Eurasian Journal of Soil Science

Abstract

XANES spectroscopy is an effective method for the study of bonds between metals and soil components. The study of structural organization in different soil samples and soil phases saturated with Cu2+ and Zn2+ ions by using XANES allowed determining the mechanism of their interaction with soil phases and all the chemical bindings taken place in the course of this process. Changes in the structure of the metal ion, in particular breakdown of the symmetry of electron orbits of atoms, take place due to interaction with soil components. Application of this method demonstrated that the state of copper and zinc introduced in chernozem as oxides did not change after one year of incubation. Copper is absorbed after being introduced as soluble salts, and copper ions are incorporated in the octahedral and tetrahedral sites of minerals and bonded with humic materials at the expense of covalent bond and the formation of coordination humate copper complexes. Zinc included into octahedric structures of layered minerals and hydro(oxides) can be inner-and outer-sphere adsorbed. It is shown that the action of the metal bound to soil components becomes weakened in case of increasing the Cu and Zn load (from 2000 to 10000 mg/kg) especially applied in the form of soluble salts. Extractive fractionation of metal compounds in chernozem samples, artificially contaminated with copper and zinc salts serves as evidence of absorbing the applied Cu2+ ions by the soil organic matter and Zn2+ ions – by silicates, carbonates, and Fe-Mn oxides.

Keywords

XANES spectroscopy, extractive fractionation, compounds, copper, zinc

References

<p>Adriano, D.C., 2001. Trace elements in terrestrial environments, Springer-Verlag, New York, Berlin, Heidelberg.</p>

<p>Akimtsev, V.V., Boldyreva, A.V., Golubev, S.N., Kudryavtsev, M.I., Rudenskaya, K.V., Sadimenko, P.A., Sobornikova, I.G., 1962. &ldquo;The Contents of Trace Elements in Soils of Rostov Oblast&rdquo;. In: Trace Elements and Natural Radioactivity of Soils (Workshop Materials), Izd. Rostovsk. Univ., Rostov-on-Don, pp. 38&ndash;41 [in Russian].</p>

<p>Alcacio, T.E., Hesterberg, D., Chou, J.W., Martin, J.D., Beauchemin, S., Sayers, D.E., 2001. Molecular scale characteristics of Cu (II) bonding in goethite-humate complexes. Geochimica et Cosmochimica Acta 65 (9): 1355&ndash;1366.</p>

<p>Berry, A.J., O&rsquo;Neil, H.S.C., 2004. A XANES determination of the oxidation state of chromium in silicate glasses. American Mineralogist 89: 1597&ndash;1609.</p>

<p>Bunau, O., Joly, Y., 2009. Self-consistent aspects of x-ray absorption calculations. Journal of Physics: Condensed Matter 21, 345501 (11 pp.).</p>

<p>Chan, J., Merrifield, M.E., Soldatov, A.V., Stillman M.J., 2005. XAFS spectral analysis of the cadmium coordination geometry in cadmium thiolate clusters in metallothionein. Inorganic Chemistry 44: 4923&ndash;4933.</p>

<p>Farrel, S.P., Fleet, M.E., Stekhin, I.E., Kravtsova, A.N, Soldatov, A.V., 2002. Evolution of Local Electronic Structure in Alabandite and Niningerite Solid Solutions [(Mn,Fe)S, (Mg,Mn)S, (Mg,Fe)S] using Sulfur K- and L-edge XANES Spectroscopy. American Mineralogist 87: 1321&ndash;1332.</p>

<p>Furnare, L.J., Strawn, D.G., Vailionis, A., 2005. Polarized XANES and EXAFS spectroscopic investigation into copper (II) complexes on vermiculite. Geochimica et Cosmochimica Acta 69 (22): 5219&ndash;5231.</p>

<p>Kostenko, A.V., Kravtsova, A.N, Soldatov, A.V., Feiters, M., 2008. Determination of the local atomic structure of the active center of bromoperoxidase protein via the analysis of X-ray absorption spectra. Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques 2 (6): 900&ndash;903.</p>

<p>Lee, Y.J., Elzinga, E.J., Reeder, R.J., 2005. Cu (II) adsorption at the calcite&ndash;water interface in the presence of natural organic matter: kinetic studies and molecular-scale characterization. Geochimica et Cosmochimica Acta 69 (1): 49&ndash;61.</p>

<p>Manceau, A., Marcus, M.A., Tamura, N., 2002. Quantitative speciation of heavy metals in soils and sediments by synchrotron X-ray techniques. Applications of Synchrotron Radiating in Low-Temperature Geochemistry and Environmental Science. Reviews in Mineralogy and Geochemistry 49, DC., Washington, pp. 341&ndash;428.</p>

