Assessment of extraction methods for studying the fractional composition of Cu and Zn in uncontaminated and contaminated soils

This study is aimed at elucidating the fractionation of Cu and Zn in Haplic Chernozem and its alteration under the contamination to evaluate the extraction selectivity of different extractants and thus the efficiency of three sequential extraction schemes (Tessier and McLaren five-step and modified BCR three-step methods). General trends in the distribution of Cu and Zn speciations revealed with these three fractionation schemes suggest that they can be applied for the soils and the obtained results can be compared. Low mobility of potentially toxic metals (PTM) in the studied soil is suggested not only by their high content in residual fraction, but also by low contents of exchangeable and carbonate bound fractions (not more than 4-5 % Cu and 5-7 % Zn in the first two fractions). The highest contribution to the absorption and retention of Cu delivered from anthropogenic sources is made by organic matter and sesquioxides (up to 29 %); for Zn, by the nonsilicate Fe and Mn compounds (up to 25 %). However, the pattern of PTM extraction from soils varies during the application of different fractionation methods. The Tessier method is distinguished by a higher extractability relative to organic matter and sesquioxides. Therefore, this method is more informative for the contaminated soils. The McLaren method makes it possible to track the weakly bound species of compounds without the risk of involving other soil components. The BCR method is marked by simplicity of application and, therefore, recommended only for the noncalcic or low-calcic soils.

___

  • Acosta, J.A., Gabarrón, M., Faz, A., Martínez-Martínez, S., Zornoza, R., Arocena, J.M., 2015. Influence of population density on the concentration and speciation of metals in the soil and street dust from urban areas. Chemosphere 134: 328-337.
  • Ahnstrom, Z.S., Parker, D.R., 1999. Development and assessment of a sequential extraction procedure for the fractionation of soil cadmium. Soil Science Society of America Journal 63(6): 1650-1658.
  • Al-Mur, B.A., 2020. Geochemical fractionation of heavy metals in sediments of the Red Sea, Saudi Arabia. Oceanologia 62(1): 31-44.
  • Anju, M., Banerjee, D.K., 2010. Comparison of two sequential extraction procedures for heavy metal partitioning in mine tailings. Chemosphere 78(11): 1393-1402.
  • Arenas-Lago, D., Andrade, M.L., Vega, F.A., Singh, B.R., 2016. TOF-SIMS and FE-SEM/EDS to verify the heavy metal fractionation in serpentinite quarry soils. Catena 136: 30-43.
  • Aten, C.F., Gupta, S.K., 1996. On heavy metals in soil; rationalization of extractions by dilute salt solutions, comparison of the extracted concentrations with uptake by ryegrass and lettuce, and the possible influence of pyrophosphate on plant uptake. Science of The Total Environment 178(1-3): 45-53.
  • Baruah, N.K., Kotoky, P., Bhattacharyya, K.G., Borah, G.C., 1996. Metal speciation in Jhanji River sediments. Science of the Total Environment 193(1): 1-12.
  • Bauer, T., Pinskii, D., Minkina, T., Mandzhieva, S., Burachevskaya, M., Kalinitchenko, V., Barakhov, A., 2018. Stabilization dynamics of easily and poorly soluble Zn compounds in the soil. Geochemistry: Exploration, Environment, Analysis 19(2): 184-192.
  • Clevenger, T.E., 1990. Use of sequential extraction to evaluate the heavy metals in mining wastes. Water, Air, & Soil Pollution 50: 241-254.
  • Coetzee, P.P., 1993. Determination and speciation of heavy metals in sediments of the Hartbeespoort Dam by sequential chemical extraction. Water SA 19: 291-300.
  • Davidson, C.M., Wilson, L.E., Ure, A.M., 1999. Effect of sample preparation on the operational speciation of cadmium and lead in a freshwater sediment. Fresenius' Journal of Analytical Chemistry 363: 134-136.
  • Diks, D.M., Allen, H.E., 1983. Correlation of copper distribution in a freshwater-sediment system to bioavailability. Bulletin of Environmental Contamination and Toxicology 30: 37–43.
  • Doelsch, E., Moussard, G., Macary, H.S., 2008. Fractionation of tropical soilborne heavy metals - Comparison of two sequential extraction procedures. Geoderma 143(1-2): 168-179.
  • Elliot, H.A., Dempsey, B.A., Maille, M.J., 1990. Content and fractionation of heavy metals in water treatment sludges. Journal of Environmental Quality 19(2): 330-334.
