Journal of Soils and Sediments

, Volume 16, Issue 4, pp 1183–1192 | Cite as

Comprehensive study of Pb (II) speciation in soil by X-ray absorption spectroscopy (XANES and EXAFS) and sequential fractionation

  • Dina G. NevidomskayaEmail author
  • Tatiana M. Minkina
  • Alexander V. Soldatov
  • Victoria A. Shuvaeva
  • Yan V. Zubavichus
  • Yulia S. Podkovyrina
Soil Pollution and Remediation



The study is aimed at the analysis of the spatial–structural organization of Pb(II) in Chernozem soils and the relationship between the metal ion and the soil components using X-ray absorption spectroscopy and chemical extractive fractionation.

Materials and methods

In a model experiment, soil samples were artificially contaminated with elevated rates of Pb(NO3)2 and PbO (2000 and 10,000 mg kg−1). The samples of mineral phases (bentonite, gibbsite, kaolinite, calcite, and hydromuscovite) were saturated with Pb2+ ions. The sequential fractionation of Pb in the soil was conducted by the Tessier method. X-ray absorption near-edge fine structure (XANES) spectra at the Pb LIII-edge (13.040 keV) were obtained on a Rigaku R-XAS Looper spectrometer. Extended X-ray absorption fine structure (EXAFS) LIII-edge Pb was measured at the Structural Materials Science beamline of the Kurchatov Center for Synchrotron Radiation.

Results and discussion

The results of successive extraction showed that Pb is associated with strongly bound organic substances, Fe and Mn (hydr)oxides, and carbonates. An increase in the portion of exchangeable fraction is observed under extreme loads. At the addition of Pb in the form of oxide and nitrate to the soil, the fractional compositions were similar, which indicates the good transformation of PbO in Chernozem. The features of XANES spectra indicate different orbital transitions in the electron shells of Pb2+ ions for monoxide (PbO) and soluble salt (Pb(NO3)2), which affect the ion properties and determine the individual structure of the coordination sphere. The analysis of XANES revealed that sorption of Pb in the soil samples and in the samples of mineral phases does not change its bond valence.


The increased degree of soil contamination with Pb is accompanied by decreasing the stable connection between metal and soil components. Lead ions in bentonite, kaolinite, hydromuscovite, gibbsite, and calcite are incorporated in the positions of the inner-sphere complex replacing some aluminum ions in the octahedral sites. This results in changes the Pb–O distances in Pb-bearing octahedrons. We may suggest that Pb2+ is also sorbed by dimer (Pb–Pb) silicate and/or aluminum groups. The structure of adsorbent surface plays the key role in the sorption of Pb2+ by mineral phases.


Pb XANES EXAFS spectroscopy Soil Chernozem Sequential fractionation 



This research was supported by the Russian Foundation for Basic Research, project no. 14-05-31469 mol_а, no. 14-05-31488 mol_а, and no. 14-05-00586 А; the Ministry of Education and Science of the Russian Federation, project no. 5.885.2014/К; and the Leading Scientific School, project no. 5548.2014.5.


