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A robust X-ray fluorescence technique for multielemental analysis of solid samples

Abstract

X-ray fluorescence (XRF) quantitation software programs are widely used for analyzing environmental samples due to their versatility but at the expense of accuracy. In this work, we propose an accurate, robust, and versatile technique for multielemental X-ray fluorescence analytical applications, by spiking solid matrices with standard solutions. National Institute of Standards and Technology (NIST)-certified soil standards were spiked with standard solutions, mixed well, desiccated, and analyzed by an energy dispersive XRF. Homogenous targets were produced and low error calibration curves, for the added and not added, neighboring, elements, were obtained. With the addition of few elements, the technique provides reliable multielemental analysis, even for concentrations of the order of milligram per kilogram (ppm). When results were compared to the ones obtained from XRF commercial quantitation software programs, which are widely used in environmental monitoring and assessment applications, they were found to fit certified values better. Moreover, in all examined cases, results were reliable. Hence, this technique can also be used to overcome difficulties associated with interlaboratory consistency and for cross-validating results. The technique was applied to samples with an environmental interest, collected from a ship/boat repainting area. Increased copper, zinc, and lead loads were observed (284, 270, and 688 mg/kg maximum concentrations in soil, respectively), due to vessels being paint stripped and repainted.

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References

  • Alyazichi, Y. M., Jones, B. G., & McLean, E. (2015). Source identification and assessment of sediment contamination of trace metals in Kogarah Bay, NSW, Australia. Environmental Monitoring and Assessment, 187, 20.

    Article  Google Scholar 

  • Beckhoff, B., Kanngießer, B., Langhoff, N., Wedell, R., & Wolf, H. (2006). Handbook of practical X-ray fluorescence analysis. Berlin: Springer.

    Book  Google Scholar 

  • Bero, B. N., Braun, M. C., Knowles, C. R., & Hammel, J. E. (1995). Further studies using X-ray fluorescence to sample lead contaminated carpeted surfaces. Environmental Monitoring and Assessment, 36(2), 123–138.

    CAS  Article  Google Scholar 

  • Brown, R. J. C., & Gillam, T. P. S. (2012). On the generalised case of sequential standard addition calibration. Chemometrics and Intelligent Laboratory Systems, 110, 97–101.

    CAS  Article  Google Scholar 

  • Clark, H. F., Hausladen, D. M., & Brabander, D. J. (2008). Urban gardens: lead exposure, recontamination mechanisms, and implications for remediation design. Environmental Research, 107, 312–319.

    CAS  Article  Google Scholar 

  • Foteinis, S., Kallithrakas-Kontos, N.G., & Synolakis, C. (2013). Heavy metal distribution in opportunistic beach nourishment: a case study in Greece. The Scientific World Journal, 2013, 5 pages, Article ID 472149, doi: 10.1155/2013/472149.

  • Galloa, L., Corapia, A., Loppib, S., & Lucadamo, L. (2014). Element concentrations in the lichen Pseudevernia furfuracea (L.) Zopf transplanted around a cement factory (S Italy). Ecological Indicators, 46, 566–574.

    Article  Google Scholar 

  • Gałuszka, A. (2005). The chemistry of soils, rocks and plant bioindicators in three ecosystems of the holy cross mountains, Poland. Environmental Monitoring and Assessment, 110(1–3), 55–70.

    Article  Google Scholar 

  • Grieken, R. E., & Markowicz, A. A. (1993). Handbook of X-ray spectrometry: methods and techniques. New York: Marcel Dekker.

    Google Scholar 

  • Hatzistavros, V. S., & Kallithrakas-Kontos, N. G. (2008). Trace element ink spiking for signature authentication. Journal of Radioanalytical and Nuclear Chemistry, 277(2), 399–404.

    CAS  Article  Google Scholar 

  • Isoyama, H., Okuyama, S., Uchida, T., Takeuchi, M., Iida, C., & Nakagawa, G. (1990). In-furnace standard addition method for the determination of trace metals in biological samples by electrothermal vaporization-inductively coupled plasma atomic emission spectrometry. Analytical Sciences, 6(4), 555–561.

    CAS  Article  Google Scholar 

  • Kankılıç, G. B., Tüzün, İ., & Kadıoğlu, Y. K. (2013). Assessment of heavy metal levels in sediment samples of Kapulukaya Dam Lake (Kirikkale) and lower catchment area. Environmental Monitoring and Assessment, 185(8), 6739–6750.