  • Filgueiras, V., Lavilla, I., Bendicho, C., 2002. Chemical sequential extraction for metal partitioning in environmental solid samples. Journal of Environmental Monitoring 4: 823–857.
  • Emmerson, R.H.C., Birkett, J.W., Scrimshawand, M., Lester, J.N., 2000. Solid phase partitioning of metals in managed retreat soils: field changes over the first year of tidal inundation. Science of The Total Environment 254(1): 75-92.
  • Evans, Z.C., Ryswyk, H.V., Huertos, M.L., Srebotnjak, T., 2019. Robust spatial analysis of sequestered metals in a Southern California Bioswale. Science of The Total Environment 650(1): 155-162.
  • Gabarrón, M., Faz, A., Martínez-Martínez, S., Zornoza, R., Acosta, J.A., 2017. Assessment of metals behaviour in industrial soil using sequential extraction, multivariable analysis and a geostatistical approach. Journal of Geochemical Exploration 172: 174-183.
  • Gauthreaux, K., Noble, C.O., Falgoust, T., Beck, M.J., Sneddon, J., Beck, J.N., 1998. Reliability and reproducibility of a sequential extraction procedure for trace metal determination in marsh sediments in Southwest Louisiana. Microchemical Journal 60(2): 175-183.
  • Gibson, M.J., Farmer, J.G., 1986. Multi-step sequential chemical extraction of heavy metals from urban soils. Environmental Pollution Series B, Chemical and Physical 11(2): 117-135.
  • Gupta, S. K., Aten, C., 1993. Comparison and evaluation of extraction media and their suitability in a simple model to predict the biological relevance of heavy metal concentrations in contaminated soils. International Journal of Environmental Analytical 51(1-4): 25-46.
  • Hall, G.E.M., Pelchat J.C., 1999. Comparibility of results obtained by the use of different selective extraction schemer for the determination of element forms in soils. Water, Air, and Soil Pollution 112: 41–53.
  • Hasan, M., Kausar, D., Akhter, G., Shah, M.H., 2018. Evaluation of the mobility and pollution index of selected essential/toxic metals in paddy soil by sequential extraction method. Ecotoxicology and Environmental Safety 147: 283-291.
  • He, Q., Ren Y., Mohamed, I., Ali, M., Hassan, W., Zeng, F., 2013. Assessment of trace and heavy metal distribution by four sequential extraction procedures in a contaminated soil. Soil and Water Research 8: 71–76.
  • Hlavay, J., Prohaska, T., Weisz, M., Wenzel, W.W., Stingeder, G.J., 2004. Determination of trace elements bound to soils and sediment fractions (IUPAC Technical Report). Pure and Applied Chemistry 76(2): 415–442.
  • Hsu, L.C., Liu, YT., Tzou Y.M., 2015. Comparison of the spectroscopic speciation and chemical fractionation of chromium in contaminated paddy soils. Journal of Hazardous Materials. 296: 230-238.
  • Hu, Y., Liu, X., Bai, J., Shih, K., Zeng, E.Y., Cheng, H., 2013. Assessing heavy metal pollution in the surface soils of a region that had undergone three decades of intense industrialization and urbanization. Environmental Science and Pollution Research 20: 6150–6159.
  • Kennedy, V.H., Sanchez, A.L., Oughton, D.H., Rowland, A.P., 1997. Use of single and sequential chemical extractants to assess radionuclide and heavy metal availability from soils for root uptake. Analyst 122: 89R-100R.
  • Kennou, B., El Meray, M., Romane, A., Arjouni, Y., 2015. Assessment of heavy metal availability (Pb, Cu, Cr, Cd, Zn) and speciation in contaminated soils and sediment of discharge by sequential extraction. Environmental Earth Sciences 74: 5849-5858.
  • Ladonin, D.V., Karpukhin, M.M., 2003. Fractionation of heavy metal compounds in soils-problems of method selection and interpretation of results. In: Proceedings of the International Geoecological Conferences on Geoecological Problems of Environmental Pollution by Heavy Metals. 2003. Moscow State University, Moscow, Russia. pp. 68-73.
  • Ladonin, D.V., Karpukhin, M.M., 2011. Fractional composition of nickel, copper, zinc, and lead compounds in soils polluted by oxides and soluble metal salts. Eurasian Soil Science 44: 874.
  • Lee, F.Y., Kittrick, J. A., 1984. Elements associated with the cadmium phase in a harbor sediment as determined with the electron beam microprobe. Journal of Environmental Quality 13(3): 337-340.