<p>Minkina, T.M., Motuzova, G.V., Nazarenko, O.G., Kryshchenko, V.S., Mandzhieva, S.S., 2008. Forms of Heavy Metal Compounds in Soils of the Steppe Zone. Eurasian Soil Science 41 (7): 708&ndash;716.</p>

<p>Minkina, T.M., Soldatov, A.V., Motuzova, G.V., Podkovyrina, Yu.S., Nevidomskaya, D.G., 2013. Molecular&ndash;structural analysis of the Cu (II) ion in ordinary chernozem: evidence from XANES spectroscopy and methods of molecular dynamics. Doklady Earth Science. 449, part 2, 418&ndash;421.</p>

<p>Palladino, L., Della, Longa, S., Reale, A., Belli, M., Scafati, A., Onori, G., and Santucci, A., 1993. X-ray absorption near edge structure (XANES) of Cu(II)-ATP and related compounds in solution: Quantitative determination of the distortion of the Cu site. Journal of Chemical Physics 98: 2720&ndash;2726.</p>

<p>Pinskii, D.L., Minkina, T.M., Gaponova, Yu.I., 2010. Сomparative analysis of mono- and polyelement adsorption of copper, lead, and zinc by an ordinary chernozem from nitrate and acetate solutions. Eurasian Soil Science 43 (7): 748&ndash;756.</p>

<p>Santillan-Medrano, J., Jurinak, J.J., 1975. The chemistry of lead and cadmium in soil solid phase formation. Soil Science Society of America Proceedings 39 (5): 851&ndash;856.</p>

<p>Smolentsev, G.Y., Soldatov A.V., 2009. Analysis of time-resolved XANES spectra for determining the organometallic compound structure in solution. Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques 3 (3): 398&ndash;401.</p>

<p>Smolentsev, G.Y., Soldatov, A.V., 2006. Quantitative local structure refinement from XANES: multy-dimensional interpolation approach. Journal of Synchrotron Radioation 13 (1): 19&ndash;29.</p>

<p>Soldatov, A.V., 2008. X-ray absorption near edge structure as a source of structural information. Journal of Structural Chemistry 49 (Supp): 102&ndash;106.</p>

<p>Synchrotron-Based Techniques in Soils and Sediments, 2010. Balwant Singh and Markus Gr&auml;fe (Eds). Elsevier B.V. The Netherlands. 34, pp. 1-480.</p>

<p>Tessier, A., Campbell, P.G.C., Bisson, M., 1979. Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry 51: 844&ndash;851.</p>

<p>Xia, K., Bleam, W., Helmke, P., 1997. Studies of nature of binding sites of first row transition elements bound to aquatic and soil humicsubstences using X-ray absorption spectroscopy. Geochimica et Cosmochimica Acta 61 (11): 2223&ndash;2235.</p>

Abstract
XANES spectroscopy is an effective method for the study of bonds between metals and soil components. The study of structural organization in different soil samples and soil phases saturated with Cu2+ and Zn2+ ions by using XANES allowed determining the mechanism of their interaction with soil phases and all the chemical bindings taken place in the course of this process. Changes in the structure of the metal ion, in particular breakdown of the symmetry of electron orbits of atoms, take place due to interaction with soil components. Application of this method demonstrated that the state of copper and zinc introduced in chernozem as oxides did not change after one year of incubation. Copper is absorbed after being introduced as soluble salts, and copper ions are incorporated in the octahedral and tetrahedral sites of minerals and bonded with humic materials at the expense of covalent bond and the formation of coordination humate copper complexes. Zinc included into octahedric structures of layered minerals and hydro(oxides) can be inner-and outer-sphere adsorbed. It is shown that the action of the metal bound to soil components becomes weakened in case of increasing the Cu and Zn load (from 2000 to 10000 mg/kg) especially applied in the form of soluble salts. Extractive fractionation of metal compounds in chernozem samples, artificially contaminated with copper and zinc salts serves as evidence of absorbing the applied Cu2+ ions by the soil organic matter and Zn2+ ions – by silicates, carbonates, and Fe-Mn oxides.

Keywords: XANES spectroscopy, extractive fractionation, compounds, copper, zinc

References

Adriano, D.C., 2001. Trace elements in terrestrial environments, Springer-Verlag, New York, Berlin, Heidelberg.

Akimtsev, V.V., Boldyreva, A.V., Golubev, S.N., Kudryavtsev, M.I., Rudenskaya, K.V., Sadimenko, P.A., Sobornikova, I.G., 1962. “The Contents of Trace Elements in Soils of Rostov Oblast”. In: Trace Elements and Natural Radioactivity of Soils (Workshop Materials), Izd. Rostovsk. Univ., Rostov-on-Don, pp. 38–41 [in Russian].

