ࡱ> supqr5@ irbjbj22 ;|XX STjTjTj8j@kj@nVnVnVnVnppp$RT>9p"p99VnVnsR9, lVnVn9op,Vn4n uZ^Tje ;h0U:4pvzD}@pppfTj5XTjTRANSFORMATION OF HEAVY METAL COMPOUNDS DURING THE REMEDIATION OF CONTAMINATED SOILS Tatiana Minkina1, Galina Motusova2, Saglara Mandzhieva1, Olga Nazarenko3, Ivan `imuni4 1Faculty of Biology and Soil Science, Department of Soil Science, Southern Federal University, Rostov-on-Don, Russia 2Faculty of Soil Science, Department of Soil Chemistry, Moscow State University, Moscow, Russia 3Department of Agriculture, Don State Agrarian University, Rostov region, Russia 4 Faculty of Agriculture, Department of Soil Amelioration, Zagreb, Croatia E-mail:  HYPERLINK "mailto:minkina@bio.rsu.ru" minkina@bio.rsu.ru Summary The effect of chalk, glauconite and semidecomposed cattle manure were used as ameliorants on ordinary chernozem contaminated with Zn and Pb was studied in a long-term field experiment. The application of ameliorants significantly decreased the mobility of metals. Their effect depended on the ameliorant and was most significant at the simultaneous application of chalk and manure. This effect was presumably due to the strong binding of metals by carbonates through chemisorption and formation of low-soluble Zn and Pb compounds and to the additional fixation in the form of complexes at the addition of organic material. The share of loosely bound metal compounds in the contaminated soils decreased to the level typical for the clean soils or even below. The general evolution of the transformation of metal compounds (from less to more strongly bound compounds) accelerated by ameliorants remained for both metals. Keywords: soil, heavy metal compounds, transformation, ameliorants INTRODUCTION The barrier function is an essential function of soil in an ecosystem. The soil protects natural waters, air, and plants from pollutants. This function is ensured by the sorption capacity of soils. It should be noted that plants also have some resistance to soil contamination. The soil under study is a highly buffering self-protecting system. However, our studies showed that the self-protection mechanisms are not always efficient. Therefore, methods should be developed for the remediation of polluted soils with the use of ameliorants. The available data on the efficiency of specific ameliorants are insufficient to reveal the processes resulting in the redistribution of heavy metal forms in contaminated soils. In addition, the efficiency of remediation methods was better studied for slightly acid chernozems and acid soddy-podzolic and podzolic soils with different particle-size distributions. At the same time, ordinary chernozems usually escape the attention of researchers. The soils of this genetic subtype occupy a significant area (mainly in the industrial regions of Rostov oblast and Krasnodar region subjected to active anthropogenic pollution) and their major part is in agricultural use; therefore, analogous studies of these soils are of current interest. The reclamation methods of arable soils contaminated with metals are mainly aimed at decreasing the content of mobile metal compounds. The selection of ameliorants should be based on the mechanisms of strong metal fixation; i.e., the action of an ameliorant should be directed to the enhancement of the barrier function of soils. Insufficient data are available on mechanisms for the strong fixation of metals by soil components, including in reclaimed soils. The analysis of the group metal composition showed the polyfunctional nature of soil components and the capacity of each of them for both strong and weak retention of contaminant metals. The selection of ameliorants for contaminated soils was based on the presumed formation of metal compounds strongly bound to soil components corresponding to their weakly bound analogues. The strong fixation of heavy metals in the soil is due to their chelation, precipitation, and fixation in the structure of minerals; therefore, manure (active agent in the complexation of metals with differently stability), chalk (active agent in the specific sorption and precipitation of metals), and glauconite (active agent in the exchangeable sorption and fixation of metals) were used as ameliorants. The high capacity of humus acids for binding and strongly retaining appreciable amounts of heavy metals found practical application for soil detoxification (Choi et al., 2008). Brown coal, which is also a source of natural humic acids, is used as a sorbent. Natural zeolites having a high sorption capacity have attracted