Determination of SO4β1 for Yttrium and the Rare Earth Elements at I = 0.66 M and T = 25°C—implications for YREE Solution Speciation in Sulfate-rich Waters

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We present a complete set of stability constants (SO4β1) for the monosulfato-complexes of yttrium and the rare earth elements (YREE), except Pm, at I = 0.66 m and t = 25°C, where SO4β1 = [MSO4+] × [M3+]−1[SO42−]−1 (M ≡ YREE and brackets indicate free ion concentrations on the molal scale). Stability constants were determined by investigating the solubility of BaSO4 in concentrated aqueous solutions of MCl3. This is the first complete set to be published in more than 30 years.

The resulting SO4β1 pattern is very similar in shape to one reported by de Carvalho and Choppin (1967a) (I = 2 mol/L; t = 25°C) that has been largely ignored. Stability constants vary little between La and Sm, but display a weak maximum at Eu. Between Eu and Lu, SO4β1 decreases by 0.2 log units, substantially exceeding the ±0.02 log unit average analytical precision. The stability constant for Y is approximately equal to that for Er. Our SO4β1 pattern is consequently distinctly different from the consensus pattern, based on a single data set from 1954, which is essentially flat, with a range of only 0.07 log units between the lowest and highest SO4β1 values within the lanthanide series (excluding Y).

Values of SO4β1 obtained in this work, in conjunction with the ion-pairing model of Millero and Schreiber (1982), allow prediction of SO4β1 between 0 and 1 m ionic strength. These results are used to assess both the absolute and relative extent of YREE sulfate complexation in acidic, sulfate-rich waters.

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Geochimica et Cosmochimica Acta, v. 68, issue 13, p. 2825-2837