  1. Adriano DC (2001) Trace elements in terrestrial environments. Springer-Verlag, New York, Berlin, HeidelbergCrossRefGoogle Scholar
  2. Alcacio TE, Hesterberg D, Chou JW, Martin JD, Beauchemin S, Sayers DE (2001) Molecular scale characteristics of Cu (II) bonding in goethite-humate complexes. Geochim Cosmochim Acta 65:1355–1366CrossRefGoogle Scholar
  3. Bezuglova OS, Nevidomskaya DG, Morozov IV (2010) Soils of municipal solid waste landfills and their ecology. Yu FU, Rostov-on-Don. (in Russian)Google Scholar
  4. Chernyshov AA, Veligzhanin AA, Zubavichus YV (2009) Structural Materials Science end-station at the Kurchatov synchrotron radiation source: recent instrumentation upgrades and experimental results. Nucl Instr Meth Phys Res A 603:95–98CrossRefGoogle Scholar
  5. Dähn R, Scheidegger A, Manceau A, Schlegel M, Baeyens B, Bradbury H (2001) Ni clay neoformation on montmorillonite surface. J Synchrotron Radiat 8:533–535CrossRefGoogle Scholar
  6. Elzinga EJ, Reeder RJ (2002) X-ray absorption spectroscopy study of Cu2+ and Zn2+ adsorption complexes at the calcite surface: implications for site-specific metal incorporation preferences during calcite crystal growth. Geochim Cosmochim Acta 66:3943–3954Google Scholar
  7. Elzinga EJ, Rouff AA, Reeder RJ (2006) The long-term fate of Cu2+, Zn2+, and Pb2+ adsorption complexes at the calcite surface: An X-ray absorption spectroscopy study. Geochim Cosmochim Acta 70:2715–2725CrossRefGoogle Scholar
  8. Furnare LJ, Strawn DG, Vailionis A (2005) Polarized XANES and EXAFS spectroscopic investigation into copper (II) complexes on vermiculite. Geochim Cosmochim Acta 69:5219–5231CrossRefGoogle Scholar
  9. Kabata-Pendias A, Pendias H (1989) Trace Elements in Soils and Plants. CRC, Boca RatonGoogle Scholar
  10. Karpukhin MM, Ladonin DV (2008) Effect of soil components on the adsorption of heavy metals under technogenic contamination. Eur Soil Sci 41:1228–1237CrossRefGoogle Scholar
  11. Klementiev KV (2001) Extraction of the fine structure from X-ray absorption spectra. J Phys D 34:209–217CrossRefGoogle Scholar
  12. Ladonin DV, Karpukhin MM (2011) Fractional composition of nickel, copper, zinc, and lead compounds in soils polluted by oxides and soluble metal salts. Eur Soil Sci 44:874–885CrossRefGoogle Scholar
  13. Lombi E, Susini J (2009) Synchrotron-based techniques for plant and soil science: opportunities, challenges and future perspectives. J Plant Soil 320:1–35CrossRefGoogle Scholar
  14. Manceau A, Matynia A (2010) The nature of Cu bonding to natural organic matter. Geochim Cosmochim Acta 74:2556–2580CrossRefGoogle Scholar
  15. Manceau A, Marcus MA, Tamura N (2002) Quantitative speciation of heavy metals in soils and sediments by synchrotron X-ray techniques. In: Applications of synchrotron radiation in low-temperature geochemistry and environmental science. Rev Mineral Geochem 49, Washington, pp 341–428Google Scholar
  16. Mandzhieva SS, Minkina TM, Motuzova GV, Golovatyi SE, Miroshnichenko NN, Lukashenko NK, Fateev AI (2014) Fractional and group composition of zinc and lead compounds as an indicator of the environmental status of soils. Eur Soil Sci 47:511–518Google Scholar
  17. Minkina TM, Motuzova GV, Nazarenko OG, Kryshchenko VS, Mandzhieva SS (2008) Combined approach for fractioning metal compounds in soils. Eur Soil Sci 41:1170–1178Google Scholar
  18. Minkina TM, Motuzova GV, Nazarenko OG, Mandzhieva SS (2009) Group composition of heavy metal compounds in the soils contaminated by emissions from the Novocherkassk Power Station. Eur Soil Sci 42:1–10CrossRefGoogle Scholar
  19. Minkina TM, Pinskii DL, Mandzhieva SS, Antonenko EM, Sushkova SN (2011) Effect of the particle size distribution on the adsorption of copper, lead, and zinc by chernozemic soils of Rostov oblast. Eur Soil Sci 44:1193–1200CrossRefGoogle Scholar
