GGR Handbook of Rock and Mineral Analysis Chapter 1 (Part 1) Geoanalytical Metrology
Corresponding Author
Kathryn L. Linge
ChemCentre, PO Box 1250 Perth, Australia
Corresponding author. e-mail: [email protected]
Search for more papers by this authorPhilip J. Potts
Faculty of Science, Technology, Engineering and Mathematics, The Open University, Walton Hall, Milton Keynes, MK7 6AA UK
Search for more papers by this authorCorresponding Author
Kathryn L. Linge
ChemCentre, PO Box 1250 Perth, Australia
Corresponding author. e-mail: [email protected]
Search for more papers by this authorPhilip J. Potts
Faculty of Science, Technology, Engineering and Mathematics, The Open University, Walton Hall, Milton Keynes, MK7 6AA UK
Search for more papers by this authorAbstract
This chapter (Geoanalytical Metrology) is a contribution to the Geostandards and Geoanalytical Research Handbook of Rock and Mineral Analysis – an online textbook that is a fully revised and updated edition of Handbook of Silicate Rock Analysis, which was written by Philip J. Potts and published in 1987 by Blackie and Son (Glasgow). This second edition comprises chapters, written by prominent research scientists, designed to provide comprehensive overviews of the relevant techniques for the elemental characterisation of rocks and minerals. Chapters are designed to allow new practitioners to the field (including research students) to attain a comprehensive understanding of the theory, practice and capabilities of each technique, as well as being of benefit to established research geoanalysts. In addition to the content, chapter titles have been revised where appropriate to reflect progress in this field.
Chapter 1, Part 1 (from Section 1 of the handbook dealing with fundamentals of measurement and instrument design) first sets out the overarching conventions that operate in analytical chemistry, including a description of the international organisations and systems that regulate the standards governing the discipline. This is followed by coverage of the statistical basis on which geoanalytical data sets are treated, analysed and interpreted, which summarises most of the relevant tests and terminology employed in this field. The methods by which the calibration of measured signals from instrumental techniques is tackled, followed by method validation, which covers aspects including measurement uncertainty, bias, precision and trueness. Sections detailing metrological traceability and quality management conclude this chapter.
Open Research
Data availability statement
Data sharing is not applicable to this article as no new data were created or analysed in this study.
1.9 References
- Abbey S. (1983) Studies in “standard samples” of silicate rocks and minerals, 1969–1982. Geological Survey of Canada Paper 83-15, Geological Survey of Canada (Ottawa), 114pp.
- Abbyad P., Tromp J., Lam J. and Salin E. (2001) Optimization of the technique of standard additions for inductively coupled plasma-mass spectrometry. Journal of Analytical Atomic Spectrometry, 16, 464–469.
- Agatemor C. and Beauchemin D. (2011) Matrix effects in inductively coupled plasma-mass spectrometry: A review. Analytica Chimica Acta, 706, 66–83.
- Analytical Methods Commitee (2004) The amazing Horwitz function. Analytical Methods Committee Technical Brief No 17, Royal Society of Chemistry, 2pp.
- Analytical Methods Commitee (2011) Sporadic blunders. AMC Technical Brief 49, Royal Society of Chemistry.
- Analytical Methods Committee (2001) Robust statistics: A method of coping with outliers. AMC Technical Brief 6, Royal Society of Chemistry.
- Analytical Methods Committee (2002) Fitting a linear functional relationship to data with error on both variables. AMC Technical Brief 10, Royal Society of Chemistry.
- Analytical Methods Committee (2012) Dark uncertainty. Analytical Methods Committee Technical Brief No 34. Analytical Methods, 4, 2609–2612.
- Analytical Methods Committee (2016) z-Scores and other scores in chemical proficiency testing – Their meanings, and some common misconceptions. Analytical Methods, 8, 5553–5555.
- Analytical Methods Committee (2020) The edge of reason: Reporting and inference near the detection limit. Analytical Methods, 12, 401–403.
- ASTM (2022) ASTM E29-22 Standard practise for using significant digits in test data to determine conformance with specifications. ASTM International (Pennsylvania, USA).