  • Leermakers, M., Mbachou, B.E., Husson, A., Lagneau, V., Descostes, M., 2019. An alternative sequential extraction scheme for the determination of trace elements in ferrihydrite rich sediments. Talanta 199: 80–88.
  • Li, X., Thornton, I., 2001. Chemical partitioning of trace and major elements in soils contaminated by mining and smelting activities. Applied Geochemistry 16(15): 1693–1706.
  • Linnik, V.G., Minkina, T.M., Bauer, T.V., Saveliev, A.A., Mandzhieva, S.S., 2019. Geochemical assessment and spatial analysis of heavy metalspollution around coal-fired power station. Environmental Geochemistry and Health [in Press].
  • Manceau, A., Marcus, M.A., Tamura, N., 2002. Quantitative speciation of heavy metals and sediments by synchrotron X-ray techniques. In: Applications of synchrotron radiation in low-temperature geochemistry and environmental science. Reviews in Mineralogy and Geochemistry 49(1): 341–428.
  • Manceau, A., Marcus, M.A, Tamura, N., Proux, O., Geoffroy, N., Lanson, B., 2004. Natural speciation of Zn at the micrometer scale in a clayey soil using X-ray fluorescence, absorption, and diffraction. Geochimica et Cosmochimica Acta 68(11): 2467-2483.
  • Manceau, A., Matynia, A., 2010. The nature of Cu bonding to natural organic matter. Geochimica et Cosmochimica Acta 74(9): 2556-2580.
  • Mandzhieva, S.S., Goncharova, L.Y., Batukaev, A.A., Minkina, T.M., Bauer, T.V., Shertnev, A.K., Chaplygin, V.A., Sushkova S.N., Poluektov, E.V., Burachevskaya, M.V., Kozlova, M.N., 2017. Current state of haplic chernozems in specially protected natural areas of the steppe zone. OnLine Journal of Biological Sciences 17(4): 363-371.
  • McBride, M.B., 1989. Reactions controlling heavy metal solubility in soils. In: Advances in Soil Science. Stewart, B.A. (Ed.). Volume 10 Springer-Verlag, New York, USA. pp. 1-56.
  • McLaren, R.G., Crawford, D.V., 1973. Studies on soil copper. I. The fractionation of copper in soils. European Journal of Soil Science 24(2): 172-181.
  • Mekapogu, M., Nadimikeri, J., Madri, P.K., Devi, S., 2018. A study on zinc speciation of Tungabhadra River sediments, Kurnool, south India: A tool in metal pollution monitoring. International Journal of Sediment Research 33(4): 510-517.
  • Mellis, E.V., Casagrande, J.C., Cruz, M.C.P., 2003. Iron oxides, pH and organic matter effects on nickel adsorption. Conference proceedings “7th international Conference on the Biogeochemistry of Trace Elements”, Uppsala, Sweden, 3: 20-21.
  • Minkina, T.M., Motuzova, G.V., Mandzhieva, S.S., Nazarenko, O.G., Burachevskaya, M.V., Antonenko, E.M., 2013a. Fractional and group composition of the Mn, Cr, Ni, and Cd compounds in the soils of technogenic landscapes in the impact zone of the Novocherkassk power station. Eurasian Soil Science 46: 375-385.
  • Minkina, T.M., Soldatov, A.V., Motuzova, G.V., Podkovyrina, Yu.S., Nevidomskaya, D.G., 2013b. Molecular–structural analysis of the Cu(II) ion in ordinary chernozem: evidence from XANES spectroscopy and methods of molecular dynamics. Doklady Earth Sciences 449: 418-421.
  • Minkina, T.M., Bauer, T.V., Batukaev, A.A., Mandzhieva, S.S., Burachevskaya, M.V., Sushkova, S.N., Varduni, T.V., Sherstnev, A.K., Kalinichenko, V.P., 2015. Transformation of technogenic Cu and Zn compounds in chernozem. Environmental Engineering and Management Journal 14: 481–486.
  • 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: 197–204.
  • Minkina, T.M., Linnik, V.G., Nevidomskaya, D.G., Bauer, T.V., Mandzhieva, S.S., Khoroshavin, V., 2018a. Forms of Cu (II), Zn (II), and Pb (II) compounds in technogenically transformed soils adjacent to the Karabashmed copper smelter. Journal of Soils and Sediments 18(6): 2217-2228.
