Comprehensive study of Pb (II) speciation in soil by X-ray absorption spectroscopy (XANES and EXAFS) and sequential fractionation
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.
KeywordsPb 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.
- 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
- 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
- Kabata-Pendias A, Pendias H (1989) Trace Elements in Soils and Plants. CRC, Boca RatonGoogle Scholar
- 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
- 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
- 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
- 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
- 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 http://dx.doi.org/ 10.1103/PhysRevB.47.14126
- Singh B, Gräfe M (2010) Synchrotron-based techniques in soils and sediments. Elsevier 34, Netherlands, pp 1–480Google Scholar
- 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
- 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
- Vodyanitskii YN (2014) Natural and technogenic compounds of heavy metal in soils. Eur Soil Sci 47:1343–1351Google Scholar
- WRB (2006) World reference base for soil resources (2006) 2nd edition. World Soil Resources Reports 103. FAO, Rome, p 132Google Scholar