recent attention of scientists dealing with the protection of soils and plants from the contamination with heavy metals (Mineev et al., 1989; Ming, Mumpton, 1989; Baidina, 1994; Knox, Adriano, 1999; Barbu et al., 2003; Kliaugiene, Baltrenas, 2003). Natural sorbents are profitable agents, because they are ecologically safe, readily available, and inexpensive. There are different opinions about the efficiency of zeolites on the soils contaminated with heavy metals. Some authors (Belousov, 2006) emphasized their high selectivity for heavy metals. Other authors (Baidina, 1994; Dabakhov et al., 1998) reported the lower efficiency of zeolites compared to lime materials and a significant limitation in the mobility of heavy metals in the soil and their input into plants only at zeolites application rates of 80100 t/ha and more. This is also true for the effect of organic fertilizers (Dabakhov et al., 1998). At the same time, it should be noted that the use of zeolites as sorbents of heavy metals is limited by the following factors. First, the volume of zeolites applied is very large, which makes them applicable only near zeolites fields. Second, along with heavy metal cations, zeolites can sorb potassium, ammonium, and microelement ions, i.e., affect the conditions of the mineral nutrition of plants (Baidina, 1994). Third, data are available that zeolites are subjected to weathering, during whish they can be transformed into other minerals with different properties of cation sorption. Fourth, exchange on some zeolites minerals proceeds even more slowly than on clay minerals. The completion of this process, i.e., the penetration of exchangeable cations into channel-shaped holes, takes much time. This property of zeolites is used in plant growing: they are mixed with organic fertilizers. Long-acting composite fertilizers are prepared by this method. Glauconite fields are common in Rostov oblast. Glauconite enters in sands, sandstones, clay, and marls. Total predicted resources of the mineral in Rostov oblast exceed 20 million m3 (Khardikov et al., 1999). The adsorption properties of zeolites are determined by the unique crystal lattice characterized by a developed internal surface and a strictly determined size of input windows. Zeolites are a sort of molecular sieves capable to sorb molecules of specific size from their mixtures. Only molecules whose size is smaller than the input window can penetrate into the adsorption cavity. Zeolites can adsorb relatively large amounts of heavy metal salts. The CEC of natural zeolites is 100300 mg/kg (Pinsky, 1997). A large number of publications deal with the use of natural zeolites for the purification of water from dissolved chemical impurities, but the use of zeolites as adsorbents of heavy metals is still insufficiently understood (Panin, Bairova, 2005). A higher efficiency of the simultaneous application of ameliorants compared to their separate application was noted repeatedly (Baidina, 1994; Chen, Looi, Liu, 1999; Geebelen, Nangronsveld, Clijsters, 1999). In the recommendations for decreasing the toxicity of soils contaminated with heavy metals (Determination of Toxicity, 1985), it was proposed to use lime materials and high rates of organic fertilizers (100150 t/ha). There are also many less common methods. The claying of coarse soils, which significantly increases their cation exchange capacity, can give good results (Sizov et al., 1990). An expensive method for decreasing the mobility of heavy metals involves the use of ion-exchange resins containing carboxyl and hydroxyl groups. Resins are used in the acid form or saturated with potassium, calcium, or magnesium ions or their mixture and applied to the soil as granules or powders. Many authors noted the high efficiency of liming the contaminated soils (Basta, Armstrong, Hanke, 2001; Brown et al., 2001; Yang et al., 2008). The Rostov oblast has immense reserves of limestone. However, liming is widely used for acid soils but not for neutral and slightly alkaline soils. Therefore, the main goal of the suggested approach is to determine the group composition and mobility of heavy metals in soils for studying the possibility of using different ameliorants in chernozem contaminated with Cu, Zn, and Pb. MATERIAL AND METHODS The object of research loamy ordinary chernozem from which has following properties: Corg, 2.3%; CaCO3, 0.4%, pH H2O, 7.6; particles <0.01 mm, 53.1%; particles <0.001 mm; exchangeable Ca2+, 29 meq/100 g; exchangeable Mg2+, 0.4 meq/100 g; and exchangeable Na+, 0.1 meq/100 g. The