Plant-matrix reference materials as a tool for ensuring the uniformity of chemical measurements in geochemistry, ecology, agriculture and pharmacology

The population needs reliable information on the chemical composition of plants and products made from them in order to preserve the environment and its safety. With the increase in cross-border trade, there is a growing demand for traceable results of determining the content of chemical elements in plants and not only proteins, fats, carbohydrates, pesticides, moisture, vitamins, etc., which can affect the quality of human life. An urgent but difficult analytical task is to obtain reliable measurements of the elemental composition of agricultural and wild plants and various products made from them. Reference materials (RMs) are a widely recognized tool for ensuring the uniformity of chemical measurements. They are designed for certification (validation) of existing and new methods (techniques) of chemical analysis, certification studies in the development of reference materials, and professional testing of laboratories. The article lists the reputable manufacturers of plant RMs in which the content of chemical elements is certified. The ratio of certified, reference, and quality control samples of plant-matrix has been assessed. The classification of certified reference materials according to the type of plant material used for their food application is provided. The contribution of different countries to the development of plant CRMs is hown. The selection of plants for the development of new RMs is discussed from two points of view, namely food composition databases (AOAC INTERNATIONAL) and the ‘Reference Plant’ chemical fingerprinting (B. Markert). Based on the consolidation of studies devoted to the development and appliance of plant-matrix reference materials, a list of the most important requirements has been compiled for reference materials that ensure the reliability and comparability of the results of chemical analysis in the fields of biology, geochemistry, ecology, agriculture, medicine, and interdisciplinary research.

1. 2010.1. IUCN red list of threatened species: summary statistics. In: International union for conservation of nature and natural resources. Available at https://www.iucnredlist.org.

2. Katz S. A. Bowen’s Kale: A brief review dedicated to the late Professor Humphry John Moule Bowen, 1929–2001. Journal of radioanalytical and nuclear chemistry. 2002;251(1):3–5. https://doi.org/10.1023/A:1015021823497.

3. Federal low «On ensuring the uniformity of measurements» No. FZ-102 of 26.06.2008. (In Russ.). Available at http://fundmetrology.ru/depository/01_npa/102-fz_2015.pdf.

4. GOST ISO/IEC17025–2019 General requirements for the competence of testing and calibration laboratories. Moscow: Standartinform Publ.; 2020. 13 p. (In Russ.).

5. Linsinger T. P. J., Emons H. The role of reference materials in chemical metrology. CHIMIA International journal for chemistry. 2009;63(10):629–631. https://doi.org/10.2533/chimia.2009.629

6. Vasil’eva, I. E., Shabanova, E. V. Certified reference materials of geological and environmental objects: Problems and solutions. Journal of analytical chemistry. 2017;72(2):99–118. https://doi.org/10.1134/S1061934817020149

7. Olivares I. R. B., Souza G. B., Nogueira A. R. A., Toledo G. T. K., Marcki D. C. Trends in developments of certified reference materials for chemical analysis – Focus on food, water, soil, and sediment matrices. TrAC Trends in analytical chemistry. 2018;100:53–64. https://doi.org/10.1016/j.trac.2017.12.013

8. Hulme N., Hammond J. Is your spectrophotometer still «pharma compliant»? A review of the new European pharmacopoeia 10th edition. SPECTROSCOPYEUROPE. 2020;32(1):14–20. Available from: https://www.spectroscopyeurope.com/article/your-spectrophotometer-still-»pharma-compliant»-review-new-european-pharmacopoeia-10th

9. Vasil’eva, I. E., Shabanova, E. V. Plant-matrix certified reference materials as a tool for ensuring the uniformity of chemical measurements. Journal of analytical chemistry. 2021;76(2):137–155. https://doi.org/10.1134/S1061934821020143

10. Сatalogue of certified reference materials of natural and man-made media compositions from A. P. Vinogradov Institute of Geochemisty SB RAS. Available at: http://www.igc.irk.ru/images/Innovation/Standarts-obr/CATALOGUE_OF_CRMs_IGC_SB_RAS_-2017.pdf