- Asuero A.G., Sayago A. and Gonzalez A.G. (2006) The correlation coefficient: An overview. Critical Reviews in Analytical Chemistry, 36, 41–59.
- Backman C. and Gustavsson N. (1996) Ruggedness test of an aqua regia extraction method made with the geochemical reference material GXR-2. Journal of Chemometrics, 10, 371–378.
- Barwick V. (2016) Eurachem/CITAC Guide: Guide to quality in analytical chemistry – An aid to accreditation ( third edition). Eurachem/CITAC, 59pp. www.eurachem.org
- Barwick V.J. (2023) EurachemGuide: Terminology in analytical measurement – Introduction to VIM 3 ( second edition). Eurachem/CITAC, 44pp. www.eurachem.org
- Bell S. (1999) Good practice guide No. 11 – A beginners guide to uncertainty of measurement. National Physical Laboratory (Teddington, UK), 34pp.
- BIPM (2019) The international system of units (SI) ( 9th edition). Bureau International des Poids et Mesures (Sèvres, France), 216pp.
- Currie L.A. (1995) Nomenclature in evaluation of analytical methods including detection and quantification capabilities (IUPAC Recommendations 1995). Pure and Applied Chemistry, 67, 1699–1723.
- Ellison S.L.R. (2006) In defence of the correlation coefficient. Accreditation and Quality Assurance, 11, 146–152.
- Ellison S.L.R., Barwick V.J. and Farrant T.J.D. (2009) Practical statistics for the analytical scientist. A Bench guide. RSC Publishing (Cambridge, UK), 268pp.
- Ellison S.L.R., King B., Rösslein M., Salit M. and Williams A. (2003) Traceability in chemical measurement. Eurachem/CITAC Working Group (UK).
- Ellison S.L.R. and Thompson M. (2008) Standard additions: Myth and reality. Analyst, 133, 992–997.
- Ellison S.L.R. and Williams A. (2012) Eurachem/CITAC guide: Quantifying uncertainty in analytical measurement (third edition). Eurachem/CITAC www.eurachem.org.
- Ellison S.L.R. and Williams A. (2019) Eurachem/CITAC guide: Metrological traceability in analytical measurement (second edition). CITAC/Eurachem. www.eurachem.org
- Gardner M.J. and Gunn A.M. (1986) Optimizing precision in standard addtitions determinations. Fresenius Zeitschrift für Analytische Chemie, 325, 263–266.
- Goodson D.Z. (2011) Mathematical methods for physical and analytical chemistry. Wiley (Hoboken), 408pp.
10.1002/9781118135204 Google Scholar
- Guevara M., Verma S.P., Velasco-Tapia F., Cruz R.L.S. and Giron P. (2005) Comparison of linear regression models for quantitative geochemical analysis: An example using X-ray fluorescence spectrometry. Geostandards and Geoanalytical Research, 29, 271–284.
- Harris G. (2019) Selected laboratory and measurement practices and procedures to support basic mass calibrations ( 2019 edition). NIST Interagency/Internal Report (NISTIR) 6969, National Institute of Standards and Technology (Gaithersburg, MD).
- Heumann K.G. (1988) Isotope dilution mass spectrometry. In: F Adams., R. Gijbels and R. Grieken (eds), Inorganic mass spectrometry chemical analysis series. Wiley (New York), 301–376.
- Heumann K.G. (2004) Isotope-dilution ICP-MS for trace element determination and speciation: from a reference method to a routine method? Analytical and Bioanalytical Chemistry, 378, 318–329.
- Hibbert D.B. (2007) Quality assurance in the analytical chemistry laboratory. Oxford University Press (Oxford), 320pp.
10.1093/oso/9780195162127.001.0001 Google Scholar
- Horwitz W. (1990) Nomenclature for sampling in analytical chemistry (Recommendations 1990). Pure and Applied Chemistry, 62, 1193–1208.
- Horwitz W., Kamps L.V.R. and Boyer K.W. (1980) Quality assurance in the analysis of foods for trace constituents. Journal of Association of Official Analytical Chemists, 63, 1344–1354.
