainties of the certified values. The traceability of the “as prepared” values was established by the gravimetric mixing procedure employed during the preparation of the CRM. NBL further recommends a minimum sample size of 1 g of the CRM material to ensure homogeneity. Samples should be dried by heating up to 110 °C for one hour before use.     

Comparability of analytical results obtained in proficiency testing based on a metrological approach

A “yes–no” type of criterion is proposed for the assessment of comparability of proficiency testing (PT) results when the PT scheme is based on a metrological approach, i.e. on the use of a reference material as the test sample, etc. The criterion tests a null hypothesis concerning the insignificance of a bias of the mean of the results from a traceable value certified in the reference material used for the PT. Reliability of such assessment is determined by the probabilities of not rejecting the null hypothesis when it is true, and rejecting it when it is false (the alternative hypothesis is true). It is shown that a number of chemical, metrological and statistical reasons should be taken into account for careful formulation of the hypotheses, enabling the avoidance of an erroneous assessment of the comparability. The criterion can be helpful for PT providers and laboratory accreditation bodies in analysis of PT results.     

Instrumental neutron activation analysis of lunar samples and the identification of primary matter in the Lunar Highlands

We describe the scheme of sequential neutron activation which was developed in our laboratory especially for the analysis of lunar samples and in which more than 50 elements are determined. Irradiations with 14 MeV, epithermal and thermal neutrons and both instrumental techniques and radiochemical separations were applied. It is shown that the achieved accuracy can compete with the best available analytical methods for most major and many trace elements. Besides the observation of “correlated elements”, the discovery of primary matter of the last accretion stage of the moon in samples from the lunar highlands is discussed in some detail.     

Comparison of neutron activation analysis with other analytical techniques for the determination of inorganic constituents of milk powder

The contribution of different analytical techniques to the results of a recent IAEA intercomparison (A-11) of the determination of the inorganic constituents of a milk powder sample is discussed. In all, 43 laboratories from 24 countries reported results on 40 elements, “recommended” concentrations for 14 elements were established. NAA was the most important of the 9 techniques used in this run, it contributed 40% of all the results and all the results for 7 elements. Accuracy and precision of NAA proved to be good compared to those of other methods.     

Performance evaluation for proficiency testing with a limited number of participants

Proficiency testing (PT) is an essential tool for laboratories to assess their competency. Also, participation in PT has become one of the mandatory requirements for laboratory to seek accreditation according to ISO/IEC 17025. For this reason, the effectiveness of performance evaluation by PT scheme is of great concern for the participants and for accreditation bodies as well. In practice, owing to unavailability of other appropriate alternatives, PT scheme providers may have to choose using consensus values to evaluate the performance of participants. However, such consensus values approach was not recommended by relevant international guidelines for PT schemes with limited number of participants. With the use of Monte Carlo simulation technique, this study attempted to investigate the effectiveness of using consensus values for performance evaluation in PT schemes with limited number of participants. The simulation process was schemed according to the statistical model provided by ISO 5725-1 for laboratory measurement results, which covered components like method bias, laboratory bias, and measurement precision. The effectiveness of the consensus value approach was expressed as the percentage of participants in a simulation run could get the same evaluation result, either satisfactory or unsatisfactory, against the “true value.” The findings indicated that the number of participants, choice of consensus values, mass fraction of analyte, method bias, laboratory bias, and measurement repeatability of participating laboratories would all affect the effectiveness of the consensus value approach but at different extent. However, under certain circumstances, use of consensus value could still be considered as an acceptable approach for performance evaluation even the number of participants was limited. Some of the findings were further verified using real data from PT schemes where appropriate certified reference materials or reliable reference values were available.     

Comparability of measurement results for pesticide residues in foodstuffs: an open issue?

