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CHEMICAL SPECIATION IN SOLUTION AND SUSPENSION OF METAL POLLUTANTS AND AS IN WATERS, CONTAMINATED BY METALLURGICAL AND MINING ACTIVITIES
Abstract
Chemical species of existence and migration of water metal pollutants in solution and suspension in the significantly contaminated Plovdiv – Assenovgrad area are identified in their dynamics. Underground, surface and technological waters in their geochemical context are investigated (more than 2 000 data) as a ground of the speciation study (30 trace and 24 major elements). All the trace elements analytical researches are carried out by HR-ICP-AES Jobin Yvon ULTIMA 2 and the speciation study – by WATEQ 4F adapted program. About 60 chemical species for the heavy metal + As pollutants in every water are proved, about 40 – for the major components. 3D-presentation and juxtaposition, priority ranges and respective interpretation for every metal pollutant, As, and the major compounds are effected. For ex. Cd appears the pollutant with the most pronounced speciation differentiation in function of the water type. In the ground waters a generalized rate for the Pb forms importance could be presented as follows: PbCO3>PbHCO3 >Pb(CO3)2 2->Pb2+>PbSO4>PbOH+>Pb(SO4)2 2- and for Zn: Zn2+>ZnHCO3 +> ZnCO3>ZnSO4>Zn(SO4)2 2->Zn(CO3)2 2->ZnOH+>ZnCl+. In surface waters only different carbonate species predominate as in waste waters (together with hydroxide and sulfate forms). The presence in solution of heavy metal mobile forms and their secondary modification are ensured by the complexation and to the good migration ability of a pronounced diversity of established chemical species, with different relative weight and accumulation possibilities. The migration form mobility, controlled by about than 200 mineral phases, more or less near to equilibrium, is very distinguished for ground and surface waters. The oversaturation is found to be typical for the more polluted waters. The separated on membrane filter 0.45 $\mu$m suspended matter in the studied waters is very abundant and the Electron Microprobe Analysis investigations identify various mineral and chemical forms and paragenesises. In technological water suspension twenty trace elements are established (Hg, Ta, Se, Y in between) and Zn, Fe, Pb, Cu oxides determine the composition. Suspended matter in some polluted ground waters is characterized by a composition like: 50\% ZnO, 4\% PbO, 24\% SiO2, 6\%Al2O3, 9\% FeO, 1\% BaO, 1\% K2O, 4\% CaO, 0,2 \% MgO, 0,5 \% MnO, 0,4 \% CuO and 0,2\% TiO. The chemical speciation analysis of individual suspended matter particles (500) using EPMA, is very good differentiated in function of the pollution quality characteristics: a) Zn together with Mn and Fe is included mainly in Al-Si-Fe (or Fe-Si and Al-Zn) particles in polluted ground waters (where the most important particle size is registered); b) in quarry lake water Al-Ca-Cl particles are enriched with Mn, Fe, P, S; c) in non polluted ground waters only Fe and Al (and some Mn) are identified in Al-Si, Fe-Si and Al-Fe rich particles. The present and future state of the dynamic equilibrium between the different species in solution and suspension (defining the biological and toxical activity of the pollutants) are so elucidated and the definitive hydrogeochemical characteristics of the waters with possibilities for preservation and forecasting of their evolution are suggested. The investigations are financed by the Bulgarian budget of the NATO Science for Peace Program Project NATO SfP 973 739 “WATMETAPOL”.
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References2
Ball J.W., Nordstrom D.K. and Zachmann D.W . (1987). WATEQ 4F – a personal computer Fortran translation of the geoc hemical model WATEQ 2 with revised data base. US Geol. Surv. Open-file Rep. 87-50: 107pp. International Standard, Internationa l Organization for Standardization, (1996) ISO 11885:1196 (E). “Water quality – Determina tion of 33 elemen ts by inductively coupled plasma atomic spectrometry”. 13pp., (Geneve, Switzerland). Pentcheva E. N., Fouillac C., and Gijbels R. (2000) Dynamics, Evol ution and Limitation of heavy metal water pollution in the Pl ovdiv Region (Bulgaria). NATO Science for Peace Program Project 973 739 “WATMETAPOL”, Sofia – Orleans. Pentcheva E. N., Veldeman E., Van’t dack L. and Gijbels R . (1992) Trace Element geochemistry of the system ”rock–therm al water–suspended matters–deposits” In: Kharaka Y.K, and Maest A. S. (Ed.) Proc. of 7-th Int. Symp . On Water – Rock Interaction – WRI-7” (Kharaka Y.K. a. Maest A.S. eds.), A.A. Balkema, Rotterdam,
1325. Pentcheva E. N., Velitchkova N. and Van’t dack L. (2002) Chemical Speciation in Solution and Suspension of Heavy metal Pollutants in Waters (Plovdiv Region, Bulgaria) In: Environmental Science and Pollution Research International, Proc. Special Issue 3, 2002, p. 213-214. International Conference
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