- IAG (2020) Protocol for the operation of the GeoPT proficiency testing scheme. International Association of Geoanalysts, 19pp. http://www.geoanalyst.org/wp-content/uploads/2020/07/GeoPT-revised-protocol-2020.pdf
- International Committee for Weights and Measures (2014) The International System of Units (SI). Bureau International des Poids et Mesures (Paris, France).
- ISO (2007) ISO/IEC Guide 99:2007 International vocabulary of metrology – Basic and general concepts and associated terms (VIM). International Organization for Standardization (Geneva), 92pp.
- ISO (2008) ISO/IEC Guide 98-3:2008 Uncertainty of measurement – Part 3: Guide to the expression of uncertainty in measurement (GUM:1995). International Organization for Standardization (Geneva), 120pp.
- ISO (2010) ISO/IEC 17043:2010 Conformity assessment – General requirements for the competence of proficiency testing providers. International Organization for Standardization (Geneva), 38pp.
- ISO (2015) ISO Guide 33:2015 Reference materials. Good practice in using reference materials. International Organization for Standardization (Geneva), 31pp.
- ISO (2016) ISO/TR 16476:2016 Reference materials – Establishing and expressing metrological traceability of quantity values assigned to reference materials. International Organization for Standardization (Geneva), 29pp.
- ISO (2017a) ISO Guide 35:2017 Reference materials. Guidance for characterization and assessment of homogeneity and stability. International Organization for Standardization (Geneva), 105pp.
- ISO (2017b) ISO/IEC 17025:2017 General requirements for the competence of testing and calibration laboratories. International Organization for Standardization (Geneva), 29pp.
- ISO (2018) ISO 45001:2018 Occupational health and safety management systems. Requirements with guidance for use. International Organization for Standardization (Geneva), 41pp.
- ISO (2019a) ISO 5725-2:2019 Accuracy (trueness and precision) of measurement methods and results. Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method. International Organization for Standardization (Geneva), 69pp.
- ISO (2019b) ISO 7870-1:2019 Control charts Part 1: General guidelines. International Organization for Standardization (Geneva), 19pp.
- ISO (2022) ISO 13528: 2022 Statistical methods for use in proficiency testing by interlaboratory comparison. International Organization for Standardization (Geneva), 93pp.
- ISO (2023) ISO 5725-1:2023 Accuracy (trueness and precision) of measurement methods and results. Part 1: General principles and definitions. International Organization for Standardization (Geneva), 19pp.
- IUPAC (2019) Compendium of chemical terminology (2nd edition) (the "Gold Book”). Compiled by A.D. McNaught and A. Wilkinson. Blackwell Scientific Publications (Oxford (1997). Online version: http://goldbook.iupac.org (2019–) created by S.J. Chalk
- IUPAC (2023) Compendium of terminology in analytical chemistry. The Royal Society of Chemistry.
- JCGM (2008) Evaluation of measurement data – Guide to the expression of uncertainty in measurement (GUM). Joint Committee for Guides in Metrology, Bureau International des Poids et Mesures (Paris, France).
- JCGM (2012) International vocabulary of metrology – Basic and general concepts and associated terms (VIM). Joint Committee for Guides in Metrology, Bureau International des Poids et Mesures (Paris, France).
- Jochum K.P., Nohl U., Herwig K., Lammel E., Stoll B. and Hofmann A.W. (2005) GeoReM: A new geochemical database for reference materials and isotopic standards. Geostandards and Geoanalytical Research, 29, 333–338.
- Jochum K.P., Weis U., Schwager B., Stoll B., Wilson S.A., Haug G.H., Andreae M.O. and Enzweiler J. (2016) Reference values following ISO guidelines for frequently requested rock reference materials. Geostandards and Geoanalytical Research, 40, 333–350.
- Kane J.S. and Potts P.J. (2002) Traceability in geochemical analysis. Geostandards Newsletter: The Journal of Geostandards and Geoanalysis, 26, 171–180.
- Linsinger T. (2010) Comparison of a measurement result with a certified value. European Reference Materials Application Note 1, European Commission – Joint Research Centre Institute for Reference Materials and Measurements (Geel, Belgium).