effect of different ameliorants on ordinary chernozem contaminated with heavy metals was studied in a long-term field experiment (2000-2008) in the Rostovskii state crop testing site. Ameliorants were applied three months after the contamination of soils with Zn and Pb acetates. Chalk (2.5 and 5 mg/m2), glauconite (2 kg/m2), and semidecomposed cattle manure (5 kg/m2) were used as ameliorants, as well as their combinations according to the following experimental design: (1) without ameliorants; (2) metal (Me); (3) Me + glauconite; (4) Me + manure; (5) Me + glauconite + manure; (6) Me + chalk, 2.5 kg/m2; (7) Me + chalk, 5 kg/m2; (8) Me + chalk, 2.5 kg/m2 + manure; (9) Me + chalk, 5 kg/m2 + manure. Experiments were conducted in triplicate. Samples were taken at a depth of 020 cm. The chalk used in the experiment contained the following metal contents (mg/kg): Zn, 10.3; Ni, 2.56; Mn, 17.3; Cr, 17.4. As, Pb, Cu, and Fe were not found in the samples (Table 1). Table 1: Heavy metal content in the chalk, mg/kg As bZn!uNiFenCr--10,3-2,56-17,317,4 Based on the results of pot experiment on soils with different contents of carbonates, the following application rates of chalk were used in the field experiment on soil remediation: 2.5 and 5 kg/m2. Glauconite was used as a natural sorbent. Glauconite (from the Greek glaucos bluish-green) is a complex potassium-containing aluminosilicate, mineral of hydromica group, layered silicate subclass, with the formula [(Fe3+, Al)1,33 (Fe2+, Mg)0,67]2 Si3,67 Al0,33 O10(OH)2-. Rock mineralogy: fraction >0.01 mm, 75% (including glauconite, 42%; quartz, 32%); fraction <0.01 mm, 25% (including glauconite, 24%; quartz, 1%). Montmorillonite, calcite, sponge spicules, and siliceous organism residues were not found in the samples. The total content of glauconite in the rock was 66%. Bulk chemical composition of rocks: SiO2, 69.5%; Al2O3, 4.9%; Fe2O3, 13.8%; FeO, 0.20%; CaO, 1.35%; MgO, 1.94%; MnO, 0.016%; K2O, 3.60%; Na2O, 0.18%; P2O5, 0.41%; TiO2, 0.30%; SO3(tot), 0.10%; CO2, not det., B2O3, 0.06%; Whygr, 2.08%; organic matter, 0.23%. The content of heavy metals in glauconite was as follows: Li, 0.0018%; Zn, 0.0034%; Cu, <0.001%; Pb, <0.01%; Ni, 0.004%; Cr, 0.0164%; V, <0.01%; F, 0.16%; Co, <0.001%; Mn, 0,010%. In the experimental glauconite samples, Pb was not found and the content of Zn was 0.1 mg/kg. With account for the application rate of 2 kg/m2, 2 mg/kg Zn arrived to the soil with glauconite. Semidecomposed cattle manure had the following parameters: water, 65.2%; ash, 26.2%; pH, 7.5; Ntot, 0.85%; P2O5tot, 0.87%; 2Otot, 0.90%. Total heavy metals in manure: Zn, 60.0 mg/kg; Pb, 12 mg/kg; Cd, 4 mg/kg; Cu, 9 mg/kg. With account for the organic fertilizer rate (5 kg/m2), 3 mg/kg Zn and 0.6 mg/kg Pb were applied to the soil. The total amount of HMs in soils was determined by X-ray fluorescence. Metals in soil extracts were determined by atomic absorption spectroscopy. We distinguish between two major fractions of heavy metal: (a) firmly bound (FB) and (b) loosely bound (LB) to the soil. To determine the total contents of heavy metals, the soil samples were digested with a mixture of concentrated (HClO4 + HF) acids. The contents of the LB metal fractions were determined in a series of extracts. The concentrations of heavy metals in the extracts were determined using atomic absorption spectrophotometer. The LB fraction includes exchangeable, complexed and specifically adsorbed metals (Minkina et al, 2008). It characterizes the pool of metals that can migrate from the soil into the adjacent media, including plants and natural waters. The scheme of sub-fractioning of the LB (potentially mobile) metal compounds and the corresponding extraction procedures are shown in Fig. 1.  Figure 1: Sub-divisions of the loosely bound metal fraction in soils and their extractants The metal compounds extracted with 1 M NH4OAc, pH 4.8 (soil : solution ratio of 1 : 5, extraction time 18 h)are classified as exchangeable. The 1 % EDTA in 1 M NH4OAc, pH 4.8 (soil : solution ratio of 1 : 5, extraction time 18 h) presumably extracts exchangeable heavy metals and those bound in the organometallic complexes. These extractants are recommended for determining the mobile forms of heavy metals in agricultural soils (Mineev, 1989). The difference between the metal contents in the 1 % EDTA in NH4OAc and 1M NH4OAc extracts should characterize the content of metals bound in complexes with the soil organic matter (Minkina et al, 2006, 2009). The 1 N HCl solution extracts (soil : solution ratio of 1 : 