Adsorption of radiotoxic heavy metals by colloid particles - evidence from mine waters of the Königstein mine


Adsorption of radiotoxic heavy metals by colloid particles - evidence from mine waters of the Königstein mine

Zänker, H.; Jenk, U.

Acidic pore waters are the waters of most chemical importance in abandoned ore mines before the mines' flooding. These waters possess high concentrations of sulfuric acid and reach pH values of 3 to 1. In particular in the case of the Königstein uranium mine they contain high amounts of sulfuric acid because of the former ore extraction technology (acidic underground leaching with sulfuric acid). Typically, acidic pore waters have iron concentrations of the range of grams per liter. This iron is partly dissolved and partly colloidal (particle size < 5 nm, cf. [1]). Most of the heavy metals, including U(VI), are truly dissolved in acidic pore waters. Only As and Pb have been found in a colloid-borne form [1].

From a chemical point of view, the flooding of a mine is primarily the dilution of the pore waters by groundwaters. The following concomitant phenomena are accompanying this process in the Königstein mine: a decrease in heavy metal concentrations, a decrease in H2SO4 concentration (increase of the pH), an ingress of oxygen and an ingress of carbonate. This gives rise to chemical reactions such as the neutralization of sulfuric acid by carbonate, the degassing of carbonate as CO2, the oxidation of Fe2+ into Fe3+ and the hydrolysis of Fe3+, i.e. the formation of Fe(III) particles. We asked ourselves what the interactions of the radiotoxic heavy metals with these Fe(III) particles are and what the behavior and later fate of the particles (possibly carrying radiotoxic heavy metals) is.

According to the existing knowledge there should not be much interaction between the < 5 nm Fe(III) particles and the radiotoxic heavy metals in the acidic pore waters (exception: 210Pb). With increasing pH, elements such as Th, Po, Ac etc. begin to adsorb strongly onto the particles. Also the uranyl increasingly tends to sorb onto the particles with increasing pH. However, uranyl adsorption to the particles is counteracted by carbonate complexation in the solution the importance of which also increases with increasing pH. Therefore, uranyl is often assumed to be truly dissolved under the conditions of real mine waters, either due to high acidity (low pH region) or due to carbonate complexation (higher pH). It remains to be elucidated if there is a pH region where also the uranyl occurs colloid-borne in a mine.

We investigated flooding waters from the Königstein mine by light scattering, centrifugation, filtration, ultrafiltration, scanning electron microscopy, laser doppler electrophoresis, ICP-MS, AAS, ion chromatography and diverse radiometric methods. The waters had a pH of 5.6 and an Eh of 450 mV, the concentrations of important constituents were CCa 0.9 mM, CFe 0.3 mM, CU 0.05 mM, Csulfate 1.2 mM, Ccarbonate 1,0 mM and CO2 0.11mM. Almost 90 % of the iron was divalent. Because of the Eh value we assume that the uranium was hexavalent. Colloid concentrations in the range of 2 to 3 mg/L were found; they rose rapidly if the access of oxygen was allowed. The particle size was about 100 nm. We measured a zeta potential of only -7.5 mV, i.e. the electrostatic stabilization of the particles was weak. Therefore the particles showed a pronounced tendency to aggregate and sediment. Strongly-sorbing radionuclides such as 210Po and 210Pb, but also significant fractions of the uranyl (up to 100 %) were colloid-borne. The amount of the sorbed uranyl was very sensitive to pH changes of only few tenth of pH units. This senstivity is obviously attributable to the fact that the pH of the water was in the vicinity of the point of inflection of the uranyl - Fe oxyhydroxide "adsorption edge". The uranium and the other radiotoxic heavy metals studied, with the exception of radium, followed the tendency of the iron(III) particles to aggregate and sediment.

We conclude that there is a pH range where the U(VI) occurs colloid-borne in mine waters, even if carbonate is present. This range is pH 4 to 6 (see also [2]). The assumption of an unretarded m...

  • Lecture (Conference)
    The 8th International Conference on Radioactive Waste Management and Environmental Remediation (ICEM'01). September 30 - October 4, 2001, Bruges (Brugge), Belgium
  • Poster
    8th International Conference on Radioactive Waste Management and Environmental Remediation (ICEM ´01). Session 68 (UMREG). Bruges (Belgium), September 30 - October 4, 2001. Proceedings Session 68
  • Contribution to proceedings
    8th International Conference on Radioactive Waste Management and Environmental Remediation (ICEM ´01). Session 68 (UMREG). Bruges (Belgium), September 30 - October 4, 2001. Proceedings Session 68

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