  • Minkina, T., Nevidomskaya, D., Bauer, T., Shuvaeva V., Soldatov A., Mandzhieva S., Zubavichus Y., Trigub A., 2018b. Determining the speciation of Zn in soils around the sediment ponds of chemical plants by XRD and XAFS spectroscopy and sequential extraction. Science of The Total Environment 634: 1165-1173.
  • Minkina, T., Nevidomskaya, D., Burachevskaya, M., Bauer, T., Shuvaeva, V., Soldatov A., Mandzhieva S., Zubavichus Y., 2019. Possibilities of chemical fractionation and X-ray spectral analysis in estimating the speciation of Cu2+ with soil solid-phase components. Applied Geochemistry 102: 55-63.
  • Naji, A., Ismail, A., Ismail, A.R., 2010. Chemical speciation and contamination assessment of Zn and Cd by sequential extraction in surface sediment of Klang River, Malaysia. Microchemical Journal 95(2): 285-292.
  • Nielsen, M.T., Scott-Fordsmand, J.J., Murphy, M.W., Kristiansen S.M., 2015. Speciation and solubility of copper along a soil contamination gradient. Journal of Soils and Sediments 15: 1558–1570.
  • Novozamsky, I., Lexmond, T.M., Houba, V.J.G., 1993. A single extraction procedure of soil for evaluation of uptake of some heavy metals by plants. International Journal of Environmental Analytical Chemistry 51(1-4): 47-58.
  • Orecchio, S., Polizzotto, G., 2013. Fractionation of mercury in sediments during draining of Augusta (Italy) coastal area by modified Tessier method. Microchemical Journal 110: 452-457.
  • Papp, C.S.E.L., Filipek, H., Smith K.S., 1991. Selectivity and effectiveness of extractants used to release metals associated with organic matter. Applied Geochemistry 6(3): 349-353.
  • Pinskii, D.L., Minkina, T.M., Mandzhieva, S.S., Fedorov, U.A., Nevidomskaya, D.G., Bauer, T.V., 2014. Adsorption features of Cu(II), Pb(II), and Zn(II) by an ordinary chernozem from nitrate, chloride, acetate, and sulfate solutions, Eurasian Soil Science, 47: 10-17.
  • Raksasataya, M., Langdon, A.G., Kim, N.D., 1996. Assessment of the extant of lead redistribution during sequential extraction by two different methods. Analytica Chimica Acta 332(1): 1-14.
  • Rapin, F., Tessier, A., Campbell, P.G.C., Carignan, R., 1986. Potential artifacts in the determination of metal partitioning in sediments by a sequential extraction procedure. Environmental Science & Technology 20(8): 836–840.
  • Rao, C.R.M., Sahuquillo, A., Lopez Sanchez, J.F., 2007. A review of the different methods applied in environmental geochemistry for single and sequential extraction of trace elements in soils and related materials. Water Air and Soil Pollution 189: 291–333.
  • Rauret, G., López-Sánchez, J.F., Sahuquillo, A., Rubio, R., Davidson, C., Ure, A., Quevauviller, P., 1999. Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials. Journal of Environmental Monitoring 1(1): 57-61.
  • Rauret, G., 1998. Extraction procedures for the determination of heavy metals in contaminated soil and sediment. Talanta 46(3): 449-455.
  • Rosado, D., Usero, J., Morillo, J., 2016. Ability of 3 extraction methods (BCR, Tessier and protease K) to estimate bioavailable metals in sediments from Huelva estuary (Southwestern Spain). Marine Pollution Bulletin 102(1): 65-71.
  • Pueyo, M., Mateu, J., Rigol, A., Vidal, M., López-Sánchez, J.F., Rauret, G., 2008. Use of the modified BCR three-step sequential extraction procedure for the study of trace element dynamics in contaminated soils. Environmental Pollution 152(2): 330-341.
  • Scheinost, A.C., Kretzchmar, R.S., Pfister, S., 2002. Combining selective sequential extractions, X-ray adsorption spectroscopy, and principal component analysis for quantitative zinc speciation in soil. Environmental Science & Technology 36: 5021-5028.
  • Shuman, L.M., 1983. Sodium hypochlorite methods for extracting microelements associated with soil organic matter. Soil Science Society of America Journal 47(4): 656-660.
  • Shaimukhametov, M.H., 1993. To the method for determining adsorbed Ca and Mg in chernozem soils. Pochvovedenie 12: 105-111. [in Russian].