11. Wolf W. R., Andrews K. W. A system for defining reference materials applicable to all food matrices Fresenius. Journal of analytical chemistry. 1995;352(1–2):73–6. https://doi.org/10.1007/BF00322300

12. Wise S. A., Phillips M. M. Evolution of reference materials for the determination of organic nutrients in food and dietary supplements – a critical review. Analytical and bioanalytical chemistry. 2019;411(1):97–127. https://doi.org/10.1007/s00216-018-1473-0

13. Markert B. Establishing of «Reference Plant» for inorganic characterization of different plant species by chemical fingerprinting. Water, Air, Soil Pollut. 1992;64(3–4):533–538. https://doi.org/10.1007/BF00483363

14. Owen J. D., Kirton S. B., Evans S. J., Stair J. L. Elemental fingerprinting of Hypericum perforatum (St John’s Wort) herb and preparations using ICP-OES and chemometrics. Journal of pharmaceutical and biomedical analysis. 2016;125(5):15–21. https://doi.org/10.1016/j.jpba.2016.02.054

15. Arsenijević J., Marković J., Šoštarić I., Ražić S. A chemometrics as a powerful tool in the elucidation of the role of metals in the biosynthesis of volatile organic compounds in Hungarian thyme samples. Plant physiology and biochemistry. 2013;71(10):298–306. https://doi.org/10.1016/j.plaphy.2013.08.002.

16. Habte G., Hwang I. M., Kim J. S., Hong J. H., Hong Y. S., Choi J. Y. et al. Elemental profiling and geographical differentiation of Ethiopian coffee samples through inductively coupled plasma-optical emission spectroscopy (ICP-OES), ICP mass spectrometry (ICPMS) and direct mercury analyzer (DMA). Food chemistry. 2016;212(Dec 1):512–520. https://doi.org/10.1016/j.foodchem.2016.05.178

17. Jurkin D., Zgorelec Z., Rinkovec J. Concentrations of Pt, Pd and Rh in soil and vegetation: A review. Journal of central European agriculture. 2019;20(2):686–699. https://doi.org//10.5513/JCEA01/20.2.2199

18. Nagajyoti P. C., Lee K. D., Sreekanth T. V. M. Heavy metals, occurrence and toxicity for plants: a review. Environmental chemistry letters. 2010;8(3):199–216. https://doi.org/10.1007/s10311-010-0297-8

19. Reimann C., Koller F., Frengstad B., Kashulina G., Niskavaara H., Englmaier P. Comparison of the element composition in several plant species and their substrate from a 1500000-km2 area in Northern Europe. Science of the Total Environment. 2001;278(1–3): 87–112. https://doi.org/10.1016/S0048–9697(00)00890-1

20. Nečemer M., Kump P., Ščančar J., Jaćimović R., Simčič J., Pelicon P., Budnar M., Jeran Z., Pongrac P., Regvar M., Vogel-Mikuš K. Application of X-ray fluorescence analytical techniques in phytoremediation and plant biology studies. Spectrochimica acta part B: atomic spectroscopy. 2008;63(11):1240–1247. https://doi.org/10.1016/j.sab.2008.07.006

21. Kroukamp E. M., Wondimu T., Forbes P. B. C. Metals and metalloids speciation in plants: Overview, instrumentation, approaches and commonly assessed elements. Trends in analytical chemistry. 2016;77:87–99. https://doi.org/10.1016/j.trac.2015.10.007.

22. Eggen O. A., Reimann C., Flem B. Reliability of geochemical analyses: deja vu all over again. Science of the total environment. 2019;670:138–148. https://doi.org/10.1016/j.scitotenv.2019.03.185

23. Khan A., Khan S., Khan M. A., Qamar Z., Waqas M. The uptake and bioaccumulation of heavy metals by food plants, their effects on plants nutrients, and associated health risk: a review. Environmental science and pollution research. 2015;22(18):13772–13799. https://doi.org/10.1007/s11356-015-4881-0

24. Pohl P., Bielawska-Pohl A., Dzimitrowicz A., Greda K., Jamroz P., Lesniewicz A. et al. Understanding element composition of medicinal plants used in herbalism – A case study by analytical atomic spectrometry. Journal of pharmaceutical and biomedical analysis. 2018;159:262–271. https://doi.org/10.1016/j.jpba.2018.06.017

25. Mengel K., Kirkby E. A., Kosegarten H., Appel T. Principles of Plant Nutrition. 5th ed. Dordrecht: Springer Netherlands; 2001. 849 p. https://doi.org/10.1007/978-94-010-1009-2.