10, extraction time 1 h) specifically adsorbed metals together with exchangeable metals and dissolves metal oxides and carbonates. A considerable part of the specifically adsorbed heavy metals is relatively loosely fixed by iron, aluminum, and manganese oxides and hydroxides and by carbonates. The contents of specifically adsorbed heavy metal compounds are calculated as the differences between their amounts extracted with 1 N HCl and 1 M NH4OAc. This group can be considered as a transitional group between loosely and firmly bound heavy metals. The calculation of the complex-forming and specifically adsorbed compounds of heavy metals from the difference in the heavy metal contents in different extracts is based on the assumption of their additivity. To verify this assumption, we used the procedure of sequential extraction of the metals with solutions of 1N NH4OAc and 1% EDTA and 1N NH4OAc and 1N HCl. The results obtained by the method of sequential extraction and those calculated from the difference of the metal contents in parallel extracts agreed with one another fairly well. The contents of FB heavy metals with the soil organic and mineral components were calculated as the difference between the bulk contents of the metals and the contents of LB metals. The FB fractions includes the metals strongly fixed in the structures of silicate and nonsilicate minerals, in difficultly soluble compounds ((hydr)oxides and carbonates) and stable organic and organomineral compounds. To characterize the mobility of heavy metals in the soils, we calculated the ratio of LB fractions to FB ones: MF = LB/FB. RESULTS AND DISCUSSION The analysis of the group composition of heavy metal compounds in the reclaimed soils revealed the mechanism of ameliorant action on the mobility of heavy metals in soils. The total content of metals in the soils with ameliorants remained almost similar to that in the contaminated soils (Table 2). However, the group of weakly bound compounds and, hence, the mobility of metals decreased (Tables 2,3) because of the decrease in the absolute content of all mobile Zn and Pb forms: exchangeable, complex, and specifically sorbed ones (Table 5). The effects of chalk, manure, and glauconite on the mobilization of metal in the soil were different. Already in the first year after the application of chalk, in distinction from other ameliorants, the content of exchangeable Zn and Pb forms in the soil decreased to the MCL level and lower. The share of weakly bound compounds (Table 3) and the value of MF (Table 4) decreased to a higher extent than at the application of glauconite or manure. The main difference between the effects of 2.5 and 5% chalk on the mobility of metals was that the share of specifically sorbed forms in the group composition of Zn and Pb increased with increasing application rate of chalk. The content of exchangeable compounds decreased respectively. Table 2: The total content (numerator) and the ratio between the weakly and strongly bound Zn and Pb compounds (denominator) during 3 years after the application of ameliorants. Experimental treatmentsZnPb1 year2 year3 year1 year2 year3 yearWithout metal addition 68 12/8865 12/8867 12/8824 15/8524 15/8528 12/88Metal (Me)356 32/68349 35/65352 36/64110 38/62101 45/55100 42/58Me + glauconite 346 14/86358 13/87344 7/93106 32/68111 31/69108 16/84Me + manure 360 17/83360 12/88353 10/90110 26/74102 27/73106 24/76Me + glauconite + manure 363 15/85365 15/85352 13/87109 22/78101 25/75111 17/83Me + chalk, 2.5 kg/m2 350 13/87341 14/86345 10/90111 18/82105 31/69101 12/88Me + chalk, 5 kg/m2 347 16/84342 16/84344 9/91108 17/83112 23/77103 17/83Me + chalk, 2.5 kg/m2 + manure 361 11/89346 12/88353 5/95105 19/81112 18/82110 16/84Me + chalk, 5 kg/m2 + manure 359 11/89350 11/89353 6/94114 13/87106 16/84104 11/89LSD0.95 for numerator 12,39,08,37,510,39,5 The effect of glauconite and manure applied separately on the fixation of Zn and Pb was lower, which could be related to the formation of their metal compounds with lower binding strength and insufficient interaction time. Manure organic matter favored the relatively rapid formation of unstable zinc complexes, which were decomposed already to the second year after application, and the released metal passed into more stable organomineral forms. For lead, the formation rates of metal complexes with manure organic substances were lower; however, their amount significantly increased for three years (Tables 3, 5). The content of specifically sorbed lead compounds increased because of the reinforcement