  • Silveira, M.L., Alleoni, L.R.F., O’Connor, G.A., Chang, A.C., 2006. Heavy metal sequential extraction methods - A modification for tropical soils. Chemosphere 64(11): 1929-1938.
  • Stone, M., Marsalek, J., 1996. Trace metal composition and speciation in street sediment: Sault Ste. Marie, Canada. Water, Air, and Soil Pollution 87: 149-169.
  • Stone, M., Droppo, I.G., 1996. Distribution of lead, copper and zinc in size-fractionated river bed sediment in two agricultural catchments of southern Ontario, Canada. Environmental Pollution 93(3): 353-362.
  • Strawn, D.G., Baker, L.L., 2008. Speciation of Cu in a contaminated agricultural soil measured by XAFS, Μ-XAFS, and Μ-XRF. Environmental Science & Technology 42(1): 37–42.
  • Sutherland, R.A., Tack, F.M.G., Tolosa, C.A., Verloo, M.G., 2000. Operationally defined metal fractions in road deposited sediment, Honolulu, Hawaii. Journal of Environmental Quality 29(5): 1431-1439.
  • Sutherland, S.A., Tack, F.M.G., 2000. Metal phase associations in soils from an urban watershed, Honolulu, Hawaii. Science of The Total Environment 256(2-3): 103-113.
  • Sulkowski, M., Hirner, A.V., 2006. Element fractionation by sequential extraction in a soil with high carbonate content. Applied Geochemistry 21(1): 16-28.
  • Tashakor, M., Yaacob, W.Z.W., Mohamad, H., Ghani, A.A., Saadati, N., 2014. Assessment of selected sequential extraction and the toxicity characteristic leaching test as indices of metal mobility in serpentinite soils. Chemical Speciation and Bioavailability 26(3): 139–147.
  • Tessier, A., Campbell, P.G.C., Bisson, M., 1979. Sequential extraction procedure for the speciation of particulate trace metals. Analytical chemistry 51(7): 844-851.
  • Tokalioglu, S., Kartal, S., Elc, L., 2000. Determination of heavy metals and their speciation in lake sediments by flame atomic absorption spectrometry after a four-stage sequential extraction procedure. Analytica Chimica Acta 413(1-2): 33-40.
  • Tyurin, I. V., 1965. Organic matter of soil and its role in fertility. Nauka, Moscow. 320p.
  • Ure, A., Quevaullier, P.H., Muntau, H., Griepink, B., 1993. Speciation of heavy metals in soils and sediments. An account of the improvement and harmonization of extraction techniques undertaken under the auspices of the BCR of the CEC. International Journal of Environmental Analytical Chemistry 51(1-4): 135–151.
  • Vadyunina, F., Korchagina, Z.A., 1986. Methods of research of physical properties of soils. Agropromizdat, Moscow, Russia. 416p. [in Russian].
  • van Hullebusch, E.D., Utomo, S., Zandvoort, M.H., Lens, P.N.L., 2005. Comparison of three sequential extraction procedures to describe metal fractionation in anaerobic granular sludges. Talanta 65(2): 549-558.
  • Vorob’eva, L.A., 2006. Theory and Practice Chemical Analysis of Soils. GEOS, Moscow, Russia. 400p. [in Russian].
  • Vodyanitsky, Y.N., 2010. Study of carrier phases of Zn, Pb in soils by methods of chemical fractionation and sichrotron x-ray analysis. Agrochemistry 8: 77-86. [in Russian].
  • Wisawapipat, W., Janlaksana, Y., Christl, L., 2017. Zinc solubility in tropical paddy soils: a multi-chemical extraction technique study. Geoderma 301: 1-10.
  • Wong, C.S.C., Li, X.D., Zhang, G., Qi, S.H., Min, Y.S., 2002. Heavy metals in agricultural soils of the Pearl River Delta, South China. Environmental Pollution 119(1): 33–44.
  • Xia, K., Bleam, W., Helmke, P.A., 1997. Studies of the nature of Cu2+ and Pb2+ binding sites in soil humic substances using X-ray absorption spectroscopy. Geochimica et Cosmochimica Acta 61(11): 2211–2221.
  • Yaylali-Abanuz, G., 2011. Heavy metal contamination of surface soil around Gebze industrial area, Turkey. Microchemical Journal 99: 82–92.
  • Zorpas, A.A., Constantinides, T., Vlyssides, A.G., Haralambous, I., Loizidou, M., 2000. Heavy metal uptake by natural zeolite and metals partitioning in sewage sludge compost. Bioresource Technology 72(2): 113-119.