Enregistrement scientifique n : 1548 Symposium n : 25 Présentation : poster. BZOWSKI Zbigniew, DAWIDOWSKI Andrzej

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1 Enregistrement scientifique n : 1548 Symposium n : 25 Présentation : poster Assessment of the Cu and Zn forms contents being available for plants, in the soils subjected to the impact of copper metallurgy, Poland L évaluation des teneurs en Cu et Zn assimilables par les plantes dans les sols exposés à l influence d une fonderie de cuivre (Pologne) BZOWSKI Zbigniew, DAWIDOWSKI Andrzej Department of Environmental Monitoring, Central Mining Institute, pl. Gwarkow 1, KATOWICE, Poland. ABSTRACT On the area adjacent from the North and East-North to the sanitary zone of the copper foundry the soil samples were taken in the translation lattice with application of the kilometre netting of the geodesy map. General characteristic of those soils as well as contents of heavy metals were presented. Detailed tests on the Cu and Zn amounts being available for plants in those soils were also carried out. Both, total amounts of copper as well as these available for plants in tested soils show the possibility of its impact on the changes of the biological activity of the soils. Availability of the other heavy metals correlates with the content of the copper being available for plants, and coexistence together with the lead in tested soils accounts for the immision-like character of the soils pollutions from the one source of emission. Determined amounts of the Zn being available for plants in the soils subjected to the impact of copper metallurgy do not present the eco-chemical problem. The method for liquidation of the excessive amounts of copper from soils adjacent to the sanitary zone and in the zone itself, may be the application of modern methods for reclamation of those soils through the procedure of fitoextraction or bioremedy actions. INTRODUCTION Soil is an important element of the natural environment. Contents of heavy metals in soils as well as their profile arrangement depends on the type of matrix rocks as well as course of soil-creating processes. Potential sources of contamination causedby heavy metals are first and foremost industrial and power plants, mineral fertilisers, sewage sediments and protective chemicals used for plants. Tests on impacts of copper metallurgy on the environment give indication of imission-like character of the degradation of soils in their vicinity (Szerszen et al. 1991, Dobrzanski,Byrdziak 1995, Straczynski,Andruszczak 1995). 1

2 The aim of the work is assessment of the amount of the copper and zinc originating probably for the copper metallurgy emission, accumulated in the soils of agriculture prove-nance, being adjacent to the sanitary zone of these metal works. TESTING MATERIAL The tests covered arable soils situated on the area adjacent from the North and East-North to the sanitary zone of "Glogów" Copper Metallurgy Plant. Samples were taken in the points of translation network of 500 m vector with the use of kilometre geodetic map graticule. Points sampling were grouped in four one-kilometre zones. In the "A" zone there were taken 10 soil samples within a distance of 2-3 kilometre from the metallurgy plant, and in subsequent zones as follows: "B"-14 samples within 3-4 kilometre, "C"-21 samples within 4-5 km and "D" - 25 samples within 5-6 kilometre. The samples were taken by punching from the A p (0-20 cm) layer, by means of a soil probe, "T" type and were prepared for transportation to the Environmental Monitoring Unit of the Central Mining Institute, Katowice. METHODS FOR TESTS The sampled soils were determined with respect to: ph, granulometric composition, organic carbon, total content of heavy metals (Cd, Cu, Pb, Zn) as well as the amounts of Cu and Zn being available for plants. The reaction was measured in solutions received after flooding the tested soils by water together with 1n KCl in the proportion 1:2.5. Granulometric composition was determined by aerometric method elaborated by Casagrande with modifications by Prószynski. Organic carbon was determined according to the modified method by Tiurin (Ostrowska et al. 1991). Available amounts of copper and zinc for plants were extracted form soils by 1n HCl with a proportion of soil-solution as 1:10. The time of shaking was equal to 1 hour (Komisarek et al. 1988). Both, heavy metal contents and available amounts of Cu and Zn for plants in the tested soils were determined by means of the emission spectrometry with induced plasma (AES - ICP). Determinations were performed in the Department of Environmental Monitoring of the Central Mining Institute, by means of the ICP Optima 3000DV, Perkin Elmer spectrometer. RESULTS AND DISCUSSION As far as granulometric properties are concerned, there are mainly medium and heavy soils in the tested area being adjacent to the sanitary zone (SZ) of the copper metallurgy plant. Contents of silly minerals range from 2.5 to 42%. The lowest contents were determined in occasionally existing sand soils. The amount over 25% of silt appear in soils of heavy clay character. The reaction of tested soils measured in water oscillates from 5.6 to 8.1; and in 1n KCl - from 4.1 to 7.7 (tab.1). Remarkable diversification of soils ph is connected with their liming. Efficiency of this process may be noticed both in the scope of the measured ph values and in means counted for particular zones from "A" to "D". Contents of organic matter in those soils oscillate in wide ranges of 0.4 to 3.1% (tab.1). 2