of their bond with soil components and transition into strongly bound compounds. Table 3: Weakly bound Zn and Pb compounds in ordinary chernozem during 3 years after the application of ameliorants, mg/kg Experimental treatmentsCompoundsExchangeable Complex Specifically sorbed 1 year2 year3 year1 year2 year3 year1 year2 year3 yearZnWithout metal addition 0,60,60,60,40,50,46,56,86,9Metal (Me)33,027,626,127,923,724,452,369,876,6Me + glauconite 27,816,26,98,16,41,3614,424,116,4Me + manure 25,118,18,414,55,77,620,317,719,1Me + glauconite + manure 25,412,63,610,65,613,219,936,229,5Me + chalk, 2.5 kg/m2 21,69,33,97,87,23,017,230,929,3Me + chalk, 5 kg/m2 18,04,51,08,814,04,8829,937,825,0Me + chalk, 2.5 kg/m2 + manure 15,46,84,78,26,150,515,327,412,1Me + chalk, 5 kg/m2 + manure 10,24,01,09,86,04,0520,026,513,2LSD0.956,48,02,31,42,012,210,39,95,1PbWithout metal addition 0,80,91,00,30,30,12,42,52,2Metal (Me)12,810,88,76,012,814,722,921,718,3Me + glauconite 8,46,13,04,98,74,820,919,49,5Me + manure 8,06,65,33,64,07,517,116,912,4Me + glauconite + manure 7,25,31,51,86,86,614,913,110,5Me + chalk, 2.5 kg/m2 6,73,22,74,59,52,69,320,06,8Me + chalk, 5 kg/m2 4,63,00,94,25,41,89,517,714,5Me + chalk, 2.5 kg/m2 + manure 5,72,21,51,57,35,112,911,110,5Me + chalk, 5 kg/m2 + manure 4,52,01,00,24,93,49,810,07,1LSD0.951,44,01,11,32,31,69,910,54,0 It should be noted that the change in mobility of heavy metals in the soil at the application of manure was related not only to the formation of metal-organic compounds, but also to the degree of organic matter decomposition. The mineralization of semidecomposed manure in the soil could be accompanied by the formation of water-soluble low-molecular-weight organic complexes, which increased the migratory capacity of metals. As organic matter was decomposed, the immobilizing effect became more manifested due to the formation of more strongly bound compounds of heavy metals with organic matter. A similar phenomenon was observed at the application of fresh manure and undecomposed and semidecomposed straw to the soil (Sizov et al., 1990). Table 4: Mobility factor (MF) of Zn and Pb in the soil during 3 yeas after the application of ameliorants Experimental treatmentsMF ZnMF Pb1 year2 year3 year1 year2 year3 yearWithout metal addition 0,10,10,10,20,20,1Metal (Me)0,50,50,60,60,80,7Me + glauconite 0,20,20,10,50,40,2Me + manure 0,20,10,10,40,40,3Me + glauconite + manure 0,20,20,20,30,30,2Me + chalk, 2.5 kg/m2 0,20,20,10,20,50,1Me + chalk, 5 kg/m2 0,20,20,10,20,30,2Me + chalk, 2.5 kg/m2 + manure 0,10,10,10,20,20,2Me + chalk, 5 kg/m2 + manure 0,10,10,10,10,20,1 Table 5: Loosely bound Zn and Pb compounds (numerator) and the ratio of their exchangeable, complex, and specifically sorbed forms (denominator) during 3 years after the application of ameliorants. Experimental treatmentsZnPb1 year2 year3 year1 year2 year3 yearWithout metal addition 8 8/5/878 8/6/868 8/5/874 23/9/684 24/8/683 30/3/67Metal (Me)113 29/25/46121 23/19/58127 21/19/6042 31/14/5545 24/28/4842 21/35/44Me + glauconite50 55/16/2947 35/14/5125 28/6/6734 25/14/6134 18/25/5717 17/28/55Me + manure60 42/24/3442 43/14/4335 24/22/5429 28/12/6028 24/15/6125 21/30/49Me + glauconite + manure56 45/20/3555 23/11/6646 8/28/6424 30/8/6225 21/27/5219 8/36/56Me + chalk, 2.5 kg/m247 46/17/3747 20/15/6536 11/8/8121 33/22/4533 10/29/6112 22/22/56Me + chalk, 5 kg/m257 32/16/5256 8/25/6731 3/16/8118 25/23/5226 11/21/6817 5/11/84Me + chalk, 2.5 kg/m2 + manure39 40/20/4040 17/15/6818 26/6/6820 28/8/6421 11/35/5417 9/30/61Me + chalk, 5 kg/m2+ manure40 25/25/5037 11/16/7318 5/22/7315 31/1/6817 12/29/5912 9/29/62LSD0,95 for numerator10.39.95.19.910.54.0Note: Data in numerator and denominator are given in mg/kg and % of the group of loosely bound compounds, respectively. According to the efficiency of the separate application of ameliorants in the fixation of Zn and Pb in the soil, they form the series: chalk > glauconite H" manure. Thus, chalk is the best sorbent for Pb, as well as for Zn. The following possible mechanisms of its effect on metals in contaminated soils are supposed: (1) chemisorption of metals on the surface of CaCO3 particles; 2) formation of separate solid phases (precipitates of heavy metal carbonates and hydroxocarbonates); 3) increase in the sorption activity of Fe, Al, and Mn oxides in the presence of carbonates; and 4) formation of heavy metal hydroxocomplexes at increasing pH, which can increase their sorption by the soil. The action of the above mechanisms was described in detail in the previous Section. The dissolution