Alcacio, T.E., Hesterberg, D., Chou, J.W., Martin, J.D., Beauchemin, S., Sayers, D.E., 2001. Molecular scale characteristics of Cu (II) bonding in goethite-humate complexes. Geochimica et Cosmochimica Acta 65 (9): 1355–1366.

Berry, A.J., O’Neil, H.S.C., 2004. A XANES determination of the oxidation state of chromium in silicate glasses. American Mineralogist 89: 1597–1609.

Bunau, O., Joly, Y., 2009. Self-consistent aspects of x-ray absorption calculations. Journal of Physics: Condensed Matter 21, 345501 (11 pp.).

Chan, J., Merrifield, M.E., Soldatov, A.V., Stillman M.J., 2005. XAFS spectral analysis of the cadmium coordination geometry in cadmium thiolate clusters in metallothionein. Inorganic Chemistry 44: 4923–4933.

Farrel, S.P., Fleet, M.E., Stekhin, I.E., Kravtsova, A.N, Soldatov, A.V., 2002. Evolution of Local Electronic Structure in Alabandite and Niningerite Solid Solutions [(Mn,Fe)S, (Mg,Mn)S, (Mg,Fe)S] using Sulfur K- and L-edge XANES Spectroscopy. American Mineralogist 87: 1321–1332.

Furnare, L.J., Strawn, D.G., Vailionis, A., 2005. Polarized XANES and EXAFS spectroscopic investigation into copper (II) complexes on vermiculite. Geochimica et Cosmochimica Acta 69 (22): 5219–5231.

Kostenko, A.V., Kravtsova, A.N, Soldatov, A.V., Feiters, M., 2008. Determination of the local atomic structure of the active center of bromoperoxidase protein via the analysis of X-ray absorption spectra. Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques 2 (6): 900–903.

Lee, Y.J., Elzinga, E.J., Reeder, R.J., 2005. Cu (II) adsorption at the calcite–water interface in the presence of natural organic matter: kinetic studies and molecular-scale characterization. Geochimica et Cosmochimica Acta 69 (1): 49–61.

Manceau, A., Marcus, M.A., Tamura, N., 2002. Quantitative speciation of heavy metals in soils and sediments by synchrotron X-ray techniques. Applications of Synchrotron Radiating in Low-Temperature Geochemistry and Environmental Science. Reviews in Mineralogy and Geochemistry 49, DC., Washington, pp. 341–428.

Minkina, T.M., Motuzova, G.V., Nazarenko, O.G., Kryshchenko, V.S., Mandzhieva, S.S., 2008. Forms of Heavy Metal Compounds in Soils of the Steppe Zone. Eurasian Soil Science 41 (7): 708–716.

Minkina, T.M., Soldatov, A.V., Motuzova, G.V., Podkovyrina, Yu.S., Nevidomskaya, D.G., 2013. Molecular–structural analysis of the Cu (II) ion in ordinary chernozem: evidence from XANES spectroscopy and methods of molecular dynamics. Doklady Earth Science. 449, part 2, 418–421.

Palladino, L., Della, Longa, S., Reale, A., Belli, M., Scafati, A., Onori, G., and Santucci, A., 1993. X-ray absorption near edge structure (XANES) of Cu(II)-ATP and related compounds in solution: Quantitative determination of the distortion of the Cu site. Journal of Chemical Physics 98: 2720–2726.

Pinskii, D.L., Minkina, T.M., Gaponova, Yu.I., 2010. Сomparative analysis of mono- and polyelement adsorption of copper, lead, and zinc by an ordinary chernozem from nitrate and acetate solutions. Eurasian Soil Science 43 (7): 748–756.

Santillan-Medrano, J., Jurinak, J.J., 1975. The chemistry of lead and cadmium in soil solid phase formation. Soil Science Society of America Proceedings 39 (5): 851–856.

Smolentsev, G.Y., Soldatov A.V., 2009. Analysis of time-resolved XANES spectra for determining the organometallic compound structure in solution. Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques 3 (3): 398–401.

Smolentsev, G.Y., Soldatov, A.V., 2006. Quantitative local structure refinement from XANES: multy-dimensional interpolation approach. Journal of Synchrotron Radioation 13 (1): 19–29.

Soldatov, A.V., 2008. X-ray absorption near edge structure as a source of structural information. Journal of Structural Chemistry 49 (Supp): 102–106.

Synchrotron-Based Techniques in Soils and Sediments, 2010. Balwant Singh and Markus Gräfe (Eds). Elsevier B.V. The Netherlands. 34, pp. 1-480.

Tessier, A., Campbell, P.G.C., Bisson, M., 1979. Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry 51: 844–851.

Xia, K., Bleam, W., Helmke, P., 1997. Studies of nature of binding sites of first row transition elements bound to aquatic and soil humicsubstences using X-ray absorption spectroscopy. Geochimica et Cosmochimica Acta 61 (11): 2223–2235.