3 Table 1 General characteristic of the tested soils adjacent to the "Glogów" Copper Metallurgy Plant sanitary zone Zone A B C D Distance to work in km Soil samples (n) ph H 2 O ph KCl C org in % Clays <0.002 mm in % High total contents of copper and lead are characteristic for the tested soils (tab.2). Particularly, amounts of Cu and Pb being co-existent in tested soils of all zones accounts for imission-like character of their presence and for origin from the same source (tab.3, figure 1) "Glogów" Copper Metallurgy Plant is that source within the tested area. Ecotoxicological denotation of so high content of copper and lead depends on complexing of the organic compounds and limiting the availability of phosphoric nourishing components for plants. This problem occurs in soils on all tested area. Table 2 Contents of heavy metals in tested soils as well as copper and zinc in forms being available for plants. Zone A B C D Distance to work in km Soil samples (n) Cu (total) Cd (total) Pb (total) Zn (total)

4 Cu 1n HCl Zn 1n HCl in in Fig. 1. Dependence between total contents of Cu and Pb in the tested soils adjacent to SZ, i.e. 2-6 kilometre from the copper metallurgy plant. Samples of soils taken on the areas adjacent to the SZ copper metallurgy plant were subjected to the tests for the amounts of copper and zinc being available for plants. In mineral soils, 80% of total contents of copper is bounded with ferric oxides, the remaining part presents exchangeable forms and is bounded in organic matter (Komisarek et al. 1988). It may be concluded then that the amounts of copper being available for plants are in a substantial dependence on a total contents. It refers also to the areas situated further from the source of contamination (Fig.2) High contents of copper in the form being available for plants cause considerable changes of biological activity of soils which has an unfavourable impact on planning of cultivated plants. Absorption of remarkable amounts of copper by plants cause the increase of contamination of plants also by other heavy metals, zinc included. 4

5 Table 3 Correlation coefficients and level their fundamentality for dependences of heavy metals contents in the tested soils of particular zones of various distances from copper metallurgy plant. For: Cu/Pb Cu/Cd Cu/Zn Pb/Cd Pb/Zn Cd/Zn Zone A (2-3km) n = 10 Zone B (3-4km) n = 14 Zone C (4-5km) n = 21 Zone D (5-6km) n = 25 r α r α r α r α

6 Fig. 2. Dependences between total amounts of copper and Cu contents being available for plants in tested soils of particular zones of various distance from copper metallurgy plant. 6

7 Fig. 3. Dependences of zinc amounts being available for plants from copper contents; a) total; b) being available, determined in the tested soils of "A" zone in a distance of 2-3 kilometre from copper metallurgy plant. The process of assimilation of heavy metals may be limited by keeping up the soil ph KCl within range of which effectively lower transmission process of total forms of heavy metals into their forms being available. However, if we consider occurrence of soils with respect to the zones, the smaller is the distance from the copper metallurgy plant, the less successful is liming performed in order to stabilise soil reaction. As far as the "C" and "D" zones are concerned (4-6 km) monitoring of the reaction for limitation of migration of heavy metals is possible, whereas in case of "A" and "B" zones (2-4 km) lowering of copper and other heavy metals contents, particularly their forms being available for plants, requires reclamation of these soils through fitoextraction or bioremedy processes. CONCLUSIONS 1. Basing on the tests of arable soils carried out on the area adjacent do the "Glogów" Copper Metallurgy Plant sanitary zone, straight-lineary dependence of coexistence of Cu and Pb in those soils was determined. Apart from that there are straight dependences between total volume of copper in those soils and copper contents in the form being available for plants. 2. Determined amounts of zinc being available for plants in soils subjected to the impact of copper metallurgy plant do not make any ecochemical problem. 3. Treatment of the tested soils and removal high contents of copper and lead in the zone from 2 to 4 km from the copper metallurgy plant requires application of biological or bio-chemical methods. REFERENCES Dobrzanski J.,Byrdziak H Impact of the polish copper industry on the environment. Agric.Sc.Probl. Polish Soil Soc. 418,

8 Komisarek J.E.,Gembarzewski H.,Kocialkowski W.Z Estimation of extraction methods for determination of available Cu, Zn, Mn and Fe forms in soil. Soil Sc.Polish Soil Soc. no 108; Ostrowska A.,Gawlinski S.,Szczubialka Z Methods of analysis and property evaluations of soils and plants (in Polish). IOS Warsaw. Straczynski S., Andruszczak E Estimation of the state of the soil and plant pollution by trace elements in the surroundings of copper smelting works "Glogów" Agric.Sc.Probl. Polish Soil Soc. 418, Szerszen L.,Karczewska A.,Roszyk E.,Chodak T Distribution of Cu, Pb and Zn in profiles of soils adjoining cooper metallurgic plants. (in Polish) Soil Sc. Annual no3/4, Key words : heavy metals, metallic pollution, Cu, Zn, plant availble content, industrial pollution, Poland Mots clés : métaux lourds, pollution industrielle, pollution métallique, Cu, Zn, teneur assimilable, Pologne 8