Behavior and Impact of Zirconium in the Soil–Plant System: Plant Uptake and Phytotoxicity

Because of the large number of sites they pollute, toxic metals that contaminate terrestrial ecosystems are increasingly of environmental and sanitary concern (Uzu et al. 2010, 2011; Shahid et al. 2011a, b, 2012a). Among such metals is zirconium (Zr), which has the atomic number 40 and is a transition metal that resembles titanium in physical and chemical properties (Zaccone et al. 2008). Zr is widely used in many chemical industry processes and in nuclear reactors (Sandoval et al. 2011; Kamal et al. 2011), owing to its useful properties like hardness, corrosion-resistance and permeable to neutrons (Mushtaq 2012). Hence, the recent increased use of Zr by industry, and the occurrence of the Chernobyl and Fukashima catastrophe have enhanced environmental levels in soil and waters (Yirchenko and Agapkina 1993; Mosulishvili et al. 1994 ; Kruglov et al. 1996)

Experimental study of uraninite solubility in aqueous HCl solutions at 500°C and 1 kbar

Uraninite solubility in 0.001–2.0 m HCl solutions was experimentally studied at 500°C, 1000 bar, and hydrogen fugacity corresponding to the Ni/NiO buffer. It was shown that the following U(IV) species dominate in the aqueous solution: U(OH)40, U(OH)2Cl20, and UOH Cl30 Using the results of uraninite solubility measurement, the Gibbs free energies of U(IV) species at 500°C and 1000 bar were calculated (kJ/mol): −9865.55 for UO2(aq), −1374.57 for U(OH)2 Cl20, and −1265.49 for UOH Cl30, and the equilibrium constants of uraninite dissolution in water and aqueous HCl solutions were estimated: UO2(cr) = UO2(aq), pK0 = 6.64; UO2(cr) + 2HCl0 = U(OH)2 Cl20, pK2 = 3.56; and UO2(cr) + 3HCl0 = UOHcl30 + H2O, pK3 = 3.05. The value pK1 ≈ 5.0 was obtained as a first approximation for the equilibrium UO2(cr) + H2O + HCl0 = U(OH)3Cl0. The constant of the reaction UO2(cr) + 4HCl0 = UCl40 + 2H2O (pK4 = 7.02) was calculated taking into account the ionization constants of U Cl40 and U(OH)40, obtained by extrapolation from 25 to 500°C at 1000 bar using the BR model. Intense dissolution and redeposition of gold (material of experimental capsules) was observed in our experiments. The analysis and modeling of this phenomenon suggested that the UO2 + x/UO2 redox pair oxidized Au(cr) to Au+(aq), which was then reduced under the influence of stronger reducers