26. Temminghoff E. E. J. M., Houba V. J. G. Plant Analysis Procedures. 2nd Ed. Dordrecht: Springer Netherlands; 2004. 179 p. https://doi.org/10.1007/978-1-4020-2976-9

27. Greenberg R. R., Bode P., Fernandes E. A. N. Neutron activation analysis: A primary method of measurement. Spectrochimica acta part B: atomic spectroscopy. 2011;66(3–4):193–241. https://doi.org/10.1016/j.sab.2010.12.011

28. Vanhoof C., Bacon J. R., Ellis A. T., Fittschen U. E. A., Vincze L. 2019 atomic spectrometry update – a review of advances in X-ray fluorescence spectrometry and its special applications. Journal of analytical atomic spectrometry. 2019;34(9):1750–1767. https://doi.org/10.1039/C9JA90042J

29. Senesi G. S., Cabral J., Menegatti C. R., Marangoni B., Nicolodelli G. Recent advances and future trends in LIBS applications to agricultural materials and their food derivatives: An overview of developments in the last decade (2010–2019). Part II. Crop plants and their food derivatives. Trends in Analytical Chemistry. 2019;118;453–469. https://doi.org/10.1016/j.trac.2019.05.052

30. Tsizin G. I., Statkus M. A., Zolotov Yu. A. Adsorption and extraction preconcentration of trace components in flow analytical systems. Journal of analytical chemistry. 2015;70(11):1289–1306. https://doi.org/10.1134/S1061934815110167

31. ISO Guide 33:2015. Reference materials. Good practice in using reference materials. Geneva; BSI: 2015. Available at https://www.iso.org/standard/46212.html

32. ISO/IEC Guide 98–3:2008. Uncertainty of measurement – Part 3: Guide to the expression of uncertainty in measurement (GUM:1995). Geneva; ISO: 2008. Available at: https://www.iso.org/standard/50461.html

33. ISO Guide 35–2015 Reference materials – General and statistical principles of certification. Moscow; Standartinform: 2016. (In Russ.).

34. World Health Organization. National policy on traditional medicine and regulation of herbal medicines: Report of a WHO global survey. Geneva, 2005.

35. State Pharmacopoeia of the Russian Federation, XIII edn. Moscow, 2016. Available at: https://www.rosminzdrav.ru/poleznye-resursy/gosudarstvennaya-farmakopeya-rossiyskoy-federatsii-xiii-izdaniya.

36. State Pharmacopoeia of the Russian Federation, XIV edn. Moscow, 2018. Available at: http://www.femb.ru/femb/pharmacopea.php.

37. Resolution of the chief state sanitary doctor of the Russian Federation «On the introduction of sanitary rules» dated November 14, 2001 No 36 (as amended on July 6, 2011). SanPiN2.3.2.1078–01. Hygienic requirements for food safety and nutritional value. Available at: https://base.garant.ru/4178234/

38. United States Pharmacopeia. General Chapter <232> Elemental Impurities – Limits: First Supplement of USP 40-NF35, Official December 1, 2017. Available at: https://www.usp.org/sites/default/files/usp/document/our-work/chemical-medicines/keyissues/232–40–35–1s.pdf.

39. United States Pharmacopeia. General Chapter <233> Elemental Impurities – Procedures / Chemical Tests: Second Supplement to USP 38–NF 33. Available at: https://www.usp.org/sites/default/files/usp/document/our-work/chemical-medicines/key-issues/c233.pdf.

40. ICH International Council for Harmonisation of Technical Requirement for Pharmaceuticals for Human Use, Harmonised Guideline, Guideline for Elemental Impurities Q3D (R1) (Final version Adopted on 22 March 2019). Available at: https://www.ema.europa.eu/e/documents/scintific-guideline/international-conference-harmonisation-technical-requirements-registration-pharmaceuticals-human-use_en-32.pdf^m