The dispersion of results from proficiency tests for the analysis of pesticide residues in foodstuffs suggests that improvements in the compatibility of measurement results are needed. Currently observed divergences can make the evaluation conclusion on foodstuffs compliance with certain legislation dependent on the consulted laboratory. This work discusses the origin and impact of this lack of compatibility, following the metrological concepts presented at the latest version of the “International Vocabulary of Metrology” (VIM3), thus allowing for a clear diagnostic of the problem. The reporting of results from different measurement methods uncorrected for the observed analyte recovery makes them traceable to different “operationally defined measurement procedures” (VIM3) and, therefore, not comparable. When results from different measurement methods are reported corrected for analyte recovery, R, and R is different for spiked and incurred residues, measurement results may be not compatible if this effect is not considered on the uncertainty budget. This discussion is illustrated with metrological models for any possible combination of “measurement performance” and “maximum residue level”. These models are complemented with experimental data of the analysis of pesticide residues in a sample of ginseng powder from a proficiency test. The adopted experimental design allowed the identification of additional threats to metrological compatibility in this field. Solutions to the faced problem are discussed for practicability and impact on regulatory issues. The use of a universal “reference measurement procedure” proves to be the most feasible way of ensuring comparability of measurements in this field.     

Comparability and compatibility of proficiency testing results in schemes with a limited number of participants

Comparability and compatibility of proficiency testing (PT) results are discussed for schemes with a limited number of participants (less than 20–30) based on the use of reference materials (RMs) as test items. Since PT results are a kind of measurement/analysis/test result, their comparability is a property conditioned by traceability to measurement standards applied in the measurement process. At the same time, metrological traceability of the certified value of the RM (sent to PT participants as test items) is also important, since the PT results are compared with the RM certified value. The RM position in the calibration hierarchy of measurement standards sets the degree of comparability for PT results, which can be assessed in the scheme. However, this assessment is influenced by commutability (adequacy or match) of the matrix RM used for PT and routine samples. Compatibility of PT results is a characteristic of the collective (group) performance of the laboratories participating in PT that can be expressed as closeness of the distribution of the PT results to the distribution of the RM data. Achieving quality-of-measurement/analysis/test results in the framework of the concept “tested once, accepted everywhere” requires both comparability and compatibility of the test results.     

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.     

Instrumental neutron activation analysis as a tool for assessing the solubility of soil mineral matter in strong acid

Fifty samples of natural surface soils with high but variable organic matter content were analyzed for 13 elements (Na, Al, K, Sc, V, Cr, Mn, Fe, Co, Zn, Sr, Ba, La) by INAA. The same samples were analyzed for the “total-recoverable” fraction of these elements by ICP-OES after decomposition with 7M HNO₃, and the results are compared. The data are discussed separately for two groups of samples with organic matter contents of respectively >80% and <70%. In the group with < 70 % organic matter the “total-recoverable” fractions show the following sequence (% of total): Co (83)>Mn (77)>La (60)>Fe=Zn (53)>V (33)>Cr (29)>Sc (25)>Al=Ba (17)>Sr (13)>K (5)>Na (2). The results are in good agreement with corresponding literature data for mineral soils in the case of Al, K, Sc, V, Cr, Fe, and La. In the case of Na, Mn, Co, Zn, Sr, and Ba the present surface soils showed significantly higher “total-recoverable” fractions than the previously studied subsoils. Possible reasons for these differences are discussed. INAA remains a convenient reference technique for determination of total concentrations with the rapidly increasing use of strong mineral acids in environmental studies of elements. This revised version was published online in July 2006 with corrections to the Cover Date.     

Chemometrics in the assessment of the sustainable development rule implementation