- Lister B. (1982) Evautation of analytical data – A practical guide for geoanalysts. Geostandards Newsletter, 6, 175–205.
- Lister B. (1984) A note on robust estimates. Geostandards Newsletter, 8, 171–171.
- Mackay L.G., Taylor C.P., Myors R.B., Hearn R. and King B. (2003) High accuracy analysis by isotope dilution mass spectrometry using an iterative exact matching technique. Accreditation and Quality Assurance, 8, 191–194.
- Magnusson B., Näykki T., Hovind H. and Krysell M. (2012) Handbook for calculation of measurement uncertainty in environmental laboratories. Nordic Innovation (Oslo).
- Magnusson B. and Örnemark U. (2014) The fitness for purpose of analytical methods – A laboratory guide to method validation and related topics. Eurachem Guide, ISBN 978-91-87461-59-0. http://www.eurachem.org
- Meisel T.C., Webb P.C. and Rachetti A. (2022) Highlights from 25 years of the GeoPT programme: What can be learnt for the advancement of geoanalysis. Geostandards and Geoanalytical Research, 46, 223–243.
- Midden W.R. (1997) Rounding numbers: Why the “New System” doesn't work. Journal of Chemical Education, 74, 405.
- NIST (2021) Calibration of mass standards. https://www.nist.gov/programs-projects/calibration-mass-standards Accessed: 9th May 2023
- NIST/SEMATECH (2023) e-Handbook of statistical methods. http://www.itl.nist.gov/div898/handbook/ Accessed: 24th January 2023
- Potts P.J. (1992) Handbook of rock analysis. Blackie and Son Ltd (United Kingdom), 622pp.
10.1007/978-1-4615-3270-5 Google Scholar
- Potts P.J. (2012) Glossary of analytical and metrological terms from the International Vocabulary of Metrology (2008). Geostandards and Geoanalytical Research, 36, 231–246.
- Potts P.J., Thompson M. and Webb P.C. (2015a) The reliability of assigned values from the GeoPT proficiency testing programme from an evaluation of data for six test materials that have been characterised as certified reference materials. Geostandards and Geoanalytical Research, 39, 407–417.
- Potts P.J., Thorpe O.W. and Watson J.S. (1981) Determination of the rare-earth element abundances in 29 international rock standards by instrumental neuron-activation analysis – A critical appraisal of calibration errors. Chemical Geology, 34, 331–352.
- Potts P.J., Webb P.C. and Thompson M. (2013) An assessment of performance in the routine analysis of silicate rocks based on an analysis of data submitted to the GeoPT proficiency testing programme for geochemical laboratories (2001–2011). Geostandards and Geoanalytical Research, 37, 403–416.
- Potts P.J., Webb P.C. and Thompson M. (2015b) Bias in the determination of Zr, Y and rare earth element concentrations in selected silicate rocks by ICP-MS when using some routine acid dissolution procedures: Evidence from the GeoPT proficiency testing programme. Geostandards and Geoanalytical Research, 39, 315–327.
- Potts P.J., Webb P.C. and Thompson M. (2019) The GeoPT proficiency testing programme as a scheme for the certification of geological reference materials. Geostandards and Geoanalytical Research, 43, 409–418.
- Prohaska T., Irrgeher J., Benefield J., Böhlke J.K., Chesson L.A., Coplen T.B., Ding T., Dunn P.J.H., Gröning M., Holden N.E., Meijer H.A.J., Moossen H., Possolo A., Takahashi Y., Vogl J., Walczyk T., Wang J., Wieser M.E., Yoneda S., Zhu X.-K. and Meija J. (2022) Standard atomic weights of the elements 2021 (IUPAC Technical Report). Pure and Applied Chemistry, 94, 573–600.
- Ramsey M.H., Ellison S.L.R. and Rostron P. (2019) Measurement uncertainty arising from sampling: A guide to methods and approaches ( second edition). Eurachem/EUROLAB/ CITAC/Nordtest/AMC Guide, Eurachem (UK).