of chalk in the field and model experiments mainly occurred in the first year after application; insignificant changes were observed in the following years (Minkina et al., 2007), which pointed to the possible formation of chemically sorbed metal carbonates and the further stabilization of the calciumcarbonate system. The formation of separate solid phases of heavy metal carbonates can play a significant role in the immobilization of pollutants, because the addition of carbonates to the contaminated soil under field experimental conditions creates conditions for the precipitation of low-soluble metal compounds. Thus, it can be supposed that chemisorption and precipitation can be the main mechanisms of Zn and Pb sorption by carbonates in ordinary chernozem. The increase in the sorption activity of FeMn (hydr)oxides in calcareous soils plays an important role in the fixation of pollutants. The simultaneous application of manure and chalk enhanced the sorption effect and resulted in the maximum decrease in the content of loosely bound Zn and Pb compounds. Already in the first year of their simultaneous use, the group ratio and, hence, the mobility of metals was similar to the analogous parameters of the initial soil (Tables 2, 4). This could be related to the fact that the stabilization of organic manure compounds with the formation of stable organomineral complexes occurred in the presence of chalk. These complexes strongly fixed heavy metals and made them unavailable for extraction by the reagents used. The addition of 10% of humic acids to calcite under model experimental conditions increased the adsorption of Zn compared to the pure CaCO3 (Brummer et al., 1983). The results of studies showed differences in the behavior of Zn and Pb under the application of manure. When the soil was composted with manure, the share of complex Zn forms and specifically sorbed Pb forms increased and the content of loosely sorbed metal compounds decreased in the first year (Table 5). In the following two years, the share of complex forms decreased for Zn and increased for Pb. This could be due to the formation of mobile Zn complexes with organic ligands and more stable Pb complexes. The efficiency of remediation was significantly higher in the second and third years after the application of ameliorants, which was related to the transformation rates of metal compounds and their more complete interaction with the sorbents. It is suggested that the effect of metal nature on the transformation of its compounds becomes the most important with time, regardless of the ameliorant. General and specific features were revealed in the transformation of compounds of two metals under the effect of ameliorants. The general tendencies were as follows: the application of all ameliorants decreased the mobility of metals; the addition of manure to chalk or glauconite increased the binding strength by soils and decreased the content of their exchangeable compounds; the highest ameliorating effect was observed at the simultaneous application of chalk and manure to the contaminated soils; in the contaminated soils and those treated with ameliorants, most of the loosely bound metal compounds were specifically sorbed forms representing the nearest reserve of strongly bound metal compounds; the transformation of metal compounds occurred in the contaminated soil during three years after the application of ameliorants, which resulted in a decrease in their mobility and in the share of the most migration-capable exchangeable forms and the corresponding increase in the content of strongly bound forms. The difference in the state of soils polluted with lead and zinc salts contained in ameliorants was that the rates of zinc fixation in soils were higher. Therefore, the share of strongly bound zinc compounds reached and even exceeded the values typical for clear soils (Table 2). As for lead, only the simultaneous application of chalk and manure increased the relative content of its strongly bound forms to the level of the initial soil. CONCLUSION The application of ameliorants significantly decreased the mobility of metals. Their effect depended on the ameliorant and was most significant at the simultaneous application of chalk and manure. This effect was presumably due to the strong binding of metals by carbonates through chemisorption and formation of low-soluble Zn and Pb compounds and to the additional fixation in the form of complexes at the addition of organic material. 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