The sustainable development rule implementation is tested by the application of chemometrics in the field of environmental pollution. A data set consisting of Cd, Pb, Cr, Zn, Cu, Mn, Ni, and Fe content in bottom sediment samples collected in the Odra River (Germany/Poland) is treated using cluster analysis (CA), principal component analysis (PCA), and source apportionment techniques. Cluster analysis clearly shows that pollution on the German bank is higher than on the Polish bank. Two latent factors extracted by PCA explain over 88 % of the total variance of the system, allowing identification of the dominant “semi-natural” and “anthropogenic” pollution sources in the river ecosystem. The complexity of the system is proved by MLR analysis of the absolute principal component scores (APCS). The apportioning clearly shows that Cd, Pb, Cr, Zn and Cu participate in an “anthropogenic” source profile, whereas Fe and Mn are “semi-natural”. Multiple regression analysis indicates that for particular elements not described by the model, the amounts vary from 4.2 % (Mn) to 13.1 % (Cr). The element Ni participates to some extent to each source and, in this way, is neither pure “semi-natural” nor pure “anthropogenic”. Apportioning indicates that the whole heavy metal pollution in the investigated river reach is 12510.45 mg·kg⁻¹. The contribution of pollutants originating from “anthropogenic sources” is 9.04 % and from “semi-natural” sources is 86.53 %.     

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.     

Charley Peirce's Head Start in Chemistry

As a youngster of perhaps 8 years, Charles S. Peirce was given a chemistry laboratory in which he probably did experiments in qualitative analysis. These experiments were modeled on the hypothetico-deductive method of inquiry. I argue that this laboratory experience initiated Peirce’s life-long interest in logic and the logic of science, and flowered in his “pragmaticism.” This revised version was published online in July 2006 with corrections to the Cover Date.     

Multivariate analysis of HT/GC-(IT)MS chromatographic profiles of triacylglycerol for classification of olive oil varieties

The ability of multivariate analysis methods such as hierarchical cluster analysis, principal component analysis and partial least squares-discriminant analysis (PLS-DA) to achieve olive oil classification based on the olive fruit varieties from their triacylglycerols profile, have been investigated. The variations in the raw chromatographic data sets of 56 olive oil samples were studied by high-temperature gas chromatography with (ion trap) mass spectrometry detection. The olive oil samples were of four different categories (“extra-virgin olive oil”, “virgin olive oil”, “olive oil” and “olive-pomace” oil), and for the “extra-virgin” category, six different well-identified olive oil varieties (“hojiblanca”, “manzanilla”, “picual”, “cornicabra”, “arbequina” and “frantoio”) and some blends of unidentified varieties. Moreover, by pre-processing methods of chemometric (to linearise the response of the variables) such as peak-shifting, baseline (weighted least squares) and mean centering, it was possible to improve the model and grouping between different varieties of olive oils. By using the first three principal components, it was possible to account for 79.50% of the information on the original data. The fitted PLS-DA model succeeded in classifying the samples. Correct classification rates were assessed by cross-validation.     

Danube River Water Data Modelling by Multivariate Data Analysis

 A data set (48×19) consisting of Danube river water analytical data collected at Galati site, Romania, during a four-year period has been treated by principal components analysis (PCA). The PCA indicated that seven latent factors (“hardness”, “biochemical”, “waste inlets”, “turbidity”, “acidity”, “soil extracts” and “organic wastes”) are responsible for the data structure and explain over 80 % of the total variance of the system. Its complexity is further proved by the application of multiple linear regression analysis on the absolute principal components scores (APCS) where the contribution of each natural or anthropogenic sources in the factor formation is shown. The apportioning makes clear that each variable participates to a different extent to each source and, in this way, no pure natural or pure anthropogenic influence could be determined. No specific seasonality for the variables in consideration is found. Received January 24, 2001. Revision July 6, 2001.     

Comparison of “bottom-up” and “top-down” strategies for the estimation of the uncertainty in organic elemental analysis

The estimation of uncertainty in organic elemental analysis for C, H, N and S is reported. Both “bottom up” and “top down” strategies are used for uncertainty calculations. The bottom up approach used the results of C, H, N, and S obtained from the homogeneity study of two pure chemicals (toluene-4-sulfonamide and 4(6)-methyl-2-thiouracil). Two calibration systems, K factor and calibration curve, were applied in this study and no significant differences were obtained. For the “top down” approach, we used the data obtained from a proficiency test on both pure chemicals from among 45 Spanish laboratories. Both approaches are compared and discussed below.