  20. Minkina TM, Endovitsky AP, Kalinichenko VP, Fedorov UA (2012) Calcium-carbonate equilibrium in the water-soil. Southern Federal University, Rostov-on-Don (in Russian)Google Scholar
  21. Minkina TM, Soldatov AV, Motuzova GV, Podkovyrina Yu S, Nevidomskaya DG (2013) Molecular–structural analysis of the Cu (II) ion in ordinary chernozem: evidence from XANES spectroscopy and methods of molecular dynamics. Dokl Earth Sci 449:418–421CrossRefGoogle Scholar
  22. Minkina TM, Soldatov AV, Motuzova GV, Podkovyrina Yu S, Nevidomskaya DG (2014) Speciation of copper and zinc compounds in artificially contaminated chernozem by X-ray absorption spectroscopy and extractive fractionation. J Geochem Explor 144:306–311CrossRefGoogle Scholar
  23. Newville M (2001) IFEFFIT: interactive XAFS analysis and FEFF fitting. J Synchrotron Rad 8:322–324. doi: 10.1107/S0909049500016964 CrossRefGoogle Scholar
  24. Newville M, Livins P, Yacoby Y, Rehr JJ, Stern EA (1993)Near-edge x-ray-absorption fine structure of Pb: a comparison of theory and experiment. Phys Rev B 47:14126 10.1103/PhysRevB.47.14126
  25. Plekhanova IO, Bambusheva VA (2010) Extraction methods for studying the fractional composition of heavy metals in soils and their comparative assessment. Eur Soil Sci 43:1004–1010CrossRefGoogle Scholar
  26. Ravel B, Newville M (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J Synchrotron Rad 12:537–541CrossRefGoogle Scholar
  27. Rouff AA, Elzinga EJ, Reeder RJ, Fisher NS (2005) The influence of pH on the kinetics, reversibility and mechanisms of Pb(II) sorption at the calcite-water interface. Geochim Cosmochim Acta 69:5173–5186CrossRefGoogle Scholar
  28. Singh B, Gräfe M (2010) Synchrotron-based techniques in soils and sediments. Elsevier 34, Netherlands, pp 1–480Google Scholar
  29. Sobornikova IG, Kizilshtein LY (1990) Copper, zinc, and lead in soils and wormwood plants in Rostov-on-Don and its suburbs. Izv Sev-Kav Tsenta Vys Shkoly Est nauki 4:3–8, (in Russian)Google Scholar
  30. Soldatov AV (2008) X-ray absorption near edge structure as a source of structural information. J Structural Chem 49:102–106CrossRefGoogle Scholar
  31. Stern EA, Newville M, Ravel B, Yacoby Y, Haskel D (1995) The UWXAFS analysis package: philosophy and details. Physica B 209:117–120CrossRefGoogle Scholar
  32. Strawn DG, Baker LL (2008) Speciation of Cu in a contaminated agricultural soil measured by XAFS, μ-XAFS, and μ-XRF. Environ Sci Technol 42:37–42Google Scholar
  33. Tessier A, Campbell PGC, Bisson M (1979) Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry 51:844–851CrossRefGoogle Scholar
  34. Vodyanitskii YN (2014) Natural and technogenic compounds of heavy metal in soils. Eur Soil Sci 47:1343–1351Google Scholar
  35. WRB (2006) World reference base for soil resources (2006) 2nd edition. World Soil Resources Reports 103. FAO, Rome, p 132Google Scholar
  36. Xia K, Bleam W, Helmke P (1997) Studies of nature of binding sites of first row transition elements bound to aquatic and soil humic substances using X-ray absorption spectroscopy. Geochim Cosmochim Acta 61:2223–2235CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Dina G. Nevidomskaya
    • 1
    Email author
  • Tatiana M. Minkina
    • 1
  • Alexander V. Soldatov
    • 2
  • Victoria A. Shuvaeva
    • 3
  • Yan V. Zubavichus
    • 4
  • Yulia S. Podkovyrina
    • 2
  1. 1.Soil Science DepartmentSouthern Federal UniversityRostov-on-DonRussia
  2. 2.International Research Center “Smart Materials”Southern Federal UniversityRostov-on-DonRussia
  3. 3.Research Institute of PhysicsSouthern Federal UniversityRostov-on-DonRussia
  4. 4.National Research CentreKurchatov InstituteMoscowRussia

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