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. 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 L-III-edge (13.040 keV) were obtained on a Rigaku R-XAS Looper spectrometer. Extended X-ray absorption fine structure (EXAFS) L-III-edge Pb was measured at the Structural Materials Science beamline of the Kurchatov Center for Synchrotron Radiation. 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.