    Article  Google Scholar 

  • Lachance, G. R., & Claisse, F. (1995). Quantitative X-ray fluorescence analysis. Chichester: Wiley.

    Google Scholar 

  • Mahapatra, N. S. (1987). An approach to the solution of matrix problems in the XRF analysis of lead–zinc ore by the use of an internal standard and mathematical corrections. X-Ray Spectrometry, 16(4), 171–176.

    CAS  Article  Google Scholar 

  • Meyer, M.C., Spötl, C., Mangini, A., & Tessadri R. (2012). Speleothem deposition at the glaciation threshold—an attempt to constrain the age and paleoenvironmental significance of a detrital-rich flowstone sequence from Entrische Kirche Cave (Austria). Palaeogeography, Palaeoclimatology, Palaeoecology, (319–320), 93–106.

  • Muia, L. M., & Grieken, R. (1991). Energy-dispersive x-ray fluorescence analysis of geological materials in borax beads using Tertian’s binary coefficient approach combined with internal standard addition. X-Ray Spectrometry, 20(4), 179–183.

    CAS  Article  Google Scholar 

  • NASA—National Aeronautics and Space Administration, Mars Science Laboratory/Curiosity, prepared by Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California, 07/2013.

  • Pind, N. (1984). Standard-addition procedure for the determination of traces of lead in solid samples by x-ray fluorescence spectrometry. Talanta, 31(12), 1118–20.

    CAS  Article  Google Scholar 

  • Sarris, A., Kokinou, E., Aidona, E., Kallithrakas-Kontos, N., Koulouridakis, P., Kakoulaki, G., Droulia, K., & Damianovits, O. (2009). Environmental study for pollution in the area of megalopolis power plant (Peloponnesos Greece). Environmental Geology, 58, 1769–1783.

    Article  Google Scholar 

  • Tertian, R., & Claisse, F. (1982). Principles of quantitative X-ray fluorescence analysis. London: Heyden.

    Google Scholar 

  • Thompson, M., (2009). Standard additions: myth and reality. Amc technical briefs, Analytical Methods Committee, AMCTB No 37, ISSN 1757- 5958.

  • Trejos, T., Koons, R., Becker, S., Berman, T., Buscaglia, J., Duecking, M., Eckert-Lumsdon, T., Ernst, T., Hanlon, C., Heydon, A., Mooney, K., Nelson, R., Olsson, K., Palenik, C., Pollock, E. C., Rudell, D., Ryland, S., Tarifa, A., Valadez, M., Weis, P., & Almirall, J. (2013). Cross-validation and evaluation of the performance of methods for the elemental analysis of forensic glass by μ-XRF, ICP-MS, and LA-ICP-MS. Analytical and Bioanalytical Chemistry, 405(16), 5393–409.

    CAS  Article  Google Scholar 

  • Tsuji, K., Nakano, K., Takahashi, Y., Hayashi, K., & Ro, C. U. (2012). X-ray spectrometry. Analytical Chemistry, 84(2), 636–68.

    CAS  Article  Google Scholar 

  • Wolf, M., Lehndorff, E., Mrowald, M., Eckmeier, E., Kehl, M., Frechen, M., & Wulf, A. (2014). Black carbon: fire fingerprints in Pleistocene loess–palaeosol archives in Germany. Organic Geochemistry, 70, 44–52.

    CAS  Article  Google Scholar 

  • Wong, M. K., Gu, W., & Ng, T. L. (1997). Sample preparation using microwave assisted digestion or extraction techniques. Analytical Sciences, 13, 97–102.

    CAS  Article  Google Scholar 

  • Yamada, Y. (2010). X-ray fluorescence analysis by fused bead method for ores and rocks. The Rigaku Journal, 26(2), 15–23.

    CAS  Google Scholar 

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Correspondence to Nikolaos Kallithrakas-Kontos.

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Kallithrakas-Kontos, N., Foteinis, S., Paigniotaki, K. et al. A robust X-ray fluorescence technique for multielemental analysis of solid samples. Environ Monit Assess 188, 120 (2016). https://doi.org/10.1007/s10661-016-5127-4

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  • DOI: https://doi.org/10.1007/s10661-016-5127-4

Keywords

  • XRF
  • Standard addition
  • Cross-validation
  • TurboQuant
  • Soil samples
  • Heavy metals