- Ratzlaff K.L. (1979) Optimizing precision in standard addition measurement. Analytical Chemistry, 51, 232–235.
- Reimann C. and Filzmoser P. (2000) Normal and lognormal data distribution in geochemistry: Death of a myth. Consequences for the statistical treatment of geochemical and environmental data. Environmental Geology, 39, 1001–1014.
- Rock N.M.S. (1988) Summary statistics in geochemistry – A study of the performance of robust estimates. Mathematical Geology, 20, 243–275.
- Sargent M. (2020) The provision and use of traceability statements for reference materials. Accreditation and Quality Assurance, 25, 367–372.
10.1007/s00769-020-01450-8 Google Scholar
- Sprent P. and Smeeton N.C. (2007) Applied nonparametric statistical methods. Chapman and Hall/CRC (Boca Raton, FL), 530pp.
- Tellinghuisen J. (2005) Simple algorithms for nonlinear calibration by the classical and standard additions methods. Analyst, 130, 370–378.
- Thompson M. (1982) Regression methods in the comparison of accuracy. Analyst, 107, 1169–1180.
- Thompson M. (2017) On the role of the mode as a location parameter for the results of proficiency tests in chemical measurement. Analytical Methods, 9, 5534–5540.
- Thompson M., Ellison S. and Wood R. (2002) Harmonized guidelines for single-laboratory validation of methods of analysis (IUPAC Technical Report). Pure and Applied Chemistry, 74, 835–855.
- Thompson M., Ellison S.L. and Wood R. (2006) The international harmonized protocol for the proficiency testing of analytical chemistry laboratories (IUPAC Technical Report). Pure and Applied Chemistry, 78, 145–196.
- Thompson M. and Ellison S.L.R. (2011) Dark uncertainty. Accreditation and Quality Assurance, 16, 483–487.
- Thompson M. and Walsh J.N. (2003) Handbook of inductively coupled plasma-atomic emission spectrometry. Viridian Publishing (United Kingdom), 380pp.
- Vessman J., Stefan R.I., van Staden J.F., Danzer K., Lindner W., Burns D.T., Fajgelj A. and Müller H. (2001) Selectivity in analytical chemistry (IUPAC Recommendations 2001). Pure and Applied Chemistry, 73, 1381–1386.
- Walsh J.N. and Howie R.A. (1980) An evaluation of the performance of an inductively coupled plasma source spectrometer for the determination of the major and trace constituents of silicate rocks and minerals. Mineralogical Magazine, 43, 967–974.
- Webb P.C., Thompson M., Potts P.J. and Burnham M. (2015) GeoPT37 – An international proficiency test for analytical geochemistry laboratories – Report on Round 37 (Rhyolite, ORPT-1). International Association of Geoanalysts, 38pp. www.geoanalyst.org/wp-content/uploads/2017/10/GeoPT37Report.pdf
- Webb P.C., Thompson M., Potts P.J. and Gowing C.J.B. (2016) GeoPT39 – An international proficiency test for analytical geochemistry laboratories – Report on Round 39 (Nepheline syenite, MNS-1). International Association of Geoanalysts, 38pp. www.geoanalyst.org/wp-content/uploads/2018/01/GeoPT39A-Full-Report.pdf
- Webb P.C., Thompson M., Potts P.J., Watson J.S. and Kriete C. (2008) GeoPT23 – An international proficiency test for analytical geochemistry laboratories – Report on Round 23 (Separation Lake pegmatite, OU-9) and 23A (Manganese nodule, FeMn-1). International Association of Geoanalysts, 64pp. http://www.geoanalyst.org/wp-content/uploads/2017/10/GeoPT23FullReport.pdf
- Woodward A., Hunter J., Bukach D., Roe F., Webb P., Ixer R., Watson J. and Potts P. (2011) An examination of prehistoric stone bracers from Britain. Oxbow Books (Oxford), 184pp.
10.2307/j.ctv13pk810 Google Scholar
- Youden W.J. and Steiner E.H. (1975) Statistical manual of the AOAC. AOAC International, 96pp.
Citing Literature
September 2024
Pages 457-503