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Öğe Chemical controls on the solubility, speciation and mobility of lanthanum at near surface conditions: A geochemical modeling study(Pergamon-Elsevier Science Ltd, 2008) Cetiner, Ziya S.; Xiong, YongliangRecent experimental determinations of the solubility products of common rare earth minerals Such as monazite and xenotime and stability constants for chloride, sulfate, carbonate and hydroxide complexes provide a basis to model quantitatively the solubility, and therefore the mobility, of rare earth elements (REE) at near surface conditions. Data on the mobility of REE and stabilities of REE complexes at near-neutral conditions are of importance to safe nuclear waste disposal, and environmental monitoring. The aim of this study is to understand REE speciation and Solubility of a given REE in natural environments. In this study, a series of formation constants for La aqueous complexes are recommended by using the specific interaction theory (SIT) for extrapolation to infinite dilution. Then, a thermodynamic model has been employed for calculation of the solubility and speciation of La in soil solutions reacted with the La end-member of mineral monazite (LaPO4), and other La-bearing solid phases including amorphous lanthanum hydroxide (La(OH)3, am) and different La carbonates, as a function of various inorganic and organic ligand concentrations. Calculations were carried out at near-neutral pH (pH 5.5-8.5) and 25 degrees C at atmospheric CO2 partial pressure. The model takes account of the species : La3+, LACl(2+), LaCl2+, LaCl30, LaCl4-, LaSO4+, La(SO4)(2)(-), LaCO3+, La(CO3)(2)(-), LaHCO32+, La(OH)(2+), LaOx(+), La(Ox)(2)(-), LaAc2+ and La(Ac)(2)(-) (where Ox(2-) = oxalate and Ac- = acetate). The calculations indicate that the La species that dominate at pH 5.5-8.5 in the baseline model soil solution (BMSS) include La3+, Laox(+), LaSO4+, LaCO3+ and La(CO3)(2)(-) in order of increasing importance as pH rises. The Solubility ofnionazite in the BMSS remains less than similar to 3 x 10(-9) M, exhibiting a minimum of similar to 2 x 10(-1)2 M at pH 7.5. The calculations quantitatively demonstrate that the concentrations of La controlled by the solubility of other La-bearing solid phases are many orders of magnitude higher than those controlled by monazite in the pH range from 5.5 to 8.5, suggesting that monazite is likely to be the Solubility-controlling phase at this pH range. The calculations also suggest that significant mobility of La (and other REE) is unlikely because high water-rock ratios on the order of at least 104 (mass ratio) are required to move 50% of the La from a soil. An increase in concentration of oxalate by one order of magnitude from that of the baseline model solution results in the dominance of LaOx(+) at pH 5.5-7.5. Similarly, the increase in concentration of SO42- by one order of magnitude makes LaSO4+ the dominant species at pH 5.5-7.5. Above pH 7.5, carbonate complexes are important. The increase in oxalate or SO42- concentrations by one order of magnitude can enhance the solubility of monazite by a factor of up to about 6 below neutral pH, in comparison with that in the baseline model soil solution. From pH 7.0 to 8.5, the solubility of monazite in the soil solutions with higher concentrations of oxalate or SO42- is similar, or almost identical, to that in the BMSS. (c) 2008 Elsevier Ltd. All rights reserved.Öğe Comment on The experimental determination of hydromagnesite precipitation rates at 22.5-75°C by Berninger, U.-N., Jordan, G., Schott, J. and Oelkers, EH(Mineralogical Soc, 2017) Xiong, Yongliang; Cetiner, ZiyaIn this work, we tested the equilibrium constant of hydromagnesite [Mg-5(CO3)(4)(OH)(2) center dot 4H(2)O] at 22.5 degrees C proposed by Berninger et al. (2014) against field observations. By field observations we mean that analytical results originate from samples in the natural environment. In our test, we calculated saturation states of hydromagnesite, using the equilibrium constant of hydromagnesite at 22.5 degrees C from Berninger et al., for the carbonate lakes in Qinghai-Xizang Plateau in China and for Salda Lake in Turkey, based on the hydrochemical data from literature. The predictions based on this equilibrium constant indicate that all of these lakes are strongly under-saturated with respect to hydromagnesite. However, hydromagnesite has been shown to form in all of these lakes. Therefore, this equilibrium constant is clearly in direct contradiction with field observations, leading to the conclusion that the equilibrium constant of hydromagnesite of Berninger et al. (2014) is not suitable for geochemical modelling.Öğe Experimental determination of equilibrium solubility quotients of the natural colemanite in NaCl solutions up to 2.0 m(Pergamon-Elsevier Science Ltd, 2007) Cetiner, Ziya; Xiong, Yongliang; Ozkan, Safak Gokhan[Anstract Not Available]
