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Soil Physical and Chemical Properties Changes After Zinc Contamination FULL COMMUNICATIONS SOIL BIOLOGY Soil physical and chemical properties changes after zinc contamination Tatiana Bauer1, Tatiana Minkina1, David Pinskii2, Inna Zamulina1, Saglara Mandzhieva1, Dina Nevidomskaya1, and Marina Burachevskaya1 1Southern Federal University, 105, Bolshaya Sadovaya Street, 344090, Rostov-on-Don, Russian Federation 2Institute of Physicochemical and Biological Problems of Soil Science, Russian Academy of Sciences, 2, Institutskaya Street, 142290, Pushchino, Russian Federation Address correspondence and requests for materials to Tatiana Bauer, [email protected] Abstract The aim of this work was to study the effect of a high rate of Zn on the chemical bond forms of metal in soil and on the physical properties and organic matter of Haplic Chernozem under model experiment conditions. The metal sequen- tial extraction procedure used in this study was the classical five-step method proposed by Tessier et al. (1979). The particle size distribution was determined by the pipette method (using the pyrophosphate procedure of soil prepara- tion) (GOST 12536-79). The microaggregate distribution was determined in the same way as the particle size distribution analysis above, except that there was no chemical dispersant (sodium pyrophosphate) applied (only mechanical agitation with water) (GOST 12536-79; Vadyunina and Korchagina, 1973). The Citation: Bauer, T., Minkina, T., qualitative composition of organic matter was determined using the Tyurin pro- Pinskii, D., Zamulina, I., Mandzhieva, S., Nevidomskaya, D., and Burachevskaya, M. cedure modified by Ponomareva and Plotnikova (Vorob’eva, 2006). Contamina- 2019. Soil physical and chemical properties tion of Haplic Chernozem with Zn acetates at high rates of 2000 mg/kg affected changes after zinc contamination. the physical and chemical properties of the soil. A significant increase in the Bio. Comm. 64(1): 46–54. https://doi. org/10.21638/spbu03.2019.106 first two soil fractions least strongly bound to the soil was observed in contami- Author’s information: Tatiana Bauer, nated soils. Silicates and Fe-Mn oxides made the largest contribution to the Zn Researcher, orcid.org/0000-0002-6751- adsorption and retention. The content of organo-mineral particles in colloidal 8686; Tatiana Minkina, Dr. of Sci. in Biology, Professor, Head of Department, orcid. size increased, which resulted in an increase of the clay fraction content up org/0000-0003-3022-0883; David Pinskii, to 4.5 % compared to the control. The qualitative composition of organic mat- Dr. of Sci. in Biology, Professor, Head of Laboratory, orcid.org/0000-0002-5834-5648; ter changed: the contents of free and sesquioxide-bound humic acids and free Inna Zamulina, Assistant Professor; Saglara fulvic acids increased. Studies of soil physical properties and organic matter Mandzhieva, PhD, Leading Researcher, orcid.org/0000-0001-6000-2209; Dina quality changes and chemical bond forms of Zn in soil are needed to better un- Nevidomskaya, PhD, Leading Researcher, derstand metal behaviors in the environment and implement repair strategies orcid.org/0000-0002-0138-4443; Marina Burachevskaya, PhD, Researcher, orcid. in different polluted soils. org/0000-0002-0533-0418 Keywords: zinc, soil, fractional composition, organic matter, particle size distri- Manuscript Editor: Evgeny Abakumov, bution, structural status, aggregate content. Department of Applied Ecology, Faculty of Biology, Saint Petersburg State University, Saint Petersburg, Russia Received: February 15, 2019; Introduction Revised: March 28, 2019; Accepted: March 30, 2019; Heavy metals (HMs) pollution of soil is an increasingly urgent problem all over the Copyright: © 2019 Bauer et al. This is an open-access article distributed under industrialized world. Elevated metals concentrations in soils can pose long-term the terms of the License Agreement with risks for soil fertility and ecosystem health. Organic matter, clay minerals, as well as Saint Petersburg State University, which permits to the authors unrestricted Fe and Mn oxides are the most important components determining the sorption of distribution, and self-archiving free of metals in soils (Vega, Covelo, and Andrade, 2006). The organic components form charge. stable metal-organic complexes with a variety of metals, while clay minerals and Funding: This work was supported by the grant of the Ministry of Education oxides concentrate heavy metal ions through surface ion exchange and metal-com- and Science of the Russian Federation, No. 5.948.2017/PP, and the Russian plex surface adsorption. Soil organic matter (SOM) that plays a key role in govern- Foundation for Basic Research, ing metal mobility consists mainly of humic substances: humic and fulvic acids. Or- No. 18-55-05023 arm_а. ganic materials have large negatively charged interfaces that compete strongly with Competing interests: The authors have declared that no competing interests exist. inorganic ligands to readily immobilize metal ions through the formation of stable BIOLOGICAL COMMUNICATIONS, vol. 64, issue 1, January–March, 2019 | https://doi.org/10.21638/spbu03.2019.106 47 complexes, thereby decreasing their phytoavailability to interaction energy of HMs with clay minerals is higher plants (Guo et al., 2006; Mohamed et al., 2010; Ok et al., than that of alkaline and alkaline-earth cations; in the 2011). In addition, dissolved organic matter and fulvic/ general case, it changes in the following order: Pb > Cu > humic acids can form soluble chelates with metals, which Ni > Co > Zn > Mn > Ba > Ca > Mg > K > Na (Pinskiy increases metal mobility, extractability and phytoavail- and Fiala, 1985). It also depends on the acid–base prop- ability under certain soil conditions (Salati, Quadri, Tam- erties of the exchanger; hence, the order can vary among bone, and Adani, 2010; Hu et al., 2016). Iron and man- soils and their components (Pinskiy, 1996). ganese oxides present in soils are frequently nanometer- It was noted that high contamination can disturb sized materials, which have a large surface area to volume the organic matter content and quality of soils: changes ratio and thus are capable of binding metals. For example, in the content of the aliphatic structures inhibit the mat- T. Phuengprasop, J. Sittiwong, and F. Unob (2011) found uration of molecules of humic acids (Grishina, Koptsik, that one gram of iron oxide-coated sludge had a capac- and Makarov, 1990), increase the share of fulvic acids ity to adsorb 17.3, 14.7 and 42.4 mg of Cu, Cd and Pb, (Karpukhin and Bushuev, 2007), and even slightly in- respectively. crease the organic matter content (Bezuglova and Yudi- The environmental behavior of HMs in soils and na, 2006). Hence, studies on native SOM quality changes potential risks to human health depend critically on the and metal-SOM interactions are needed to better under- form in which they occur. The manner in which an ele- stand metal behaviors in the environment and imple- ment is bound to the components of the soil complex ment repair strategies in different polluted soils. influences the mobility and, ultimately, the bioavailabil- The aim of this work was to study the effect of a high ity and toxicity of the element to organisms (Bacon and rate of Zn on the chemical bond forms of metal in soil and Davidson, 2008). The availability depends on the nature on the physical properties and organic matter of Haplic of the chemical association between the metal and or- Chernozem under model experimental conditions. ganic and/or inorganic soil constituents (Wang, Zhou, and Cang, 2009). Materials and Methods Determination of the chemical forms of trace ele- ments in complex environmental matrices such as soils SOIL CHARACTERISTIC can be achieved by sequential extraction. Sequential ex- traction, although operationally defined, can give infor- Soil for model laboratory experiments was collected from mation about the association of heavy metals with the the humus-accumulative A1 horizon of Haplic Cherno- geochemical phases of soil. Thus, sequential extraction zem (Clayic) (IUSS, 2015) in the Persianovskaya Steppe is widely used to reveal the distribution of heavy metals Specially Protected Natural Territory, Rostov Oblast, in soil fractions and to assess the mobility and toxicity of Russia. The soil has the following chemical composi- tion: Corg 3.7 %; CaCO3 0.4 %; pHH2O 7.6; exchangeable metals in soil (Guo et al., 2011). 2+ 2+ + It is known that HMs contamination also changes cations (mM(+)/100 g): Ca 31.0; Mg 6.0; Na 0.06; the quality of the soil. The HMs adsorbed by soils can cation exchange capacity (CEC) — 38.0 mM(+)/100 g. affect the physical and chemical properties of the soil. The content of the physical clay fraction (particles Many authors have studied the effects of HM cations on <0.01 mm) is 63.6 %; the content of the clay fraction the specific surface area of soils, microstructure of clay (particles <0.001 mm) is 28.1 %. minerals, sorption of water vapors, thermodynamic state The mineralogy of the clay and fine silt (0.005– of water in clay minerals, mineralogy of the clay frac- 0.001 mm) fractions in the humus-accumulative hori- tion, and distribution of HMs in aggregates of soils of zon (0–20 cm upper layer) of Haplic Chernozem is char- different genesis (Vityazev, Kaurichev, and Rabii, 1980; acterized by the following phase composition of layered Vityazev, Chizhikova, and Shevchenko, 1983; Manucha- silicates: illite, 51–54 % in the clay fraction and 51–60 % rov, Kharitonova, Chernomorchenko, and Zemlyanukh- in the fine silt fraction; labile silicates, 23–27 % in the clay fraction and 12–27 % in the fine silt fraction; kaolin- in, 2001; Smagin et al., 2004; Fedotov et al., 2008). It was SOIL ite, 22–23 % in the clay fraction and 22–28 % in the fine shown that the intensities of reflections corresponding BIOLOGY to montmorillonites and illites on the X-ray diffraction silt fraction. The fine silt fraction also contains micas, patterns of the clay fractions from heavy loamy soddy- amorphous silica, and crystallized iron and aluminum podzolic soil and heavy loamy chernozem changed after oxides and hydroxides (Sokolova, 1985; Kryshchenko treatment with Zn and Cu salts (Motuzova et al., 2012).
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