Combining selective sequential extractions, X-Ray Absorption Spectroscopy, and X-Ray Powder Diffraction for Cu (II) speciation in soil and mineral phases

Abstract

Interaction of Cu (II) ions with the matrix of soil and mineral phases of layered silicates was assessed by the Miller method of selective sequential fractionation and a set of synchrotron X-ray methods, including X-ray powder diffraction (XRD) and X-ray absorption spectroscopy (XANES). It was shown that the input of Cu into Calcic Chernozem in the form of monoxide (CuO) and salt (Cu(NO3)2) affected the transformation of Cu compounds and their affinity for metal-bearing phases. It was found that the contamination of soil with a soluble Cu(II) salt increased the bioavailability of the metal and the role of organic matter and Fe oxides in the fixation and retention of Cu. During the incubation of soil with Cu monoxide, the content of the metal in the residual fractions increased, which was related to the possible entry of Cu in the form of isomorphic impurities into silicates, as well as to the incomplete dissolution of exogenic compounds at the high level of their input into the soil. A mechanism for the structural transformation of minerals was revealed, which showed that ion exchange processes result in the sorption of Cu (II) ions from the saturated solution by active sites on the internal surface of the lattice of dioctahedral aluminosilicates. Surface hydroxyls at the octahedral aluminum atom play the main role. X-ray diagnostics revealed that excess Cu(II) ions are removed from the system due to the formation and precipitation of coarsely crystalline Cu(NO3)(OH)3. 

Keywords

• Cu (II) ions
• calcic chernozem
• mineral phases
• sequential fractionation
• XRD
• XANES Spectroscopy

References

1. Akimtsev, V.V., Boldyreva, A.V., Golubev, S.N., 1962. Content of microelements in soils of Rostov oblast. In: Microelements and Natural Radioactivity. RGU, Rostov-on-Don, Russia. pp. 37-42. [in Russian].
2. Berti, W.R., Jacobs, L.W., 1996. Chemistry and phytotoxicity of soil trace elements from repeated sewage sludge applications. Journal of Environmental Quality 25(5): 1025-1032.
3. Chernyshov, A.A., Veligzhanin, A.A., Zubavichus, Y.V., 2009. Structural Materials Science end-station at the Kurchatov synchrotron radiation source: recent instrumentation upgrades and experimental results. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment 603(1-2): 95-98.
4. FAO, 2006. World reference base for soil resources 2006. World soil resources reports 103. Food and Agriculture Organization of the United Nations, Rome, Italy. 132 p.
5. 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.
6. Gräfe, M., Donner, E., Collins, R.N., Lombi, E., 2014. Speciation of metal(loid)s in environmental samples by X-ray absorption spectroscopy: A critical review. Analytica Chimica Acta 822: 1-22.
7. Hesterberg, D., Duff, M.C., Dixon, J.B., Vepraskas, M.J. 2010. X-ray microspectroscopy and chemical reactions in soil microsites. Journal of Environmental Quality 40(3): 667-678.
8. Kosheleva, N.E., Kasimov, N.S., Samonova, O.A., 2002. Regression models for the behavior of heavy metals in soils of the Smolensk–Moscow Upland. Eurasian Soil Science 35(8): 954-966.

9. Kryshchenko, V.S., Kuznetsov, R.V., 2003. Clay minerals in soils of the Lower Don and Northern Caucasus regions. IzvestiyaVuzov. Severo-Kavkazskii Region. Seriya Estestvennye Nauki 3: 86-92. [in Russian].
10. Miller, P.W., Martens, D.C., Zelazny, L.W., 1986. Effect of sequence in extraction of trace metals from soils. Soil Science Society of America Journal 50(3): 598-601.
11. Minkina, T.M., Mandzhieva, S.S., Motusova, G.V., Burachevskaya, M.V., Nazarenko, O.G., Sushkova, S.N., Kızılkaya, R., 2014. Heavy metal compounds in a soil of technogenic zone as indicate of its ecological state. Eurasian Journal of Soil Science 3(2): 144-151.
12. Minkina, T.M., Motusova, G.V., Nazarenko, O.G., Mandzhieva, S.S., 2010. Heavy metal compounds in soil: Transformation upon soil pollution and ecological significance. Nova Science Publishers Inc. New York, USA. 184p.
13. 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(2): 418-421.
14. Minkina, T.M., Soldatov, A.V., Nevidomskaya, D.G., Motuzova, G.V., Podkovyrina, Yu.S.,Mandzhieva, S.S., 2016. New approaches to studying heavy metals in soils by X-ray absorption spectroscopy (XANES) and extractive fractionation. Geochemistry International 54(2): 197-204.
15. Natoli, C.R., 1984. Distance dependence of continuum and bound state of excitonic resonances in X-ray absorption near edge structure (XANES), in: Hodgson, K.O., Penner-Hahn, J. (Eds.), EXAFS and Near Edge Structure III. Springer Proceedings in Physics 2. Springer, Berlin, pp. 38-42.
16. Nevidomskaya, D.G., Minkina, T.M., Soldatov, A.V., Shuvaeva, V.A., Zubavichus, Y.V., Podkovyrina, Yu.S., 2016. Comprehensive study of Pb(II) speciation in soil by X-ray absorption spectroscopy (XANES and EXAFS) and sequential fractionation. Journal of Soils and Sediments 16(4): 1183-1192.
17. Orlov, D.S., Sadovnikova, L.K., Sukhanova, N.I. 2005. Soil chemistry. VyshshayaSchkola, Moscow, Russia. [in Russian].
18. Perelomov, L.V., 2001. Immobilization factors of heavy metals in gray forest and alluvial soils of the Central Russian upland. Dissertation, Moscow, Russia. [in Russian].
19. Ponizovskii, A.A., Mironenko, E.V., 2001. Mechanisms of lead (II) sorption in soils. Eurasian Soil Science 34: 371-381.
20. Ponizovskii, A.A., Studenikina, T.A., Mironenko, E.V., 1999. Adsorption of copper (II) ions by soil as influenced by organic components of soil solutions. Eurasian Soil Science 32: 766-775.
21. Strawn, D.G., Baker, L.L., 2009. Molecular characterization of cupper in soils using X-ray absorption spectroscopy. Environmental Pollution 157(10): 2813-2821.
22. Vinogradov, A.P., 1957. Geochemistry of rare and dispersed chemical elements in soils. Moscow, Russia. [in Russian].
23. Vodyanitskii, Yu.N., 2008. Affinity of heavy metals and metalloids for carriers in contaminated soils. Agrokhimiya 9: 87-94.
24. Vodyanitskii, Yu.N., 2010. Study of Zn and Pb carrier phases in soils by chemical fractionation and synchrotron X-ray. Agrokhimiya 8: 77-86.